JP5348587B2 - Resin-filled carrier for electrophotographic developer and electrophotographic developer using the resin-filled carrier - Google Patents
Resin-filled carrier for electrophotographic developer and electrophotographic developer using the resin-filled carrier Download PDFInfo
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- JP5348587B2 JP5348587B2 JP2009086522A JP2009086522A JP5348587B2 JP 5348587 B2 JP5348587 B2 JP 5348587B2 JP 2009086522 A JP2009086522 A JP 2009086522A JP 2009086522 A JP2009086522 A JP 2009086522A JP 5348587 B2 JP5348587 B2 JP 5348587B2
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- resin
- carrier
- filled
- electrophotographic developer
- core material
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Landscapes
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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に使用される樹脂充填型キャリアに関し、詳しくは帯電の立ち上がり速度が速く、更に絶縁破壊電圧が高くて、かつ粒子の破壊強度も高い電子写真現像剤用樹脂充填型キャリア及び該樹脂充填型キャリアを用いた電子写真現像剤に関する。 The present invention relates to a resin-filled carrier used for a two-component electrophotographic developer used in a copying machine, a printer, and the like. Specifically, the charge rising speed is high, the dielectric breakdown voltage is high, and particle breakage is caused. The present invention relates to a resin-filled carrier for electrophotographic developer having high strength and an electrophotographic developer using the resin-filled carrier.
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 electrophotographic development 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 composed of toner particles and carrier particles. The two-component developer and the one-component developer using only toner particles.
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、各種の、鉄粉キャリア、フェライトキャリア、樹脂被覆フェライトキャリア、磁性粉分散型樹脂キャリア等が使用されていた。 Conventionally, various types of iron powder carriers, ferrite carriers, resin-coated ferrite carriers, magnetic powder-dispersed resin carriers, and the like have been used as carrier particles for forming a two-component developer.
最近、オフィスのネットワーク化が進み、単機能の複写機から複合機への時代に進化し、サービス体制も、契約したサービスマンが定期的にメンテナンスを行って現像剤等を交換するようなシステムから、メンテナンスフリーシステムの時代へシフトしてきており、市場からは、現像剤の更なる長寿命化に対する要求が一層高まってきている。 Recently, the networking of offices has progressed and evolved from the single-function copying machine to the multifunctional machine, and the service system has been changed from a system in which contracted service personnel regularly perform maintenance and replace developer etc. However, there has been a shift to the era of maintenance-free systems, and the demand for further extending the life of the developer is increasing from the market.
このような中で、キャリア粒子の軽量化を図り、現像剤寿命を伸ばすことを目的として、特許文献１（特開平５−４０３６７号公報）等には、微細な磁性微粒子を樹脂中に分散させた磁性粉分散型キャリアも多く提案されている。 Under such circumstances, for the purpose of reducing the weight of carrier particles and extending the developer life, Patent Document 1 (Japanese Patent Laid-Open No. 5-40367) discloses that fine magnetic fine particles are dispersed in a resin. Many magnetic powder dispersed carriers have also been proposed.
このような磁性粉分散型キャリアは、磁性微粒子の量を少なくすることにより真密度を下げることができ、攪拌によるストレスを軽減できるため、被膜の削れや剥離を防止することができ、長期にわたって安定した画像特性を得ることができる。 Such a magnetic powder-dispersed carrier can reduce the true density by reducing the amount of magnetic fine particles, and can reduce stress due to stirring, so it can prevent the film from being scraped or peeled off, and is stable over a long period of time. Image characteristics can be obtained.
しかしながら、磁性粉分散型キャリアは、バインダー樹脂が磁性微粒子を覆っているため、キャリア抵抗が高い。そのため、充分な画像濃度を得ることが難しいという問題がある。 However, the magnetic powder-dispersed carrier has a high carrier resistance because the binder resin covers the magnetic fine particles. Therefore, there is a problem that it is difficult to obtain a sufficient image density.
また、磁性粉分散型キャリアは、磁性微粒子をバインダー樹脂で固めているものであり、撹拌ストレスや現像機内での衝撃により磁性微粒子が脱離したり、従来用いられてきた鉄粉キャリアやフェライトキャリアに比べ機械的強度に劣るためか、キャリア粒子自体が割れたりするという問題が発生することがあった。そして、脱離した磁性微粒子や割れたキャリア粒子は感光体に付着し、画像欠陥を引き起こす原因となることがあった。 In addition, the magnetic powder-dispersed carrier is obtained by solidifying magnetic fine particles with a binder resin. The magnetic fine particles are detached due to agitation stress or impact in a developing machine, or the conventional iron powder carrier or ferrite carrier is used. In some cases, the mechanical strength may be inferior, or the carrier particles may be broken. The detached magnetic fine particles and broken carrier particles may adhere to the photoreceptor and cause image defects.
さらに、磁性粉分散型キャリアは、微細な磁性微粒子を用いるため、残留磁化及び保磁力が高くなり、現像剤の流動性が悪くなるという欠点がある。特にマグネットロール上に磁気ブラシを形成した場合、残留磁化及び保磁力があるために、磁気ブラシの穂が硬くなり、高画質を得にくい。また、マグネットロールを離れても、キャリアの磁気凝集がほぐれず、補給されたトナーとの混合が速やかに行われないため、帯電量の立ち上がりが悪く、トナー飛散やかぶりといった画像欠陥を起こすという問題があった。 Furthermore, since the magnetic powder-dispersed carrier uses fine magnetic fine particles, there are disadvantages that the residual magnetization and the coercive force are increased and the fluidity of the developer is deteriorated. In particular, when a magnetic brush is formed on a magnet roll, since the residual magnetization and the coercive force are present, the ears of the magnetic brush become hard and it is difficult to obtain high image quality. In addition, even when the magnet roll is separated, the magnetic aggregation of the carrier is not loosened and the toner is not quickly mixed with the replenished toner, so that the charge amount rises poorly and causes image defects such as toner scattering and fogging. was there.
さらに、磁性粉分散型キャリアは、粉砕法と重合法の２種類の方法によって作ることができるが、粉砕法は歩留まりが悪く、重合法は製造工程が複雑なため、どちらも製造コストが高いという問題がある。 Furthermore, the magnetic powder-dispersed carrier can be made by two methods, a pulverization method and a polymerization method, but the pulverization method has a low yield, and the polymerization method has a complicated manufacturing process. There's a problem.
磁性粉分散型キャリアに代わるものとして多孔性キャリア芯材の空隙に樹脂を充填した樹脂充填型キャリアが提案されている。例えば特許文献２（特開平１１−２９５９３３号公報）及び特許文献３（特開平１１−２９５９３５号公報）には、柔磁性コア又は硬磁性コアと、コアの細孔に含まれるポリマーと、コアを覆うコーティングとを含むキャリアが記載されている。これらの樹脂充填型キャリアにより、衝撃が少なく、所望の流動性を持ち、摩擦帯電値の範囲が広く、所望の伝導率であり、体積平均粒径が一定範囲にあるキャリアが得られるとされている。 As an alternative to a magnetic powder-dispersed carrier, a resin-filled carrier has been proposed in which a void in a porous carrier core material is filled with a resin. For example, in Patent Document 2 (Japanese Patent Laid-Open No. 11-295933) and Patent Document 3 (Japanese Patent Laid-Open No. 11-295935), a soft magnetic core or a hard magnetic core, a polymer contained in the pores of the core, and a core A carrier including an overlying coating is described. These resin-filled carriers are said to provide a carrier with less impact, desired fluidity, a wide triboelectric charge range, desired conductivity, and a volume average particle diameter in a certain range. Yes.
ここで、特許文献２には、芯材として、既知の多孔性コア等の、様々な適当な多孔性固体状コアキャリア物質を用いることができるとされている。特に重要なのは、多孔性であることと所望の流動性を持つことであると記載され、注目すべき性質として、柔磁性とＢＥＴ面積で示される多孔度及び体積平均粒径が挙げられている。 Here, Patent Document 2 states that various appropriate porous solid core carrier materials such as a known porous core can be used as the core material. Of particular importance is described as being porous and having the desired fluidity, and notable properties include softness and porosity and volume average particle size as indicated by the BET area.
しかし、同文献の実施例に記載の様に、ＢＥＴ面積が１６００ｃｍ２／ｇ程度の多孔度では、樹脂を充填させても充分な低比重化が図れず、近年、ますます高まる現像剤の長寿命化への要求に応えられるものではなかった。 However, as described in the Examples of the same document, with a porosity having a BET area of about 1600 cm 2 / g, it is not possible to achieve a sufficiently low specific gravity even if the resin is filled. It was not able to meet the demand for life extension.
さらに、同文献に記載されているように、ただ単純にＢＥＴ面積で表現される多孔性をコントロールするだけでは、樹脂充填後のキャリアにおける比重や機械的強度を精度良く制御することは困難である。 Furthermore, as described in the same document, it is difficult to accurately control the specific gravity and mechanical strength of the carrier after filling with the resin simply by controlling the porosity expressed by the BET area. .
ＢＥＴ面積の測定原理は、特定の気体の物理吸着及び化学吸着を測定するものであり、芯材の多孔度とは相関しないものである。つまり、孔がほとんど存在しない芯材であっても、その粒径、粒度分布及び表面材質等によってＢＥＴ面積が変わることは一般的であり、そのようにして測定されたＢＥＴ面積で多孔度をコントロールしても、樹脂が充分に充填できる芯材であるとは言えない。ＢＥＴ面積の数値は高いが、多孔性でない芯材、もしくは多孔性が充分でない芯材に多量の樹脂を充填しようとすると、充填しきれなかった樹脂が、芯材と密着せずに単独で存在し、キャリア中で浮遊したり、粒子間の凝集が多量発生し、流動性が悪くなったり、実使用期間中に凝集が解れた際に、帯電特性が大きく変動する等、安定した特性を得ることが困難である。 The measurement principle of the BET area is to measure physical adsorption and chemical adsorption of a specific gas and does not correlate with the porosity of the core material. In other words, even if the core material has few pores, it is common for the BET area to change depending on the particle size, particle size distribution, surface material, etc., and the porosity is controlled by the BET area thus measured. Even so, it cannot be said that the core material can be sufficiently filled with resin. Although the BET area value is high, if you try to fill a large amount of resin into a core material that is not porous or insufficiently porous, the resin that could not be filled alone will not be in close contact with the core material. In addition, it is possible to obtain stable characteristics such as floating in the carrier, large amount of aggregation between particles, poor fluidity, and large change in charging characteristics when aggregation is released during the actual use period. Is difficult.
加えて、同文献には、多孔性コアを用い、そこに充填する樹脂とさらにその表面を被覆する樹脂の総含有量がキャリアの約０．５〜約１０重量％であることが好ましいとされている。さらに同文献の実施例では、それらの樹脂は、キャリアに対して高々６重量％に満たない。このような少量の樹脂では、所望とする低比重を実現することはできず、従来から使用されてきた樹脂被覆キャリアと同様の性能しか得ることができない。 In addition, the same document states that it is preferable to use a porous core, and the total content of the resin filling the core and the resin covering the surface thereof is about 0.5 to about 10% by weight of the carrier. ing. Furthermore, in the examples of the document, those resins are less than 6% by weight based on the carrier. With such a small amount of resin, a desired low specific gravity cannot be realized, and only the same performance as that of a resin-coated carrier that has been used conventionally can be obtained.
また、特許文献４（特開昭５４−７８１３７号公報）には、実質的に無孔質のものよりも嵩比重の小さい多孔質又は表面粗度の大きな磁性粒子の孔及び表面のへこみ部分に電気絶縁性樹脂の微粉末を充填した静電像現像剤用キャリアが開示されている。 Patent Document 4 (Japanese Patent Application Laid-Open No. Sho 54-78137) describes pores and surface dents in magnetic particles having a smaller bulk specific gravity or a larger surface roughness than those substantially nonporous. An electrostatic image developer carrier filled with a fine powder of an electrically insulating resin is disclosed.
特許文献５（特開２００６−３３７５７９号公報）には、空隙率が１０〜６０％であるフェライト芯材に樹脂を充填してなる樹脂充填型キャリアが、特許文献６（特開２００７−５７９４３号公報）には立体的積層構造を持つ樹脂充填型キャリアが提案されている。これらの文献では、樹脂充填キャリア用芯材に、樹脂を充填する方法として、様々な方法が使用できるとし、その方法としては、例えば乾式法、流動床によるスプレードライ方式、ロータリドライ方式、万能攪拌機等による液浸乾燥法等が挙げられ、これらの方法は、使用する芯材、樹脂によって適当な方法が選択されることが開示されている。 Patent Document 5 (Japanese Patent Laid-Open No. 2006-337579) discloses a resin-filled carrier obtained by filling a ferrite core material having a porosity of 10 to 60% with a resin, as disclosed in Patent Document 6 (Japanese Patent Laid-Open No. 2007-57943). (Patent Publication) proposes a resin-filled carrier having a three-dimensional laminated structure. In these documents, various methods can be used as a method for filling a resin-filled carrier core material with a resin. Examples of the methods include a dry method, a spray-dry method using a fluidized bed, a rotary dry method, and a universal agitator. It is disclosed that an appropriate method is selected depending on the core material and resin to be used.
また、特許文献６には、樹脂を充填する際には、充填する装置内を減圧しておくことが好ましい旨、常圧もしくは加圧状態では、空隙内を樹脂で充填することが困難であり、減圧することによって、粒子内部の空隙に、効率的かつ充分に樹脂を充填することができ、立体的積層構造を形成しやすくなる旨の開示がある。 Further, in Patent Document 6, when filling the resin, it is preferable to reduce the pressure inside the filling device, and it is difficult to fill the gap with the resin under normal pressure or in a pressurized state. There is a disclosure that by reducing the pressure, the voids inside the particles can be efficiently and sufficiently filled with resin, and a three-dimensional laminated structure can be easily formed.
さらには、特許文献７（特開２００７−１３３１００号公報）には、多孔性の磁性体中に樹脂を含浸させたキャリアや芯材の表面に多量の樹脂を被覆したキャリアが記載されている。これらのキャリアは真比重が軽いため、トナーとキャリアを有する補給用現像剤を現像装置に補給しながら現像し、現像装置内部で過剰になったキャリアを必要に応じて現像装置から排出する二成分現像方法の補給用現像剤中に用いることで、余剰のキャリアをトナーとともにスムーズに排出することができるとしている。 Furthermore, Patent Document 7 (Japanese Patent Laid-Open No. 2007-133100) describes a carrier in which a porous magnetic material is impregnated with a resin and a carrier in which a surface of a core material is coated with a large amount of resin. Since these carriers have a low true specific gravity, they are developed while supplying a replenishment developer having toner and carrier to the developing device, and the excess carrier inside the developing device is discharged from the developing device as necessary. By using it in the developer for replenishment in the development method, it is said that the excess carrier can be smoothly discharged together with the toner.
これら特許文献５〜７に記載の多孔性磁性粉は、ＢＥＴや吸油量で芯材の空孔体積を検討している例がある。しかし、ＢＥＴはあくまでも表面積であり、その値からは実際の空孔度はわからない。また吸油量は、ある程度空孔体積を反映したものであるが、その測定原理から考えて、粒子間の空隙も合わせて測定しまい、実際の空孔体積ではない。また、一般的に、実際の粒子内の空孔体積に比べて、粒子間の空隙の方が大きく、過度な過不足なく樹脂を充填しようとした際の指標としては、精度に欠けるものであった。更には、これら特許文献には、樹脂が充填されるフェライト表面に存在する空孔の径に関する記載及びその空孔径の分布に関する記載がないため、実際に樹脂を充填させた場合、充填樹脂の粒子間バラツキや樹脂充填の均一性に欠けてしまう。そのため、樹脂充填の不充分な粒子については、強度が劣るため、実機上での使用においては、キャリア粒子の割れや、微粒子が発生し、画像欠陥の原因となる。更には、これら多孔性磁性粉に充填させる樹脂量は、通常の樹脂コートキャリアに比べ、多量の樹脂を使用するため、キャリア粒子内での電荷の移動がスムーズに行われず、帯電の立ち上がり速度が遅くなる。更には、キャリア自体の比重も軽いため、トナーとの適度なストレスが与えられず、帯電の立ち上がり速度は低下する。その結果、実機上での使用においては、現像終了後の再帯電のレベルが低くなり、トナー飛散等の原因になる。 These porous magnetic powders described in Patent Documents 5 to 7 have examples in which the pore volume of the core material is examined by BET or oil absorption. However, BET is a surface area to the last, and the actual porosity is not known from the value. The amount of oil absorption reflects the pore volume to some extent, but considering the measurement principle, the gap between particles is also measured and is not an actual pore volume. In general, the void volume between the particles is larger than the actual void volume in the particle, and the index when attempting to fill the resin without excessive excess or deficiency is not accurate. It was. Furthermore, since these patent documents do not have a description about the diameter of the pores existing on the ferrite surface filled with the resin and a description about the distribution of the pore diameter, the particles of the filled resin are actually filled with the resin. There will be a lack of uniformity and resin filling uniformity. For this reason, the particles with insufficient resin filling are inferior in strength, so that when used on an actual machine, carrier particles are cracked and fine particles are generated, causing image defects. Furthermore, since the amount of resin to be filled in these porous magnetic powders is larger than that of a normal resin-coated carrier, the charge movement within the carrier particles is not smoothly performed, and the charge rising speed is increased. Become slow. Furthermore, since the specific gravity of the carrier itself is light, an appropriate stress with the toner is not given, and the rising speed of charging is lowered. As a result, when used on an actual machine, the level of recharging after the completion of development is lowered, causing toner scattering and the like.
特許文献８（特開２００７−２１８９５５公報）には、芯材粒子の細孔径、細孔容積等について記載されている。すなわち、特許文献８には、樹脂被覆前のキャリア芯材の段階において、高電圧印加条件で高抵抗を維持できる耐久性を具備させておくことで、電子写真現像剤として使用された時点における高電圧印加時での高抵抗維持が顕著に改善され、ブレークダウンの防止や画像特性の劣化防止を図ることができること、また耐スペント性についても、ある特定の細孔分布特性を持つ多孔性磁性粉体を作り、これを高抵抗化処理することによってキャリア芯材を得ることが重要である旨が開示されている。 Patent Document 8 (Japanese Patent Laid-Open No. 2007-218955) describes the pore diameter, pore volume, and the like of the core material particles. That is, Patent Document 8 discloses a high durability at the time of use as an electrophotographic developer by providing durability that can maintain high resistance under a high voltage application condition at the stage of a carrier core material before resin coating. Maintaining high resistance when a voltage is applied is significantly improved, and it is possible to prevent breakdown and prevent deterioration of image characteristics. Also, with respect to spent resistance, porous magnetic powder having specific pore distribution characteristics It is disclosed that it is important to obtain a carrier core material by making a body and subjecting it to a high resistance treatment.
しかし、特許文献８に記載されているキャリアにおいても、その芯材に高抵抗処理を施しているため、電荷の移動がスムーズに行われず、帯電の立ち上がり速度が遅いという欠点がある。 However, the carrier described in Patent Document 8 also has a drawback in that the core material is subjected to a high resistance treatment, so that the charge movement is not smoothly performed and the charge rising speed is slow.
キャリア芯材の細孔分布特性と電気抵抗の両方を満足するものでない場合には、特許文献８の比較例４のように、所望の特性を得ることができないことが判っている。 It has been found that if the carrier core material does not satisfy both the pore distribution characteristics and the electrical resistance, the desired characteristics cannot be obtained as in Comparative Example 4 of Patent Document 8.
これは、特許文献８に記載されているような細孔分布特性では十分でないことを意味しており、より好ましい細孔分布特性をより精度良く制御したキャリア芯材が望まれている。 This means that the pore distribution characteristics described in Patent Document 8 are not sufficient, and a carrier core material in which more preferable pore distribution characteristics are controlled with higher accuracy is desired.
上述した樹脂充填型キャリアにあっては、高電圧下での電荷リークが発生し易く、絶縁破壊電圧が低い、並びに強撹拌時にキャリア粒子の割れ、微粒子の発生があり、粒子の破壊強度が低いという問題がある。 In the resin-filled carrier described above, charge leakage is likely to occur under high voltage, the dielectric breakdown voltage is low, carrier particles are cracked and fine particles are generated during strong stirring, and the particle breaking strength is low. There is a problem.
特許文献９（特開平９−２６５２１２号公報）には、キャリアの帯電立ち上がり特性を改善させるため、芯材内部に、帯電付与能力のある原料、例えば「Ｍｇ化合物」や、抵抗の低い原料、例えば「Ｃｕ化合物」を、製造条件により一部フェライト化させずに、残留させる方法の記載がある。その未反応の原料の量を規定するため、焼結後のコアの粉末Ｘ線回折スペクトルの強度と、未焼結でフェライト化されていない原料の粉末Ｘ線回折スペクトルの強度との強度比を定めている。 In Patent Document 9 (Japanese Patent Laid-Open No. 9-265212), in order to improve the charge rising characteristics of the carrier, a material having a charge imparting ability, for example, “Mg compound”, a material having low resistance, for example, There is a description of a method in which the “Cu compound” is left to be partially ferritized depending on manufacturing conditions. In order to define the amount of the unreacted raw material, the intensity ratio between the intensity of the powder X-ray diffraction spectrum of the core after sintering and the intensity of the powder X-ray diffraction spectrum of the raw material not sintered and ferritized is It has established.
しかしながら、芯材原料をフェライト化させずに、一部残存させるということは、一部の芯材粒子に磁化特性の低い粒子が存在するということであり、これは、キャリア付着等の致命的な画像欠陥の原因となる。また、原料の残存は、芯材粒子の結晶成長が粒子間でばらつく原因となるため、この様な結晶成長の粒子間ばらつきは、樹脂が充填される空孔の径の大きさ（細孔径）や空孔の容積（細孔容積）が粒子間でばらつく原因になるため、樹脂充填系用の芯材としては、好ましくない。 However, leaving the core material raw material partly without making it ferritic means that some core material particles have particles with low magnetization characteristics, which is fatal such as carrier adhesion. Cause image defects. In addition, the remaining of the raw material causes the crystal growth of the core material particles to vary between the particles, and thus, the variation in the crystal growth between the particles is the size of the pores filled with the resin (pore diameter). And the volume of pores (pore volume) varies among particles, and is not preferable as a core material for resin-filled systems.
このように、上記した樹脂充填型キャリアの利点を保持しつつ、帯電の立ち上がり速度が速く、更に絶縁破壊電圧が高くて、かつ粒子の破壊強度も高い電子写真現像剤用樹脂充填型キャリアが求められていた。 Thus, there is a need for a resin-filled carrier for an electrophotographic developer that retains the advantages of the resin-filled carrier described above, has a high charge rising speed, has a high dielectric breakdown voltage, and has a high particle breakage strength. It was done.
従って、本発明の目的は、樹脂充填型キャリアの利点を保持しつつ、帯電量の立ち上がり速度が速く、また絶縁破壊電圧が高く、かつ粒子の破壊強度も高い電子写真現像剤用樹脂充填型キャリア及び該樹脂充填型キャリアを用いた電子写真現像剤を提供することにある。 Accordingly, an object of the present invention is to provide a resin-filled carrier for an electrophotographic developer that maintains the advantages of a resin-filled carrier, has a fast charge rising speed, a high dielectric breakdown voltage, and a high particle breaking strength. And providing an electrophotographic developer using the resin-filled carrier.
本発明者らは、上記のような課題を解決すべく鋭意検討した結果、上記目的を達成するためには、多孔質フェライト芯材の粉末Ｘ線回折スペクトルにおいて、３６°≦２θ≦４６°での（ＦｅＯ）（ＭｎＯ）とＦｅ２ＭｎＯ４とのピーク強度比が一定の範囲にあることが重要であることを知見した。 As a result of intensive studies to solve the above-described problems, the inventors of the present invention achieved the above object by satisfying 36 ° ≦ 2θ ≦ 46 ° in the powder X-ray diffraction spectrum of the porous ferrite core material. It was found that it is important that the peak intensity ratio between (FeO) (MnO) and Fe 2 MnO 4 in a certain range.
このピーク強度比が一定の範囲内にあると、従来の樹脂を多量に使用する樹脂充填型キャリアにおいても、キャリア粒子内での電荷の移動がスムーズに行われ、帯電量の立ち上がり速度は改善される。さらに、絶縁破壊電圧や粒子の破壊強度が低いという問題が生じる一因として充填度合いが粒子によってばらつきがあることを知見し、このようなばらつきを解消するには、多孔質フェライト芯材の細孔容積とピーク細孔径とを特定範囲とすることが好ましいことを見出し、本発明に至った。 If this peak intensity ratio is within a certain range, even in a resin-filled carrier that uses a large amount of conventional resin, the charge movement within the carrier particles is performed smoothly, and the rising speed of the charge amount is improved. The In addition, we found that the degree of filling varies from particle to particle as one cause of problems such as low breakdown voltage and low particle breakdown strength, and in order to eliminate such variation, the pores of the porous ferrite core material The inventors have found that it is preferable to set the volume and the peak pore diameter within a specific range, and have reached the present invention.
すなわち、本発明は、Ｍｎ、Ｆｅ及びＯを主成分とし、Ｍｇ及び／又はＳｒを含む、多孔質フェライト芯材に樹脂を充填させて得られる電子写真現像剤用樹脂充填型キャリアであって、該多孔質フェライト芯材の粉末Ｘ線回折スペクトルにおいて、３６°≦２θ≦４６°での（ＦｅＯ）（ＭｎＯ）とＦｅ２ＭｎＯ４とのピーク強度比が５〜１５０であることを特徴とする電子写真現像剤用樹脂充填型キャリアを提供するものである。 That is, the present invention is a resin-filled carrier for an electrophotographic developer obtained by filling a porous ferrite core material with Mn, Fe and O as main components and containing Mg and / or Sr, In the powder X-ray diffraction spectrum of the porous ferrite core material, the peak intensity ratio of (FeO) (MnO) and Fe 2 MnO 4 at 36 ° ≦ 2θ ≦ 46 ° is 5 to 150 A resin-filled carrier for an electrophotographic developer is provided.
本発明に係る上記電子写真現像剤用樹脂充填型キャリアでは、上記多孔質フェライト芯材の細孔容積が０．０５５〜０．１６ｍｌ／ｇ、ピーク細孔径が０．２〜０．７μmであることが望ましい。 In the resin-filled carrier for an electrophotographic developer according to the present invention, the porous ferrite core material has a pore volume of 0.055 to 0.16 ml / g and a peak pore diameter of 0.2 to 0.7 μm. It is desirable.
本発明に係る上記電子写真現像剤用樹脂充填型キャリアでは、上記多孔質フェライト芯材の細孔系分布において、下記式（１）で表される細孔径のばらつきｄｖが１．０以下であることが望ましい。 In the resin-filled carrier for an electrophotographic developer according to the present invention, the pore diameter distribution dv represented by the following formula (1) is 1.0 or less in the pore distribution of the porous ferrite core material. It is desirable.
本発明に係る上記電子写真現像剤用樹脂充填型キャリアでは、上記多孔質フェライト芯材に充填する樹脂の量が、上記多孔質フェライト芯材１００重量部に対して、６〜３０重量部であることが望ましい。 In the resin-filled carrier for an electrophotographic developer according to the present invention, the amount of the resin filled in the porous ferrite core material is 6 to 30 parts by weight with respect to 100 parts by weight of the porous ferrite core material. It is desirable.
本発明に係る上記電子写真現像剤用樹脂充填型キャリアは、樹脂により表面が被覆されていることが望ましい。 The resin-filled carrier for an electrophotographic developer according to the present invention is preferably coated on the surface with a resin.
本発明に係る上記電子写真現像剤用樹脂充填型キャリアでは、上記樹脂の被覆量が、上記樹脂を充填してなる樹脂充填型フェライト１００重量部に対して、０．１〜５．０重量部であることが望ましい。 In the resin-filled carrier for an electrophotographic developer according to the present invention, the coating amount of the resin is 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the resin-filled ferrite formed by filling the resin. It is desirable that
本発明に係る上記電子写真現像剤用樹脂充填型キャリアは、平均粒径が２０〜６０μｍであることが望ましい。 The resin-filled carrier for an electrophotographic developer according to the present invention preferably has an average particle size of 20 to 60 μm.
本発明に係る上記電子写真現像剤用樹脂充填型キャリアは、飽和磁化が３０〜８０Ａｍ２／ｋｇであることが望ましい。 The resin-filled carrier for an electrophotographic developer according to the present invention preferably has a saturation magnetization of 30 to 80 Am 2 / kg.
本発明に係る上記電子写真現像剤用樹脂充填型キャリアは、ピクノメーター密度が２．５〜４．５ｇ／ｃｍ３であることが望ましい。 The resin-filled carrier for an electrophotographic developer according to the present invention preferably has a pycnometer density of 2.5 to 4.5 g / cm 3 .
本発明に係る上記電子写真現像剤用樹脂充填型キャリアは、見掛け密度が１．０〜２．５ｇ／ｃｍ３であることが望ましい。 The resin-filled carrier for an electrophotographic developer according to the present invention preferably has an apparent density of 1.0 to 2.5 g / cm 3 .
また、本発明は、上記樹脂充填型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 above resin-filled carrier and toner.
本発明に係る上記電子写真現像剤は、補給用現像剤としても用いられる。 The electrophotographic developer according to the present invention is also used as a replenishment developer.
本発明に係る電子写真現像剤用樹脂充填型キャリアは、樹脂充填型フェライトキャリアであるため、軽量化が図れるため、耐久性に優れ長寿命化が達成でき、また流動性に優れ、帯電量等の制御が容易にでき、しかも磁性粉分散型キャリアに比して高強度であり、かつ熱や衝撃による割れ、変形、溶融がない。また、本発明に係る電子写真現像剤用樹脂充填型キャリアは、多孔質フェライト芯材の粉末Ｘ線回折スペクトルにおいて、３６°≦２θ≦４６°での（ＦｅＯ）（ＭｎＯ）とＦｅ２ＭｎＯ４とのピーク強度比が一定の範囲にあるために、帯電量の立ち上がり速度が速く、また絶縁破壊電圧や、粒子の破壊強度も高い。 Since the resin-filled carrier for an electrophotographic developer according to the present invention is a resin-filled ferrite carrier, the weight can be reduced, so that the durability is excellent and a long life can be achieved, the fluidity is excellent, the charge amount, etc. Can be easily controlled, and has higher strength than the magnetic powder-dispersed carrier, and does not crack, deform or melt due to heat or impact. The resin-filled carrier for an electrophotographic developer according to the present invention has (FeO) (MnO) and Fe 2 MnO 4 at 36 ° ≦ 2θ ≦ 46 ° in the powder X-ray diffraction spectrum of the porous ferrite core material. Therefore, the rising rate of the charge amount is fast, and the dielectric breakdown voltage and the breakdown strength of the particles are high.
以下、本発明を実施するための形態について説明する。
＜本発明に係る電子写真現像剤用樹脂充填型キャリア＞
本発明に係る電子写真現像剤用樹脂充填型キャリアは、Ｍｎ、Ｆｅ及びＯを主成分とし、さらにＭｇ及び／又はＳｒが含まれる多孔質フェライト芯材の空隙に樹脂を充填させて得られるものである。
Hereinafter, modes for carrying out the present invention will be described.
<Resin-filled carrier for electrophotographic developer according to the present invention>
The resin-filled carrier for an electrophotographic developer according to the present invention is obtained by filling a resin in a void of a porous ferrite core material containing Mn, Fe and O as main components and further containing Mg and / or Sr. It is.
この多孔質フェライト芯材の粉末Ｘ線回折スペクトルにおいて、３６°≦２θ≦４６°での(ＦｅＯ)（ＭｎＯ）とＦｅ２ＭｎＯ４とのピーク強度比は５〜１５０であることが必要である。また、この多孔質フェライトの(ＦｅＯ)（ＭｎＯ）とＦｅ２ＭｎＯ４とのピーク強度比は好ましくは１０〜８０である。 In the powder X-ray diffraction spectrum of this porous ferrite core material, the peak intensity ratio of (FeO) (MnO) and Fe 2 MnO 4 at 36 ° ≦ 2θ ≦ 46 ° needs to be 5 to 150. . Further, the peak intensity ratio of (FeO) (MnO) and Fe 2 MnO 4 of the porous ferrite is preferably 10 to 80.
多孔質フェライト芯材の(ＦｅＯ)（ＭｎＯ）とＦｅ２ＭｎＯ４とのピーク強度比が５未満であると、芯材中においても、電荷の移動がスムーズに行われず、全体としてキャリアの帯電量の立ち上がり速度が悪化する。また、ピーク強度比が１５０を超えると、芯材中での電荷の移動速度が速く、よって芯材の抵抗が過剰に低抵抗となり、樹脂充填を行った後でも、絶縁破壊電圧の安定性が損なわれる原因となり得る。 When the peak intensity ratio of (FeO) (MnO) and Fe 2 MnO 4 of the porous ferrite core material is less than 5, the charge transfer is not smoothly performed in the core material, and the charge amount of the carrier as a whole The rising speed of is worse. Also, if the peak intensity ratio exceeds 150, the movement speed of the charge in the core material is high, so that the resistance of the core material becomes excessively low and the breakdown voltage stability is stable even after resin filling. It can cause damage.
［ＸＲＤ測定］
ＸＲＤによるピーク強度比の測定は、下記の様に行った。Ｘ線回折装置として、ブルカ−エイエックスエス社製の「Ｍ２１Ｘ」を使用し,測定条件は、管球Ｃｕ（波長１．５４１８Å）、加速電圧４０ｋＶ、電流２００ｍＡであり、測定範囲は５〜８０°、ステップ幅０．０２°、スキャンスピードは４°／ｍｉｎで実施した。 (ＦｅＯ)（ＭｎＯ）とＦｅ２ＭｎＯ４のピーク強度比は、得られたＸ線回折スペクトルデーターから、３６°≦２θ≦４６°での、(ＦｅＯ)（ＭｎＯ）のピーク強度をＸ、Ｆｅ２ＭｎＯ４のピーク強度をＹとした時、「Ｘ／Ｙ×１００」で算出される。
[XRD measurement]
The measurement of the peak intensity ratio by XRD was performed as follows. As an X-ray diffractometer, “M21X” manufactured by Bruker AXS Co., Ltd. is used. The measurement conditions are tube Cu (wavelength 1.5418 mm), acceleration voltage 40 kV, current 200 mA, and measurement range 5-80. °, step width 0.02 °, scan speed 4 ° / min. From the obtained X-ray diffraction spectrum data, the peak intensity ratio of (FeO) (MnO) to Fe 2 MnO 4 is expressed by the peak intensity of (FeO) (MnO) at 36 ° ≦ 2θ ≦ 46 ° as X, Fe 2 Calculated as “X / Y × 100”, where Y is the peak intensity of MnO 4 .
この多孔質フェライト芯材の細孔容積は０．０５５〜０．１６ｍｌ／ｇ、ピーク細孔径は０．２〜０．７μｍであることが必要である。また、この多孔質フェライトの細孔容積は、好ましくは、０．０６〜０．１４ｍｌ／ｇである。またピーク細孔径に関しては、好ましくは、０．４〜０．６μｍである。 This porous ferrite core material needs to have a pore volume of 0.055 to 0.16 ml / g and a peak pore size of 0.2 to 0.7 μm. The pore volume of the porous ferrite is preferably 0.06 to 0.14 ml / g. The peak pore diameter is preferably 0.4 to 0.6 μm.
多孔質フェライト芯材の細孔容積が０．０５５ｍｌ／ｇ未満であると、十分な量の樹脂を充填することができないため軽量化が図れない。また、多孔質フェライト芯材の細孔容積が０．１６ｍｌ／ｇを超えると、樹脂を充填してもキャリアの強度を保つことができない。 If the pore volume of the porous ferrite core material is less than 0.055 ml / g, it is not possible to reduce the weight because a sufficient amount of resin cannot be filled. On the other hand, if the pore volume of the porous ferrite core material exceeds 0.16 ml / g, the strength of the carrier cannot be maintained even if the resin is filled.
多孔質フェライト芯材のピーク細孔径が０．２μｍ未満であると、芯材中心部まで樹脂を充填することが著しく困難になる。また、多孔質フェライト芯材のピーク細孔径が０．７μｍを超えると、充填後のキャリアに極端な凹凸が発生するため、粒子の強度が劣り、また電荷リークやトナースペントの原因となるため好ましくない。 When the peak pore diameter of the porous ferrite core material is less than 0.2 μm, it becomes extremely difficult to fill the resin up to the center of the core material. In addition, if the peak pore diameter of the porous ferrite core material exceeds 0.7 μm, extreme unevenness occurs in the carrier after filling, which is inferior in strength of the particles, and also causes charge leakage and toner spent. Absent.
このように、細孔容積とピーク細孔径が上記範囲にあることで、上記した各不具合がなく、適度に軽量化された樹脂充填型キャリアを得ることができる。 Thus, when the pore volume and the peak pore diameter are in the above ranges, it is possible to obtain a resin-filled carrier that does not have the above-described problems and is appropriately reduced in weight.
〔多孔質フェライト芯材の細孔径及び細孔容積〕
この多孔質フェライト芯材の細孔径及び細孔容積の測定は、次のようにして行われる。すなわち、水銀ポロシメーターＰａｓｃａｌ１４０とＰａｓｃａｌ２４０（ＴｈｅｒｍｏＦｉｓｈｅｒ Ｓｃｉｅｎｔｉｆｉｃ社製）を用いて測定した。ディラトメータはＣＤ３Ｐ（粉体用）を使用し、サンプルは複数の穴を開けた市販のゼラチン製カプセルに入れて、ディラトメータ内に入れた。Ｐａｓｃａｌ１４０で脱気後、水銀を充填し低圧領域（０〜４００Ｋｐａ）を測定し、１ｓｔ Ｒｕｎとした。次に再び脱気と低圧領域（０〜４００Ｋｐａ）の測定を行い、２ｎｄ Ｒｕｎとした。２ｎｄ Ｒｕｎの後、ディラトメーターと水銀とカプセルとサンプルを合わせた重量を測定した。次にＰａｓｃａｌ２４０で高圧領域（０．１Ｍｐａ〜２００Ｍｐａ）を測定した。この高圧部の測定で得られた水銀圧入量をもって、多孔質フェライト芯材の細孔容積、細孔径分布及びピーク細孔径を求めた。また、細孔径を求める際には水銀の表面張力を４８０ｄｙｎ／ｃｍ、接触角を１４１．３°として計算した。
[Pore diameter and pore volume of porous ferrite core material]
The pore diameter and pore volume of the porous ferrite core material are measured as follows. That is, it measured using mercury porosimeter Pascal140 and Pascal240 (ThermoFisher Scientific company make). CD3P (for powder) was used as the dilatometer, and the sample was put in a commercially available gelatin capsule having a plurality of holes and placed in the dilatometer. After degassing with Pascal 140, it was filled with mercury and the low pressure region (0 to 400 Kpa) was measured to obtain 1st Run. Next, deaeration and measurement of the low pressure region (0 to 400 Kpa) were performed again to obtain 2nd Run. After 2nd Run, the combined weight of the dilatometer, mercury, capsule and sample was measured. Next, the high pressure region (0.1 Mpa to 200 Mpa) was measured with Pascal240. The pore volume, the pore size distribution, and the peak pore size of the porous ferrite core material were determined from the mercury intrusion amount obtained by the measurement of the high pressure part. Further, when determining the pore diameter, the surface tension of mercury was 480 dyn / cm and the contact angle was 141.3 °.
本発明に係る電子写真現像剤用樹脂充填型キャリアでは、多孔質フェライト芯材の細孔径分布において、細孔径のばらつきｄｖが１．０以下であることが望ましい。ここで、高圧領域における全水銀圧入量を１００％とし、圧入量が８４％に達した時の水銀への印加圧力から計算した細孔径をｄ８４、圧入量が１６％に達した時の水銀への印加圧力から計算した細孔径をｄ１６とした。また、ｄｖ値は下記式（１）により計算した。 In the resin-filled carrier for an electrophotographic developer according to the present invention, the pore diameter variation dv is preferably 1.0 or less in the pore diameter distribution of the porous ferrite core material. Here, assuming that the total mercury intrusion amount in the high pressure region is 100%, the pore diameter calculated from the pressure applied to mercury when the indentation amount reaches 84% is d 84 , and the mercury when the indentation amount reaches 16%. the pore size calculated from the pressure applied to that the d 16. The dv value was calculated by the following formula (1).
多孔質フェライト芯材の細孔径のばらつきｄｖが１．０を超えると、充填度合いの粒子間ばらつきが発生し易く、また樹脂充填後の芯材露出度合いの粒子間及び個々の粒子内におけるばらつきも発生し易い。これらのばらつきにより、粒子の強度や絶縁破壊電圧の安定性が損なわれる原因となる。さらに、粒子表面の凹凸が大きくなるため、電荷リークやトナースペントの原因となる。 When the variation dv of the pore diameter of the porous ferrite core material exceeds 1.0, variation in the degree of filling between particles is likely to occur, and the degree of core material exposure after resin filling also varies between particles and within individual particles. It is easy to generate. These variations cause the strength of the particles and the stability of the breakdown voltage to be impaired. Furthermore, the irregularities on the particle surface become large, which causes charge leakage and toner spent.
本発明に係る電子写真現像剤用樹脂充填型キャリアは、多孔質フェライト芯材に樹脂を充填する。樹脂の充填量は、多孔質フェライト芯材１００重量部に対して６〜３０重量部が望ましく、より望ましくは６〜２０重量部、更に望ましくは７〜１８重量部、最も好ましくは８〜１７重量部である。樹脂の充填量が６重量部未満であると、十分な軽量化が図れない。また、樹脂の充填量が３０重量部を超えると、充填しきれずに残った遊離樹脂が多量に発生するため、帯電不良等の不具合の原因となる。 The resin-filled carrier for an electrophotographic developer according to the present invention fills a porous ferrite core material with a resin. The resin filling amount is desirably 6 to 30 parts by weight with respect to 100 parts by weight of the porous ferrite core material, more desirably 6 to 20 parts by weight, still more desirably 7 to 18 parts by weight, and most desirably 8 to 17 parts by weight. Part. If the filling amount of the resin is less than 6 parts by weight, sufficient weight reduction cannot be achieved. On the other hand, if the amount of the resin is more than 30 parts by weight, a large amount of free resin that cannot be completely filled is generated, which causes problems such as charging failure.
充填する樹脂は、特に制限されず、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。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。使用中の機械的ストレスによる樹脂の脱離を考慮すると、熱硬化性樹脂が好ましく用いられる。具体的な熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂、シリコーン樹脂、不飽和ポリエステル樹脂、尿素樹脂、メラミン樹脂、アルキッド樹脂及びそれらを含有する樹脂が挙げられる。 The resin to be filled is not particularly limited and can be appropriately selected depending on the toner to be combined, the environment in which it is used, and the like. 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, acrylic-styrene resin, silicone resin, Alternatively, modified silicone resins modified with resins such as acrylic resin, polyester resin, epoxy resin, polyamide resin, polyamideimide resin, alkyd resin, urethane resin, and fluororesin can be used. In view of the detachment of the resin due to mechanical stress during use, a thermosetting resin is preferably used. Specific examples of thermosetting resins include epoxy resins, phenol resins, silicone resins, unsaturated polyester resins, urea resins, melamine resins, alkyd resins, and resins containing them.
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、充填樹脂中に導電剤を含有することができる。導電剤はそれ自身の持つ電気抵抗が低いことから、含有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、充填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。 A conductive agent can be contained in the filled resin for the purpose of controlling the electric resistance, charge amount, and charging speed of the carrier. Since the conductive agent has a low electric resistance, if the content is too large, it is likely to cause a rapid 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 filled 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、充填樹脂中には、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。これは多量の樹脂を充填した場合、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。 In addition, the charge 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 a large amount of resin is filled, the charge imparting ability may be lowered, but it can be controlled by adding various charge control agents and silane coupling agents. 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.
本発明に係る電子写真現像剤用樹脂充填型キャリアは、被覆樹脂により表面被覆することが望ましい。キャリア特性、特に帯電特性を初めとする電気特性はキャリア表面に存在する材料や性状に影響されることが多い。従って、適当な樹脂を表面被覆することによって、所望とするキャリア特性を、精度良く調整することができる。 The resin-filled carrier for an electrophotographic developer according to the present invention is preferably surface-coated with a coating resin. Carrier characteristics, particularly electrical characteristics such as charging characteristics, are often affected by materials and properties existing on the carrier surface. Therefore, the desired carrier characteristics can be adjusted with high accuracy by coating the surface with an appropriate resin.
被覆樹脂は特に制限されない。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。使用中の機械的ストレスによる樹脂の脱離を考慮すると、熱硬化性樹脂が好ましく用いられる。具体的な熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂、シリコーン樹脂、不飽和ポリエステル樹脂、尿素樹脂、メラミン樹脂、アルキッド樹脂及びそれらを含有する樹脂等が挙げられる。樹脂の被覆量は、充填型キャリア（樹脂被覆前）１００重量部に対して、０．５〜５．０重量部が好ましい。 The coating resin 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, acrylic-styrene resin, silicone resin, Alternatively, modified silicone resins modified with resins such as acrylic resin, polyester resin, epoxy resin, polyamide resin, polyamideimide resin, alkyd resin, urethane resin, and fluororesin can be used. In view of the detachment of the resin due to mechanical stress during use, a thermosetting resin is preferably used. Specific examples of thermosetting resins include epoxy resins, phenol resins, silicone resins, unsaturated polyester resins, urea resins, melamine resins, alkyd resins, and resins containing them. The coating amount of the resin is preferably 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the filling type carrier (before resin coating).
これら被覆樹脂中にも上記と同様な目的で導電剤や帯電制御剤を含有することができる。導電性剤や帯電制御剤の種類や添加量は、上記充填樹脂の場合と同様である。 These coating resins can also contain a conductive agent and a charge control agent for the same purpose as described above. The kind and addition amount of the conductive agent and the charge control agent are the same as in the case of the above filling resin.
本発明に係る電子写真現像剤用樹脂充填型キャリアの平均粒径は、２０〜６０μｍであることが望ましく、この範囲でキャリア付着が防止され、また良好な画質が得られる。平均粒径が２０μｍ未満であると、キャリア付着の原因となるため好ましくない。また、平均粒径が６０μｍを超えると、帯電付与能力の低下による画質劣化の原因となるため好ましくない。 The average particle size of the resin-filled carrier for an electrophotographic developer according to the present invention is desirably 20 to 60 μm. In this range, carrier adhesion is prevented and good image quality is obtained. An average particle size of less than 20 μm is not preferable because it causes carrier adhesion. On the other hand, if the average particle diameter exceeds 60 μm, it is not preferable because it causes deterioration of image quality due to a decrease in charging ability.
〔平均粒径（マイクロトラック）〕
この平均粒径は、次のようにして測定される。すなわち、日機装株式会社製マイクロトラック粒度分析計（Ｍｏｄｅｌ９３２０−Ｘ１００）を用いて測定される。分散媒には水を用いた。試料１０ｇと水８０ｍｌを１００ｍｌのビーカーに入れ、分散剤（ヘキサメタリン酸ナトリウム）を２〜３滴添加する。次いで超音波ホモジナイザー（ＳＭＴ．Ｃｏ．ＬＴＤ．製ＵＨ−１５０型）を用い、出力レベル４に設定し、２０秒間分散を行った。その後、ビーカー表面にできた泡を取り除き、試料を装置へ投入した。
[Average particle size (Microtrack)]
This average particle diameter is measured as follows. That is, it is measured using a Nikkiso Co., Ltd. Microtrac particle size analyzer (Model 9320-X100). Water was used as the dispersion medium. Place 10 g of sample and 80 ml of water in a 100 ml beaker and add 2-3 drops of dispersant (sodium hexametaphosphate). Subsequently, using an ultrasonic homogenizer (UH-150 type manufactured by SMT Co Ltd), the output level was set to 4 and dispersion was performed for 20 seconds. Thereafter, bubbles formed on the beaker surface were removed, and the sample was put into the apparatus.
本発明に係る電子写真現像剤用樹脂充填型キャリアの飽和磁化は、３０〜８０Ａｍ２／ｋｇが望ましい。飽和磁化が３０Ａｍ２／ｋｇ未満であると、キャリア付着の原因となるため望ましくない。飽和磁化が８０Ａｍ２／ｋｇを超えると、磁気ブラシの穂が硬くなるために、良好な画質を得ることが難しい。 The saturation magnetization of the resin-filled carrier for an electrophotographic developer according to the present invention is preferably 30 to 80 Am 2 / kg. If the saturation magnetization is less than 30 Am 2 / kg, it is not desirable because it causes carrier adhesion. When the saturation magnetization exceeds 80 Am 2 / kg, the ears of the magnetic brush become hard, and it is difficult to obtain good image quality.
〔飽和磁化〕
ここで、磁化の測定は、積分型Ｂ−ＨトレーサーＢＨＵ−６０型（株式会社理研電子製）を使用して測定した。電磁石間に磁場測定用Ｈコイル及び磁化測定用４πＩコイルを入れる。この場合、試料は４πＩコイルに入れる。電磁石の電流を変化させ磁場Ｈを変化させたＨコイル及び４πＩコイルの出力をそれぞれ積分し、Ｈ出力をＸ軸に、４πＩコイルの出力をＹ軸に、ヒステリシスループを記録紙に描く。ここで測定条件としては、試料充填量：約１ｇ、試料充填セル：内径７ｍｍφ±０．０２ｍｍ、高さ１０ｍｍ±０．１ｍｍ、４πＩコイル：巻数３０回にて測定した。
[Saturation magnetization]
Here, the magnetization was measured using an integral BH tracer BHU-60 type (manufactured by Riken Denshi Co., Ltd.). A magnetic field measuring H coil and a magnetization measuring 4πI coil are placed between the electromagnets. In this case, the sample is placed in a 4πI coil. The outputs of the H coil and the 4πI coil whose magnetic field H is changed by changing the current of the electromagnet are respectively integrated, and the H output is drawn on the X axis, the output of the 4πI coil is drawn on the Y axis, and a hysteresis loop is drawn on the recording paper. As measurement conditions, sample filling amount: about 1 g, sample filling cell: inner diameter 7 mmφ ± 0.02 mm, height 10 mm ± 0.1 mm, 4πI coil: measured with 30 turns.
本発明に係る電子写真現像剤用樹脂充填型キャリアのピクノメーター密度は２．５〜４．５ｇ／ｃｍ３であることが望ましい。ピクノメーター密度が２．５ｇ／ｃｍ３未満であると、キャリアが軽量過ぎるために帯電付与能力が低下し易い。また、ピクノメーター密度が４．５ｇ／ｃｍ３を超えると、キャリアの軽量化が十分でなく、耐久性に劣る。 The pycnometer density of the resin-filled carrier for an electrophotographic developer according to the present invention is desirably 2.5 to 4.5 g / cm 3 . If the pycnometer density is less than 2.5 g / cm 3 , the charge imparting ability tends to decrease because the carrier is too light. On the other hand, if the pycnometer density exceeds 4.5 g / cm 3 , the weight of the carrier is not sufficient and the durability is poor.
〔ピクノメーター密度〕
ピクノメーター密度は、次のようにして測定した。すなわち、ＪＩＳ Ｒ９３０１−２−１に準拠して、ピクノメーターを用いて測定した。ここで、溶媒としてメタノールを用い、温度２５℃にて測定を行った。
[Pycnometer density]
The pycnometer density was measured as follows. That is, it measured using the pycnometer based on JISR9301-2-1. Here, methanol was used as a solvent, and measurement was performed at a temperature of 25 ° C.
本発明に係る電子写真現像剤用樹脂充填型キャリアの見掛け密度は、１．０〜２．５ｇ／ｃｍ３であることが望ましい。見掛け密度が１．０ｇ／ｃｍ３未満であると、キャリアが軽量過ぎるために帯電付与能力が低下し易い。見掛け密度が２．５ｇ／ｃｍ３を超えると、キャリアの軽量化が十分でなく、耐久性に劣る。 The apparent density of the resin-filled carrier for an electrophotographic developer according to the present invention is desirably 1.0 to 2.5 g / cm 3 . If the apparent density is less than 1.0 g / cm 3 , the carrier is too light and the charge imparting ability tends to be lowered. When the apparent density exceeds 2.5 g / cm 3 , the weight of the carrier is not sufficiently reduced and the durability is inferior.
〔見掛け密度〕
この見掛け密度の測定は、ＪＩＳ−Ｚ２５０４（金属粉の見掛け密度試験法）に従って測定される。
[Apparent density]
The apparent density is measured in accordance with JIS-Z2504 (Apparent density test method for metal powder).
本発明の電子写真現像剤用樹脂充填型キャリアは、その印加電圧１００Ｖの電気抵抗が１×１０７Ω以上であることが好ましい。電気抵抗が１×１０７Ω未満では、実際の使用において電荷リーク、絶縁破壊が発生し易く好ましくない。 The resin-filled carrier for an electrophotographic developer of the present invention preferably has an electric resistance of 1 × 10 7 Ω or more at an applied voltage of 100V. If the electric resistance is less than 1 × 10 7 Ω, charge leakage and dielectric breakdown are likely to occur in actual use, which is not preferable.
〔電気抵抗〕
電極間間隔１．０ｍｍにて非磁性の平行平板電極（１０ｍｍ×４０ｍｍ）を対抗させ、その間に、試料２００ｍｇを秤量して充填する。磁石（表面磁束密度：１５００Ｇａｕｓｓ、電極に接する磁石の面積：１０ｍｍ×３０ｍｍ）を平行平板電極に付けることにより電極間に試料を保持させ、１００Ｖの電圧を印加し、抵抗を絶縁抵抗計（ＳＭ−８２１０、東亜ディケーケー（株）製）にて測定した。なお、室温２５℃、湿度５５％に制御された恒温恒湿室内で測定を行った。
[Electric resistance]
A non-magnetic parallel plate electrode (10 mm × 40 mm) is made to oppose with an inter-electrode spacing of 1.0 mm, and 200 mg of a sample is weighed and filled between them. A sample is held between the electrodes by attaching a magnet (surface magnetic flux density: 1500 Gauss, area of the magnet in contact with the electrode: 10 mm × 30 mm) to the parallel plate electrodes, a voltage of 100 V is applied, and the resistance is measured by an insulation resistance meter (SM- 8210, manufactured by Toa Decay Co., Ltd.). Note that the measurement was performed in a constant temperature and humidity room controlled at a room temperature of 25 ° C. and a humidity of 55%.
本発明の電子写真現像剤用樹脂充填型キャリアは、充填状態の粒子間のばらつきが少ないことが望ましい。粒子間のばらつきが多いと、絶縁破壊電圧の低下や粒子の破壊強度の低下を招くため好ましくない。また、割れや微粒子が存在しないことが望ましい。割れや微粒子が存在すると、帯電不良、使用中における特性変動、白斑等の問題が発生するので好ましくない。 The resin-filled carrier for an electrophotographic developer of the present invention desirably has little variation between filled particles. A large variation among particles is not preferable because it causes a decrease in dielectric breakdown voltage and a decrease in particle breakdown strength. Further, it is desirable that no cracks or fine particles exist. The presence of cracks and fine particles is not preferable because problems such as poor charging, characteristic fluctuations during use, and white spots occur.
〔充填樹脂状態の粒子間のばらつき〕
キャリアを走査電子顕微鏡（ＪＳＭ−６１００型、日本電子株式会社製）で４５０倍の倍率で観察することによって行った。
[Variation among particles in filled resin state]
The carrier was observed with a scanning electron microscope (JSM-6100, manufactured by JEOL Ltd.) at a magnification of 450 times.
充填樹脂状態の粒子間ばらつきの評価の基準は以下の通りである。
樹脂の充填度合、芯材の露出度合が粒子間において偏りが観察されず、かつ凝集粒子や遊離樹脂微粉も観察されないものを「◎」、樹脂の充填度合、芯材の露出度合の粒子間における偏りがやや観察され、凝集粒子がわずかに観察されるものを「○」とし、「◎」「○」と評価されたものを合格範囲とした。また、樹脂の充填度合、芯材の露出度合の粒子間における偏りが多く観察され、凝集粒子や遊離樹脂微粉も観察され、さらにキャリア表面に充填しきれなかった樹脂が僅かに観察されるものを「△」、樹脂の充填度合、芯材の露出度合の粒子間における偏りが著しく、かつ凝集粒子や遊離樹脂微粉も多く観察され、さらにキャリア表面に充填しきれなかった樹脂が多く観察されるものに関しては「×」と評価し、「△」「×」と評価されたものを不合格とした。
The criteria for evaluating the interparticle variation in the filled resin state are as follows.
Resin filling degree, core material exposure degree is not observed between particles, and aggregated particles and free resin fine powder are not observed `` ◎ '', resin filling degree, core material exposure degree between particles The case where the bias was slightly observed and the agglomerated particles were slightly observed was defined as “◯”, and the case evaluated as “◎” and “◯” was defined as the acceptable range. In addition, a large amount of unevenness between the particles of the resin filling degree and the core material exposure degree is observed, aggregated particles and free resin fine powder are also observed, and a resin that cannot be completely filled on the carrier surface is observed. “△”, the degree of resin filling and the degree of exposure of the core material are markedly uneven among the particles, a large number of aggregated particles and free resin fine powder are observed, and a large amount of resin that cannot be fully filled on the carrier surface is observed. Was evaluated as “×”, and those evaluated as “Δ” and “×” were rejected.
本発明の電子写真現像剤用樹脂充填型キャリアは、一定の強度を有することが望ましく、強度的に劣る場合には、実際の使用時において割れや削れ又は微粒子が生じる。 The resin-filled carrier for an electrophotographic developer of the present invention desirably has a certain strength. When the strength is inferior, cracks, scrapes or fine particles are generated during actual use.
〔キャリア強度試験（割れや削れ、微粒子の評価法）〕
キャリアの強度試験は、充填キャリア５０ｇを、５０ｃｃガラス瓶に入れ、そのガラス瓶を直径１３０ｍｍ、高さ２００ｍｍの円柱のホルダーに収納、固定し、ターブラーミキサーで３６０分攪拌した。
[Carrier strength test (evaluation method for cracks, shavings, fine particles)]
In the carrier strength test, 50 g of the filled carrier was placed in a 50 cc glass bottle, and the glass bottle was stored and fixed in a cylindrical holder having a diameter of 130 mm and a height of 200 mm, and stirred for 360 minutes with a tumbler mixer.
攪拌した後のキャリアを、走査型電子顕微鏡（ＪＳＭ−６１００型日本電子株式会社製）を用いて、４５０倍の倍率で観察を行い、充填キャリアの破砕状況を確認した。攪拌前と変わらないものを「◎」、削れ、及び破砕により発生した浮遊樹脂などの微小粒子が、僅かに観察されるものを「○」とし、「◎」「○」と評価されたものについて合格とした。削れ及び浮遊樹脂などの微粒子が多く観察されるものは「△」とし、削れ及び浮遊樹脂などの微粒子が著しく多く観察され、さらに粒子の割れの発生も観察されたものについては「×」と評価し、「△」「×」と評価されたものについて不合格とした。 The carrier after stirring was observed at a magnification of 450 times using a scanning electron microscope (JSM-6100, manufactured by JEOL Ltd.) to confirm the crushing state of the filled carrier. What is the same as before stirring, "◎", those where fine particles such as floating resin generated by shaving and crushing are slightly observed are "○", and those evaluated as "◎" and "○" Passed. “△” indicates that a large amount of fine particles such as scraped and floating resin are observed, and “×” indicates a case where a significant amount of fine particles such as scraped and floating resin are observed and further cracks are observed. However, those evaluated as “Δ” and “×” were rejected.
本発明の電子写真現像剤用樹脂充填型キャリアは、トナースペントが８０％以上であることが望ましい。 The resin-filled carrier for an electrophotographic developer of the present invention preferably has a toner spent of 80% or more.
〔トナースペント〕
トナースペントの評価方法は、下記の通りである。すなわち、トナー濃度７％とした現像剤を調製し、３６時間攪拌後の現像剤からキャリアのみを抜き取り、トルエンでスペントしたトナーを洗浄した後、上澄み液の、波長５６０ｎｍの光の透過率（％）を可視光分光光度計（ＪＥＮＷＡＹ社製、ＭＯＤＥＬ６１００）により測定し、透過率９５％以上を合格として評価した。
[Toner spent]
The evaluation method for toner spent is as follows. That is, a developer having a toner concentration of 7% was prepared, only the carrier was extracted from the developer after stirring for 36 hours, and the toner spent with toluene was washed, and then the light transmittance (%) of the supernatant liquid at a wavelength of 560 nm was obtained. ) Was measured with a visible light spectrophotometer (manufactured by JENWAY, MODEL 6100), and a transmittance of 95% or more was evaluated as acceptable.
本発明に係る電子写真現像剤用樹脂充填型キャリアの帯電量は、その立ち上がり速度が速いものが好ましい。帯電量の立ち上がり速度は、下記の方法により測定される。ここで、帯電立ち上がり速度のおおよその目安は、以下の通りである。
８０％未満：トナー補給時に帯電量が速やかに立ち上がらないため、トナー飛散やカブリ等の画像欠陥が発生するため、使用に耐え得るレベルではない。
８０％以上９０％未満：トナー補給時に帯電量が速やかに立ち上がらないため、トナー飛散やカブリ等は若干発生するが、ぎりぎり使用に耐え得るレベルである。
９０％以上９５％未満：トナー補給時に帯電量が十分立ち上がるため、トナー飛散やカブリ等の発生はみられず、良好なレベルである。
９５％以上：トナー補給時に帯電量が速やかに立ち上がり、トナー飛散やカブリ等の発生は全くみられず、非常に良好なレベルである。
The charge amount of the resin-filled carrier for an electrophotographic developer according to the present invention preferably has a fast rise speed. The rising speed of the charge amount is measured by the following method. Here, the rough standard of the charge rising speed is as follows.
Less than 80%: Since the charge amount does not rise quickly when the toner is replenished, image defects such as toner scattering and fogging occur, so that it is not at a level that can withstand use.
80% or more and less than 90%: The amount of charge does not rise rapidly when the toner is replenished, and thus toner scattering, fogging, etc. occur slightly, but at a level that can withstand the last minute use.
90% or more and less than 95%: Since the charge amount rises sufficiently when the toner is replenished, toner scattering, fogging and the like are not observed, and the level is satisfactory.
95% or more: When the toner is replenished, the charge amount rises rapidly, and no toner scattering or fogging is observed, which is a very good level.
〔帯電量の立ち上がり速度〕
帯電量の立ち上がり速度は、次のようにして測定される。すなわち、フルカラープリンターに使用されている市販の負極性トナー（シアントナー、富士ゼロックス株式会社製ＤｏｃｕＰｒｉｎｔＣ３５３０用）を用い、トナー濃度を５重量％（トナー重量＝１．５ｇ、キャリア重量＝３８．５ｇ）に調整した。調整した現像剤を５０ｃｃのガラス瓶に入れ、１００ｒｐｍの回転数にて、３分及び３０分間撹拌を行い、各々の帯電量を、吸引式帯電量測定装置（Ｅｐｐｉｎｇ ｑ／ｍ−ｍｅｔｅｒ、ＰＥＳ−Ｌａｂｏｒａｔｏｒｉｕｍｕ社製）により測定し求めた。ここで、下記式により帯電量の立ち上がり速度を算出する。数値が１００％に近いほど、帯電量の立ち上がり速度が速い事を表す。
[Rise rate of charge amount]
The rising speed of the charge amount is measured as follows. That is, a commercially available negative polarity toner (cyan toner, for DocuPrint C3530 manufactured by Fuji Xerox Co., Ltd.) used in a full color printer is used, and the toner concentration is 5% by weight (toner weight = 1.5 g, carrier weight = 38.5 g). Adjusted. The adjusted developer is put in a 50 cc glass bottle and stirred at a rotation speed of 100 rpm for 3 minutes and 30 minutes. Each charge amount is measured by a suction-type charge amount measuring device (Epping q / m-meter, PES-Laboratorium). Measured by the company). Here, the rising speed of the charge amount is calculated by the following equation. The closer the value is to 100%, the faster the rising speed of the charge amount.
＜本発明に係る電子写真現像剤用樹脂充填型キャリアの製造方法＞
本発明に係る電子写真現像剤用樹脂充填型キャリアの製造方法について説明する。
<Method for producing resin-filled carrier for electrophotographic developer according to the present invention>
A method for producing a resin-filled carrier for an electrophotographic developer according to the present invention will be described.
本発明に係る電子写真現像剤用樹脂充填型キャリアの製造方法において、多孔質フェライト芯材を製造するには、まず、原材料を適量秤量した後、ボ−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。原料は、Ｍｎ，Ｆｅ及びＯを主成分とし、Ｍｇ及びＳｒから選ばれる少なくとも１種を含む元素を含有する組成となるように選択することが望ましい。 In the method for producing a resin-filled carrier for an electrophotographic developer according to the present invention, in order to produce a porous ferrite core material, first, an appropriate amount of raw materials are weighed and then 0.5 hours by a ball mill or a vibration mill. Above, preferably pulverized and mixed for 1 to 20 hours. The raw material is desirably selected so as to have a composition containing an element containing Mn, Fe and O as main components and containing at least one selected from Mg and Sr.
このようにして得られた粉砕物を加圧成型機等を用いてペレット化した後、７００〜１２００℃の温度で仮焼成する。加圧成型機を使用せずに、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。仮焼成後さらにボ−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、スプレードライヤーにて粒状化し、造粒を行う。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良い。 The pulverized material thus obtained is pelletized using 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, add water to make a slurry, and granulate using a spray dryer. After calcination, the mixture is further pulverized with a ball mill or a vibration mill, and then water and, if necessary, a dispersant and a binder are added. After adjusting the viscosity, the mixture is granulated with a spray dryer and granulated. When pulverizing after calcination, water may be added and pulverized by a wet ball mill, a wet vibration mill or the like.
上記のボールミルや振動ミル等の粉砕機は特に限定されないが、原料を効果的かつ均一に分散させるためには、使用するメディアに１ｍｍ以下の粒径を持つ微粒なビーズを使用することが好ましい。また使用するビーズの径、組成、粉砕時間を調整することによって、粉砕度合いをコントロールすることができる。 The pulverizer such as the above-mentioned ball mill and vibration mill is not particularly limited, but in order to disperse the raw materials effectively and uniformly, it is preferable to use fine beads having a particle diameter of 1 mm or less for the medium to be used. Further, the degree of grinding can be controlled by adjusting the diameter, composition and grinding time of the beads used.
その後、得られた造粒物を、６００〜８００℃の温度で脱倍を行った後、酸素濃度の制御された雰囲気下で、８００〜１５００℃の温度で、１〜２４時間保持し、本焼成を行う。その際、ロータリー式電気炉やバッチ式電気炉または連続式電気炉等を使用し、焼成時の雰囲気も、窒素等の不活性ガスや水素や一酸化炭素等の還元性ガスを打ち込んで、酸素濃度の制御を行っても良い。あるいは、脱倍を行わずに、本焼成を行い、造粒時に添加したバインダーを炉内で分解させて、発生したガスにより炉内を還元性雰囲気にして、酸素濃度の制御を行っても良い。また、ロータリー式電気炉の場合、雰囲気や焼成温度を変更して、多数回焼成を行っても良い。 Thereafter, the resulting granulated product was descaled at a temperature of 600 to 800 ° C., and then held at a temperature of 800 to 1500 ° C. for 1 to 24 hours in an atmosphere with a controlled oxygen concentration. Firing is performed. At that time, a rotary electric furnace, a batch electric furnace or a continuous electric furnace is used, and an atmosphere at the time of firing is oxygenated by implanting an inert gas such as nitrogen or a reducing gas such as hydrogen or carbon monoxide. The concentration may be controlled. Alternatively, the baking may be performed without de-magnifying, the binder added at the time of granulation may be decomposed in the furnace, and the inside of the furnace may be reduced by the generated gas to control the oxygen concentration. . In the case of a rotary electric furnace, firing may be performed many times by changing the atmosphere and firing temperature.
このように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、沈降法など用いて所望の粒径に粒度調整する。 The fired product thus obtained 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皮膜処理を施し、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℃で熱処理を行うことができる。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、高抵抗になりすぎたりするため、所望の特性を得にくくなり好ましくない。また、必要に応じて、酸化被膜処理の前に還元を行っても良い。このようにして、（ＦｅＯ）（ＭｎＯ）とＦｅ２ＭｎＯ４とのピーク強度比が特定範囲にある多孔質フェライト芯材を調製する。 Then, if necessary, the surface can be heated at a low temperature to perform an oxide film treatment to adjust the electric resistance. The oxide film treatment can be performed by heat treatment at, for example, 300 to 700 ° C. using a general rotary electric furnace, batch electric furnace or the like. 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 it is difficult to obtain desired characteristics. Moreover, you may reduce | restore before an oxide film process as needed. In this way, a porous ferrite core material having a peak intensity ratio of (FeO) (MnO) and Fe 2 MnO 4 in a specific range is prepared.
上記のような、電子写真現像剤用キャリアのフェライト芯材の、（ＦｅＯ）（ＭｎＯ）とＦｅ２ＭｎＯ４とのピーク強度比や細孔容積、ピーク細孔径、細孔径のバラツキをコントロールする方法としては、配合する原料種、原料の粉砕度合い、仮焼の有無、仮焼温度、仮焼時間、スプレードライヤーによる造粒時のバインダー量、焼成方法、焼成温度、焼成時間、焼成雰囲気等、様々な方法で行うことができる。これらのコントロール方法は特に限定されるものではないが、その一例を以下に示す。 A method for controlling the peak intensity ratio, pore volume, peak pore diameter, and pore diameter variation of (FeO) (MnO) and Fe 2 MnO 4 in the ferrite core material of the carrier for an electrophotographic developer as described above. As the raw material species to be blended, the degree of pulverization of the raw material, the presence or absence of calcination, the calcination temperature, the calcination time, the binder amount during granulation with a spray dryer, the firing method, the firing temperature, the firing time, the firing atmosphere, etc. Can be done in any way. These control methods are not particularly limited, but an example is shown below.
（ＦｅＯ）（ＭｎＯ）とＦｅ２ＭｎＯ４とのピーク強度比は、焼成時の雰囲気を還元性にすると大きくなりやすい。その際、水素や一酸化炭素等の還元性ガスを導入しても良いし、脱倍工程を行わずに、本焼成を行い、造粒時に添加したバインダーを炉内で分解させて、発生したガスにより炉内を還元性雰囲気にしても良い。逆に、焼成時の雰囲気を酸化性にすると、（ＦｅＯ）（ＭｎＯ）とＦｅ２ＭｎＯ４とのピーク強度比は小さくなりやすい。 The peak intensity ratio between (FeO) (MnO) and Fe 2 MnO 4 tends to increase when the firing atmosphere is reduced. At that time, a reducing gas such as hydrogen or carbon monoxide may be introduced, and the main firing is performed without performing the de-magnifying process, and the binder added at the time of granulation is decomposed in the furnace and generated. The inside of the furnace may be made a reducing atmosphere with gas. Conversely, when the firing atmosphere is made oxidizing, the peak intensity ratio between (FeO) (MnO) and Fe 2 MnO 4 tends to be small.
すなわち、配合する原料種として、水酸化物や炭酸塩を用いた方が、酸化物を用いた場合に比べて細孔容積は大きくなりやすく、また、仮焼成を行わないか、または仮焼性温度が低い方、もしくは本焼成温度が低く、焼成時間が短い方が、細孔容積は大きくなりやすい。 That is, as a raw material species to be blended, the use of hydroxide or carbonate tends to increase the pore volume as compared with the case of using an oxide, and no calcining or calcining is performed. The pore volume tends to be larger when the temperature is lower, or the firing temperature is lower and the firing time is shorter.
ピーク細孔径については、使用する原料、特に仮焼後の原料の粉砕度合を強くし、粉砕の一次粒子径が細かい方が小さくなりやすい。また、本焼成時に窒素等の不活性ガスを用いるよりは、水素や一酸化炭素等の還元性ガスを導入することで、ピーク細孔径を小さくすることが可能となる。 As for the peak pore diameter, the degree of pulverization of the raw material to be used, particularly the raw material after calcination, is strengthened, and the smaller the primary particle diameter of the pulverization tends to be smaller. Further, it is possible to reduce the peak pore diameter by introducing a reducing gas such as hydrogen or carbon monoxide rather than using an inert gas such as nitrogen during the main firing.
更に、細孔径のばらつきについては、本焼成時において、原料の焼結性を均一に進めることでばらつきを低くすることが可能になる。具体的には、トンネル式の連続炉を用いるよりは、原料に均一に熱を加えることのできるロータリー式電気炉を用いる方が望ましい。また、使用する原料、特に仮焼後の原料の粉砕度合を強くし、粉砕粒径の分布をシャープにすることでも、細孔径のばらつきを低くするができる。 Furthermore, with regard to the variation in pore diameter, it is possible to reduce the variation by uniformly advancing the sinterability of the raw material during the main firing. Specifically, it is preferable to use a rotary electric furnace that can uniformly heat the raw material, rather than using a tunnel-type continuous furnace. In addition, the variation in pore diameter can be reduced by increasing the degree of pulverization of the raw material used, particularly the raw material after calcination, and sharpening the distribution of the pulverized particle diameter.
これらのコントロール方法を、単独もしくは組み合わせて使用することにより、所望の細孔容積、ピーク細孔径及び細孔径のばらつきをもった多孔質フェライト芯材得ることができる。 By using these control methods singly or in combination, a porous ferrite core material having a desired pore volume, peak pore diameter, and variation in pore diameter can be obtained.
このようにして得られた多孔質フェライト芯材に樹脂を充填する。充填方法としては、様々な方法が使用できる。その方法としては、例えば乾式法、流動床によるスプレードライ方式、ロータリードライ方式、万能攪拌機等による液浸乾燥法等が挙げられる。ここで用いられる樹脂としては、上述した通りである。 The porous ferrite core material thus obtained is filled with a resin. Various methods can be used as the filling method. Examples of the method include a dry method, a spray drying method using a fluidized bed, a rotary drying method, an immersion drying method using a universal stirrer, and the like. The resin used here is as described above.
上記樹脂を充填する工程において、減圧下で多孔質フェライト芯材と充填樹脂を混合撹拌しながら、多孔質フェライト芯材の空孔に樹脂を充填することが好ましい。このように減圧下で樹脂を充填することによって、空孔部分に効率良く樹脂を充填することができる。減圧の程度としては、１０〜７００ｍｍＨｇが好ましい。７００ｍｍＨｇを超えると減圧する効果がなく、１０ｍｍＨｇ未満では、充填工程中に樹脂溶液が沸騰しやすくなるため、効率良い充填ができなくなる。 In the step of filling the resin, it is preferable to fill the pores of the porous ferrite core material with the resin while mixing and stirring the porous ferrite core material and the filling resin under reduced pressure. By filling the resin under reduced pressure in this way, it is possible to efficiently fill the hole portion with the resin. The degree of decompression is preferably 10 to 700 mmHg. If it exceeds 700 mmHg, there is no effect of reducing the pressure, and if it is less than 10 mmHg, the resin solution tends to boil during the filling step, so that efficient filling cannot be performed.
上記樹脂を充填する工程を複数回に分けて行うことが好ましい。１回の充填工程で樹脂を充填することは可能である。あえて複数回に分ける必要はない。しかし、樹脂の種類によっては、一度に多量の樹脂を充填しようとした場合、粒子の凝集が発生する場合がある。凝集が発生するとキャリアとして現像機内で使用した場合、現像器の撹拌ストレスによって凝集が解れることがある。凝集していた粒子の界面は、帯電特性が大きく異なるため、経時で帯電変動が発生し、好ましくない。このような場合には、複数回に分けて充填することによって、凝集を防ぎつつ、過不足なく充填が行える。 The step of filling the resin is preferably performed in a plurality of times. It is possible to fill the resin in a single filling step. There is no need to divide it multiple times. However, depending on the type of resin, when a large amount of resin is filled at once, particle aggregation may occur. When aggregation occurs, when it is used as a carrier in a developing machine, the aggregation may be released due to agitation stress of the developing device. The interface of the aggregated particles is not preferable because the charging characteristics are greatly different, and charging fluctuation occurs over time. In such a case, the filling can be performed without being excessive or deficient by preventing the agglomeration by filling in a plurality of times.
樹脂を充填させた後、必要に応じて各種の方式によって加熱し、充填した樹脂を芯材に密着させる。加熱方式としては、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。温度は、充填する樹脂によって異なるが、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ことにより、衝撃に対して強い樹脂充填型キャリアを得ることができる。 After filling the resin, the resin is heated by various methods as necessary, and the filled resin is brought into close contact with the core material. The heating method may be either an external heating method or an internal heating method, and may be, for example, a fixed or fluid electric furnace, a rotary electric furnace, a burner furnace, or a microwave baking. The temperature varies depending on the resin to be filled, but a temperature higher than the melting point or glass transition point is necessary. With a thermosetting resin or a condensation-crosslinking resin, etc., it is resistant to impact by raising the temperature to a point where the curing proceeds sufficiently. A resin-filled carrier can be obtained.
上述のように、多孔質フェライト芯材に樹脂を充填した後、樹脂により表面を被覆することが望ましい。キャリア特性、特に帯電特性を初めとする電気特性はキャリア表面に存在する材料や性状に影響されることが多い。従って、適当な樹脂を表面被覆することによって、所望とするキャリア特性を、精度良く調整することができる。被覆する方法としては、公知の方法、例えば刷毛塗り法、乾式法、流動床によるスプレードライ方式、ロータリードライ方式、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。樹脂被覆後、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。 As described above, after filling the porous ferrite core material with a resin, it is desirable to coat the surface with the resin. Carrier characteristics, particularly electrical characteristics such as charging characteristics, are often affected by materials and properties existing on the carrier surface. Therefore, the desired carrier characteristics can be adjusted with high accuracy by coating the surface with an appropriate resin. As a coating method, the coating can be performed by a known method such as a brush coating method, a dry 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. In the case of baking after resin coating, either an external heating method or an internal heating method may be used. For example, a stationary or fluid electric furnace, a rotary electric furnace, a burner furnace, or microwave baking 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.
＜本発明に係る電子写真現像剤＞
次に、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、上記した電子写真現像剤用樹脂充填型キャリアとトナーとからなるものである。
<Electrophotographic developer according to the present invention>
Next, the electrophotographic developer according to the present invention will be described.
The electrophotographic developer according to the present invention comprises the above-described resin-filled carrier for an electrophotographic developer and a toner.
本発明の電子写真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 electrophotographic 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、更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.
更に、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 the production of 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。更に、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 both 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.
更に、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 improver, a natural wax such as carnauba wax, an olefin wax such as polypropylene or polyethylene can be used as the fixability improver. .
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.
更に、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。 Furthermore, 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、電子写真現像剤を得ることができる。キャリアとトナーの混合比、すなわちトナー濃度は、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。 An electrophotographic developer can be obtained by mixing the carrier and toner manufactured 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.
上記のように製造されたキャリアとトナーとを混合し得られた現像剤を、補給用現像剤として用いることができる。この場合、キャリアとトナーの混合比、キャリア１重量部に対して、トナー２〜５０重量部の比率で混合される。 A developer obtained by mixing the carrier and toner manufactured as described above can be used as a replenishment developer. In this case, the toner is mixed at a ratio of 2 to 50 parts by weight of the toner with respect to 1 part by weight of the carrier and toner.
本発明に係る電子写真現像剤は、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 electrophotographic 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電子写真現像剤は、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 electrophotographic developer according to the present invention prepared as described above uses an electrostatic latent image formed on a latent image holding member having an organic photoconductor layer, while applying a bias electric field to the toner and the carrier. The present invention can be used in digital copiers, printers, fax machines, printers, and the like that use a developing method in which reversal development is performed using a two-component developer 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が、これにより本発明が何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example etc., this invention is not limited at all by this.
ＭｎＯ：３８ｍｏｌ％、ＭｇＯ：９．５ｍｏｌ％、Ｆｅ２Ｏ３：５２ｍｏｌ％及びＳｒＯ：０．５ｍｏｌ％になるように原料を秤量し、乾式のメディアミル（振動ミル、１／８インチ径のステンレスビーズ）で５時間粉砕し、得られた粉砕物をローラーコンパクターにて、約１ｍｍ角のペレットにした。ＭｎＯ原料としては四酸化三マンガンを、ＭｇＯ原料としては水酸化マグネシウムを、ＳｒＯ原料としては、炭酸ストロンチウムを用いた。このペレットを目開き３ｍｍの振動篩にて粗粉を除去し、次いで目開き０．５ｍｍの振動篩にて微粉を除去した後、１０００℃で３時間加熱し、仮焼成を行った。次いで、乾式のメディアミル（振動ミル、１／８インチ径のステンレスビーズ）を用いて平均粒径が４．１μｍまで粉砕した後、水を加え、さらに湿式のメディアミル（縦型ビーズミル、１／１６インチ径のステンレスビーズ）を用いて３時間粉砕した。このスラリーの粒径（粉砕の一次粒子径）をマイクロトラックにて測定した結果、Ｄ５０は２．４１μｍであった。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し、次の焼成工程において還元性雰囲気を実現するため、バインダーとしてＰＶＡ(１０％溶液)をスラリーの固形分に対して１２重量％添加し、次いでスプレードライヤーにより造粒、乾燥し、得られた粒子の粒度調整を行った。 MnO: 38mol%, MgO: 9.5mol %, Fe 2 O 3: 52mol% and SrO: materials were weighed so that 0.5 mol%, dry media mill (vibration mill, 1/8-inch diameter stainless steel The resulting pulverized product was formed into pellets of about 1 mm square using a roller compactor. Trimanganese tetraoxide was used as the MnO raw material, magnesium hydroxide was used as the MgO raw material, and strontium carbonate was used as the SrO raw material. The coarse powder was removed from the pellets with a vibrating sieve having a mesh opening of 3 mm, and then the fine powder was removed with a vibrating sieve having a mesh opening of 0.5 mm, followed by heating at 1000 ° C. for 3 hours to perform preliminary firing. Next, after pulverizing to an average particle size of 4.1 μm using a dry media mill (vibration mill, 1/8 inch diameter stainless steel beads), water was added, and a wet media mill (vertical bead mill, 1 / 16-inch diameter stainless steel beads) for 3 hours. The slurry particle size (primary particle diameter of the grinding) results measured at Microtrac, D 50 was 2.41Myuemu. An appropriate amount of a dispersant is added to the slurry, and the strength of the granulated particles is ensured. In order to realize a reducing atmosphere in the next firing step, PVA (10% solution) is used as a binder with respect to the solid content of the slurry. 12% by weight, and then granulated and dried with a spray dryer, and the particle size of the obtained particles was adjusted.
上述のようにして得られた造粒物を、次に述べる様な本焼成を、２回行った。まず、ロータリー式電気炉にて、炉内を正圧に保ち、還元性雰囲気下、温度９１５℃、１時間保持し、１回目の本焼成を行った。また、還元性雰囲気は、スプレードライヤーで造粒する際に添加した分散剤及びバインダーの加熱分解ガスを利用した。次に、得られた焼成物を、同じくロータリー式電気炉にて、窒素の不活性ガス雰囲気中で、焼成温度９４０℃、１時間保持して、２回目の本焼成を行った。 The granulated product obtained as described above was subjected to main firing as described below twice. First, in the rotary electric furnace, the inside of the furnace was kept at a positive pressure, and was held at a temperature of 915 ° C. for 1 hour in a reducing atmosphere, and the first firing was performed. Moreover, the reducing atmosphere utilized the thermal decomposition gas of the dispersing agent and binder which were added when granulating with a spray dryer. Next, the obtained fired product was similarly subjected to a second main firing in a rotary electric furnace in a nitrogen inert gas atmosphere with a firing temperature of 940 ° C. for 1 hour.
その後、解砕し、さらに分級して粒度調整を行い、磁力選鉱により低磁力品を分別し、多孔質フェライト粒子の芯材を得た。この多孔質フェライト芯材の(ＦｅＯ)（ＭｎＯ）とＦｅ２ＭｎＯ４のＸＲＤによるピーク強度比は２０、細孔容積は０．０６８ｍｌ／ｇ、ピーク細孔径は０．４５μｍ、細孔径のばらつきｄｖは０．１５であった。 Thereafter, the mixture was crushed, further classified to adjust the particle size, and the low magnetic product was separated by magnetic separation, thereby obtaining a core material of porous ferrite particles. In this porous ferrite core material, the peak intensity ratio by XRD of (FeO) (MnO) and Fe 2 MnO 4 is 20, the pore volume is 0.068 ml / g, the peak pore diameter is 0.45 μm, and the pore diameter variation dv Was 0.15.
次に、上記多孔質フェライト粒子１００重量部と、Ｔ単位とＤ単位からなる縮合架橋型シリコーン樹脂（重量平均分子量：約８０００）を準備し、このシリコーン樹脂溶液４５重量部（樹脂溶液濃度２０％のため固形分としては９重量部、希釈溶媒：トルエン）にアミノシランカップリング剤（γ―アミノプロピルトリメトキシシラン）を、樹脂固形分に対して１０重量％添加し、６０℃、４．０ｋＰａの減圧下で混合撹拌し、トルエンを揮発させながら、樹脂を多孔質フェライト芯材内部に浸透、充填させた。 Next, 100 parts by weight of the porous ferrite particles and a condensation-crosslinking type silicone resin (weight average molecular weight: about 8000) composed of T units and D units were prepared, and 45 parts by weight of this silicone resin solution (resin solution concentration 20%). Therefore, the amino silane coupling agent (γ-aminopropyltrimethoxysilane) is added to the solid content of 9 parts by weight as the solid content, and the diluent solvent: toluene. The mixture was stirred under reduced pressure, and the resin was permeated and filled into the porous ferrite core material while evaporating toluene.
トルエンが充分揮発したことを確認した後、さらに３０分撹拌を続け、トルエンをほぼ完全に除去したのち、充填装置内から取り出し、容器に入れ、熱風加熱式のオーブンに入れ、２２０℃で２時間、加熱処理を行った。 After confirming that toluene was fully volatilized, stirring was continued for another 30 minutes. After toluene was almost completely removed, the toluene was taken out from the filling device, placed in a container, and placed in a hot air heating type oven at 220 ° C. for 2 hours. The heat treatment was performed.
その後、室温まで冷却し、樹脂が硬化されたフェライト粒子を取り出し、２００Ｍの目開きの振動篩にて粒子の凝集を解し、磁力選鉱機を用いて、非磁性物を取り除いた。その後、再度振動篩にて粗大粒子を取り除き樹脂が充填された樹脂充填粒子を得た。 Then, it cooled to room temperature, the ferrite particle | grains by which resin was hardened were taken out, the aggregation of particle | grains was released with the vibration sieve of 200M opening, and the nonmagnetic substance was removed using the magnetic separator. Thereafter, coarse particles were removed again with a vibrating sieve to obtain resin-filled particles filled with resin.
得られた粒子の表面に、充填した樹脂と同じシリコーン樹脂を充填後粒子の重量に対して樹脂固形分として０．２重量％、希釈溶剤としてトルエンを１．８重量％加え、流動床コート装置を用いてコーティングを行った。この際、被覆した樹脂中に帯電制御剤として、アミノシランカップリング剤（γ―アミノプロピルトリメトキシシラン）を被覆樹脂固形分に対して１０重量％添加した。被覆した後、２２０℃で２時間加熱を行い、その後、室温まで冷却し、樹脂が硬化されたフェライト粒子を取り出し、２００Ｍの目開きの振動篩にて粒子の凝集を解し、磁力選鉱機を用いて、非磁性物を取り除いた。その後、再度振動篩にて粗大粒子を取り除き、表面に樹脂被覆を施した樹脂充填型キャリアを得た。 The surface of the obtained particles is filled with the same silicone resin as the filled resin, 0.2% by weight as the resin solid content and 1.8% by weight of toluene as the diluent solvent are added to the weight of the particles, and the fluidized bed coater Was used for coating. At this time, an aminosilane coupling agent (γ-aminopropyltrimethoxysilane) was added to the coated resin as a charge control agent by 10% by weight based on the solid content of the coated resin. After coating, heat at 220 ° C. for 2 hours, then cool to room temperature, take out the ferrite particles with cured resin, disaggregate the particles with a vibrating sieve with 200M mesh, Used to remove non-magnetic material. Thereafter, coarse particles were again removed with a vibrating sieve to obtain a resin-filled carrier having a resin coating on the surface.
ロータリー式電気炉での２回目の焼成温度を１１００℃に変えた以外は、実施例１と同様にして表面に樹脂被覆を施した樹脂充填型キャリアを得た。 A resin-filled carrier having a surface coated with a resin was obtained in the same manner as in Example 1 except that the second baking temperature in the rotary electric furnace was changed to 1100 ° C.
ロータリー式電気炉での１回目の焼成温度を１０１０℃とし、２回目の焼成を行わないで、多孔質フェライト粒子の芯材を得て、充填するシリコーン樹脂溶液を３５重量部（樹脂溶液濃度２０％のため固形分としては７重量部）にした以外は、実施例１と同様にして表面に樹脂被覆を施した樹脂充填型キャリアを得た。 The first firing temperature in the rotary electric furnace is set to 1010 ° C., and the core material of the porous ferrite particles is obtained without performing the second firing, and 35 parts by weight of the silicone resin solution to be filled (resin solution concentration 20) %, So that the solid content was 7 parts by weight), and a resin-filled carrier having a surface coated with a resin was obtained in the same manner as in Example 1.
仮焼成後の粉砕条件を、乾式のメディアミル（振動ミル、１／８インチ径のステンレスビーズ）を用いて平均粒径が４．１μｍまで粉砕した後、水を加え、さらに湿式のメディアミル（縦型ビーズミル、１／１６インチ径のステンレスビーズ）を用いて１０時間粉砕し、スラリー粒径（粉砕の一次粒子径）Ｄ５０を１．１１μｍまで細かくし、更に本焼成の条件として、ロータリー式電気炉にて、１回目の焼成温度を８６０℃とし、２回目の焼成を行わないで、多孔質フェライト粒子の芯材を得て、充填するシリコーン樹脂溶液を７５重量部（樹脂溶液濃度２０％のため固形分としては１５重量部）にした以外は、実施例１と同様にして、樹脂充填型キャリアを得た。 After calcination, the grinding conditions were as follows: a dry media mill (vibration mill, 1/8 inch diameter stainless steel beads) was ground to an average particle size of 4.1 μm, water was added, and a wet media mill ( Using a vertical bead mill, 1/16 inch stainless steel beads) for 10 hours, the slurry particle size (pulverized primary particle size) D 50 is reduced to 1.11 μm. In the electric furnace, the first firing temperature was set to 860 ° C., and the core material of the porous ferrite particles was obtained without performing the second firing, and 75 parts by weight of the silicone resin solution to be filled (resin solution concentration 20%) Therefore, a resin-filled carrier was obtained in the same manner as in Example 1 except that the solid content was 15 parts by weight.
仮焼成後の粉砕条件を、乾式のメディアミル（振動ミル、１／８インチ径のステンレスビーズ）を用いて平均粒径が４．１μｍまで粉砕した後、水を加え、さらに湿式のメディアミル（縦型ビーズミル、１／１６インチ径のステンレスビーズ）を用いて１時間粉砕し、スラリー粒径（粉砕の一次粒子径）Ｄ５０を３．２５μｍまで細かくし、更に本焼成の条件として、ロータリー式電気炉にて、１回目の焼成温度を８６０℃とした以外は、実施例１と同様にして、樹脂充填型キャリアを得た。 After calcination, the grinding conditions were as follows: a dry media mill (vibration mill, 1/8 inch diameter stainless steel beads) was ground to an average particle size of 4.1 μm, water was added, and a wet media mill ( Using a vertical bead mill, 1/16 inch stainless steel beads) for 1 hour, the slurry particle size (pulverized primary particle size) D 50 is reduced to 3.25 μm. A resin-filled carrier was obtained in the same manner as in Example 1 except that the first baking temperature was 860 ° C. in an electric furnace.
［比較例１］
ロータリー式電気炉での１回目の焼成温度を１０５０℃とし、２回目の焼成を行わないで、多孔質フェライト粒子の芯材を得て、充填するシリコーン樹脂溶液を２０重量部（樹脂溶液濃度２０％のため固形分としては４重量部）にした以外は実施例１と同様にして表面に樹脂被覆を施した樹脂充填型キャリアを得た。
[Comparative Example 1]
The first baking temperature in the rotary electric furnace is set to 1050 ° C., and the second baking is not performed to obtain the core material of the porous ferrite particles, and 20 parts by weight of the silicone resin solution to be filled (resin solution concentration 20 % To obtain a resin-filled carrier having a surface coated with a resin, except that the solid content was 4 parts by weight.
［比較例２］
ロータリー式電気炉での２回目の焼成条件として、焼成温度を１０００℃、焼成雰囲気として、炉内の酸素濃度が１０ｖｏｌ％になるように、炉内にＮ２とエアーの混合ガスを導入した以外は、実施例１と同様にして表面に樹脂被覆を施した樹脂充填型キャリアを得た。
[Comparative Example 2]
As the second firing condition in the rotary electric furnace, except for introducing a mixed gas of N 2 and air into the furnace so that the firing temperature is 1000 ° C. and the firing atmosphere is such that the oxygen concentration in the furnace is 10 vol%. In the same manner as in Example 1, a resin-filled carrier having a surface coated with a resin was obtained.
［比較例３］
実施例１と同様にして得られた造粒物を、ロータリー式電気炉で、７００℃で２時間加熱し、分散剤やバインダーといった有機成分の除去を行い、トンネル式電気炉にて、焼成温度１０５０℃、窒素ガス雰囲気下にて、５時間保持した。その後は、実施例１と同様にして表面に樹脂被覆を施した樹脂充填型キャリアを得た。
[Comparative Example 3]
The granulated material obtained in the same manner as in Example 1 was heated in a rotary electric furnace at 700 ° C. for 2 hours to remove organic components such as a dispersant and a binder, and in the tunnel electric furnace, the firing temperature It was kept at 1050 ° C. under a nitrogen gas atmosphere for 5 hours. Thereafter, in the same manner as in Example 1, a resin-filled carrier having a surface coated with a resin was obtained.
［比較例４］
実施例１と同様にして得られた造粒物を、ロータリー式電気炉で、７００℃で２時間加熱し、分散剤やバインダーといった有機成分の除去を行い、トンネル式電気炉にて、焼成温度１１５０℃、窒素ガス雰囲気下にて、５時間保持した。その後は、実施例１と同様にして表面に樹脂被覆を施した樹脂充填型キャリアを得た。
[Comparative Example 4]
The granulated material obtained in the same manner as in Example 1 was heated in a rotary electric furnace at 700 ° C. for 2 hours to remove organic components such as a dispersant and a binder, and in the tunnel electric furnace, the firing temperature The temperature was maintained at 1150 ° C. under a nitrogen gas atmosphere for 5 hours. Thereafter, in the same manner as in Example 1, a resin-filled carrier having a surface coated with a resin was obtained.
実施例１〜５及び比較例１〜４の(ＦｅＯ)（ＭｎＯ）とＦｅ２ＭｎＯ４のＸＲＤによるピーク強度比、細孔容積、ピーク細孔径、細孔径のばらつきｄｖ及び樹脂充填量を表１に示す。また、得られた樹脂充填型キャリアの各特性及び評価結果を表２に示す。表１及び表２の測定及び評価方法は、上述の通りである。 Table 1 shows the peak intensity ratio, pore volume, peak pore diameter, pore diameter variation dv and resin filling amount by XRD of (FeO) (MnO) and Fe 2 MnO 4 in Examples 1 to 5 and Comparative Examples 1 to 4. Shown in In addition, Table 2 shows the characteristics and evaluation results of the obtained resin-filled carrier. The measurement and evaluation methods in Tables 1 and 2 are as described above.
表２に示した結果から明らかなように、実施例１〜５に示した樹脂充填型キャリアは、 (ＦｅＯ)（ＭｎＯ）とＦｅ２ＭｎＯ４のＸＲＤによるピーク強度比が適切であり、また、適切な細孔容積、ピーク細孔径及び細孔径のばらつきｄｖを保持している芯材を使用しているため、充填樹脂も過不足無く十分に行われた結果、帯電量の立ち上がり速度が速く、また、電気抵抗値も好ましい範囲内にあり、従って良好な絶縁破壊電圧を保持している。更に充填樹脂の粒子間ばらつきは小さく、強度試験においても削れや割れは合格の範囲内にあり、トナースペント評価においても、良好な結果が得られた。 As is apparent from the results shown in Table 2, the resin-filled carriers shown in Examples 1 to 5 have an appropriate peak intensity ratio by XRD of (FeO) (MnO) and Fe 2 MnO 4 , and Since the core material holding the appropriate pore volume, peak pore diameter, and pore diameter variation dv is used, the filling resin is sufficiently performed without excess and deficiency. Further, the electric resistance value is also within a preferable range, and therefore a good breakdown voltage is maintained. Furthermore, there was little variation among the particles of the filled resin, scraping and cracking were within the acceptable range in the strength test, and good results were obtained in the toner spent evaluation.
これらのことから、実施例１〜５に示した樹脂充填型キャリアを、現像剤に実際に使用した場合、トナー補給時にも帯電量が速やかに立ち上がるため、トナー飛散やカブリといった画像欠陥のない良好な画像品質が得られることが容易に想像される。また電荷リークの発生や実機内でのストレスによるキャリア粒子の破砕や劣化が防止され、白斑等の画像欠陥が生じることなく、経時的に安定し良好な画像品質が得られることも容易に想像される。また、補給用現像剤としても好適に使用できることが推察できる。 From these facts, when the resin-filled carriers shown in Examples 1 to 5 are actually used as a developer, the charge amount rises quickly even when the toner is replenished, so that there is no image defect such as toner scattering and fogging. It is easily imagined that a good image quality can be obtained. It is also easily imagined that good image quality can be obtained over time without the occurrence of charge leaks and the destruction and deterioration of carrier particles due to stress in the actual machine, without causing image defects such as vitiligo. The It can also be inferred that it can be suitably used as a replenishment developer.
一方で、比較例１〜４に示したキャリアは、(ＦｅＯ)（ＭｎＯ）とＦｅ２ＭｎＯ４のＸＲＤによるピーク強度比と細孔容積、ピーク細孔径及び細孔径のばらつきｄｖが適正な範囲にないため、帯電立ち上がり速度、電気抵抗値、充填樹脂の粒子間ばらつき、強度試験及びトナースペントに関する評価結果が、悪いものであった。 On the other hand, in the carriers shown in Comparative Examples 1 to 4, the peak intensity ratio by XRD of (FeO) (MnO) and Fe 2 MnO 4 and the pore volume, the peak pore diameter, and the variation dv of the pore diameter are within an appropriate range. Therefore, the evaluation results regarding the charge rising speed, the electric resistance value, the inter-particle variation of the filled resin, the strength test, and the toner spent were poor.
これらのことから、比較例１〜４で得られたキャリアを実際に使用した場合、トナー補給時に帯電量が速やかに立ち上がらないためにトナー飛散やカブリといった画像欠陥を引き起こしたり、絶縁破壊電圧が低いため、実機内でのストレスにより凝集していた粒子が解れたり、粒子自体が破壊されるため、電荷リークの発生や、強度が低いことにより、破砕された微粒子が発生する可能性もあり、微粒子による白斑等の画像欠陥が発生し易く、良好な画像品質を安定的に維持できないことが容易に想像される。 From these facts, when the carriers obtained in Comparative Examples 1 to 4 are actually used, the charge amount does not rise rapidly when the toner is replenished, thereby causing image defects such as toner scattering and fogging, and low dielectric breakdown voltage. Therefore, the aggregated particles are released by the stress in the actual machine, or the particles themselves are destroyed, so there is a possibility that crushed fine particles may be generated due to the occurrence of charge leakage and low strength. It is easy to imagine that image defects such as white spots are likely to occur, and good image quality cannot be stably maintained.
本発明に係る電子写真現像剤用樹脂充填型キャリアは、樹脂充填型キャリアの利点を保持しつつ、帯電量の立ち上がり速度が速く、また絶縁破壊電圧や、粒子の破壊強度も高い。 The resin-filled carrier for an electrophotographic developer according to the present invention maintains the advantages of the resin-filled carrier, has a fast charge rising speed, and has a high dielectric breakdown voltage and high particle breaking strength.
従って、本発明に係る電子写真現像剤用樹脂充填型キャリアは、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 resin-filled carrier for an electrophotographic developer according to the present invention can be widely used in fields such as a full-color machine requiring high image quality and a high-speed machine requiring image maintenance reliability and durability.
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