JP2006163373A - Resin-coated ferrite carrier for electrophotographic developer, its production method, and electrophotographic developer using the resin-coated ferrite carrier - Google Patents
Resin-coated ferrite carrier for electrophotographic developer, its production method, and electrophotographic developer using the resin-coated ferrite carrier Download PDFInfo
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- JP2006163373A JP2006163373A JP2005319895A JP2005319895A JP2006163373A JP 2006163373 A JP2006163373 A JP 2006163373A JP 2005319895 A JP2005319895 A JP 2005319895A JP 2005319895 A JP2005319895 A JP 2005319895A JP 2006163373 A JP2006163373 A JP 2006163373A
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- Prior art keywords
- resin
- carrier
- coated
- electrophotographic developer
- particles
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Abstract
Description
本発明は、複写機、プリンター等に用いられる二成分系電子写真現像剤用の樹脂被覆フェライトキャリア及びその製造方法、並びに該フェライトキャリアを用いた電子写真現像剤に関し、詳しくは均一で異臭等の問題を生じない樹脂被覆フェライトキャリア及びその製造方法、並びに該フェライトキャリアを用い、長期に渡って良好な特性を有し、高速化及びフルカラー化に充分に対応できる電子写真現像剤に関する。 The present invention relates to a resin-coated ferrite carrier for a two-component electrophotographic developer used in a copying machine, a printer, and the like, a method for producing the same, and an electrophotographic developer using the ferrite carrier. The present invention relates to a resin-coated ferrite carrier that does not cause a problem, a method for producing the same, and an electrophotographic developer that uses the ferrite carrier and has good characteristics over a long period of time and can sufficiently cope with high speed and full color.
電子写真法に使用される二成分系現像剤はトナーとキャリアとにより構成されており、キャリアは現像剤ボックス内でトナーと混合攪拌され、トナーに所望の電荷を与え、電荷を帯びたトナーを感光体上の静電潜像に運び、トナー像を形成させる担体物質である。キャリアはトナー像を形成した後も、マグネットに保持され現像ロール上に残り、さらに再び現像ボックスに戻り、新たなトナー粒子と再び混合攪拌され、一定期間繰り返し使用される。 The two-component developer used in electrophotography is composed of a toner and a carrier, and the carrier is mixed and stirred with the toner in the developer box to give the toner a desired charge, and the charged toner is removed. A carrier material that carries the electrostatic latent image on the photoreceptor to form a toner image. Even after the toner image is formed, the carrier is held by the magnet and remains on the developing roll. The carrier is returned to the developing box again, mixed and stirred again with new toner particles, and used repeatedly for a certain period.
この二成分系現像剤は、一成分系現像剤と異なり、キャリアが、トナー粒子を攪拌し、トナー粒子に所望の帯電性を付与すると共に、トナーを搬送する機能を有しており、現像剤設計において制御性がよいため、特に高画質の要求されるフルカラー機並びに画像維持の信頼性及び耐久性の要求される高速機の分野に広く使用されている。 Unlike the one-component developer, the two-component developer has a function in which the carrier stirs the toner particles, imparts desired chargeability to the toner particles, and transports the toner. Since it has good controllability in design, it is widely used in the field of full-color machines especially requiring high image quality and high-speed machines requiring image maintenance reliability and durability.
このような二成分系電子写真現像剤においては、従来、キャリアとして酸化皮膜鉄粉、樹脂被覆鉄粉等の鉄粉系キャリアが用いられていた。例えば特許文献１（特開平６−１９２１４号公報）には、キャリア芯材として鉄粉及び球形フェライトの混合物を用い、被覆樹脂は２層からなり、下層被覆材がポリアミドイミド樹脂を含む四フッ化エチレン系樹脂であり、表面被覆材が四フッ化エチレンパーフロロアルキルビニルエーテル共重合樹脂であるフルカラー複写機用キャリアが記載されている。 In such a two-component electrophotographic developer, iron powder carriers such as oxide film iron powder and resin-coated iron powder have been conventionally used as carriers. For example, in Patent Document 1 (Japanese Patent Laid-Open No. 6-19214), a mixture of iron powder and spherical ferrite is used as a carrier core material, the coating resin consists of two layers, and the lower layer coating material contains a polyamidoimide resin. There is described a carrier for a full-color copying machine which is an ethylene resin and whose surface coating material is a tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin.
特許文献１に記載されているような鉄粉系キャリアは、一粒子の真比重が大きいため、現像機内でのストレスが大きく、その長寿命化が困難である。また、２層からなる樹脂被覆キャリアは、層間剥離の問題が生じる。
The iron powder carrier as described in
そこで、鉄粉系キャリアに比べて真比重が小さい、Ｃｕ−Ｚｎフェライト、Ｎｉ−Ｚｎフェライト等のフェライトキャリアが用いられている。また、これらのフェライトキャリアは従来の鉄粉系キャリアに比べ高画質画像を得るのに有利な特質を多く持っている。 Therefore, ferrite carriers such as Cu—Zn ferrite and Ni—Zn ferrite, which have a smaller true specific gravity than iron powder carriers, are used. Moreover, these ferrite carriers have many advantageous properties for obtaining high-quality images as compared with conventional iron powder carriers.
これらフェライトキャリアとしては球状のものが一般に用いられている。しかし、球状フェライトキャリアのみでは、耐トナースペント性に劣るため、近年の高耐久化に対応できなくなっている。 As these ferrite carriers, spherical ones are generally used. However, the spherical ferrite carrier alone is inferior in toner spent resistance, and thus cannot cope with the recent increase in durability.
このため、フェライト粒子をキャリア芯材とし、その表面に樹脂を被覆した樹脂被覆フェライトキャリアが用いられている。ここに用いられる被覆樹脂としては、シリコーン樹脂やフッ素エポキシ樹脂等が用いられている。 For this reason, a resin-coated ferrite carrier in which ferrite particles are used as a carrier core and the surface thereof is coated with a resin is used. As the coating resin used here, a silicone resin, a fluorine epoxy resin, or the like is used.
しかし、シリコーン樹脂を被覆した樹脂被覆フェライトキャリアにおいては、連続印刷における機内温度上昇に伴う、帯電量変化により、カブリ及びキャリア付着の発生が問題となった。また、フッ素エポキシ樹脂を被覆した樹脂被覆キャリアにおいては、耐刷に伴うトナースペントによる帯電低下により、トナーの飛散及びカブリの発生が問題となり、また経時において帯電量も低下し、耐久性に劣る。また、フッ素エポキシ樹脂を用いる場合には、溶剤はメチルイソブチルケトンのような臭気強度の強い有機溶剤を含む必要があるが、この場合には製造時に異臭等の問題があった。 However, in the resin-coated ferrite carrier coated with a silicone resin, the occurrence of fog and carrier adhesion has become a problem due to the change in the charge amount accompanying the increase in the in-machine temperature during continuous printing. In addition, in a resin-coated carrier coated with a fluoroepoxy resin, toner scattering and fogging become a problem due to a decrease in charge due to toner spent accompanying printing, and the amount of charge decreases with time, resulting in poor durability. In addition, when a fluorine epoxy resin is used, the solvent needs to contain an organic solvent having a strong odor strength such as methyl isobutyl ketone. In this case, however, there is a problem such as a bad odor at the time of production.
このため、被覆樹脂としてフッ素系樹脂を用いることが提案されている。特許文献２（特開昭５５−６７７５４号公報）には、ポリテトラフルオロエチレン５〜５５％、フッ素化されたポリエチレンプロピレン５〜５５％、ポリ（アミド─イミド）からなる樹脂系被覆によってコアが覆われているキャリアを用いた現像剤が記載されている。 For this reason, it has been proposed to use a fluorine-based resin as the coating resin. In Patent Document 2 (Japanese Patent Laid-Open No. 55-67754), a core is formed by a resin-based coating composed of 5 to 55% polytetrafluoroethylene, 5 to 55% fluorinated polyethylene propylene, and poly (amide-imide). A developer using a covered carrier is described.
しかし、特許文献２で用いられるキャリア芯材はキャリアビーズであり、フェライト粒子ではない。また、特許文献２で用いられる被覆樹脂は、ポリテトラフロロエチレンを含むものであり、ポリテトラフロロエチレンを含む樹脂をキャリア芯材に被覆した場合には、被覆樹脂は粘土状となり、良好な被覆が得られない。このため、このような樹脂被覆キャリアを用いた現像剤は、種々の特性が劣ったものとなる。
However, the carrier core material used in
また、特許文献３（特開昭５４−１２６０４０号公報）には、キャリア芯材の表面にフルオロポリマーより低融点で誘電率の大きな樹脂を含む中間層を介してフルオロポリマーを含む材料からなる外皮層を設けた電子写真現像剤用キャリア材が記載されています。そして、中間層としてポリアミド樹脂、エチレン−酢酸ビニル樹脂が例示されている。 Further, Patent Document 3 (Japanese Patent Laid-Open No. Sho 54-122040) discloses an outer layer made of a material containing a fluoropolymer through an intermediate layer containing a resin having a lower melting point and a higher dielectric constant than the fluoropolymer on the surface of the carrier core material. A carrier material for electrophotographic developer with a skin layer is described. Examples of the intermediate layer include polyamide resin and ethylene-vinyl acetate resin.
しかし、この特許文献３においても用いられるキャリア芯材は鋼ビーズであり、フェライト粒子ではない（実施例参照）。また、２層からなる樹脂被覆キャリアは、層間剥離の問題が生じ、しかもポリアミドイミド樹脂を被覆樹脂の成分として用いるものでもない。 However, the carrier core material used also in Patent Document 3 is a steel bead, not a ferrite particle (see Examples). In addition, the resin-coated carrier composed of two layers has a problem of delamination and does not use a polyamideimide resin as a component of the coating resin.
このように、樹脂被覆キャリアを用いる試みは種々なされているが、均一な被覆がなされ、また異臭等の問題を生じず、しかも電子写真現像剤としたときに長期にわたって良好な種々の特性を有する樹脂被覆キャリアは得られてない。 As described above, various attempts have been made to use the resin-coated carrier. However, it has a uniform coating, does not cause a problem such as a bad odor, and has various characteristics that are good for a long time when used as an electrophotographic developer. A resin-coated carrier has not been obtained.
一方、特許文献４（特開２００２−１４８８６９号公報）には、樹脂コートキャリアの被覆樹脂層が、フッ素樹脂、バインダー樹脂及び特定比表面積及び特定平均粒径を有するシリカ粒子を含む樹脂コートキャリアが記載されている。このシリカ粒子は、フッ素樹脂との相乗作用により、キャリア表面へのトナーによるスペントが防止され、シリカ粒子によりキャリアの流動性が良好となるとされている。 On the other hand, Patent Document 4 (Japanese Patent Application Laid-Open No. 2002-148869) discloses a resin-coated carrier in which a coating resin layer of a resin-coated carrier includes a fluororesin, a binder resin, and silica particles having a specific surface area and a specific average particle diameter. Are listed. It is said that the silica particles are prevented from spent by the toner on the carrier surface due to a synergistic action with the fluororesin, and the carrier fluidity is improved by the silica particles.
しかし、この特許文献４においても、上記したのと同様に、均一な被覆がなされ、また異臭等の問題を生じず、しかも電子写真現像剤としたときに長期にわたって良好な種々の特性を有する樹脂被覆キャリアは得られてない。 However, in this Patent Document 4 as well, as described above, a resin that has a uniform coating, does not cause a problem such as off-flavor, and has various characteristics that are favorable over the long term when used as an electrophotographic developer. No coated carrier has been obtained.
従って、本発明の目的は、均一な樹脂被覆が得られ、異臭等のない樹脂被覆フェライトキャリア及びその製造方法、並びに該樹脂フェライトキャリアを用い、長期に渡り帯電安定性及び画質安定性に優れ、しかもカブリやキャリア付着も少なく、また画像濃度及び環境依存性も良好な、高速化及びフルカラー化に充分に対応できる電子写真現像剤を提供することにある。 Therefore, the object of the present invention is to obtain a uniform resin coating, a resin-coated ferrite carrier free from off-flavors and the like, a method for producing the same, and the resin ferrite carrier. In addition, an object of the present invention is to provide an electrophotographic developer that can sufficiently cope with high speed and full color, with less fog and carrier adhesion, and good image density and environmental dependency.
本発明者らは、鋭意検討の結果、バインダー樹脂を水系溶剤に溶解した樹脂溶液に、特定のフッ素系樹脂及び酸化ケイ素を分散させることによって得られた樹脂含有水溶液によって、フェライト粒子（キャリア芯材）の表面を被覆することによって、上記目的が達成し得ることを知見し、本発明に至った。 As a result of intensive studies, the present inventors have made it possible to obtain ferrite particles (carrier core material) by using a resin-containing aqueous solution obtained by dispersing a specific fluorine-based resin and silicon oxide in a resin solution obtained by dissolving a binder resin in an aqueous solvent. It was found that the above object can be achieved by coating the surface of (2), and the present invention has been achieved.
すなわち、本発明は、フェライト粒子の表面が、４フッ化エチレン・６フッ化プロピレン共重合体又は４フッ化エチレン・パーフロロアルキルビニルエーテル共重合体とポリアミドイミド樹脂との混合樹脂で被覆されており、該混合樹脂が酸化ケイ素を含有していることを特徴とする電子写真現像剤用樹脂被覆フェライトキャリアを提供するものである。 That is, in the present invention, the surface of the ferrite particles is coated with a mixed resin of a tetrafluoroethylene / hexafluoropropylene copolymer or a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer and a polyamideimide resin. The present invention provides a resin-coated ferrite carrier for an electrophotographic developer, wherein the mixed resin contains silicon oxide.
本発明に係る樹脂被覆フェライトキャリアにおいて、上記混合樹脂中の４フッ化エチレン・６フッ化プロピレン共重合体又は４フッ化エチレン・パーフロロアルキルビニルエーテル共重合体とポリアミドイミド樹脂との混合重量比が９：１〜６：４であることが好ましい。 In the resin-coated ferrite carrier according to the present invention, the mixing weight ratio of the tetrafluoroethylene / hexafluoropropylene copolymer or the tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer and the polyamideimide resin in the mixed resin is It is preferably 9: 1 to 6: 4.
本発明に係る樹脂被覆フェライトキャリアにおいて、また、上記酸化ケイ素を混合樹脂中に０．１〜５重量％含有することが好ましい。 In the resin-coated ferrite carrier according to the present invention, the silicon oxide is preferably contained in an amount of 0.1 to 5% by weight in the mixed resin.
本発明に係る樹脂被覆フェライトキャリアにおいて、上記混合樹脂の被覆量が、上記フェライト粒子に対して０．０１〜１０重量％であることが好ましい。 In the resin-coated ferrite carrier according to the present invention, the coating amount of the mixed resin is preferably 0.01 to 10% by weight with respect to the ferrite particles.
また、本発明は、ポリアミドイミド樹脂を水系溶剤に溶解した樹脂溶液に、４フッ化エチレン・６フッ化プロピレン共重合体又は４フッ化エチレン・パーフロロアルキルビニルエーテル共重合体と酸化ケイ素とを分散させて樹脂含有水溶液を調製し、該水溶液を用いてフェライト粒子表面に上記樹脂を被覆することを特徴とする電子写真現像剤用樹脂被覆フェライトキャリアの製造方法を提供するものである。 In the present invention, a polytetrafluoroethylene / hexafluoropropylene copolymer or a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer and silicon oxide are dispersed in a resin solution obtained by dissolving a polyamideimide resin in an aqueous solvent. Thus, a method for producing a resin-coated ferrite carrier for an electrophotographic developer is provided, wherein a resin-containing aqueous solution is prepared, and the resin is coated on the surface of ferrite particles using the aqueous solution.
また、本発明、上記樹脂被覆フェライトキャリアとトナーとからなる電子写真現像剤を提供するものである。 The present invention also provides an electrophotographic developer comprising the resin-coated ferrite carrier and a toner.
本発明に係る樹脂被覆フェライトキャリアの製造方法によって、キャリア粒子表面に均一な樹脂被覆が得られ、また水系溶媒を用いているため有機溶剤に起因する異臭等の問題が生じない。また、本発明に係る樹脂被覆フェライトキャリアを用いた電子写真現像剤は、長期に渡り帯電安定性及び画質安定性に優れ、しかもカブリやキャリア付着も少なく、また画像濃度及び環境依存性も良好である。 By the method for producing a resin-coated ferrite carrier according to the present invention, a uniform resin coating is obtained on the surface of the carrier particles, and since an aqueous solvent is used, problems such as a bad odor caused by an organic solvent do not occur. In addition, the electrophotographic developer using the resin-coated ferrite carrier according to the present invention is excellent in charging stability and image quality stability over a long period of time, has little fogging and carrier adhesion, and has good image density and environmental dependency. is there.
以下、本発明を実施するための最良の形態について説明する。 Hereinafter, the best mode for carrying out the present invention will be described.
＜本発明に係る樹脂被覆フェライトキャリア＞
本発明に係る樹脂被覆フェライトキャリアは、フェライト粒子(キャリア芯材)の表面が、４フッ化エチレン・６フッ化プロピレン共重合体又は４フッ化エチレン・パーフロロアルキルビニルエーテル共重合体とポリアミドイミド樹脂との混合樹脂で被覆されている。
<Resin-coated ferrite carrier according to the present invention>
In the resin-coated ferrite carrier according to the present invention, the surface of the ferrite particles (carrier core material) is a tetrafluoroethylene / hexafluoropropylene copolymer or a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer and a polyamideimide resin. And coated with a mixed resin.
本発明に用いられるフェライト粒子(キャリア芯材)としては、その組成は特に限定されないが、好ましくは化１に示す下記式(１)の組成を有するものである。 The composition of the ferrite particles (carrier core material) used in the present invention is not particularly limited, but preferably has the composition of the following formula (1) shown in Chemical Formula 1.
また、上記(１)式中の（ＭｎＯ）及び／又は（ＭｇＯ）の一部を、ＳｒＯ、Ｌｉ２Ｏ、ＣａＯ、ＴｉＯ、ＣｕＯ、ＺｎＯ、ＮｉＯ、Ｂｉ２Ｏ３、ＺｒＯ２から選ばれる１種類以上の酸化物で置換してもよい。 In addition, a part of (MnO) and / or (MgO) in the above formula (1) is selected from SrO, Li 2 O, CaO, TiO, CuO, ZnO, NiO, Bi 2 O 3 , ZrO 2 You may substitute with the oxide more than a kind.
このような特定組成のフェライト粒子は、磁化が高く、磁化の均一性がよいため(磁化のばらつきが少なく)、本発明において好ましく用いられる。 Ferrite particles having such a specific composition are preferably used in the present invention because of high magnetization and good magnetization uniformity (small variation in magnetization).
本発明に用いられる４フッ化エチレン・６フッ化プロピレン共重合体（以下、場合によりＦＥＰと称する）は、融点２５０〜２７０℃のフッ素系樹脂である。また、本発明に用いられる４フッ化エチレン・パーフロロアルキルビニルエーテル共重合体（以下、場合によりＰＦＡと称する）は、融点３００〜３１０℃のフッ素系樹脂である。 The tetrafluoroethylene / hexafluoropropylene copolymer (hereinafter sometimes referred to as FEP) used in the present invention is a fluororesin having a melting point of 250 to 270 ° C. Further, the tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (hereinafter sometimes referred to as PFA) used in the present invention is a fluororesin having a melting point of 300 to 310 ° C.
本発明に用いられるポリアミドイミド樹脂はバインダー樹脂として用いられるもので、その製法、特性等は特に制限されないが、無水トリメリット酸と有機ビスアミン、例えば４，４′─ジアミノジフェニルメタンとの共重合体が代表的である。このような共重合体の平均分子量は代表的には１５０００〜３００００、好ましくは２００００〜２５０００である。その他、無水ピロメリット酸とビスアミン、特に芳香族ビスアミンとの共重合体が使用可能である。このようなポリアミドイミド樹脂をバインダー樹脂として用いることにより、現像剤に高帯電性や機内環境変化に対する安定性、良好な耐スペント性を付与する。 The polyamideimide resin used in the present invention is used as a binder resin, and its production method and characteristics are not particularly limited, but a copolymer of trimellitic anhydride and an organic bisamine such as 4,4'-diaminodiphenylmethane is used. Representative. The average molecular weight of such a copolymer is typically 15000 to 30000, preferably 20000 to 25000. In addition, a copolymer of pyromellitic anhydride and bisamine, particularly an aromatic bisamine can be used. By using such a polyamideimide resin as a binder resin, the developer is imparted with high chargeability, stability against changes in the in-machine environment, and good spent resistance.
上記混合樹脂中の４フッ化エチレン・６フッ化プロピレン共重合体（ＦＥＰ）又は４フッ化エチレン・パーフロロアルキルビニルエーテル共重合体（ＰＦＡ）とポリアミドイミド樹脂との混合重量比は、好ましくは９：１〜６：４であり、さらに好ましくは８：２〜６：４である。ＦＥＰ又はＰＦＡとポリアミドイミド樹脂の混合重量比において、ＦＥＰ又はＰＦＡが上記範囲より混合量が少ないと耐スペント性及び帯電安定性が悪化し、上記範囲より混合量が多いと耐久性が低下する。 The mixing weight ratio of the tetrafluoroethylene / hexafluoropropylene copolymer (FEP) or the tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) and the polyamide-imide resin in the mixed resin is preferably 9 : 1 to 6: 4, more preferably 8: 2 to 6: 4. In the mixing weight ratio of FEP or PFA and polyamide-imide resin, if the amount of FEP or PFA is less than the above range, the spent resistance and charging stability deteriorate, and if the amount is more than the above range, the durability decreases.
本発明に係る樹脂被覆フェライトキャリアにおいては、混合樹脂中に酸化ケイ素を含有する。混合樹脂中に酸化ケイ素を含有することによって、均一な樹脂皮膜が得られ、コア粒子との密着性が向上する。酸化ケイ素の含有量は、混合樹脂中、好ましくは０．１〜５重量％である。酸化ケイ素の含有量が０．１重量％未満では含有効果がなく、５重量％を超えると耐久性が低下する。 In the resin-coated ferrite carrier according to the present invention, the mixed resin contains silicon oxide. By containing silicon oxide in the mixed resin, a uniform resin film is obtained, and the adhesion to the core particles is improved. The content of silicon oxide is preferably 0.1 to 5% by weight in the mixed resin. If the content of silicon oxide is less than 0.1% by weight, there is no effect of inclusion, and if it exceeds 5% by weight, the durability decreases.
上記混合樹脂の被覆量は、上記フェライト粒子（キャリア芯材）に対して、好ましくは０．０１〜１０重量％であり、０．３〜７重量％がさらに好ましい。最も好ましくは０．５〜５重量％である。被覆量が０．０１重量％未満ではキャリア表面に均一な被覆層を形成することが難しく、また１０重量％を超えるとキャリア同士の凝集が発生してしまい、歩留まり低下等の生産性の低下と共に、実機内での流動性あるいは帯電量等の現像剤特性変動の原因となる。 The coating amount of the mixed resin is preferably 0.01 to 10% by weight and more preferably 0.3 to 7% by weight with respect to the ferrite particles (carrier core material). Most preferably, it is 0.5 to 5% by weight. When the coating amount is less than 0.01% by weight, it is difficult to form a uniform coating layer on the carrier surface. When the coating amount exceeds 10% by weight, the carriers are aggregated together with a decrease in productivity such as a decrease in yield. This causes fluctuations in developer characteristics such as fluidity or charge amount in the actual machine.
本発明に係る樹脂被覆フェライトキャリアは、球状であることが望ましく、その平均粒径は、好ましくは２０〜１００μｍであり、さらに好ましくは３０〜７０μｍである。平均粒径が２０μｍ未満であると、キャリア付着が発生しやすくなり、白斑の原因となる。また、１００μｍを超えると、画質が粗くなり、所望の解像度が得られにくくなる。 The resin-coated ferrite carrier according to the present invention is desirably spherical, and the average particle diameter is preferably 20 to 100 μm, more preferably 30 to 70 μm. When the average particle size is less than 20 μm, carrier adhesion tends to occur, causing white spots. On the other hand, if it exceeds 100 μm, the image quality becomes coarse and it becomes difficult to obtain a desired resolution.
また、上記被覆樹脂中には、帯電制御剤としてシランカップリング剤を含有することができる。使用できるカップリング剤の種類は特に限定されないが、負極性トナーの場合はアミノシランカップリング剤が、正極性トナーの場合はフッ素系シランカップリング剤が好ましい。 In addition, the coating resin can contain a silane coupling agent as a charge control agent. The type of coupling agent that can be used is not particularly limited, but an aminosilane coupling agent is preferable for a negative toner, and a fluorine-based silane coupling agent is preferable for a positive toner.
また、上記被覆樹脂中には、導電性微粒子を添加することができる。導電性微粒子としては、導電性カーボンや酸化チタン、酸化スズ等の酸化物、各種の有機系導電剤等が挙げられる。 Conductive fine particles can be added to the coating resin. Examples of the conductive fine particles include conductive carbon, oxides such as titanium oxide and tin oxide, and various organic conductive agents.
＜本発明に係る現像剤用フェライトキャリアの製造方法＞
次に、本発明に係る樹脂被覆フェライトキャリアの製造方法について説明する。
<Method for Producing Ferrite Carrier for Developer According to the Present Invention>
Next, a method for producing a resin-coated ferrite carrier according to the present invention will be described.
先ず、所定組成となるように、フェライト原料を適量秤量した後、ボールミル又は振動ミル等で０．５時間以上、好ましくは１〜２０時間粉砕、混合する。このようにして得られた粉砕物を加圧成型器等によりペレット化した後、７００〜１２００℃の温度で仮焼成する。加圧成型器を使用せずに、粉砕した後、水を加えてスラリー化し、スプレードライヤーを用いて粒状化しても良い。また見掛け密度を下げたい場合は仮焼成の工程は省いてもよい。 First, an appropriate amount of a ferrite raw material is weighed so as to have a predetermined composition, and then ground and mixed with a ball mill or a vibration mill for 0.5 hour or more, preferably 1 to 20 hours. The pulverized material thus obtained is pelletized with a pressure molding machine or the like, and then calcined at a temperature of 700 to 1200 ° C. You may grind | pulverize without using a pressure molding machine, and you may add water to make a slurry, and you may granulate using a spray dryer. Moreover, when it is desired to reduce the apparent density, the preliminary firing step may be omitted.
仮焼成後、さらにボールミル又は振動ミル等で粉砕した後、水及び必要に応じ分散剤、バインダー等を添加し、粘度調整後、造粒し、酸素濃度を制御し、１０００〜１５００℃の温度で１〜２４時間保持し、本焼成を行う。仮焼後に粉砕する際は、水を加えて湿式ボールミルや湿式振動ミル等で粉砕してもよい。 After calcination, and further pulverized with a ball mill or vibration mill, etc., water and, if necessary, a dispersant, a binder, etc. are added, the viscosity is adjusted, granulated, and the oxygen concentration is controlled at a temperature of 1000 to 1500 ° C. Hold for 1 to 24 hours and perform main firing. When pulverizing after calcination, water may be added and pulverized by a wet ball mill, a wet vibration mill or the like.
このように本焼成して得られた焼成物を、粉砕し、分級する。分級方法としては、既存の風力分級、メッシュ濾過法、沈降法等を用いて所望の粒径に粒度調整する。 The fired product obtained through the main firing in this way is pulverized and classified. As a classification method, the particle size is adjusted to a desired particle size using an existing air classification, mesh filtration method, sedimentation method, or the like.
その後、必要に応じて、表面を低温加熱することで酸化被膜処理を施し、電気抵抗調整を行うことができる。酸化被膜処理は、一般的なロータリー式電気炉、バッチ式電気炉等を用い、例えば、３００〜７００℃で熱処理を行う。この処理によって形成された酸化被膜の厚さは、０．１ｎｍ〜５μｍであることが好ましい。０．１ｎｍ未満であると、酸化被膜層の効果が小さく、５μｍを超えると、磁化が低下したり、高抵抗になりすぎるため、現像能力が低下する等の不具合が発生しや易くなる。また、必要に応じて、酸化被膜処理の前に還元を行ってもよい。 Thereafter, if necessary, the surface can be heated at a low temperature to perform an oxide film treatment to adjust electric resistance. For the oxide film treatment, a general rotary electric furnace, batch electric furnace or the like is used, and for example, heat treatment is performed at 300 to 700 ° C. The thickness of the oxide film formed by this treatment is preferably 0.1 nm to 5 μm. If the thickness is less than 0.1 nm, the effect of the oxide film layer is small, and if it exceeds 5 μm, the magnetization is lowered or the resistance becomes too high, so that problems such as a reduction in developing ability are likely to occur. Moreover, you may reduce | restore before an oxide film process as needed.
次いで、上記フェライト粒子（キャリア芯材）の表面に、ポリアミドイミド樹脂とからなる混合樹脂（被覆樹脂）を被覆する。本発明に係る製造方法では、上記ポリアミドイミド樹脂を水系溶剤に溶解した樹脂溶液に、上述したＦＥＰ又はＰＦＡと酸化ケイ素を分散させて樹脂含有水溶液を調製し、該水溶液を用いて上記フェライト粒子の表面に上記混合樹脂を被覆する。フェライト粒子の表面を被覆する樹脂としてフッ素エポキシ樹脂を用いる場合には、溶剤はメチルイソブチルケトンのような臭気強度の強い有機溶剤を含む必要があるが、この場合には製造時に異臭等の問題があった。これに対して、本発明で用いられる混合樹脂は、水に可溶であるため水系溶剤を使用することができるので、上記のような問題が生じない。また、電子写真現像剤を製造した場合に種々の特性が向上する。 Next, a mixed resin (coating resin) composed of a polyamideimide resin is coated on the surface of the ferrite particles (carrier core material). In the production method according to the present invention, the above-mentioned FEP or PFA and silicon oxide are dispersed in a resin solution obtained by dissolving the polyamideimide resin in an aqueous solvent to prepare a resin-containing aqueous solution, and the aqueous solution is used to prepare the ferrite particles. The mixed resin is coated on the surface. When using a fluorine epoxy resin as a resin to coat the surface of the ferrite particles, the solvent needs to contain an organic solvent having a strong odor strength such as methyl isobutyl ketone. there were. On the other hand, since the mixed resin used in the present invention is soluble in water, an aqueous solvent can be used, and thus the above problems do not occur. In addition, when an electrophotographic developer is produced, various characteristics are improved.
被覆する方法としては、公知の方法、例えば刷毛塗り法、流動床によるスプレードライ方式、ロータリドライ方式、万能攪拌機による液浸乾燥法等により被覆することができる。被覆率を向上させるためには、流動床による方法が好ましい。 As a coating method, it can be coated by a known method such as a brush coating method, a spray drying method using a fluidized bed, a rotary drying method, an immersion drying method using a universal stirrer, or the like. In order to improve the coverage, a fluidized bed method is preferred.
樹脂をキャリア芯材に被覆後、焼き付けする場合には、外部加熱方式又は内部加熱方式のいずれでもよく、例えば固定式又は流動式電気炉、ロータリー式電気炉、バーナー炉でもよく、もしくはマイクロウェーブによる焼き付けでもよい。 When the resin is coated on the carrier core and then baked, either an external heating method or an internal heating method may be used, for example, a fixed or fluid electric furnace, a rotary electric furnace, a burner furnace, or by microwave It can be burned.
＜本発明に係る電子写真現像剤＞
本発明に係る電子写真現像剤について説明する。
本発明に係る電子写真現像剤は、上記した樹脂被覆キャリアとトナーとからなる。
<Electrophotographic developer according to the present invention>
The electrophotographic developer according to the present invention will be described.
The electrophotographic developer according to the present invention comprises the above resin-coated carrier and toner.
本発明の現像剤を構成するトナー粒子には、粉砕法によって製造される粉砕トナー粒子と、重合法により製造される重合トナー粒子とがある。本発明ではいずれの方法により得られたトナー粒子を使用することができる。 The toner particles constituting the developer of the present invention include pulverized toner particles produced by a pulverization method and polymerized toner particles produced by a polymerization method. In the present invention, toner particles obtained by any method can be used.
粉砕トナー粒子は、例えば、結着樹脂、荷電制御剤、着色剤をヘンシェルミキサー等の混合機で充分に混合し、次いで、二軸押出機等で溶融混練し、冷却後、粉砕、分級し、外添剤を添加後、ミキサー等で混合することにより得ることができる。 The pulverized toner particles are, for example, a binder resin, a charge control agent, and a colorant are sufficiently mixed with a mixer such as a Henschel mixer, then melt-kneaded with a twin screw extruder or the like, cooled, pulverized, classified, After adding the external additive, it can be obtained by mixing with a mixer or the like.
粉砕トナー粒子を構成する結着樹脂としては特に限定されるものではないが、ポリスチレン、クロロポリスチレン、スチレン−クロロスチレン共重合体、スチレン−アクリル酸エステル共重合体、スチレン−メタクリル酸共重合体、さらにはロジン変性マレイン酸樹脂、エポキシ樹脂、ポリエステル樹脂及びポリウレタン樹脂等を挙げることができる。これらは単独または混合して用いられる。 The binder resin constituting the pulverized toner particles is not particularly limited, but polystyrene, chloropolystyrene, styrene-chlorostyrene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid copolymer, Furthermore, rosin-modified maleic acid resin, epoxy resin, polyester resin, polyurethane resin and the like can be mentioned. These may be used alone or in combination.
荷電制御剤としては、任意のものを用いることができる。例えば正荷電性トナー用としては、ニグロシン系染料及び４級アンモニウム塩等を挙げることができ、また、負荷電性トナー用としては、含金属モノアゾ染料等を挙げることができる。 Any charge control agent can be used. For example, nigrosine dyes and quaternary ammonium salts can be used for positively charged toners, and metal-containing monoazo dyes can be used for negatively charged toners.
着色剤（色剤）としては、従来より知られている染料、顔料が使用可能である。例えば、カーボンブラック、フタロシアニンブルー、パーマネントレッド、クロムイエロー、フタロシアニングリーン等を使用することができる。その他、トナーの流動性、耐凝集性向上のためのシリカ粉体、チタニア等のような外添剤をトナー粒子に応じて加えることができる。 As the colorant (colorant), conventionally known dyes and pigments can be used. For example, carbon black, phthalocyanine blue, permanent red, chrome yellow, phthalocyanine green, etc. can be used. In addition, external additives such as silica powder and titania for improving the fluidity and aggregation resistance of the toner can be added according to the toner particles.
重合トナー粒子は、懸濁重合法、乳化重合法、乳化凝集法、エステル伸長重合法、相転乳化法といった公知の方法で製造されるトナー粒子である。このような重合法トナー粒子は、例えば、界面活性剤を用いて着色剤を水中に分散させた着色分散液と、重合性単量体、界面活性剤及び重合開始剤を水性媒体中で混合攪拌し、重合性単量体を水性媒体中に乳化分散させて、攪拌、混合しながら重合させた後、塩析剤を加えて重合体粒子を塩析させる。塩析によって得られた粒子を、濾過、洗浄、乾燥させることにより、重合トナー粒子を得ることができる。その後、必要により乾燥されたトナー粒子に外添剤を添加する。 The polymerized toner particles are toner particles produced by a known method such as a suspension polymerization method, an emulsion polymerization method, an emulsion aggregation method, an ester elongation polymerization method, or a phase inversion emulsification method. Such polymerized toner particles are prepared by, for example, mixing and stirring a colored dispersion in which a colorant is dispersed in water using a surfactant, a polymerizable monomer, a surfactant, and a polymerization initiator in an aqueous medium. Then, the polymerizable monomer is emulsified and dispersed in an aqueous medium, polymerized while stirring and mixing, and then a salting-out agent is added to salt out the polymer particles. Polymerized toner particles can be obtained by filtering, washing and drying the particles obtained by salting out. Thereafter, if necessary, an external additive is added to the dried toner particles.
さらに、この重合トナー粒子を製造するに際しては、重合性単量体、界面活性剤、重合開始剤、着色剤以外に、定着性改良剤、帯電制御剤を配合することができ、これらにより得られた重合トナー粒子の諸特性を制御、改善することができる。また、水性媒体への重合性単量体の分散性を改善するとともに、得られる重合体の分子量を調整するために連鎖移動剤を用いることができる。 Further, in producing the polymerized toner particles, in addition to the polymerizable monomer, the surfactant, the polymerization initiator, and the colorant, a fixability improving agent and a charge control agent can be blended and obtained. Various characteristics of the polymerized toner particles can be controlled and improved. A chain transfer agent can be used to improve the dispersibility of the polymerizable monomer in the aqueous medium and adjust the molecular weight of the resulting polymer.
上記重合トナー粒子の製造に使用される重合性単量体に特に限定はないが、例えば、スチレン及びその誘導体、エチレン、プロピレン等のエチレン不飽和モノオレフィン類、塩化ビニル等のハロゲン化ビニル類、酢酸ビニル等のビニルエステル類、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸２−エチルヘキシル、アクリル酸ジメチルアミノエステル及びメタクリル酸ジエチルアミノエステル等のα−メチレン脂肪族モノカルボン酸エステル類等を挙げることができる。 The polymerizable monomer used for the production of the polymerized toner particles is not particularly limited. For example, styrene and its derivatives, ethylene unsaturated monoolefins such as ethylene and propylene, vinyl halides such as vinyl chloride, Α-methylene aliphatic monocarboxylic acids such as vinyl esters such as vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, dimethylamino acrylate and diethylaminoester methacrylate Examples include esters.
上記重合トナー粒子の調製の際に使用される着色剤（色材）としては、従来から知られている染料、顔料が使用可能である。例えば、カーボンブラック、フタロシアニンブルー、パーマネントレッド、クロムイエロー及びフタロシアニングリーン等を使用することができる。また、これらの着色剤はシランカップリング剤やチタンカップリング剤等を用いてその表面が改質されていてもよい。 Conventionally known dyes and pigments can be used as the colorant (coloring material) used in the preparation of the polymerized toner particles. For example, carbon black, phthalocyanine blue, permanent red, chrome yellow, phthalocyanine green, and the like can be used. Moreover, the surface of these colorants may be modified using a silane coupling agent, a titanium coupling agent, or the like.
上記重合トナー粒子の製造に使用される界面活性剤としては、アニオン系界面活性剤、カチオン系界面活性剤、両イオン性界面活性剤及びノニオン系界面活性剤を使用することができる。 As the surfactant used in the production of the polymerized toner particles, an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant can be used.
ここで、アニオン系界面活性剤としては、オレイン酸ナトリウム、ヒマシ油等の脂肪酸塩、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム等のアルキル硫酸エステル、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、アルキルリン酸エステル塩、ナフタレンスルホン酸ホルマリン縮合物、ポリオキシエチレンアルキル硫酸エステル塩等を挙げることができる。また、ノニオン性界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンアルキルアミン、グリセリン、脂肪酸エステル、オキシエチレン−オキシプロピレンブロックポリマー等を挙げることができる。さらに、カチオン系界面活性剤としては、ラウリルアミンアセテート等のアルキルアミン塩、ラウリルトリメチルアンモニウムクロライド、ステアリルトリメチルアンモニウムクロライド等の第４級アンモニウム塩等を挙げることができる。また、両イオン性界面活性剤としては、アミノカルボン酸塩、アルキルアミノ酸等を挙げることができる。 Here, examples of the anionic surfactant include fatty acid salts such as sodium oleate and castor oil, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate, and alkyl naphthalene sulfonic acids. Salt, alkyl phosphate ester salt, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salt and the like. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin, fatty acid ester, and oxyethylene-oxypropylene block polymer. . Furthermore, examples of the cationic surfactant include alkylamine salts such as laurylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride and stearyltrimethylammonium chloride. Examples of amphoteric surfactants include aminocarboxylates and alkylamino acids.
上記のような界面活性剤は、重合性単量体に対して、通常は０．０１〜１０重量％の範囲内の量で使用することができる。このような界面活性剤の使用量は、単量体の分散安定性に影響を与えるとともに、得られた重合トナー粒子の環境依存性にも影響を及ぼすことから、単量体の分散安定性が確保され、かつ重合トナー粒子の環境依存性に過度の影響を及ぼしにくい上記範囲内の量で使用することが好ましい。 The surfactant as described above can be used usually in an amount in the range of 0.01 to 10% by weight with respect to the polymerizable monomer. The amount of such a surfactant used affects the dispersion stability of the monomer and also affects the environmental dependency of the obtained polymerized toner particles. It is preferably used in an amount within the above range that is ensured and does not exert an excessive influence on the environment dependency of the polymerized toner particles.
重合トナー粒子の製造には、通常は重合開始剤を使用する。重合開始剤には、水溶性重合開始剤と油溶性重合開始剤とがあり、本発明ではいずれをも使用することができる。本発明で使用することができる水溶性重合開始剤としては、例えば、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、水溶性パーオキサイド化合物を挙げることができ、また、油溶性重合開始剤としては、例えば、アゾビスイソブチロニトリル等のアゾ系化合物、油溶性パーオキサイド化合物を挙げることができる。 For the production of polymerized toner particles, a polymerization initiator is usually used. The polymerization initiator includes a water-soluble polymerization initiator and an oil-soluble polymerization initiator, and any of them can be used in the present invention. Examples of the water-soluble polymerization initiator that can be used in the present invention include persulfates such as potassium persulfate and ammonium persulfate, water-soluble peroxide compounds, and oil-soluble polymerization initiators. Examples thereof include azo compounds such as azobisisobutyronitrile and oil-soluble peroxide compounds.
また、本発明において連鎖移動剤を使用する場合には、この連鎖移動剤としては、例えば、オクチルメルカプタン、ドデシルメルカプタン、ｔｅｒｔ−ドデシルメルカプタン等のメルカプタン類、四臭化炭素等を挙げることができる。 When a chain transfer agent is used in the present invention, examples of the chain transfer agent include mercaptans such as octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, carbon tetrabromide, and the like.
さらに、本発明で使用する重合トナー粒子が、定着性改善剤を含む場合、この定着性改良剤としては、カルナバワックス等の天然ワックス、ポリプロピレン、ポリエチレン等のオレフィン系ワックス等を使用することができる。 Further, when the polymerized toner particles used in the present invention contain a fixability improving agent, a natural wax such as carnauba wax, an olefinic wax such as polypropylene or polyethylene can be used as the fixability improving agent. .
また、本発明で使用する重合トナー粒子が、帯電制御剤を含有する場合、使用する帯電制御剤に特に制限はなく、ニグロシン系染料、４級アンモニウム塩、有機金属錯体、含金属モノアゾ染料等を使用することができる。 Further, when the polymerized toner particles used in the present invention contain a charge control agent, the charge control agent to be used is not particularly limited, and nigrosine dyes, quaternary ammonium salts, organometallic complexes, metal-containing monoazo dyes, etc. Can be used.
また、重合トナー粒子の流動性向上等のために使用される外添剤としては、シリカ、酸化チタン、チタン酸バリウム、フッ素樹脂微粒子、アクリル樹脂微粒子等を挙げることができ、これらは単独であるいは組み合わせて使用することができる。 Examples of the external additive used for improving the fluidity of polymerized toner particles include silica, titanium oxide, barium titanate, fluororesin fine particles, and acrylic resin fine particles. Can be used in combination.
さらに、水性媒体から重合粒子を分離するために使用される塩析剤としては、硫酸マグネシウム、硫酸アルミニウム、塩化バリウム、塩化マグネシウム、塩化カルシウム、塩化ナトリウム等の金属塩を挙げることができる。 Further, examples of the salting-out agent used for separating the polymer particles from the aqueous medium include metal salts such as magnesium sulfate, aluminum sulfate, barium chloride, magnesium chloride, calcium chloride, and sodium chloride.
上記のようにして製造されたトナー粒子の平均粒径は、２〜１５μｍ、好ましくは３〜１０μｍの範囲内にあり、重合トナー粒子の方が粉砕トナー粒子よりも、粒子の均一性が高い。トナー粒子が２μｍよりも小さくなると、帯電能力が低下しカブリやトナー飛散を引き起こし易く、１５μｍを超えると、画質が劣化する原因となる。 The average particle size of the toner particles produced as described above is in the range of 2 to 15 μm, preferably 3 to 10 μm, and the polymerized toner particles have higher particle uniformity than the pulverized toner particles. If the toner particles are smaller than 2 μm, the charging ability is lowered and fog and toner scattering are likely to occur, and if it exceeds 15 μm, the image quality is deteriorated.
上記のように製造されたキャリアとトナーとを混合し、電子写真用現像剤を得ることができる。キャリアとトナーの混合比、即ちトナー濃度は、３〜１５％に設定することが好ましい。３％未満であると所望の画像濃度が得にくく、１５％を超えると、トナー飛散やかぶりが発生し易くなる。 An electrophotographic developer can be obtained by mixing the carrier and toner produced as described above. The mixing ratio of the carrier and the toner, that is, the toner concentration is preferably set to 3 to 15%. If it is less than 3%, it is difficult to obtain a desired image density, and if it exceeds 15%, toner scattering and fogging tend to occur.
上記のように調製された現像剤は、有機光導電体層を有する潜像保持体に形成されている静電潜像を、バイアス電界を付与しながら、トナー及びキャリアを有する二成分現像剤の磁気ブラシによって反転現像する現像方式を用いたデジタル方式のコピー機、プリンター、ＦＡＸ、印刷機等に使用することができる。また、磁気ブラシから静電潜像側に現像バイアスを印加する際に、ＤＣバイアスにＡＣバイアスを重畳する方法である交番電界を用いるフルカラー機等にも適用可能である。 The developer prepared as described above is a two-component developer having a toner and a carrier while applying a bias electric field to an electrostatic latent image formed on a latent image holding member having an organic photoconductor layer. The present invention can be used in digital copying machines, printers, fax machines, printing machines, etc., which use a developing method that reversely develops with a magnetic brush. Further, the present invention can also be applied to a full color machine using an alternating electric field, which is a method of superimposing an AC bias on a DC bias when a developing bias is applied from the magnetic brush to the electrostatic latent image side.
以下、実施例等に基づき本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described based on examples and the like.
＜キャリア製造実施例１＞
ＭｎＯ換算で３９．７ｍｏｌ％、ＭｇＯ換算で９．９ｍｏｌ％、Ｆｅ２０３換算で４９．６ｍｏｌ％、ＳｒＯ換算で０．８ｍｏｌ％になるように各原材料を適量配合し、水を加え、湿式ボールミルで１０時間粉砕、混合し、乾燥させ、９５０℃で４時間保持した後、湿式ボールミルで２４時間粉砕を行ったスラリーを造粒乾燥し、酸素濃度２％雰囲気の中で１２７０℃、６時間保持した後、解砕、粒度調整を行い、マンガン系フェライト粒子（キャリア芯材）を得た。このマンガンフェライト粒子は、平均粒径が３５μｍであり、印加磁場が３０００（１０３／４π・Ａ／ｍ）の時の飽和磁化が７０Ａｍ２／ｋｇであった。
<Carrier Production Example 1>
39.7Mol% in terms of MnO, 9.9 mol% in terms of MgO, 49.6Mol% in Fe 2 0 3 in terms of the respective raw materials was adequate amount to be 0.8 mol% in terms of SrO, water was added, wet The mixture was pulverized, mixed and dried for 10 hours in a ball mill, held at 950 ° C. for 4 hours, and then the slurry which had been pulverized for 24 hours in a wet ball mill was granulated and dried. After holding, pulverization and particle size adjustment were performed to obtain manganese-based ferrite particles (carrier core material). The manganese ferrite particles had an average particle size of 35 μm and a saturation magnetization of 70 Am 2 / kg when the applied magnetic field was 3000 (10 3 / 4π · A / m).
次に、ポリアミドイミド樹脂（無水トリメリット酸と４，４′─ジアミノジフェニルメタンとの共重合体）を水で希釈し、樹脂溶液を調製し、次いで４フッ化エチレン・６フッ化プロピレン共重合体（ＦＥＰ）を分散させ、さらに酸化ケイ素（樹脂全体量の２重量％）を分散させた被覆層形成液を固形分換算で１５０ｇ得た。この時の樹脂溶液の固形分比は１０重量％であった。この際のポリアミドイミド樹脂とＦＥＰの重量組成比は２／８であった。この被覆層形成液を用い、上記フェライト粒子１０ｋｇと共に流動床被覆装置に投入して被覆を行った。その後、２５０℃で１時間、焼付けを行い、樹脂被覆量１．５重量％の樹脂被覆フェライトキャリア１を製造した。
Next, a polyamide-imide resin (copolymer of trimellitic anhydride and 4,4'-diaminodiphenylmethane) is diluted with water to prepare a resin solution, and then a tetrafluoroethylene / hexafluoropropylene copolymer 150 g of a coating layer forming solution in which (FEP) was dispersed and silicon oxide (2% by weight of the total amount of the resin) was dispersed was obtained in terms of solid content. The solid content ratio of the resin solution at this time was 10% by weight. At this time, the weight composition ratio of the polyamideimide resin and FEP was 2/8. Using this coating layer forming solution, 10 kg of the ferrite particles were put into a fluidized bed coating apparatus for coating. Thereafter, baking was performed at 250 ° C. for 1 hour to produce a resin-coated
＜現像剤製造実施例１＞
上記キャリア１とトナー１（京セラミタ社製ＫＭ−Ｃ２６３０トナー、色：マゼンタ、組成：ポリエステル、製法：粉砕法）とを用い、トナー濃度６重量％の現像剤Ａを調製し、評価機としてＫＭ−Ｃ２６３０（京セラミタ社製）を用い、初期及び１００Ｋ後の画像評価を行った。初期の画像評価は、帯電量、トナー濃度、画像濃度、カブリ、画質及びキャリア付着について行い、１００Ｋ後の画像評価は、帯電量、トナー濃度、画像濃度、カブリ、画質、環境依存性及びキャリア付着について行った。結果を図１に一覧表にして示す。また、評価方法を下記に示す。
<Developer Production Example 1>
Using the
（帯電量）
Ｅｐｐｉｎｇ社製Ｑ／Ｍメーターを使用して測定した。
(Charge amount)
It measured using the Q / M meter by Epping.
（画像濃度）
適正露光条件下で現像を行い、ベタ部の画像濃度を日本平版機材社製Ｘ−Ｒｉｔｅ９３８によって測定し、ランク付けを行った。画像濃度目標値は１．２５以上である。
(Image density)
Development was performed under appropriate exposure conditions, and the image density of the solid portion was measured by X-Rite 938 manufactured by Nihon Kikei Kaisha Co., Ltd. and ranked. The image density target value is 1.25 or more.
（カブリ）
日本電色工業社製色差計Ｚ−３００Ａを使用して測定した。カブリ目標値は５以下である。
(Fog)
It measured using the Nippon Denshoku Industries color difference meter Z-300A. The fog target value is 5 or less.
（画質）
適正露光下で現像を行い、画質評価を目視によって判定し、下記の基準で評価した。
○：良好
△：実用レベルでの使用は問題なし
×：使用不可
(image quality)
Development was performed under proper exposure, and the image quality evaluation was judged by visual observation, and evaluation was performed according to the following criteria.
○: Good △: No problem in practical use ×: Unusable
（キャリア付着）
適正露光条件下で現像を行い、画像上のキャリア付着、白斑のレベルを目視によって判定し、下記の基準で評価した。
○：良好
△：実用レベルでの使用は問題なし
×：使用不可
(Carrier adhesion)
Development was carried out under appropriate exposure conditions, the level of carrier adhesion and vitiligo on the image was judged by visual observation, and evaluation was performed according to the following criteria.
○: Good △: No problem in practical use ×: Unusable
（環境依存性）
Ｌ／Ｌ及びＨ／Ｈ環境下において、適正露光下で現像を行い、画質評価を目視によって判定し、下記の基準で評価した。
○：良好
△：実用レベルでの使用は問題なし
×：使用不可
(Environment dependency)
Development was performed under appropriate exposure in L / L and H / H environments, and the image quality evaluation was judged visually and evaluated according to the following criteria.
○: Good △: No problem in practical use ×: Unusable
＜キャリア製造実施例２＞
実施例１と同様の方法でフェライト粒子を製造し、フッ素系樹脂としてＦＥＰに代えて４フッ化エチレン・パーフロロアルキルビニルエーテル共重合体（ＰＦＡ）を用いた以外は、実施例１と同様にして混合樹脂をキャリア粒子の表面に被覆し、樹脂被覆量１．５重量％の樹脂被覆フェライトキャリア２を製造した。
<Carrier Production Example 2>
Ferrite particles were produced in the same manner as in Example 1, and the same procedure as in Example 1 was performed except that tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) was used as the fluororesin instead of FEP. The surface of the carrier particles was coated with the mixed resin to produce a resin-coated
＜現像剤製造実施例２＞
上記キャリア２と実施例１で使用したのと同様のトナー１とを用い、トナー濃度６重量％の現像剤Ｂを調製し、実施例１と同様に初期及び１００Ｋ後の画像評価を行った。結果を図１の一覧表に示す。
<Developer Production Example 2>
Using the
＜キャリア製造実施例３＞
実施例１と同様の方法でフェライト粒子を製造し、ポリアミドイミド樹脂と４フッ化エチレン・６フッ化プロピレン共重合体（ＦＥＰ）の混合重量比を４／６に変更した以外は、実施例１と同様にして混合樹脂をキャリア粒子の表面に被覆し、樹脂被覆量１．５重量％の樹脂被覆フェライトキャリア３を製造した。
<Carrier Production Example 3>
Example 1 except that ferrite particles were produced in the same manner as in Example 1 and the mixing weight ratio of the polyamideimide resin and the tetrafluoroethylene / hexafluoropropylene copolymer (FEP) was changed to 4/6. The mixed resin was coated on the surface of the carrier particles in the same manner as described above to produce a resin-coated ferrite carrier 3 having a resin coating amount of 1.5% by weight.
＜現像剤製造実施例３＞
上記キャリア３と実施例１で使用したのと同様のトナー１とを用い、トナー濃度６重量％の現像剤Ｃを調製し、実施例１と同様に初期及び１００Ｋ後の画像評価を行った。結果を図１の一覧表に示す。
<Developer Production Example 3>
Using the carrier 3 and the
＜キャリア製造実施例４＞
実施例１と同様の方法でフェライト粒子を製造し、溶剤を水に代えてメチルエチルケトンを用いた以外は、実施例１と同様にして混合樹脂をキャリア粒子の表面に被覆し、樹脂被覆量１．５重量％の樹脂被覆フェライトキャリア４を製造した。
<Carrier Production Example 4>
The mixed resin was coated on the surface of the carrier particles in the same manner as in Example 1 except that ferrite particles were produced by the same method as in Example 1, and methyl ethyl ketone was used instead of water as the solvent. A 5% by weight resin-coated ferrite carrier 4 was produced.
＜現像剤製造実施例４＞
上記キャリア４と実施例１で使用したのと同様のトナー１とを用い、トナー濃度６重量％の現像剤Ｄを調製し、実施例１と同様に初期及び１００Ｋ後の画像評価を行った。結果を図１の一覧表に示す。
<Developer Production Example 4>
Using the carrier 4 and the
＜キャリア製造実施例５＞
実施例１と同様の方法でフェライト粒子を製造し、ポリアミドイミド樹脂と４フッ化エチレン・６フッ化プロピレン共重合体（ＦＥＰ）の混合重量比を６／４に変更した以外は、実施例１と同様にして混合樹脂をキャリア粒子の表面に被覆し、樹脂被覆量１．５重量％の樹脂被覆フェライトキャリア５を製造した。
<Carrier Production Example 5>
Example 1 except that ferrite particles were produced in the same manner as in Example 1 and the mixing weight ratio of the polyamideimide resin and the tetrafluoroethylene / hexafluoropropylene copolymer (FEP) was changed to 6/4. In the same manner, the surface of the carrier particles was coated with the mixed resin to produce a resin-coated
＜現像剤製造実施例５＞
上記キャリア５と実施例１で使用したのと同様のトナー１とを用い、トナー濃度６重量％の現像剤Ｅを調製し、実施例１と同様に初期及び１００Ｋ後の画像評価を行った。結果を図１の一覧表に示す。
<Developer Production Example 5>
Using the
＜キャリア製造実施例６＞
実施例１と同様の方法でフェライト粒子を製造し、酸化ケイ素の含有量を樹脂全体の６重量％に変更した以外は、実施例１と同様にして混合樹脂をキャリア粒子の表面に被覆し、樹脂被覆量１．５重量％の樹脂被覆フェライトキャリア６を製造した。
<Carrier Production Example 6>
Ferrite particles were produced by the same method as in Example 1, and the mixed resin was coated on the surface of the carrier particles in the same manner as in Example 1 except that the silicon oxide content was changed to 6% by weight of the total resin. A resin-coated
＜現像剤製造実施例６＞
上記キャリア６と実施例１で使用したのと同様のトナー１とを用い、トナー濃度６重量％の現像剤Ｆを調製し、実施例１と同様に初期及び１００Ｋ後の画像評価を行った。結果を図１の一覧表に示す。
<Developer Production Example 6>
Using the
（比較例１）
＜キャリア製造比較例７＞
実施例１と同様の方法でフェライト粒子を製造し、フッ素系樹脂としてＦＥＰに代えてテトラフロロエチレン樹脂（ＰＴＦＥ）を用いた以外は、実施例１と同様にして混合樹脂をキャリア粒子の表面に被覆し、樹脂被覆量１．５重量％の樹脂被覆フェライトキャリア７を製造した。
(Comparative Example 1)
<Carrier Production Comparative Example 7>
Ferrite particles were produced in the same manner as in Example 1, and the mixed resin was applied to the surface of the carrier particles in the same manner as in Example 1 except that tetrafluoroethylene resin (PTFE) was used instead of FEP as the fluororesin. A resin-coated
＜現像剤製造比較例７＞
上記キャリア７と実施例１で使用したのと同様のトナー１とを用い、トナー濃度６重量％の現像剤Ｇを調製し、実施例１と同様に初期及び１００Ｋ後の画像評価を行った。結果を図１の一覧表に示す。
<Developer Production Comparative Example 7>
Using the
（比較例２）
＜キャリア製造比較例８＞
実施例１と同様の方法でフェライト粒子を製造し、バインダー樹脂としてポリアミドイミド樹脂に代えてエポキシ樹脂を用いた以外は、実施例１と同様にして混合樹脂をキャリア粒子の表面に被覆し、樹脂被覆量１．５重量％の樹脂被覆フェライトキャリア８を製造した。
(Comparative Example 2)
<Carrier Production Comparative Example 8>
Ferrite particles were produced by the same method as in Example 1, and the mixed resin was coated on the surface of the carrier particles in the same manner as in Example 1 except that an epoxy resin was used instead of the polyamideimide resin as the binder resin. A resin-coated
＜現像剤製造比較例８＞
上記キャリア８と実施例１で使用したのと同様のトナー１とを用い、トナー濃度６重量％の現像剤Ｈを調製し、実施例１と同様に初期及び１００Ｋ後の画像評価を行った。結果を図１の一覧表に示す。
<Developer Production Comparative Example 8>
Using the
（比較例３）
＜キャリア製造比較例９＞
実施例１と同様の方法で製造したフェライト粒子に扁平鉄粉を混合（重量比４０／６０）してキャリア芯材を製造した。
(Comparative Example 3)
<Carrier Production Comparative Example 9>
Flat core powder was mixed with the ferrite particles produced by the same method as in Example 1 (weight ratio 40/60) to produce a carrier core material.
次に、このキャリア芯材の表面に、実施例１と同様に混合樹脂を被覆し、樹脂被覆量１．５重量％の樹脂被覆フェライトキャリア９を製造した。 Next, the surface of this carrier core material was coated with a mixed resin in the same manner as in Example 1 to produce a resin-coated ferrite carrier 9 having a resin coating amount of 1.5% by weight.
＜現像剤製造比較例９＞
上記キャリア９と実施例１で使用したのと同様のトナー１とを用い、トナー濃度６重量％の現像剤Ｉを調製し、実施例１と同様に初期及び１００Ｋ後の画像評価を行った。結果を図１の一覧表に示す。
<Developer Production Comparative Example 9>
Using the carrier 9 and the
（比較例４）
＜キャリア製造比較例１０＞
実施例１と同様の方法で製造したフェライト粒子に球状マグネタイトを混合（重量比２０／８０）してキャリア芯材を製造した。
(Comparative Example 4)
<Carrier Production Comparative Example 10>
Spherical magnetite was mixed with the ferrite particles produced by the same method as in Example 1 (weight ratio 20/80) to produce a carrier core material.
次に、このキャリア芯材の表面に、実施例１と同様に混合樹脂を被覆し、樹脂被覆量１．５重量％の樹脂被覆フェライトキャリア１０を製造した。 Next, the surface of this carrier core material was coated with a mixed resin in the same manner as in Example 1 to produce a resin-coated ferrite carrier 10 having a resin coating amount of 1.5% by weight.
＜現像剤製造比較例１０＞
上記キャリア１０と実施例１で使用したのと同様のトナー１とを用い、トナー濃度６重量％の現像剤Ｊを調製し、実施例１と同様に初期及び１００Ｋ後の画像評価を行った。結果を図１の一覧表に示す。
<Developer Production Comparative Example 10>
Using the carrier 10 and the
（比較例５）
＜キャリア製造比較例１１＞
実施例１と同様の方法でフェライト粒子を製造し、樹脂中に酸化ケイ素を添加しない以外は、実施例１と同様の方法で樹脂被覆量１．５重量％の樹脂被覆フェライトキャリア１１を製造した。
(Comparative Example 5)
<Carrier Production Comparative Example 11>
Ferrite particles were produced in the same manner as in Example 1, and a resin-coated ferrite carrier 11 having a resin coating amount of 1.5% by weight was produced in the same manner as in Example 1 except that no silicon oxide was added to the resin. .
上記キャリア１１と実施例１で使用したのと同様のトナー１とを用い、トナー濃度６重量％の現像剤Ｋを調製し、実施例１と同様に初期及び１００Ｋ後の画像評価を行った。結果を図１の一覧に示す。
Using the carrier 11 and the
＜現像剤製造比較例１１＞
上記キャリア１０と実施例１で使用したのと同様のトナー１とを用い、トナー濃度６重量％の現像剤Ｋを調製し、実施例１と同様に初期及び１００Ｋ後の画像評価を行った。結果を図１の一覧表に示す。
<Developer Production Comparative Example 11>
Using the carrier 10 and the
実施例と比較例との対比： 図１の一覧表から明らかなように、実施例１〜６は、経時においても高い帯電量を維持し、カブリ、画質、環境依存性及びキャリア付着も良好である。特に、本発明に係る製造方法を用い、かつポリアミドイミド樹脂と４フッ化エチレン・６フッ化プロピレン共重合体（ＦＥＰ）の混合重量比を一定範囲とし、また酸化ケイ素の含有量を特定範囲とした実施例1〜３は、優れた特性を有する。これに対して、比較例１〜４は、経時において帯電量が低下し、カブリ、画質及び環境依存性等に劣ったものとなる。また、樹脂中に酸化ケイ素を含有しない比較例５は、被膜が均一に形成されないため、耐久性が劣ったものと思われる。 Comparison of Examples and Comparative Examples: As is apparent from the list of FIG. 1, Examples 1 to 6 maintain a high charge amount over time, and have good fog, image quality, environment dependency, and carrier adhesion. is there. In particular, the production method according to the present invention is used, the mixing weight ratio of the polyamideimide resin and the tetrafluoroethylene / hexafluoropropylene copolymer (FEP) is within a certain range, and the silicon oxide content is within a specific range. Examples 1 to 3 have excellent characteristics. On the other hand, in Comparative Examples 1 to 4, the charge amount decreases with time, and the fog, image quality, environment dependency, and the like are inferior. Moreover, since the film is not formed uniformly in the comparative example 5 which does not contain a silicon oxide in resin, it is thought that durability was inferior.
本発明に係る樹脂被覆フェライトキャリアの製造方法によって、キャリア粒子表面に均一な樹脂被覆が得られ、また水系溶媒を用いているため有機溶剤に起因する異臭等の問題が生じない。また、本発明に係る樹脂被覆フェライトキャリアを用いた電子写真現像剤は、長期に渡り帯電安定性及び画質安定性に優れ、しかもカブリやキャリア付着も少なく、また画像濃度及び環境依存性も良好である。
従って、本発明に係る電子写真現像剤は、複写機、プリンター等の用途に用いられ、現像機の高速化及びフルカラー化に充分対応することができる。
By the method for producing a resin-coated ferrite carrier according to the present invention, a uniform resin coating is obtained on the surface of the carrier particles, and since an aqueous solvent is used, problems such as a bad odor caused by an organic solvent do not occur. In addition, the electrophotographic developer using the resin-coated ferrite carrier according to the present invention is excellent in charging stability and image quality stability over a long period of time, has little fogging and carrier adhesion, and has good image density and environmental dependency. is there.
Therefore, the electrophotographic developer according to the present invention is used for applications such as copying machines and printers, and can sufficiently cope with the speeding up and full color of the developing machine.
Claims (6)
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| JP2005319895A JP4646781B2 (en) | 2004-11-11 | 2005-11-02 | Resin-coated ferrite carrier for electrophotographic developer, production method thereof, and electrophotographic developer using the resin-coated ferrite carrier |
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| JP2005319895A JP4646781B2 (en) | 2004-11-11 | 2005-11-02 | Resin-coated ferrite carrier for electrophotographic developer, production method thereof, and electrophotographic developer using the resin-coated ferrite carrier |
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| JP2010225710A Division JP2011008298A (en) | 2004-11-11 | 2010-10-05 | Resin-coated ferrite carrier for electrophotographic developer, production method of the same, and electrophotographic developer using the resin-coated ferrite carrier |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009109570A (en) * | 2007-10-26 | 2009-05-21 | Kyocera Mita Corp | Developer for electrophotography |
| JP2009258700A (en) * | 2008-03-26 | 2009-11-05 | Powdertech Co Ltd | Carrier for electrophotographic developer and electrophotographic developer using the carrier |
| JP2010134022A (en) * | 2008-12-02 | 2010-06-17 | Konica Minolta Business Technologies Inc | Two-component developer |
| JP2010224054A (en) * | 2009-03-19 | 2010-10-07 | Powdertech Co Ltd | Ferrite carrier for electrophotographic developer and electrophotographic developer using the ferrite carrier |
| US8298742B2 (en) | 2007-12-20 | 2012-10-30 | Canon Kabushiki Kaisha | Method for producing electrophotographic carrier and electrophotographic carrier produced by using the method |
| JP2012220864A (en) * | 2011-04-13 | 2012-11-12 | Ricoh Co Ltd | Method for manufacturing electrophotographic carrier |
| US9176412B2 (en) | 2012-11-15 | 2015-11-03 | Kyocera Document Solutions Inc. | Two-component developer |
| US9256150B2 (en) | 2013-10-16 | 2016-02-09 | Kyocera Document Solutions Inc. | Two-component developer and method for producing two-component developer |
| JP2017161716A (en) * | 2016-03-09 | 2017-09-14 | 京セラドキュメントソリューションズ株式会社 | Developer, image forming apparatus and image forming method |
| JP2019095650A (en) * | 2017-11-24 | 2019-06-20 | 京セラドキュメントソリューションズ株式会社 | Carrier and two-component developer |
| JP2021056325A (en) * | 2019-09-27 | 2021-04-08 | キヤノン株式会社 | Toner and two-component developer |
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| JP7362094B2 (en) | 2017-08-09 | 2023-10-17 | パウダーテック株式会社 | Carriers and electrophotographic developers |
| WO2020166654A1 (en) | 2019-02-13 | 2020-08-20 | パウダーテック株式会社 | Carrier, xerographic developer, and carrier production method |
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| JP2001013720A (en) * | 1999-06-25 | 2001-01-19 | Canon Inc | Two-component developer |
| JP2002148869A (en) * | 2000-11-15 | 2002-05-22 | Powdertech Co Ltd | Dry process two-component based developing resin coated carrier and developer having this carrier |
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| JP2001013720A (en) * | 1999-06-25 | 2001-01-19 | Canon Inc | Two-component developer |
| JP2002148869A (en) * | 2000-11-15 | 2002-05-22 | Powdertech Co Ltd | Dry process two-component based developing resin coated carrier and developer having this carrier |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009109570A (en) * | 2007-10-26 | 2009-05-21 | Kyocera Mita Corp | Developer for electrophotography |
| KR101262011B1 (en) * | 2007-12-20 | 2013-05-08 | 캐논 가부시끼가이샤 | Method for producing electrophotographic carrier and electrophotographic carrier produced by using the method |
| US8298742B2 (en) | 2007-12-20 | 2012-10-30 | Canon Kabushiki Kaisha | Method for producing electrophotographic carrier and electrophotographic carrier produced by using the method |
| JP2009258700A (en) * | 2008-03-26 | 2009-11-05 | Powdertech Co Ltd | Carrier for electrophotographic developer and electrophotographic developer using the carrier |
| JP2010134022A (en) * | 2008-12-02 | 2010-06-17 | Konica Minolta Business Technologies Inc | Two-component developer |
| JP2010224054A (en) * | 2009-03-19 | 2010-10-07 | Powdertech Co Ltd | Ferrite carrier for electrophotographic developer and electrophotographic developer using the ferrite carrier |
| JP2012220864A (en) * | 2011-04-13 | 2012-11-12 | Ricoh Co Ltd | Method for manufacturing electrophotographic carrier |
| US9176412B2 (en) | 2012-11-15 | 2015-11-03 | Kyocera Document Solutions Inc. | Two-component developer |
| US9256150B2 (en) | 2013-10-16 | 2016-02-09 | Kyocera Document Solutions Inc. | Two-component developer and method for producing two-component developer |
| JP2017161716A (en) * | 2016-03-09 | 2017-09-14 | 京セラドキュメントソリューションズ株式会社 | Developer, image forming apparatus and image forming method |
| JP2019095650A (en) * | 2017-11-24 | 2019-06-20 | 京セラドキュメントソリューションズ株式会社 | Carrier and two-component developer |
| JP2021056325A (en) * | 2019-09-27 | 2021-04-08 | キヤノン株式会社 | Toner and two-component developer |
| JP7330839B2 (en) | 2019-09-27 | 2023-08-22 | キヤノン株式会社 | Toner and two-component developer |
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