JP5434156B2 - Ferrite carrier core material for electrostatic latent image development, ferrite carrier, and electrostatic latent image developer using the ferrite carrier - Google Patents
Ferrite carrier core material for electrostatic latent image development, ferrite carrier, and electrostatic latent image developer using the ferrite carrier Download PDFInfo
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- JP5434156B2 JP5434156B2 JP2009057053A JP2009057053A JP5434156B2 JP 5434156 B2 JP5434156 B2 JP 5434156B2 JP 2009057053 A JP2009057053 A JP 2009057053A JP 2009057053 A JP2009057053 A JP 2009057053A JP 5434156 B2 JP5434156 B2 JP 5434156B2
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- ferrite carrier
- core material
- carrier
- electrostatic latent
- latent image
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Description
本発明は、複写機、プリンター等に用いられる静電潜像現像用フェライトキャリア芯材、フェライトキャリア及び該フェライトキャリアを用いた静電潜像現像剤に関する。 The present invention relates to a ferrite carrier core material for developing an electrostatic latent image used in a copying machine, a printer, and the like, a ferrite carrier, and an electrostatic latent image developer using the ferrite carrier.
静電潜像（電子写真）現像方法は、現像剤中のトナー粒子を感光体上に形成された静電潜像に付着させて現像する方法であり、この方法で使用される現像剤は、トナー粒子とキャリア粒子からなる二成分系現像剤及びトナー粒子のみを用いる一成分系現像剤に分けられる。 The electrostatic latent image (electrophotographic) developing method is a method in which toner particles in a developer are attached to an electrostatic latent image formed on a photoreceptor and developed, and the developer used in this method is: A two-component developer composed of toner particles and carrier particles and a one-component developer using only toner particles are classified.
こうした現像剤のうち、トナー粒子とキャリア粒子からなる二成分系現像剤を用いた現像方法としては、古くはカスケード法等が採用されていたが、現在では、マグネットロールを用いる磁気ブラシ法が主流である。 Among these developers, as a developing method using a two-component developer composed of toner particles and carrier particles, the cascade method has been used in the past, but at present, the magnetic brush method using a magnet roll is the mainstream. It is.
二成分系現像剤において、キャリア粒子は、現像剤が充填されている現像ボックス内において、トナー粒子と共に攪拌されることによって、トナー粒子に所望の電荷を付与し、さらにこのように電荷を帯びたトナー粒子を感光体の表面に搬送して感光体上にトナー像を形成するための担体物質である。マグネットを保持する現像ロール上に残ったキャリア粒子は、この現像ロールから再び現像ボックス内に戻り、新たなトナー粒子と混合・攪拌され、一定期間繰り返して使用される。 In the two-component developer, the carrier particles are agitated together with the toner particles in the developing box filled with the developer, thereby imparting a desired charge to the toner particles, and thus being charged. A carrier material for transporting toner particles to the surface of the photoreceptor to form a toner image on the photoreceptor. The carrier particles remaining on the developing roll holding the magnet are returned to the developing box from the developing roll, mixed and stirred with new toner particles, and used repeatedly for a certain period.
二成分系現像剤は、一成分系現像剤とは異なり、キャリア粒子はトナー粒子と混合・攪拌され、トナー粒子を帯電させ、さらに搬送する機能を有しており、現像剤を設計する際の制御性が良い。従って、二成分系現像剤は高画質が要求されるフルカラー現像装置及び画像維持の信頼性、耐久性が要求される高速印刷を行う装置等に適している。 Unlike the one-component developer, the two-component developer has the function of mixing and stirring the carrier particles with the toner particles, charging the toner particles, and further transporting the toner particles. Good controllability. Therefore, the two-component developer is suitable for a full-color developing device that requires high image quality and a device that performs high-speed printing that requires image maintenance reliability and durability.
このようにして用いられる二成分系現像剤においては、画像濃度、カブリ、白斑、階調性、解像力等の画像特性が、初期の段階から所定の値を示し、しかもこれらの特性が耐刷期間中に変動せず、安定に維持されることが必要である。これらの特性を安定に維持するためには、二成分系現像剤中に含有されるキャリア粒子の特性が安定していることが必要になる。 In the two-component developer used in this manner, image characteristics such as image density, fog, vitiligo, gradation, and resolving power show predetermined values from the initial stage, and these characteristics are in the printing life period. It needs to be kept stable without fluctuating inside. In order to maintain these characteristics stably, it is necessary that the characteristics of the carrier particles contained in the two-component developer are stable.
二成分系現像剤を形成するキャリア粒子として、従来は、表面を酸化被膜で覆った鉄粉あるいは表面を樹脂で被覆した鉄粉等の鉄粉キャリアが使用されていた。このような鉄粉キャリアは、磁化が高く、導電性も高いことから、ベタ部の再現性のよい画像が得られやすいという利点がある。 Conventionally, iron powder carriers such as iron powder whose surface is covered with an oxide film or iron powder whose surface is coated with a resin have been used as carrier particles for forming a two-component developer. Since such an iron powder carrier has high magnetization and high conductivity, there is an advantage that an image with a good reproducibility of the solid portion can be easily obtained.
しかしながら、このような鉄粉キャリアは真比重が約７．８と重く、また磁化が高すぎることから、現像ボックス中におけるトナー粒子との攪拌・混合により、鉄粉キャリア表面へのトナー構成成分の融着、いわゆるトナースペントが発生しやすくなる。このようなトナースペントの発生により有効なキャリア表面積が減少し、トナー粒子との摩擦帯電能力が低下しやすくなる。 However, such an iron powder carrier has a heavy true specific gravity of about 7.8 and is too high in magnetization, so that the toner constituent components on the surface of the iron powder carrier are mixed by stirring and mixing with toner particles in the developing box. Fusing, so-called toner spent, is likely to occur. The generation of such toner spent reduces the effective carrier surface area and tends to reduce the triboelectric charging ability with the toner particles.
また、樹脂被覆鉄粉キャリアでは、耐久時のストレスにより表面の樹脂が剥離し、高導電性で絶縁破壊電圧が低い芯材（鉄粉）が露出することにより、電荷のリークが生ずることがある。このような電荷のリークにより、感光体上に形成された静電潜像が破壊され、ベタ部にハケスジ等が発生し、均一な画像が得られにくい。これらの理由から、酸化被膜鉄粉及び樹脂被覆鉄粉等の鉄粉キャリアは、現在では使用されなくなってきている。 Moreover, in the resin-coated iron powder carrier, the resin on the surface peels off due to stress during durability, and the core material (iron powder) with high conductivity and low dielectric breakdown voltage is exposed, which may cause charge leakage. . Due to such charge leakage, the electrostatic latent image formed on the photoconductor is destroyed, and a crack or the like is generated in the solid portion, so that it is difficult to obtain a uniform image. For these reasons, iron powder carriers such as oxide-coated iron powder and resin-coated iron powder are no longer used.
近年は、鉄粉キャリアに代わって真比重約５．０程度と軽く、また磁化も低いフェライトをキャリアとして用いたり、さらに表面に樹脂を被覆した樹脂コートフェライトキャリアが多く使用されたりしており、現像剤寿命は飛躍的に伸びてきた。 In recent years, instead of the iron powder carrier, the true specific gravity is light as about 5.0, and the ferrite with low magnetization is used as the carrier, or the resin coated ferrite carrier with the resin coated on the surface is often used. Developer life has increased dramatically.
この樹脂被覆キャリアにおいても、トナーと共に現像剤としたときに、キャリア飛散が生じる、あるいは現像特性や画質特性に劣るとった課題を有する。現像剤中のキャリアによって感光体等に傷が付くといった課題もある。 This resin-coated carrier also has a problem that carrier scattering occurs when it is used as a developer together with toner, or the development characteristics and image quality characteristics are inferior. There is also a problem that the photoconductor and the like are damaged by the carrier in the developer.
このような課題を解決すべく、キャリアの平均円形度に着目した提案がなされている。特許文献１（特開２００８−１４５８６４号公報）には、平均円形度が０．９８〜１．００であり、残留磁化が２〜１０ｅｍｕ／ｇであるキャリアが記載されている。この特許文献1によれば、キャリアの平均円形度を０．９８〜１．００とすることにより、キャリアが有する突起や角のため感光体の傷やクリーニング部材の部材のかけ、破損の発生を低減できるとしている。 In order to solve such problems, proposals have been made focusing on the average circularity of the carrier. Patent Document 1 (Japanese Patent Laid-Open No. 2008-145864) describes a carrier having an average circularity of 0.98 to 1.00 and a residual magnetization of 2 to 10 emu / g. According to this Patent Document 1, by setting the average circularity of the carrier to 0.98 to 1.00, the protrusions and corners of the carrier cause damage to the photosensitive member, the cleaning member, and damage. It can be reduced.
また、特許文献２（特開２００７−１６３７２８号公報）には、平均円形度Ｃが０．８５０〜０．９５０であり、円形度の３０％値Ｃ３０との間に０≦（Ｃ−Ｃ３０）≦０．２０の関係を満足する樹脂と磁性体とを含有する磁性体含有樹脂キャリアが記載されている。この特許文献２では、平均円形度Ｃが０．８５０〜０．９５０とは、真球状乃至ある程度楕円状であり、ＣとＣ３０とを上記関係、すなわち円形度の分布を狭くコントロールすることによって、トナーへの帯電付与性に優れ、かつキャリア付着しにくく、キャリア付着した場合でも感光体表面のキズ発生を抑制すると記載されている。 Moreover, in patent document 2 (Unexamined-Japanese-Patent No. 2007-163728), average circularity C is 0.850-0.950, and 0 <= (C-C30) between 30% value C30 of circularity A magnetic substance-containing resin carrier containing a resin and a magnetic substance satisfying the relationship of ≦ 0.20 is described. In Patent Document 2, an average circularity C of 0.850 to 0.950 is true spherical or somewhat elliptical, and C and C30 are controlled by the above relationship, that is, by controlling the circularity distribution narrowly. It is described that it is excellent in charge imparting property to toner, hardly adheres to a carrier, and suppresses generation of scratches on the surface of the photoreceptor even when the carrier adheres.
特許文献３（特開２００５−３３８０９号公報）には、平均円形度Ｃが０．８３０乃至０．９５０であり、（平均円形度Ｃ−２σ）以下の円形度を有する粒子（σはキャリア円形度の標準偏差）が２０個数％以下のキャリアが記載されている。特許文献３によれば、このようなキャリアは、トナーへの帯電付与性に優れ、かつキャリア付着しにくく、キャリア付着した場合でも感光体表面のキズ発生が抑制されるとされている。 In Patent Document 3 (Japanese Patent Application Laid-Open No. 2005-33809), particles having an average circularity C of 0.830 to 0.950 and a circularity of (average circularity C-2σ) or less (σ is a carrier circle) A carrier having a standard deviation of 20 degrees or less is described. According to Patent Document 3, such a carrier is excellent in charge imparting property to the toner, hardly adheres to the carrier, and even when the carrier adheres, generation of scratches on the surface of the photoreceptor is suppressed.
これら特許文献１〜３は、キャリア粒子全体に関する平均円形度や平均円形度及びその分布を規定したものであり、感光体傷やクリーニング部材の破損の原因となる小粒径キャリア粒子の円形度を規定したものでないため、感光体へキャリアが飛散し易く、その効果は低いものと推察できる。 These Patent Documents 1 to 3 prescribe the average circularity and average circularity and distribution of the carrier particles as a whole, and determine the circularity of small-sized carrier particles that cause damage to the photoreceptor and the cleaning member. Since it is not specified, it can be inferred that the carrier is likely to be scattered on the photosensitive member and the effect is low.
特許文献４（特開２００７−３２８７７号公報）には、平均円形度が０．９７５〜１．０００であり、さらにこの平均形状のみならず、不定形粒子量を特性値とするキャリアが記載されており、キャリアならびに潜像担持体の長寿命化を達成することができるとしている。この特許文献４では、平均円形度が０．９７５〜１．０００とかなり真球に近く、表層に設けられる被覆樹脂層が均一に形成されてしまうため、十分な現像特性が得られない。 Patent Document 4 (Japanese Patent Application Laid-Open No. 2007-32877) describes a carrier having an average circularity of 0.975 to 1.000 and having not only this average shape but also an amorphous particle amount as a characteristic value. The service life of the carrier and the latent image carrier can be extended. In Patent Document 4, since the average circularity is 0.975 to 1.000, which is very close to a true sphere, and the coating resin layer provided on the surface layer is uniformly formed, sufficient development characteristics cannot be obtained.
特許文献５（特開２００８−１９１６４３号公報）には、磁性体を含有するキャリアコアと該キャリアコアの表面に樹脂被覆層とからなり、円相当径０．５乃至２００．０μｍの範囲内における個数基準の円相当径５０％値が１５乃至７０μｍであり、円相当径０．５乃至２００．０μｍの範囲内における円形度０．２００乃至１．０００での平均円形度が０．９６０以上であり、円相当径１５．０乃至１００．０μｍの範囲内における円形度０．２００乃至０．９２５の粒子の割合が１５．０個数％以下のキャリアが記載されている。特許文献５によれば、このようなキャリアによって、トナーと混合して二成分系現像剤を調製した場合や長期間使用した場合に凝集物がほぐされて生成したキャリアでキャリア芯材面が露出することがなく、キャリアへの電荷注入が抑制され、リークが防止され、静電潜像の乱れをなくし、ドットの再現性に優れるとされている。 Patent Document 5 (Japanese Patent Laid-Open No. 2008-191643) includes a carrier core containing a magnetic material and a resin coating layer on the surface of the carrier core, and has a circle equivalent diameter in the range of 0.5 to 200.0 μm. The number-based circle equivalent diameter 50% value is 15 to 70 μm, and the average circularity with a circularity of 0.200 to 1.000 in the range of the equivalent circle diameter of 0.5 to 200.0 μm is 0.960 or more. There is described a carrier in which the ratio of particles having a circularity of 0.200 to 0.925 within a range of equivalent circle diameter of 15.0 to 100.0 μm is 15.0% by number or less. According to Patent Document 5, when a two-component developer is prepared by mixing with a toner using such a carrier or when it is used for a long period of time, the carrier core surface is exposed by a carrier generated by loosening aggregates. Therefore, charge injection into the carrier is suppressed, leakage is prevented, disturbance of the electrostatic latent image is eliminated, and dot reproducibility is excellent.
この特許文献５は、キャリア粒子全体に関する平均の円形度及びその分布を規定したものであるが、上記した特許文献１〜３と同様に、感光体傷やクリーニング部材の破損の原因となる小粒径キャリア粒子の円形度を規定したものでないため、感光体へキャリアが飛散し易く、その効果は低いものと考えられる。 This Patent Document 5 defines the average circularity and the distribution of the carrier particles as a whole, but in the same manner as in Patent Documents 1 to 3, small particles that cause damage to the photoreceptor and the cleaning member. Since the circularity of the diameter carrier particles is not defined, the carrier is likely to be scattered to the photoreceptor, and the effect is considered to be low.
このように、キャリアの円形度等を規定して現像剤特性を向上させ、感光体等への傷の発生を低減させる試みはなされているが、現像剤としたときに、キャリア飛散を防止し、優れた現像特性や画質特性を有すると共に、感光体等への傷の発生を低減したキャリア及びこれを用いた現像剤は得られていない。 In this way, attempts have been made to improve the developer characteristics by regulating the circularity of the carrier and reduce the occurrence of scratches on the photoreceptor, but when the developer is used, carrier scattering is prevented. In addition, a carrier having excellent development characteristics and image quality characteristics and reduced generation of scratches on a photoreceptor and a developer using the carrier have not been obtained.
従って、本発明の目的は、現像剤としたときに、キャリア飛散を防止し、優れた現像特性や画質特性を有すると共に、感光体等への傷の発生を低減した静電潜像現像用フェライトキャリア芯材、フェライトキャリア及びこれを用いた静電潜像現像剤を提供することにある。 Accordingly, an object of the present invention is to provide an electrostatic latent image developing ferrite that, when used as a developer, prevents carrier scattering, has excellent development characteristics and image quality characteristics, and reduces the occurrence of scratches on a photoreceptor. It is an object to provide a carrier core material, a ferrite carrier, and an electrostatic latent image developer using the same.
本発明者らは、検討の結果、フェライトキャリア芯材の平均円形度を特定範囲とすると共に、円相当径が１５μｍ以下でアスペクト比が１．５以上の粒子の割合を一定量以下とし、かつＢＥＴ比表面積を特定範囲とすることによって、上記目的が達成されることを知見して本発明に至った。 As a result of the study, the inventors set the average circularity of the ferrite carrier core material as a specific range, and the ratio of particles having an equivalent circle diameter of 15 μm or less and an aspect ratio of 1.5 or more to a certain amount or less , And it was discovered that the above object was achieved by setting the BET specific surface area within a specific range, and the present invention was achieved.
すなわち、本発明は、平均円形度が０．８１〜０．８７であり、円相当径が１５μｍ以下でアスペクト比が１．５以上の粒子の含有率が１．０個数％以下であり、ＢＥＴ比表面積が０．０７〜０．１９ｍ ２ ／ｇであることを特徴とする静電潜像現像用フェライトキャリア芯材を提供するものである。 That is, the present invention has an average circularity is 0.81 to 0.87 state, and are content 1.0% by number of the circle equivalent diameter is an aspect ratio of 1.5 or more or less 15μm particles, BET specific surface area is to provide a 0.07~0.19m 2 / g der Rukoto electrostatic latent image developing ferrite carrier core material according to claim.
本発明に係る上記静電潜像現像用フェライトキャリア芯材は、平均円相当径が２５〜４５μｍであることが望ましい。 The ferrite carrier core material for developing an electrostatic latent image according to the present invention preferably has an average equivalent circle diameter of 25 to 45 μm.
本発明に係る上記静電潜像現像用フェライトキャリア芯材は、１０００×１０３／４π×Ａ／ｍの磁場における磁化が５０〜６５Ａｍ２／ｋｇであることが望ましい。 The ferrite carrier core material for developing an electrostatic latent image according to the present invention preferably has a magnetization of 50 to 65 Am 2 / kg in a magnetic field of 1000 × 10 3 / 4π × A / m.
本発明に係る上記静電潜像現像用フェライトキャリア芯材は、その組成が、Ｍｎ、Ｍｇ、Ｌｉ、Ｃａ、Ｓｒ、Ｃｕ、Ｚｎ、Ｔｉから選ばれる少なくとも１種を含むことが望ましい。 The ferrite carrier core material for developing an electrostatic latent image according to the present invention preferably contains at least one selected from Mn, Mg, Li, Ca, Sr, Cu, Zn, and Ti.
また、本発明は、上記フェライトキャリア芯材の表面に樹脂を被覆してなる静電潜像現像用フェライトキャリアを提供するものである。 The present invention also provides a ferrite carrier for developing an electrostatic latent image, wherein the surface of the ferrite carrier core material is coated with a resin.
また、本発明は、上記フェライトキャリアとトナーとからなる静電潜像現像剤を提供するものである。 The present invention also provides an electrostatic latent image developer comprising the ferrite carrier and a toner.
また、本発明に係る上記静電潜像現像剤は、補給用現像剤としても用いられる。 The electrostatic latent image developer according to the present invention is also used as a replenishment developer.
本発明に係る静電潜像現像用フェライトキャリア芯材、フェライトキャリア及びこれを用いた静電潜像現像剤によって、現像中のキャリア飛散が防止され、優れた現像特性や画質特性を有する。また、現像剤中のキャリアに起因する感光体等への傷の発生が低減される。 The ferrite carrier core material for electrostatic latent image development, the ferrite carrier, and the electrostatic latent image developer using the same according to the present invention prevent carrier scattering during development and have excellent development characteristics and image quality characteristics. Further, the occurrence of scratches on the photoconductor due to the carrier in the developer is reduced.
以下、本発明を実施するための形態について説明する。
＜本発明に係る静電潜像現像用フェライトキャリア芯材及びフェライトキャリア＞
本発明に係る静電潜像現像用フェライトキャリア芯材は、平均円形度が０．８１〜０．８７である。ここで平均円形度とは、各キャリア芯材粒子の投影面積と等しい円を仮定した際の円周長を粒子周囲長で割った数値を平均化したものであり、数値が１に近いほど真円状のキャリア芯材粒子が多いことを示す。
Hereinafter, modes for carrying out the present invention will be described.
<Ferrite carrier core material for developing electrostatic latent image and ferrite carrier according to the present invention>
The ferrite carrier core material for developing an electrostatic latent image according to the present invention has an average circularity of 0.81 to 0.87 . Here, the average circularity is an average of numerical values obtained by dividing the circumferential length when the circle equal to the projected area of each carrier core particle is divided by the peripheral length of the particle. This indicates that there are many circular carrier core particles.
このフェライトキャリア芯材の平均円形度は、キャリア芯材粒子表面の凹凸度合いを表したものである。数値が１に近いほど真円状であり、上記のように、０．８１〜０．８７の範囲であれば扁平形状ではなく、表面に適度な凹凸を有するキャリア芯材粒子の集合体であることを示す。上記のようなキャリア芯材に樹脂被覆を施したキャリアは、樹脂層と芯材表面が良好な比率で存在する。より詳細には、被覆樹脂層はキャリア芯材表面の凹部に優先的に埋め込まれるように存在し、凸部にはキャリア芯材表面が露出している状態にある。凸部にキャリア芯材表面が露出した状態であれば、トナーを感光体に移行させるための適度な電気抵抗を持たせることができ、高現像性を得ることができる。凹部に樹脂層を存在させることは、適度な電気抵抗を持たせるとともに、耐刷において現像槽内でのストレスを受け難いことから樹脂層の残存率が増加し、帯電能力等の安定性が図れ、また、キャリア粒子の凹部部分に付着し易いスペントトナーに対しても有効である。より好ましくは０．８３〜０．８７である。 The average circularity of the ferrite carrier core material represents the degree of unevenness on the surface of the carrier core material particles. As the numerical value is closer to 1, it is a perfect circle, and as described above, it is an aggregate of carrier core particles having moderate irregularities on the surface, not a flat shape as long as it is in the range of 0.81 to 0.87. It shows that. In the carrier obtained by applying the resin coating to the carrier core material as described above, the resin layer and the core material surface are present in a good ratio. More specifically, the coating resin layer exists so as to be preferentially embedded in the concave portion on the surface of the carrier core material, and the carrier core material surface is exposed in the convex portion. If the surface of the carrier core material is exposed at the convex portion, it is possible to provide an appropriate electric resistance for transferring the toner to the photosensitive member, and high developability can be obtained. The presence of the resin layer in the recesses provides an appropriate electrical resistance and is less susceptible to stress in the developing tank during printing, so the residual rate of the resin layer increases and stability such as charging ability can be achieved. It is also effective for spent toner that easily adheres to the concave portions of the carrier particles. More preferably, it is 0.83-0.87.
また、本発明に係る静電潜像現像用フェライトキャリア芯材は、円相当径が１５μｍ以下でアスペクト比が１．５以上の粒子の含有率が１．０個数％以下である。ここで、円相当径とは、測定したキャリア芯材粒子の投影面積と等しい面積を持つ円を仮定した際の、その円の直径であり、キャリア芯材粒子の直径を表す。また、アスペクト比とは、キャリア芯材粒子の２次元投影像における、粒子の周上の任意の２点間の内の最大の長さである最大長と、最大長に対して平行な２本の直線で粒子を挟んだ時の２直線間の最短距離である最大垂直長の比であり、数値が１に近いほど真円状となり、数値が大きいほど扁平度が高いことを示し、針状形状に近づく。 Further, an electrostatic latent image developing ferrite carrier core material according to the present invention, the content of the particles on the aspect ratio of 1.5 or less in circle equivalent diameter of 15μm or less is 1.0% by number or less. Here, the equivalent circle diameter is the diameter of the circle when assuming a circle having an area equal to the measured projected area of the carrier core particle, and represents the diameter of the carrier core particle. The aspect ratio is the maximum length that is the maximum length between any two points on the circumference of the particle in the two-dimensional projection image of the carrier core particle, and two parallel to the maximum length. This is the ratio of the maximum vertical length, which is the shortest distance between two straight lines when a particle is sandwiched between the straight lines. The closer the value is to 1, the more round the shape is. The larger the value, the higher the flatness, and the needle shape. Approach the shape.
トナーを感光体に移行させる際に、微量ではあるがキャリア粒子も感光体に移行されてしまっている。通常は、転写プロセスが終了した後に感光体に残ったトナー粒子とともにクリーニングブレードにて回収され、系外に排出されるが、粒径が小さく、且つ、扁平（針状）形状を持つキャリア粒子は回収され難く、クリーニングブレードと感光体の間に挟まれ、両者に損傷を与える。特に、キャリア粒子は非常に硬いものであるため、感光体表層を傷つけ、この傷が耐刷中に成長し、画像欠陥として印刷画像に表れてしまう。上記のキャリア粒子の形状は、表層に形成する樹脂層も影響するが、キャリア芯材粒子形状によるものが大きく、キャリア芯材粒子の形状を制御する必要がある。特に、キャリア芯材の円相当径が１５μｍ以下でアスペクト比が１．５以上のキャリア芯材粒子が上記現象の原因となり易く、キャリア芯材粒子全体の１．０個数％以下に含有量を抑制することが望ましい。円相当径が１５μｍ以下でアスペクト比が１．５以上のキャリア芯材粒子を０．５個数％以下にすることがより好ましい。 When the toner is transferred to the photoconductor, the carrier particles are also transferred to the photoconductor although the amount is small. Usually, the toner particles remaining on the photoreceptor after the transfer process are collected together with the cleaning blade and discharged out of the system, but the carrier particles having a small particle size and a flat (needle-like) shape are It is difficult to collect and is sandwiched between the cleaning blade and the photosensitive member and damages both. In particular, since the carrier particles are very hard, the surface layer of the photoreceptor is damaged, and the scratches grow during printing durability and appear as printed defects in the printed image. The shape of the carrier particles described above is affected by the resin layer formed on the surface layer, but is largely due to the shape of the carrier core material particles, and it is necessary to control the shape of the carrier core material particles. In particular, carrier core particles having an equivalent circle diameter of 15 μm or less and an aspect ratio of 1.5 or more tend to cause the above phenomenon, and the content is suppressed to 1.0% or less of the entire carrier core particles. It is desirable to do. More preferably, the number of carrier core particles having an equivalent circle diameter of 15 μm or less and an aspect ratio of 1.5 or more is 0.5% by number or less.
本発明に係る静電潜像現像用フェライトキャリア芯材の平均円相当径が２５〜４５μｍであることが望ましい。キャリア粒子の感光体への移行を抑制する手段として、キャリア粒子径を制御することが有効である。キャリア粒子径もキャリア芯材粒子径の影響を大きく受けることから、キャリア芯材平均円相当径を２５μｍ以上とすることが望ましい。しかしながら、４５μｍを超えると画質劣化が生じる。従って、上記範囲が望ましい。 The average equivalent circle diameter of the ferrite carrier core material for developing an electrostatic latent image according to the present invention is preferably 25 to 45 μm. Controlling the carrier particle diameter is effective as a means for suppressing the transfer of carrier particles to the photoreceptor. Since the carrier particle diameter is also greatly affected by the carrier core particle diameter, it is desirable that the average equivalent diameter of the carrier core is 25 μm or more. However, when it exceeds 45 μm, image quality deterioration occurs. Therefore, the above range is desirable.
これらキャリア芯材の平均円形度、円相当径及びアスペクト比は、下記によって測定される。
（平均円形度、円相当径及びアスペクト比）
セイシン企業社製粒度形状分布測定器ＰＩＴＡ−１を用いた。測定原理としては、分散媒流中を流れているキャリア粒子を静止画像として撮影し、画像解析を行なう。
キャリア０．１ｇを、分散媒：シリコーンオイル、キャリア液１流量：１０μｌ／ｓｅｃ、キャリア液２流量：１０μｌ／ｓｅｃ、サンプル液流量：０．０８μｌ／ｓｅｃの条件にて分散させ、セル内を通過させる。取り込む粒子を決定する二値化第１レベルを８０にて、取り込んだ粒子の輪郭を決定する二値化第１レベルを２００にて、二値化処理を行いながら、分散させたキャリア粒子３０００個の投影画像を１０倍の対物レンズを有するモノクロＣＣＤカメラにて撮影する。撮影された３０００投影画像から下記のようにそれぞれ算出する。
円形度＝（粒子投影画像と同じ面積を持つ円の周囲長）／（粒子投影画像の周囲長）
平均円形度：３０００個の粒子の円形度の平均値
円相当径：粒子投影画像と同じ面積を持つ円の直径
平均円相当径：３０００個の粒子の円相当径の平均値
アスペクト比＝（最大長）／（最大垂直長）
The average circularity, equivalent circle diameter, and aspect ratio of these carrier core materials are measured as follows.
(Average circularity, equivalent circle diameter and aspect ratio)
A grain size distribution analyzer PITA-1 manufactured by Seishin Enterprise Co., Ltd. was used. As a measurement principle, carrier particles flowing in a dispersion medium flow are photographed as a still image and image analysis is performed.
0.1 g of carrier is dispersed under the conditions of dispersion medium: silicone oil, carrier liquid 1 flow rate: 10 μl / sec, carrier liquid 2 flow rate: 10 μl / sec, sample liquid flow rate: 0.08 μl / sec, and pass through the cell. Let The binarized first level for determining the particles to be captured is 80, the binarized first level for determining the contours of the captured particles is 200, and 3000 carrier particles dispersed while performing binarization processing. Is projected with a monochrome CCD camera having a 10 × objective lens. Each is calculated as follows from the 3000 projected images taken.
Circularity = (perimeter of a circle having the same area as the particle projection image) / (perimeter of the particle projection image)
Average circularity: Average value of the circularity of 3000 particles Circle equivalent diameter: Diameter of a circle having the same area as the particle projection image Average circle equivalent diameter: Average value of equivalent circle diameter of 3000 particles Aspect ratio = (Maximum Length) / (maximum vertical length)
本発明に係る静電潜像現像用フェライトキャリア芯材は、１０００×１０３／４π・Ａ／ｍの磁場における磁化が５０〜６５Ａｍ２／ｋｇであることが望ましい。キャリア粒子の感光体への移行を抑制するもう一つの手段として、磁化を制御することが有効であり、このため、キャリア芯材の磁化を上記範囲とすることが望ましい。上記１０００×１０３／４π・Ａ／ｍにおける磁化が５０Ａｍ２／ｇ未満であると、飛散物磁化が悪化しキャリア付着による画像欠陥の原因となる可能性があり、６５Ａｍ２／ｇを超えると、磁気ブラシ上における現像剤の穂が硬くなりすぎ画質を劣化させる可能性がある。この磁化は、下記によって測定される。 The ferrite carrier core material for electrostatic latent image development according to the present invention preferably has a magnetization of 50 to 65 Am 2 / kg in a magnetic field of 1000 × 10 3 / 4π · A / m. As another means for suppressing the transfer of carrier particles to the photoconductor, it is effective to control the magnetization. For this reason, it is desirable that the magnetization of the carrier core material be within the above range. When the magnetization at 1000 × 10 3 / 4π · A / m is less than 50 Am 2 / g, the scattered matter magnetization may be deteriorated and cause image defects due to carrier adhesion, and when the magnetization exceeds 65 Am 2 / g, There is a possibility that the ears of the developer on the magnetic brush become too hard and deteriorate the image quality. This magnetization is measured by:
（磁気特性）
東栄工業社製振動形磁力計(ＶＳＭ−Ｃ７−１０)を用いた。専用セルに１６０ｍｇのキャリアを充填し、１／２ループモード、１０００×１０３／４π×Ａ／ｍの磁場にて磁化を測定した。
(Magnetic properties)
A vibration type magnetometer (VSM-C7-10) manufactured by Toei Kogyo Co., Ltd. was used. A dedicated cell was filled with 160 mg of carrier, and the magnetization was measured in a 1/2 loop mode and a magnetic field of 1000 × 10 3 / 4π × A / m.
本発明に係る静電潜像現像用フェライトキャリア芯材は、ＢＥＴ比表面積が０．０７〜０．１９ｍ２／ｇである。上述したように、本発明に係る静電潜像現像用フェライトキャリア芯材は、平均円形度を０．８１〜０．８７とすることで、キャリア表面に適度な凹凸が生じさせ、適度な電気抵抗を持たせることで、高現像性を得ることができるが、キャリア芯材表面に微細な空孔が存在すると、その部分に被覆樹脂が浸透してしまい、十分な樹脂層がキャリア芯材表面に存在することができなくなる。よって、キャリア芯材のＢＥＴ比表面積は０．１９ｍ２／ｇを超えないことが必要である。また、キャリア芯材の比表面積は主にキャリア芯材焼成時の焼成温度で制御するが、焼成温度を高くし過ぎるとキャリア芯材粒子の粒子間凝集、あるいはそれをほぐすための解砕機のストレスによりキャリア芯材粒子を破砕し、平均円形度円相当径やアスペクト比に悪影響を及ぼすため、０．０７ｍ２／ｇ以上であることが必要である。好ましくは、０．０８〜０．１４ｍ２／ｇである。このＢＥＴ比表面積は、下記により測定される。 An electrostatic latent image developing ferrite carrier core material according to the present invention, BET specific surface area of Ru 0.07~0.19m 2 / g der. As described above, the ferrite carrier core material for developing an electrostatic latent image according to the present invention has an average circularity of 0.81 to 0.87 , so that moderate irregularities are generated on the carrier surface, so By providing resistance, high developability can be obtained. However, if fine pores exist on the surface of the carrier core material, the coating resin penetrates into that portion, and a sufficient resin layer forms the surface of the carrier core material. Can no longer exist. Therefore, it is necessary that the BET specific surface area of the carrier core material does not exceed 0.19 m 2 / g. The specific surface area of the carrier core material is controlled mainly by the firing temperature at the time of firing the carrier core material, but if the firing temperature is too high, the interaggregation of the carrier core material particles or the stress of the crusher to loosen it The carrier core material particles are crushed and adversely affect the average circularity equivalent circle diameter and aspect ratio , so that it is necessary to be 0.07 m 2 / g or more . Good Mashiku is 0.08~0.14m 2 / g. This BET specific surface area is measured by the following.
（ＢＥＴ比表面積）
マウンテック社製ＢＥＴ比表面積測定装置（Ｍａｃｓｏｒｂ ＨＭ ｍｏｄｅｌ １２１０）を用いた。セルに充填したキャリア５ｇをプレヒーターにセットし、脱気温度２００℃にて６０分間前処理。自然冷却した後、Ｈｅ及びＮ２を用い、一点法にてＢＥＴ比表面積を測定した。
(BET specific surface area)
A BET specific surface area measuring device (Macsorb HM model 1210) manufactured by Mountec Corporation was used. The carrier 5g filled in the cell is set in a preheater and pretreated for 60 minutes at a degassing temperature of 200 ° C. After natural cooling, the BET specific surface area was measured by a one-point method using He and N 2 .
本発明に係る静電潜像現像用静電潜像現像用フェライトキャリア芯材は、フェライトであれば特に限定されないが、Ｍｎ、Ｍｇ、Ｌｉ、Ｃａ、Ｓｒ、Ｃｕ、Ｚｎ、Ｔｉから選ばれる少なくとも１種を含むことが望ましい。これらのフェライトのなかでも、抵抗が低いＭｎ系フェライトよりは、ある程度の電気抵抗が得られるＭｎ−Ｍｇ−Ｓｒ系フェライト及びＬｉ−Ｍｎ系フェライトが好ましい。また、Ｍｎ−Ｍｇ−Ｓｒ系フェライトは、Ｍｇ及びＳｒを含有しているため、Ｍｎ系フェライトやＣｕ−Ｚｎ系フェライト等に比べて、キャリア芯材としての帯電量レベルも高いのが特徴である。従って、皮膜が削れてキャリア芯材が露出し始めても、ある程度の帯電レベルを維持できるため好ましい。 The ferrite carrier core material for electrostatic latent image development for electrostatic latent image development according to the present invention is not particularly limited as long as it is ferrite, but at least selected from Mn, Mg, Li, Ca, Sr, Cu, Zn, Ti. It is desirable to include one kind. Among these ferrites, Mn—Mg—Sr ferrite and Li—Mn ferrite that can provide a certain electric resistance are preferable to Mn ferrite having low resistance. Further, since Mn-Mg-Sr ferrite contains Mg and Sr, it is characterized by a higher charge level as a carrier core material than Mn ferrite and Cu-Zn ferrite. . Therefore, even if the film is shaved and the carrier core material starts to be exposed, it is preferable because a certain level of charge can be maintained.
本発明に係る静電潜像現像用フェライトキャリアは、上記キャリア芯材の表面に樹脂を被覆してなるものである。ここに用いられる被覆樹脂としては、組み合わせるトナー、使用される環境等によって適宜選択できる。その種類は特に限定されないが、例えば、フッ素樹脂、アクリル樹脂、エポキシ樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリエステル樹脂、不飽和ポリエステル樹脂、尿素樹脂、メラミン樹脂、アルキッド樹脂、フェノール樹脂、フッ素アクリル樹脂、アクリル−スチレン樹脂、シリコーン樹脂、あるいはアクリル樹脂、ポリエステル樹脂、エポキシ樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、アルキッド樹脂、ウレタン樹脂、フッ素樹脂等の各樹脂で変性した変性シリコーン樹脂等が挙げられる。本発明では、アクリル樹脂、シリコーン樹脂又は変性シリコーン樹脂が最も好ましく用いられる。 The ferrite carrier for developing an electrostatic latent image according to the present invention is obtained by coating the surface of the carrier core material with a resin. The coating resin used here can be appropriately selected depending on the toner to be combined, the environment in which it is used, and the like. The type is not particularly limited, for example, fluorine resin, acrylic resin, epoxy resin, polyamide resin, polyamideimide resin, polyester resin, unsaturated polyester resin, urea resin, melamine resin, alkyd resin, phenol resin, fluorine acrylic resin, Examples thereof include acrylic-styrene resins, silicone resins, or modified silicone resins modified with resins such as acrylic resins, polyester resins, epoxy resins, polyamide resins, polyamideimide resins, alkyd resins, urethane resins, and fluororesins. In the present invention, acrylic resin, silicone resin or modified silicone resin is most preferably used.
ここで被覆樹脂量は、フェライトキャリア芯材に対して０．１〜１０重量％が望ましい。被覆樹脂量が０．０１重量％未満ではキャリア表面に均一な被覆樹脂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。 Here, the coating resin amount is preferably 0.1 to 10% by weight with respect to the ferrite carrier core material. When the coating resin amount is less than 0.01% by weight, it is difficult to form a uniform coating resin layer on the carrier surface. When the coating resin amount exceeds 10% by weight, the carriers are aggregated, resulting in low yield. Along with the decrease, it causes a change in developer characteristics such as fluidity or charge amount in the actual machine.
またキャリアの電気抵抗や帯電量、帯電速度をコントロールすることを目的に、被覆樹脂中に導電性剤を添加することができる。導電性剤はそれ自身の持つ電気抵抗が低いことから、添加量が多すぎると急激な電荷リークを引き起こしやすい。従って、含有量としては、被覆樹脂の固形分に対し０．２５〜２０．０重量％であり、好ましくは０．５〜１５．０重量％、特に好ましくは１．０〜１０．０重量％である。導電性剤としては、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が挙げられる。 In addition, a conductive agent can be added to the coating resin for the purpose of controlling the electric resistance, charge amount, and charging speed of the carrier. Since the conductive agent itself has a low electric resistance, an excessive amount of the conductive agent tends to cause an abrupt charge leak. Accordingly, the content is 0.25 to 20.0% by weight, preferably 0.5 to 15.0% by weight, particularly preferably 1.0 to 10.0% by weight, based on the solid content of the coating resin. It is. Examples of the conductive agent include conductive carbon, oxides such as titanium oxide and tin oxide, and various organic conductive agents.
また、上記被覆樹脂中には、帯電制御剤を含有させることができる。帯電制御剤の例としては、トナー用に一般的に用いられる各種の帯電制御剤や、各種シランカップリング剤が挙げられる。これは被膜形成によって芯材露出面積を比較的小さくなるように制御した場合、帯電付与能力が低下することがあるが、各種の帯電制御剤やシランカップリング剤を添加することにより、コントロールできるためである。使用できる帯電制御剤やカップリング剤の種類は特に限定されないが、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の帯電制御剤、アミノシランカップリング剤やフッ素系シランカップリング剤等が好ましい。 Further, the coating resin can contain a charge control agent. Examples of the charge control agent include various charge control agents generally used for toners and various silane coupling agents. This is because, when the core material exposed area is controlled to be relatively small by film formation, the charge imparting ability may decrease, but it can be controlled by adding various charge control agents and silane coupling agents. It is. The types of charge control agents and coupling agents that can be used are not particularly limited, but charge control agents such as nigrosine dyes, quaternary ammonium salts, organometallic complexes, and metal-containing monoazo dyes, aminosilane coupling agents, and fluorine-based silane couplings. An agent or the like is preferable.
＜本発明に係る静電潜像現像用フェライトキャリア芯材及びフェライトキャリアの製造方法＞
次に、本発明に係る静電潜像現像用フェライトキャリア芯材及びフェライトキャリアの製造方法について説明する。
<Ferrite carrier core material for developing electrostatic latent image and method for producing ferrite carrier according to the present invention>
Next, a method for producing a ferrite carrier core material for developing an electrostatic latent image and a ferrite carrier according to the present invention will be described.
先ず、所定組成となるように、キャリア芯材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、９００〜１２００℃の温度で仮焼成する。仮焼成温度が９００℃未満では、本焼成後のキャリア表面形状が凹凸になってしまい、１２００℃を超えると、粉砕が困難となる。加圧成型器は使用せずに、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よい。 First, an appropriate amount of the carrier core material is weighed so as to have a predetermined composition, and then pulverized and mixed in a ball mill or a vibration mill for 0.5 hours or more, preferably 1 to 20 hours. The pulverized material thus obtained is pelletized with a pressure molding machine or the like, and then temporarily fired at a temperature of 900 to 1200 ° C. When the pre-baking temperature is less than 900 ° C., the carrier surface shape after the main baking becomes uneven, and when it exceeds 1200 ° C., pulverization becomes difficult. 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.
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、水及び必要に応じて分散剤、ＰＶＡ等のバインダー等を適量添加してスラリーとなし、粘度調整後、スプレードライヤーにて造粒し、脱バイ後、酸素濃度８体積％以下の条件にて１０５０〜１３５０℃で１〜２４時間保持し、本焼成を行う。仮焼成後に粉砕する際は、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 preliminary calcination, further pulverized with a ball mill or vibration mill, etc., water and, if necessary, a dispersant, a binder such as PVA, etc., are added to form a slurry, after adjusting the viscosity, granulated with a spray dryer, After debuying, main baking is performed by holding at 1050 to 1350 ° C. for 1 to 24 hours under an oxygen concentration of 8% by volume or less. When pulverizing after calcination, water may be added and pulverized with 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、解砕し、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したフェライトキャリア芯材を得る。その後、必要に応じて酸化皮膜処理を施し、表面に酸化皮膜を形成し、電気抵抗調整を行うことができる。酸化皮膜処理は、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、３００〜８００℃で熱処理を行う。酸化皮膜を均一に芯材粒子に形成させるためにはロータリー式電気炉を用いることが好ましい。 The fired product obtained by the main firing in this way is crushed and classified. As a classification method, a ferrite carrier core material whose particle size is adjusted to a desired particle size using an existing air classification, mesh filtration method, sedimentation method or the like is obtained. Then, if necessary, an oxide film treatment is performed to form an oxide film on the surface, and the electric resistance can be adjusted. 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 800 ° C. In order to uniformly form the oxide film on the core particles, it is preferable to use a rotary electric furnace.
本発明に係る静電潜像現像用キャリア芯材の平均円形度、円相当径及びアスペクト比は、上記した製造方法において、例えば下記（１）〜（４）の方法によって所望の範囲に制御することができる。
（１）キャリア芯材の造粒工程のおけるスラリー粒径の制御。
（２）キャリア芯材の焼成工程における焼成温度の制御。
（３）キャリア芯材の解砕工程における焼成物の解砕ストレスの制御。
（４）キャリア芯材の解砕工程における小粒径粒子及び低アスペクト比粒子の除去。
The average circularity, the equivalent circle diameter, and the aspect ratio of the carrier core material for developing an electrostatic latent image according to the present invention are controlled in a desired range by the following methods (1) to (4), for example. be able to.
(1) Control of the slurry particle diameter in the granulation process of the carrier core material.
(2) Control of the firing temperature in the carrier core firing step.
(3) Control of the crushing stress of the fired product in the crushing step of the carrier core material.
(4) Removal of small particle diameter particles and low aspect ratio particles in the crushing step of the carrier core material.
本発明に係る静電潜像現像用フェライトキャリアは、上記のようにして製造されたフェライトキャリア芯材の表面に、上記した樹脂を被覆することにより得られる。 The ferrite carrier for developing an electrostatic latent image according to the present invention is obtained by coating the surface of the ferrite carrier core material produced as described above with the above-described resin.
樹脂を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。 The resin 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.
樹脂をフェライト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。
ＵＶ硬化樹脂を用いる場合は、ＵＶ加熱器を用いる。焼き付けの温度は使用する樹脂により異なるが、融点又はガラス転移点以上の温度は必要であり、熱硬化性樹脂又は縮合架橋型樹脂等では、充分硬化が進む温度まで上げる必要がある。
When the resin is coated on the ferrite 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 a microwave oven Baking by may be used.
When a UV curable resin is used, a UV heater is used. Although the baking temperature varies depending on the resin to be used, a temperature equal to or higher than the melting point or the glass transition point is necessary. For a thermosetting resin or a condensation-crosslinking resin, it is necessary to raise the temperature to a point where the curing proceeds sufficiently.
＜本発明に係る静電潜像現像剤＞
次に、本発明に係る静電潜像現像剤について説明する。
本発明に係る静電潜像現像剤は、上記した静電潜像現像用キャリアとトナーとからなるものである。
<Electrostatic latent image developer according to the present invention>
Next, the electrostatic latent image developer according to the present invention will be described.
The electrostatic latent image developer according to the present invention comprises the above-described electrostatic latent image developing carrier and toner.
本発明の静電潜像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 electrostatic latent image 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。これらは単独又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（色材）としては、従来、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。 Conventionally known dyes and pigments can be used as the colorant (coloring material). 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, Vinyl esters such as vinyl acetate, α-methylene aliphatic monocarboxylic acids such as 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やすく、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 liable 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、静電潜像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重量％に設定することが好ましい。３重量％未満であると所望の画像濃度が得にくく、１５重量％を超えると、トナー飛散やかぶりが発生しやすくなる。 The electrostatic latent image 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% by weight. If it is less than 3% by weight, it is difficult to obtain a desired image density. If it exceeds 15% by weight, toner scattering and fogging are likely to occur.
本発明に係る静電潜像現像剤は、補給用現像剤として用いることもできる。この際のキャリアとトナーの混合比、即ちトナー濃度は１００〜３０００重量％に設定することが好ましい。 The electrostatic latent image developer according to the present invention can also be used as a replenishment developer. At this time, the mixing ratio of the carrier and the toner, that is, the toner concentration is preferably set to 100 to 3000% by weight.
上記のように調製された本発明に係る静電潜像現像剤は、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 electrostatic latent image developer according to the present invention prepared as described above is obtained by applying a toner and a latent electrostatic image formed on a latent image holding member having an organic photoconductor layer while applying a bias electric field. The present invention can be used for a digital copying machine, a printer, a FAX, a printing machine, and the like using a developing method in which reversal development is performed by a magnetic brush of a two-component developer having a carrier. 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.
Ｆｅ２Ｏ３、ＭｎＯ及びＭｇＯをモル比で５０：４０：１０の割合で計量し、さらに、上記混合物１００モルに対して酸化ストロンチウム（ＳｒＯ）を０．８モル加えて併せて混合した。次いで、１時間、乾式粉砕し、加圧式成形機にてペレット化した後、１０００℃の温度で仮焼成した。得られた仮焼成物を乾式粉砕した後、水を加えて粉砕し、湿式のメディアミルで５時間粉砕して、固形分５０重量％のスラリーを作製した。このスラリーに分散剤を適量添加し、また、造粒される粒子の強度を確保する目的で、バインダーとしてＰＶＡを固形分に対して１重量％添加し、次いでスプレードライヤーにてアトマイザーディスクの回転数をコントロールしながら造粒し、平均粒径４５μｍの造粒物を得た。 Fe 2 O 3 , MnO and MgO were weighed in a molar ratio of 50:40:10, and 0.8 mol of strontium oxide (SrO) was added to 100 mol of the mixture and mixed together. Subsequently, after dry grinding for 1 hour and pelletizing with a pressure molding machine, it was calcined at a temperature of 1000 ° C. The obtained calcined product was dry pulverized, then pulverized with water, and pulverized with a wet media mill for 5 hours to prepare a slurry having a solid content of 50% by weight. In order to add an appropriate amount of a dispersant to this slurry and to ensure the strength of the granulated particles, 1% by weight of PVA as a binder is added as a binder, and then the number of revolutions of the atomizer disk with a spray dryer Was controlled to obtain a granulated product having an average particle size of 45 μm.
得られた造粒物を６５０℃にて大気中で脱バイ後、電気炉にて、温度１２７０℃、酸素濃度０．５体積％で４時間保持し、本焼成を行った。その後、ヤリヤ機械製作所社製ハンマークラッシャーにて解砕し、徳寿工作所社製ジャイロシフターにて３５０Ｍｅｓｈの篩網を用い、粗粒子を除去し、さらに、日清エンジニアリング社製ターボクラシファイアにて１４００ｒｐｍの条件で微粒子を除去し、その後、磁力選鉱により低磁力品を分別し、フェライトキャリア芯材を得た。 The obtained granulated product was deburied in the atmosphere at 650 ° C., and then held in an electric furnace at a temperature of 1270 ° C. and an oxygen concentration of 0.5% by volume for 4 hours to perform main firing. After that, it was crushed with a hammer crusher manufactured by Yarya Machinery Co., Ltd., and coarse particles were removed using a 350 mesh sieve screen with a gyro shifter manufactured by Tokuju Kogakusha Co., Ltd. Fine particles were removed under the conditions, and then the low-magnetic force product was fractionated by magnetic separation to obtain a ferrite carrier core material.
次に、以下のように樹脂溶液を調製した。
・シリコーン系樹脂（商品名：ＳＲ−２４１１、固形分２０重量％、東レ・ダウコーニング・シリコーン社製）：５００重量部
・γ−アミノプロピルトリエトキシシラン：１０重量部
・トルエン：３００重量部
Next, a resin solution was prepared as follows.
Silicone resin (trade name: SR-2411, solid content 20% by weight, manufactured by Toray Dow Corning Silicone): 500 parts by weight γ-aminopropyltriethoxysilane: 10 parts by weight Toluene: 300 parts by weight
このように調製された樹脂溶液を上記フェライト粒子（キャリア芯材）１００００重量部に流動床コート装置を用いてコーティングし、さらに２５０℃で２時間焼付けを行い、上記樹脂によって被覆されたフェライトキャリアを得た。 The resin solution thus prepared is coated on 10000 parts by weight of the above ferrite particles (carrier core material) using a fluidized bed coater, and further baked at 250 ° C. for 2 hours to obtain a ferrite carrier coated with the above resin. Obtained.
本焼成時の酸素濃度を３体積％に上げた以外は、実施例１と同様にしてフェライトキャリア芯材を得た。このフェライトキャリア芯材の表面に実施例１と同様に樹脂を被覆してフェライトキャリアを得た。 A ferrite carrier core material was obtained in the same manner as in Example 1 except that the oxygen concentration during the main firing was increased to 3% by volume. The surface of this ferrite carrier core material was coated with a resin in the same manner as in Example 1 to obtain a ferrite carrier.
本焼成時の温度を１３２０℃に上げ、解砕時にヤリヤ機械製作所社製ハンマークラッシャーに加え、セイシン企業社製ジェットミルにて解砕、分級処理を行い、本焼成及び解砕後の分級時の日清エンジニアリング社製ターボクラシファイアの条件を１２００ｒｐｍと、より微粒子が除去できる条件とした以外は、実施例１と同様にしてフェライトキャリア芯材を得た。このフェライトキャリア芯材の表面に実施例１と同様に樹脂を被覆してフェライトキャリアを得た。 The temperature during the main firing is raised to 1320 ° C., and in addition to the hammer crusher manufactured by Yarya Machinery Co., Ltd. during crushing, crushing and classification are performed using a jet mill manufactured by Seishin Enterprise Co., Ltd. A ferrite carrier core material was obtained in the same manner as in Example 1 except that the condition of a turbo classifier manufactured by Nissin Engineering Co., Ltd. was changed to 1200 rpm and a condition where fine particles could be removed. The surface of this ferrite carrier core material was coated with a resin in the same manner as in Example 1 to obtain a ferrite carrier.
本焼成及び解砕後の分級において、徳寿工作所社製ジャイロシフターの篩網を３２５Ｍｅｓｈとし、日清エンジニアリング社製ターボクラシファイアの条件を１６００ｒｐｍとした以外は、実施例１と同様にしてフェライトキャリア芯材を得た。このフェライトキャリア芯材の表面に実施例１と同様に樹脂を被覆してフェライトキャリアを得た。 In the classification after the main firing and pulverization, the ferrite carrier core was made in the same manner as in Example 1 except that the screen of the gyro shifter manufactured by Tokuju Kogakusho Co. was set to 325 Mesh and the condition of the turbo classifier manufactured by Nissin Engineering Co. was set to 1600 rpm. The material was obtained. The surface of this ferrite carrier core material was coated with a resin in the same manner as in Example 1 to obtain a ferrite carrier.
造粒時のアトマイザーディスクの回転数を変え、平均粒径５０μｍの造粒物とし、本焼成及び解砕後の分級において、徳寿工作所社製ジャイロシフターの篩網を３００Ｍｅｓｈとし、日清エンジニアリング社製ターボクラシファイアの条件を１０００ｒｐｍとした以外は、実施例１と同様にしてフェライトキャリア芯材を得た。このフェライトキャリア芯材の表面に実施例１と同様に樹脂を被覆してフェライトキャリアを得た。 Nissin Engineering Co., Ltd. changed the rotation speed of the atomizer disk during granulation to obtain a granulated product with an average particle size of 50 μm, and the classification of the gyro shifter made by Tokuju Kakusho Co., Ltd. was 300 Mesh in the classification after the main firing and crushing. A ferrite carrier core material was obtained in the same manner as in Example 1 except that the turbo classifier condition was 1000 rpm. The surface of this ferrite carrier core material was coated with a resin in the same manner as in Example 1 to obtain a ferrite carrier.
造粒時のアトマイザーディスクの回転数を変え、平均粒径３０μｍの造粒物とし、本焼成及び解砕後の分級において、徳寿工作所社製ジャイロシフターの篩網を４５０Ｍｅｓｈとし、日清エンジニアリング社製ターボクラシファイアの条件を１８００ｒｐｍとした以外は、実施例１と同様にしてフェライトキャリア芯材を得た。このフェライトキャリア芯材の表面に実施例１と同様に樹脂を被覆してフェライトキャリアを得た。 Nissin Engineering Co., Ltd. changed the rotation speed of the atomizer disk at the time of granulation to obtain a granulated product with an average particle size of 30 μm. A ferrite carrier core material was obtained in the same manner as in Example 1 except that the turbo classifier condition was 1800 rpm. The surface of this ferrite carrier core material was coated with a resin in the same manner as in Example 1 to obtain a ferrite carrier.
本焼成時の酸素濃度を０体積％に下げた以外は、実施例１と同様にしてフェライトキャリア芯材を得た。このフェライトキャリア芯材の表面に実施例１と同様に樹脂を被覆してフェライトキャリアを得た。 A ferrite carrier core material was obtained in the same manner as in Example 1 except that the oxygen concentration during the main firing was reduced to 0% by volume. The surface of this ferrite carrier core material was coated with a resin in the same manner as in Example 1 to obtain a ferrite carrier.
造粒時のアトマイザーディスクの回転数を変え、平均粒径３０μｍの造粒物とし、本焼成時の酸素濃度を３体積％に上げた以外は、実施例１と同様にしてフェライトキャリア芯材を得た。このフェライトキャリア芯材の表面に実施例１と同様に樹脂を被覆してフェライトキャリアを得た。 The ferrite carrier core material was changed in the same manner as in Example 1 except that the rotation speed of the atomizer disk during granulation was changed to a granulated product having an average particle size of 30 μm and the oxygen concentration during the main firing was increased to 3% by volume. Obtained. The surface of this ferrite carrier core material was coated with a resin in the same manner as in Example 1 to obtain a ferrite carrier.
（比較例１）
本焼成時の温度を１３２０℃に上げた以外は、実施例１と同様にしてフェライトキャリア芯材を得た。このフェライトキャリア芯材の表面に実施例１と同様に樹脂を被覆してフェライトキャリアを得た。
(Comparative Example 1)
A ferrite carrier core material was obtained in the same manner as in Example 1 except that the temperature during the main firing was increased to 1320 ° C. The surface of this ferrite carrier core material was coated with a resin in the same manner as in Example 1 to obtain a ferrite carrier.
（比較例２）
本焼成時の温度を１３００℃に上げ、酸素濃度を５体積％に上げた以外は、実施例６と同様にしてフェライトキャリア芯材を得た。このフェライトキャリア芯材の表面に実施例１と同様に樹脂を被覆してフェライトキャリアを得た。
(Comparative Example 2)
A ferrite carrier core material was obtained in the same manner as in Example 6 except that the temperature during the main firing was increased to 1300 ° C. and the oxygen concentration was increased to 5% by volume. The surface of this ferrite carrier core material was coated with a resin in the same manner as in Example 1 to obtain a ferrite carrier.
（比較例３）
ＭｎＯ及びＦｅ２Ｏ３をモル比で２０：８０となるように原料を秤量し、さらに秤量した原料１００重量部に対してＴｉＯ２０．１重量部、カーボンブラック０．２重量部を添加して、高速攪拌羽根を有する混合機で混合し、加圧式成形機にて造粒した後、９５０℃で１時間保持し仮焼成を行なった。これをロール式粉砕機にて粉砕した後、気流分級機と振動篩を用いて粒度調整を行った。この仮焼物を電気炉にて、温度１３００℃、酸素濃度０．１％で４時間保持し、本焼成を行なった。その後、解砕及び分級してフェライトキャリア芯材を得た。このフェライトキャリア芯材の表面に実施例１と同様に樹脂を被覆してフェライトキャリアを得た。
(Comparative Example 3)
The raw materials were weighed so that the molar ratio of MnO and Fe 2 O 3 was 20:80, and 0.1 parts by weight of TiO 2 and 0.2 parts by weight of carbon black were added to 100 parts by weight of the weighed raw materials. Then, after mixing with a mixer having high-speed stirring blades and granulating with a pressure molding machine, the mixture was kept at 950 ° C. for 1 hour and calcined. This was pulverized by a roll type pulverizer, and then the particle size was adjusted using an air classifier and a vibrating sieve. This calcined product was held in an electric furnace at a temperature of 1300 ° C. and an oxygen concentration of 0.1% for 4 hours to perform main firing. Then, the ferrite carrier core material was obtained by crushing and classification. The surface of this ferrite carrier core material was coated with a resin in the same manner as in Example 1 to obtain a ferrite carrier.
（比較例４）
実施例１と同様にして得られた造粒物を用い、これをプロパン：酸素＝８Ｎｍ３／ｈｒ：３２Ｎｍ３／ｈｒの可燃性ガス燃焼炎中に、流速約４０ｍ／ｓｅｃの条件で投入し、急冷し、回収した後、分級を行ってフェライトキャリア芯材を作製した。このフェライトキャリア芯材の表面に実施例１と同様に樹脂を被覆してフェライトキャリアを得た。
(Comparative Example 4)
The granulated product obtained in the same manner as in Example 1 was used, and this was put into a combustible gas combustion flame of propane: oxygen = 8 Nm 3 / hr: 32 Nm 3 / hr at a flow rate of about 40 m / sec. After rapid cooling and recovery, classification was performed to prepare a ferrite carrier core material. The surface of this ferrite carrier core material was coated with a resin in the same manner as in Example 1 to obtain a ferrite carrier.
（比較例５）
Ｆｅ２Ｏ３、Ｌｉ２ＣＯ３及びＭｎ３Ｏ４をモル比で、７６．３：１３．３：１０．４の割合になるように秤量し、混合した後、１時間、乾式粉砕した。得られた粉砕物をペレット化した後、１０００℃の温度で仮焼成した。得られた仮焼成物を乾式粉砕した後、固形分５０％となるように、水とバインダー成分と分散剤を加え、１／８インチ径のステンレスビーズを用いて湿式ボールミルで１時間粉砕した後、さらに１／１６インチ径のステンレスビーズを用いて４時間粉砕した。このスラリーに分散剤を適量添加し、また造粒される粒子の強度を確保する目的で、バインダーとしてＰＶＡを固形分に対して１重量％添加し、次いでスプレードライヤーにより造粒した。
(Comparative Example 5)
Fe 2 O 3 , Li 2 CO 3 and Mn 3 O 4 were weighed in a molar ratio of 76.3: 13.3: 10.4, mixed, and then dry pulverized for 1 hour. The obtained pulverized product was pelletized and then calcined at a temperature of 1000 ° C. After dry pulverizing the obtained calcined product, water, a binder component and a dispersant are added so that the solid content is 50%, and then pulverized with a wet ball mill for 1 hour using 1/8 inch diameter stainless steel beads. Further, it was pulverized for 4 hours using 1/16 inch diameter stainless steel beads. For the purpose of adding an appropriate amount of a dispersant to the slurry and ensuring the strength of the granulated particles, 1% by weight of PVA as a binder was added relative to the solid content, and granulated by a spray dryer.
得られた造粒物を６５０℃にて大気中で脱バイ後、電気炉にて、１１６５℃、酸素濃度１体積％の条件で４時間焼成し、焼成物を得た。得られた焼成物をハンマークラッシャーで解砕、分級、磁力選鉱を行い、フェライトキャリア芯材を得た。このフェライトキャリア芯材の表面に実施例１と同様に樹脂を被覆してフェライトキャリアを得た。 The obtained granulated product was deburied in the atmosphere at 650 ° C., and then baked in an electric furnace for 4 hours under the conditions of 1165 ° C. and oxygen concentration of 1 volume% to obtain a baked product. The obtained fired product was crushed with a hammer crusher, classified, and magnetically separated to obtain a ferrite carrier core material. The surface of this ferrite carrier core material was coated with a resin in the same manner as in Example 1 to obtain a ferrite carrier.
（比較例６）
本焼成時の温度を１１００℃に下げ、酸素濃度を０体積％に下げた以外は、実施例１と同様にしてフェライトキャリア芯材を得た。このフェライトキャリア芯材の表面に実施例１と同様に樹脂を被覆してフェライトキャリアを得た。
(Comparative Example 6)
A ferrite carrier core material was obtained in the same manner as in Example 1 except that the temperature during the main firing was lowered to 1100 ° C. and the oxygen concentration was lowered to 0% by volume. The surface of this ferrite carrier core material was coated with a resin in the same manner as in Example 1 to obtain a ferrite carrier.
実施例１〜８及び比較例１〜６により得られたフェライトキャリア芯材の平均円形度、円相当径１５μｍ以下でアスペクト比１．５以上の粒子含有率、平均円相当径、磁化、ＢＥＴ比表面積及びフェライトキャリア芯材の組成を表１に示す。これらの測定方法は、上述の通りである。 Average circularity of ferrite carrier core materials obtained in Examples 1 to 8 and Comparative Examples 1 to 6 , particle content with an equivalent circle diameter of 15 μm or less and an aspect ratio of 1.5 or more, average equivalent circle diameter, magnetization, BET ratio Table 1 shows the surface area and the composition of the ferrite carrier core material. These measurement methods are as described above.
実施例１〜８及び比較例１〜６により得られたフェライトキャリアと市販のＲｉｃｏｈ社製ｉｍａｇｉｏＭＰＣ２５００のマゼンタトナーを、トナー濃度８重量％の１ｋｇの現像剤量になるように秤量を行った後、３０分間撹拌を行い、静電潜像現像剤を得た。 After the ferrite carriers obtained in Examples 1 to 8 and Comparative Examples 1 to 6 and a commercially available magenta toner of Imagio MPC 2500 manufactured by Ricoh were weighed so that the amount of developer was 1 kg with a toner concentration of 8 wt%, Stirring was performed for 30 minutes to obtain an electrostatic latent image developer.
この静電潜像現像剤について、現像特性、感光体傷、キャリア飛散、画質及び総合評価を下記の方法によって評価し、その結果を表２に示す。 With respect to this electrostatic latent image developer, development characteristics, photoconductor scratches, carrier scattering, image quality and comprehensive evaluation were evaluated by the following methods. The results are shown in Table 2.
（現像特性評価）
適正露光条件下で現像を行い、ベタ部の画像濃度をＸ−Ｒｉｔｅ（Ｘ−Ｒｉｔｅ，Ｉｎｃ．社製）によって測定し、ランク付けを行った。
◎：１．４以上。
○：１．２以上１．４未満。
△：１．０以上１．２未満。
×：１．０未満。
(Development characteristics evaluation)
Development was performed under appropriate exposure conditions, and the image density of the solid portion was measured by X-Rite (X-Rite, Inc.) and ranked.
A: 1.4 or more.
○: 1.2 or more and less than 1.4.
Δ: 1.0 or more and less than 1.2.
X: Less than 1.0.
（感光体傷評価）
適正露光条件下で３００００枚耐刷印刷を行なった後、感光体表面を目視観察し、ランク付けを行った。
◎：感光体表面に傷が全くなく、きれいな状態が保たれている。
○：多少感光体表面に傷が見られるが、きれいな状態である。
△：感光体表面に傷が見られるが、問題ないレベルである。
×：感光体表面に傷がひどく、用紙上にも問題が現れてしまう。
(Photoconductor scratch evaluation)
After performing 30000 plate printing under proper exposure conditions, the surface of the photoreceptor was visually observed and ranked.
A: The surface of the photoconductor is not damaged at all and is kept clean.
○: Some scratches are observed on the surface of the photoreceptor, but the surface is clean.
(Triangle | delta): Although a damage | wound is seen on the photoreceptor surface, it is a level which is satisfactory.
X: The surface of the photoconductor is severely scratched and a problem appears on the paper.
（キャリア飛散）
適正露光条件下で現像を行い、画像上のキャリア付着による白斑のレベルを目視によって判定し、ランク付けを行った。
◎：Ａ３用紙１０枚中に白斑が無いこと。
○：Ａ３用紙１０枚中に１〜５個。
△：Ａ３用紙１０枚中に６〜１０個。
×：Ａ３用紙１０枚中に２１個以上。
(Carrier scattering)
Development was performed under appropriate exposure conditions, and the level of vitiligo due to carrier adhesion on the image was visually determined to perform ranking.
A: No white spots on 10 sheets of A3 paper.
A: 1 to 5 pieces in 10 A3 sheets.
Δ: 6 to 10 in 10 A3 sheets.
X: 21 or more in 10 A3 sheets.
（画質評価）
適正露光条件下で現像を行い、Ａ３全面ハーフトーン（スクリーン面積率５０％）をＸ−Ｒｉｔｅ（Ｘ−Ｒｉｔｅ，Ｉｎｃ．社製）によって測定し、ランク付けを行った。
◎：濃度の濃淡差が０．１未満であり、濃度ムラが視認できない。
○：濃度の濃淡差が０．１〜０．２あり、濃度ムラが視認できない。
△：濃度の濃淡差が０．２を超え、濃度ムラとして認識されるが、耐刷印刷時にはムラとして認識されない。
×：耐刷印刷時において濃度ムラが認識される。
(Image quality evaluation)
Development was performed under appropriate exposure conditions, and A3 full-surface halftone (screen area ratio 50%) was measured by X-Rite (manufactured by X-Rite, Inc.) and ranked.
A: Difference in density is less than 0.1, and density unevenness cannot be visually recognized.
A: The density difference is 0.1 to 0.2, and density unevenness cannot be visually recognized.
Δ: The density difference exceeds 0.2 and is recognized as density unevenness, but is not recognized as unevenness at the time of printing.
X: Density unevenness is recognized during printing printing.
（総合判定）
◎：全てにおいて非常に良好である。
○：良好である。
△：若干悪い点もあるが使用可能レベル。
×：使用に耐えない。
(Comprehensive judgment)
A: Very good in all cases.
○: Good.
(Triangle | delta): Although there are some bad points, it is a usable level.
X: Unbearable for use.
表２の結果から明らかなように、実施例１〜８は、現像特性、感光体傷、キャリア飛散及び画質の各評価において、若干悪い点もあるが、使用可能な水準にある。これらの実施例の中でも実施例１〜３及び４が良好な結果を示し、特に実施例１が良好であった。これに対して、比較例１〜３は感光体に傷がひどく発生した。比較例１及び３は画質も劣化した。また、比較例２はキャリア飛散が生じた。一方、比較例４は現像特性に劣るものであった。比較例５及び６は総合評価では許容範囲であるが、現像特性が充分ではなかった。 As is apparent from the results in Table 2, Examples 1 to 8 are at a usable level although there are some bad points in the evaluation of development characteristics, photoconductor scratches, carrier scattering and image quality. Among these examples, Examples 1 to 3 and 4 showed good results, and Example 1 was particularly good. On the other hand, in Comparative Examples 1 to 3, the photoconductor was severely damaged. In Comparative Examples 1 and 3, the image quality was also deteriorated. In Comparative Example 2, carrier scattering occurred. On the other hand, Comparative Example 4 was inferior in development characteristics. Comparative Examples 5 and 6 were acceptable in comprehensive evaluation, but the development characteristics were not sufficient.
本発明に係る静電潜像現像用フェライトキャリア芯材、フェライトキャリア及びこれを用いた静電潜像現像剤によって、現像中のキャリア飛散が防止され、優れた現像特性や画質特性を有する。また、現像剤中のキャリアに起因する感光体等への傷の発生が低減される。 The ferrite carrier core material for electrostatic latent image development, the ferrite carrier, and the electrostatic latent image developer using the same according to the present invention prevent carrier scattering during development and have excellent development characteristics and image quality characteristics. Further, the occurrence of scratches on the photoconductor due to the carrier in the developer is reduced.
従って、本発明は、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等の分野に広く使用可能である。 Therefore, the present invention can be widely used in the fields of full-color machines that require high image quality and high-speed machines that require image maintenance reliability and durability.
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| JP2017062421A (en) * | 2015-09-25 | 2017-03-30 | 富士ゼロックス株式会社 | Image forming apparatus and process cartridge |
| JP7335579B2 (en) | 2019-01-25 | 2023-08-30 | パウダーテック株式会社 | Electrophotographic developer carrier core material, manufacturing method thereof, and electrophotographic developer carrier and developer provided with the carrier core material |
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