JP4561427B2 - Magnetic one-component developer, image forming method, and image forming apparatus - Google Patents
Magnetic one-component developer, image forming method, and image forming apparatus Download PDFInfo
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- JP4561427B2 JP4561427B2 JP2005087297A JP2005087297A JP4561427B2 JP 4561427 B2 JP4561427 B2 JP 4561427B2 JP 2005087297 A JP2005087297 A JP 2005087297A JP 2005087297 A JP2005087297 A JP 2005087297A JP 4561427 B2 JP4561427 B2 JP 4561427B2
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Images
Landscapes
- Developing Agents For Electrophotography (AREA)
Description
本発明は、電子写真複写装置あるいはプリンター等、静電潜像を現像剤で現像する際に用いられる磁性一成分現像剤、並びに、該磁性一成分現像材を用いた画像形成方法及び画像形成装置に関する。 The present invention relates to a magnetic one-component developer used when developing an electrostatic latent image with a developer, such as an electrophotographic copying apparatus or a printer, and an image forming method and an image forming apparatus using the magnetic one-component developer. About.
電子写真プロセスとしては従来から多数知られている。電子写真プロセスにおいては、光導電性物質を利用した静電潜像保持体上に種々の手段により電気的に潜像を形成し、この潜像をトナーを用いて現像し、静電潜像保持体上のトナー潜像を中間転写体を介して又は介さずに、紙等の被転写体にトナー画像を転写した後、この転写画像を加熱、加圧、加熱加圧あるいは溶剤蒸気等により定着する、という複数の工程を経て、定着画像が形成される。静電潜像保持体上に残ったトナーは必要により種々の方法でクリーニングされ、前記複数の工程が繰り返される。電子写真プロセスを用いたプリンターや複写機は広く普及しており、年々その性能・画質に対する要求は厳しくなっている。 Many electrophotographic processes have been known. In the electrophotographic process, a latent image is electrically formed on the electrostatic latent image holding member using a photoconductive substance by various means, and the latent image is developed with toner to hold the electrostatic latent image. The toner image on the body is transferred to a transfer medium such as paper with or without an intermediate transfer medium, and then the transfer image is fixed by heating, pressing, heating and pressing, or solvent vapor. A fixed image is formed through a plurality of processes. The toner remaining on the electrostatic latent image holding member is cleaned by various methods as necessary, and the plurality of steps are repeated. Printers and copiers using an electrophotographic process have become widespread, and requirements for performance and image quality have become stricter year by year.
電子写真プロセスにおける現像方式には、一成分現像方式と二成分現像方式がある。
二成分現像方式は、高速化に対して有利であることから、最も広く用いられている現像方式であるが、現像剤がキャリア表面へ付着することにより現像剤が劣化したり、現像剤のみが消費される方式であるため、現像剤中の現像剤濃度割合が低下しないようにキャリアとの混合割合を一定に保たなければならず、そのために現像装置が大型化してしまうといった欠点がある。
一方、一成分現像方式では上記のような欠点が無いことから、装置の小型化、低コスト化などへの利点を有しており、スモールオフィス環境やパーソナルユーザ向けの分野における現像方式の主流と成りつつある。
Development methods in the electrophotographic process include a one-component development method and a two-component development method.
The two-component development method is the most widely used development method because it is advantageous for speeding up, but the developer deteriorates due to the developer adhering to the carrier surface, or only the developer Since this method is consumed, there is a drawback that the mixing ratio with the carrier must be kept constant so that the developer concentration ratio in the developer does not decrease, and the developing device becomes large.
On the other hand, since the one-component development method does not have the above-described drawbacks, it has advantages for downsizing and cost reduction of the apparatus, and the development method is mainstream in the field for small office environments and personal users. It is becoming.
一成分現像方式は、非磁性一成分現像方式と磁性一成分現像方式に大別される。
非磁性一成分現像方式は、トナー中に磁性粉を含まないことからカラー化には適している。
一方、磁性一成分現像方式は、トナー中の磁性粉により、トナー担持体上に磁力を用いてトナーを担持させておくことができることから、トナーの搬送性や非画像部へのトナーのカブリを抑制しやすく、白黒静電複写方式においては磁性一成分現像方式が主流となっている。
The one-component development method is roughly classified into a non-magnetic one-component development method and a magnetic one-component development method.
The non-magnetic one-component development method is suitable for colorization because the toner does not contain magnetic powder.
On the other hand, in the magnetic one-component development method, the magnetic powder in the toner allows the toner to be carried on the toner carrying member by using a magnetic force. Therefore, the toner transportability and the toner fog to the non-image portion are prevented. It is easy to suppress, and in the black-and-white electrostatic copying system, the magnetic one-component development system is the mainstream.
しかし、一成分現像方式は、キャリアの帯電付与力、現像剤搬送力、現像剤攪拌力を利用できないことから、トナー担持体上へのトナー搬送性が不安定になることや、トナー帯電分布が広くなってしまう等のために、画像濃度の低下が発生するなどの問題がある。
さらに、近年、高速化が進んでいるため、トナーに付与できる帯電量は限られ、画像濃度の安定化がより困難となりつつある。
However, in the one-component development method, since the charge imparting force of the carrier, the developer conveying force, and the developer agitating force cannot be used, the toner conveying property on the toner carrier becomes unstable, and the toner charge distribution is There is a problem that the image density is lowered due to widening.
Furthermore, in recent years, since the speed is increasing, the amount of charge that can be applied to the toner is limited, and stabilization of the image density is becoming more difficult.
トナーの帯電量が充分に与えられない場合には、トナーと現像剤担持体との付着性を低下させ、現像しやすくすることが重要であり、その達成手段として、小粒径のシリカ粒子と大粒径のシリカ粒子を組み合わせる方法が種々提案されている。 When the charge amount of the toner is not sufficiently given, it is important to reduce the adhesion between the toner and the developer carrying member and to facilitate the development. Various methods for combining large-diameter silica particles have been proposed.
例えば、荷電性トナーに、平均粒径の異なる２種類のシリカを混合外添する静電荷現像用トナーが開示されている（例えば、特許文献１参照。）。この方法では、小粒径のシリカは流動性向上用シリカであり、大粒径のシリカは接着防止用シリカである。 For example, an electrostatic charge developing toner is disclosed in which two types of silica having different average particle diameters are mixed and added to a chargeable toner (see, for example, Patent Document 1). In this method, the silica having a small particle size is a fluidity improving silica, and the silica having a large particle size is an adhesion preventing silica.
また、一次粒子の平均粒径が３０〜６０ｎｍ、ＢＥＴ比表面積が１００〜２００ｍ2／ｇであるシリカ粒子（Ａ）と、一次粒子の平均粒径が５〜２５ｎｍ、ＢＥＴ比表面積が１００〜２５０ｍ2／ｇであるシリカ粒子（Ｂ）と、球形度が１．０〜１．３である有機粒子とを含有する外添剤を含む電子写真現像用トナーについても開示されている（例えば、特許文献２参照。）。 Further, silica particles (A) having an average primary particle size of 30 to 60 nm and a BET specific surface area of 100 to 200 m 2 / g, an average primary particle size of 5 to 25 nm, and a BET specific surface area of 100 to 250 m. Also disclosed is an electrophotographic developing toner containing an external additive containing silica particles (B) of 2 / g and organic particles having a sphericity of 1.0 to 1.3 (for example, patents). Reference 2).
さらに、特定の現像剤担持体を用い、少なくともシリコーンオイル処理されたシリカＡ及びシリカＢを有し、該シリコーンオイル処理されたシリカＡ及びシリカＢが、特定の関係式を満足している画像形成方法が開示されている（例えば、特許文献３参照。）。 Further, an image formation using a specific developer carrying member and having at least silica A and silica B treated with silicone oil, and the silica A and silica B treated with silicone oil satisfy a specific relational expression. A method is disclosed (for example, see Patent Document 3).
しかしいずれの場合にも、相対的に大粒径のシリカはトナーとの付着が弱いため、トナー全体としてシリカが剥がれ落ち易い弱付着の状態になりやすい。このため、現像器内のストレスにより、トナーからシリカ粒子の脱離が起きやすく、初期的には現像性に効果が得られたとしても、プリントを続けていくうちに外添剤の効果が得られにくくなり、結果、安定した高画質を得るのが困難となる。 However, in any case, since silica having a relatively large particle diameter is weakly adhered to the toner, the toner as a whole tends to be in a weakly adhered state where the silica is easily peeled off. For this reason, silica particles are likely to be detached from the toner due to stress in the developing device, and the effect of the external additive can be obtained as printing continues even if the effect on the developability is initially obtained. As a result, it becomes difficult to obtain a stable high image quality.
また、脱離しやすい外添剤は、感光体表面に付着、フィルミングしやすく、筋などの画像欠陥を引き起こす場合がある。
さらに、感光体にバイアス電圧が印加された帯電部材を接触させ帯電させる方式では、帯電部材表面を外添剤が汚染し、画質を低下させるなどの問題が発生する。
In addition, an external additive that is easily detached easily adheres to and is filmed on the surface of the photoreceptor, and may cause image defects such as streaks.
Further, in the system in which a charging member to which a bias voltage is applied is brought into contact with the photosensitive member and charged, there is a problem that the surface of the charging member is contaminated with an external additive and the image quality is lowered.
したがって、従来の手段では、感光体や帯電部材の汚染を起こさずに、安定した高画質画像を得るのは困難であった。
本発明の課題は、プリントの初期からトナー使い切りまで、充分な画像濃度を有する高画質なプリントを可能とする磁性一成分現像剤、該磁性一成分現像剤を用いた画像形成方法及び画像形成装置を提供することである。 An object of the present invention is to provide a magnetic one-component developer capable of high-quality printing having a sufficient image density from the beginning of printing to using up the toner, an image forming method and an image forming apparatus using the magnetic one-component developer. Is to provide.
上記各問題を鑑みて鋭意検討を行った結果、下記発明によって課題解決に至った。 As a result of intensive investigations in view of the above problems, the following invention has been solved.
＜１＞ 結着樹脂、磁性体及びワックスを含むトナー粒子と外添剤とを含有する磁性一成分現像剤であって、
前記外添剤は、１次粒径の異なる少なくとも２種のシリカ粒子群からなるシリカ粒子を含み、
第１のシリカ粒子群は、Ａｌ ２ Ｏ ３ 又はＴｉＯ ２ にて被覆され且つその表面がシランカップリング剤で処理され、１次粒子の数平均粒径が４０ｎｍ以上２００ｎｍ以下であり、前記トナー粒子１００重量部に対し０．１重量部以上２重量部以下含有され、
第２のシリカ粒子群は、ジメチルシリコーンオイル又はヘキサメチルシラザンで処理され、１次粒子の数平均粒径が１２ｎｍ以上１６ｎｍ以下であり、前記トナー粒子１００重量部に対し０．５重量部以上５重量部以下含有され、
前記外添剤に含まれるシリカ粒子全体の強付着割合が、１５％以上５０％以下であることを特徴とする磁性一成分現像剤。
<1> binder resin, a magnetic one-component developer containing the toner particles and an external additive comprising a magnetic substance and a wax,
The external additive includes silica particles composed of at least two types of silica particles having different primary particle sizes,
The first silica particles are coated and the surface at Al 2 O 3 or TiO 2 is treated with a silane coupling agent, and the number average particle size of the primary particles is 40 nm or more size less than 200 nm, the 0.1 to 2 parts by weight with respect to 100 parts by weight of toner particles,
The second silica particle group is treated with dimethyl silicone oil or hexamethylsilazane, and the number average particle diameter of the primary particles is 12 nm or more and 16 nm or less, and 0.5 parts by weight with respect to 100 parts by weight of the toner particles. More than 5 parts by weight,
A magnetic one-component developer, wherein the ratio of strong adhesion of the entire silica particles contained in the external additive is 15% or more and 50% or less.
＜２＞ 少なくとも、静電担持体上に静電潜像を形成する工程と、前記静電潜像を現像剤により現像してトナー像を前記静電担持体上に形成する工程と、前記トナー像を前記静電担持体から転写体上に転写する工程と、前記転写体上に転写された前記トナー像を熱定着ロールと該熱定着ロールに圧着される圧力部材とにより前記転写体に定着させる工程と、を含む画像形成方法であって、
前記現像剤が、前記＜１＞に記載の磁性一成分現像剤であることを特徴とする画像形成方法。
< 2 > At least a step of forming an electrostatic latent image on the electrostatic carrier, a step of developing the electrostatic latent image with a developer to form a toner image on the electrostatic carrier, and the toner A process of transferring an image from the electrostatic carrier onto a transfer member, and fixing the toner image transferred onto the transfer member to the transfer member by a heat fixing roll and a pressure member pressed against the heat fixing roll. An image forming method comprising the steps of:
The image forming method, wherein the developer is the magnetic one-component developer according to <1 > .
＜３＞ 少なくとも、静電担持体と、前記静電担持体を帯電させる帯電装置と、帯電した前記静電担持体を露光して静電潜像を形成させる露光装置と、前記静電潜像を現像剤により現像してトナー像を形成させる現像装置と、前記トナー像を前記静電担持体から転写体に転写する転写装置と、を備え、
前記現像装置に含有される前記現像剤が、前記＜１＞に記載の磁性一成分現像剤であることを特徴とする画像形成装置。
< 3 > At least an electrostatic carrier, a charging device for charging the electrostatic carrier, an exposure device for exposing the charged electrostatic carrier to form an electrostatic latent image, and the electrostatic latent image A developing device that forms a toner image by developing the toner image with a developer, and a transfer device that transfers the toner image from the electrostatic carrier to a transfer body,
The image forming apparatus, wherein the developer contained in the developing device is the magnetic one-component developer described in <1 > .
本発明によれば、プリントの初期からトナー使い切りまで、充分な画像濃度を有する高画質なプリントを可能とする磁性一成分現像剤、該磁性一成分現像剤を用いた画像形成方法及び画像形成装置を提供することができる。 According to the present invention, a magnetic one-component developer capable of high-quality printing having a sufficient image density from the beginning of printing to toner exhaustion, an image forming method and an image forming apparatus using the magnetic one-component developer Can be provided.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明にかかる現像剤は、１次粒径の異なる少なくとも２種のシリカ粒子群からなるシリカ粒子を含み、第１のシリカ粒子群は、Ａｌ ２ Ｏ ３ 又はＴｉＯ ２ にて被覆され且つその表面がシランカップリング剤で処理され、１次粒子の数平均粒径が４０ｎｍ以上２００ｎｍ以下であり、トナー粒子１００重量部に対し０．１重量部以上２重量部以下含有され、第２のシリカ粒子群は、ジメチルシリコーンオイル又はヘキサメチルシラザンで処理され、１次粒子の数平均粒径が１２ｎｍ以上１６ｎｍ以下であり、トナー粒子１００重量部に対し０．５重量部以上５重量部以下含有され、前記外添剤に含まれるシリカ粒子全体の強付着割合が、１５％以上５０％以下であることを特徴とする。 The developer according to the present invention includes silica particles composed of at least two types of silica particle groups having different primary particle diameters, and the first silica particle group is coated with Al 2 O 3 or TiO 2 and has a surface thereof. Is treated with a silane coupling agent, the number average particle size of the primary particles is 40 nm or more and 200 nm or less, and is contained in an amount of 0.1 parts by weight or more and 2 parts by weight or less with respect to 100 parts by weight of the toner particles . The silica particle group is treated with dimethyl silicone oil or hexamethylsilazane, and the number average particle diameter of the primary particles is 12 nm or more and 16 nm or less, and 0.5 parts by weight or more and 5 parts by weight or more with respect to 100 parts by weight of the toner particles. The strong adhesion ratio of the entire silica particles contained below and contained in the external additive is 15% or more and 50% or less.
第１のシリカ粒子群の１次粒子の数平均粒径は、４０ｎｍ以上２００ｎｍ以下である。 The number average particle size of the primary particles of the first silica particles are size less than 200 nm and 40 nm or more.
第１のシリカ粒子群のシリカ粒子は主として、トナー粒子どうし、或いはトナー粒子と現像剤担持体との間でスペーサーとなり、トナー粒子どうし又はトナー粒子と現像剤担持体との付着を弱める効果を担う。
１次粒子の数平均粒径が４０ｎｍ以上２００ｎｍ以下のシリカ粒子が存在しない場合には、付着性を弱める効果が得られず、画像濃度の低下などの問題を引き起こすことがあるため好ましくない。
The silica particles of the first silica particle group mainly serve as spacers between the toner particles or between the toner particles and the developer carrier, and have an effect of weakening the adhesion between the toner particles or between the toner particles and the developer carrier. .
In the absence of silica particles having a primary particle number average particle size of 40 nm or more and 200 nm or less, the effect of weakening the adhesion cannot be obtained, and this may cause problems such as a decrease in image density. .
１次粒子の数平均粒径が２００ｎｍより大きいシリカ粒子の場合には、トナー粒子から脱離しやすくなり、４０ｎｍよりも小さい場合には、経時的にシリカ粒子がトナー内部に埋め込まれてしまい、トナー粒子どうし又はトナー粒子と現像剤担持体との付着を弱める効果が薄れてしまう。 When the number average particle diameter of the primary particles is greater than 200 nm, the silica particles are easily detached from the toner particles. When the number average particle diameter is smaller than 40 nm, the silica particles are embedded in the toner over time. In addition, the effect of weakening the adhesion between the toner particles or between the toner particles and the developer carrier is reduced.
なお、シリカ粒子の１次粒子の数平均粒径は走査式電子顕微鏡にて、シリカ粒子を観察し、その観察像から個数平均の１次粒子径を求めることができる。 The number average particle diameter of the primary particles of the silica particles can be obtained by observing the silica particles with a scanning electron microscope and determining the number average primary particle diameter from the observed image.
また、第１のシリカ粒子群のシリカ粒子の比表面積は、１００ｍ2／ｇ以下が好ましく、より好ましくは９０ｍ2／ｇ以下、さらに好ましくは８０ｍ2／ｇ以下である。
ＢＥＴ比表面積が１００ｍ2／ｇより大きい場合には、トナー粒子と現像剤担持体の付着性を小さくする効果を得ることができず、画像濃度低下が発生することがある。
Further, the specific surface area of the silica particles of the first silica particle group is preferably 100 m 2 / g or less, more preferably 90 m 2 / g or less, and further preferably 80 m 2 / g or less.
When the BET specific surface area is larger than 100 m 2 / g, the effect of reducing the adhesion between the toner particles and the developer carrying member cannot be obtained, and the image density may be lowered.
前記ＢＥＴ比表面積の測定は、窒素置換法によって行う。具体的にはＳＡ３１００比表面積測定装置（コールター株式会社製）を用いて、３点法により測定する。 The BET specific surface area is measured by a nitrogen substitution method. Specifically, it is measured by a three-point method using an SA3100 specific surface area measuring device (manufactured by Coulter, Inc.).
第１のシリカ粒子群のシリカ粒子は、トナー１００重量部に対し、０．１重量部以上２重量部以下含有され、より好ましくは０．１５重量部以上１．８重量部以下、さらに好ましくは、０．２重量部以上１．６重量部以下である。 The silica particles of the first silica particle group are contained in an amount of 0.1 to 2 parts by weight , more preferably 0.15 to 1.8 parts by weight, and still more preferably 100 parts by weight of the toner. Is 0.2 parts by weight or more and 1.6 parts by weight or less.
０．１重量部未満の場合には、トナー粒子どうしの付着あるいはトナー粒子と現像剤担持体との付着を弱める効果が充分でないために、画像濃度の低下やゴーストの発生を引き起こすことがある。２重量部より多い場合には、トナーの流動性が損なわれるために、現像剤担持体上のトナー量が不安定となり、画像ムラなどが発生し好ましくない。 When the amount is less than 0.1 part by weight, the effect of weakening the adhesion between toner particles or between the toner particles and the developer carrying member is not sufficient, and this may cause a decrease in image density and ghosting. When the amount is more than 2 parts by weight, the fluidity of the toner is impaired, so that the amount of toner on the developer carrying member becomes unstable and image unevenness occurs, which is not preferable.
第２のシリカ粒子群の１次粒子の数平均粒径は、１２ｎｍ以上１６ｎｍ以下である。 The number average particle diameter of the primary particles of the second silica particle group is 12 nm or more and 16 nm or less.
第１のシリカ粒子群と第２のシリカ粒子群とにおける、１次粒子の数平均粒径の関係は、第１のシリカ粒子群は第２のシリカ粒子群の１．３倍〜５０倍であることが好ましく、１．５倍〜３０倍であることがより好ましい。 The relationship between the number average particle diameters of the primary particles in the first silica particle group and the second silica particle group is such that the first silica particle group is 1.3 times to 50 times the second silica particle group. It is preferable that it is 1.5 times to 30 times.
第２のシリカ粒子群のシリカ粒子は主として、トナー粒子表面を被覆することにより現像剤の流動性を高めるとともに、トナー粒子に均一な帯電量を付与する効果を担うため、１次粒子の数平均粒径が１６ｎｍ以下のシリカ粒子が存在しない場合には、トナーの流動性、帯電性が充分でなく、画像濃度が低下しやすい。 The silica particles of the second silica particle group mainly have the effect of increasing the fluidity of the developer by coating the surface of the toner particles and imparting a uniform charge amount to the toner particles. When silica particles having a particle size of 16 nm or less are not present, the toner has insufficient fluidity and chargeability, and the image density tends to decrease.
第２のシリカ粒子群の１次粒子の数平均粒径が１２ｎｍよりも小さい場合には、ストレスによりシリカ粒子がトナーに埋め込まれやすくなるため、画像濃度が低下しやすくなる。一方、１６ｎｍよりも大きい場合には、現像剤の流動性を高める効果が小さくなり、画像ムラなどの画質欠陥を引き起こしやすくなる。また、帯電付与能力が不十分となり、十分な画像濃度が得られにくくなる。 When the number average particle diameter of the primary particles of the second silica particle group is smaller than 12 nm, the silica particles are easily embedded in the toner due to the stress, so that the image density is likely to be lowered. On the other hand, if it is larger than 16 nm, the effect of improving the fluidity of the developer is reduced, and image quality defects such as image unevenness are likely to occur. Further, the charge imparting ability becomes insufficient, and it becomes difficult to obtain a sufficient image density.
第２のシリカ粒子群におけるシリカ粒子の比表面積は、５０ｍ2／ｇ以上５００ｍ2／ｇ以下が好ましく、より好ましくは６０以上４００ｍ2／ｇ以下、さらに好ましくは８０以上３００ｍ2／ｇ以下である。
ＢＥＴ比表面積が５００ｍ2／ｇより大きい場合には、シリカ粒子がトナーに埋め込まれやすくなるため、現像器内でストレスを受けると画像濃度が低下するため好ましくない。５０ｍ2／ｇ以下の場合には、シリカ粒子が凝集体として存在しやすくなるため、トナーの帯電性が一様でなくなり、画像ムラなどの画質欠陥を引き起こす場合があり好ましくない。
The specific surface area of the silica particles in the second silica particle group is preferably from 50 m 2 / g to 500 m 2 / g, more preferably from 60 to 400 m 2 / g, still more preferably from 80 to 300 m 2 / g. .
When the BET specific surface area is larger than 500 m 2 / g, the silica particles are easily embedded in the toner. Therefore, when the stress is applied in the developing device, the image density is lowered, which is not preferable. In the case of 50 m 2 / g or less, the silica particles are likely to be present as aggregates, so that the chargeability of the toner is not uniform, and image quality defects such as image unevenness may be caused.
第２のシリカ粒子群のシリカ粒子は、トナー１００重量部に対し、０．５重量部以上５重量部以下添加され、より好ましくは０．６重量部以上４重量部以下、さらに好ましくは、０．７重量部以上３重量部以下である。
０．５重量部未満の場合には、帯電量付与効果が充分でなく、トナーの流動性が低下するために、十分な画像濃度が得られなかったり、白抜けを引き起こすことがあり好ましくない。５重量部より多い場合には、トナーから遊離したシリカ粒子により感光体や帯電部材の汚染により画像欠陥が発生し好ましくない。
The silica particles of the second silica particle group are added in an amount of 0.5 to 5 parts by weight , more preferably 0.6 to 4 parts by weight, and still more preferably 100 parts by weight of the toner. 0.7 parts by weight or more and 3 parts by weight or less.
When the amount is less than 0.5 part by weight, the effect of imparting the charge amount is not sufficient, and the fluidity of the toner is lowered, so that a sufficient image density cannot be obtained or white spots are caused. When the amount is more than 5 parts by weight, it is not preferable because silica particles released from the toner cause image defects due to contamination of the photosensitive member and the charging member.
本発明においては、外添剤に含まれるシリカ粒子全体の強付着割合は、１５％以上５０％以下であり、より好ましくは、１６％以上４５％以下、さらに好ましくは１８％以上４０％以下である。
シリカ粒子全体における強付着割合が１５％未満の場合には、シリカ粒子が感光体表面に付着、フィルミングしやすく、筋などの画像欠陥を引き起こす場合があり、また、初期の現像性は向上するものの、シリカ粒子の脱離が起き、プリント枚数が増えると現像性が低下し画像濃度の低下を充分抑制できず、好ましくない。
強付着割合が５０％を超える場合には、トナー中に埋め込まれた状態のシリカ粒子数が増加し、帯電性や流動性が悪化し、画像濃度の低下などを招くため好ましくない。
In the present invention, the strong adhesion ratio of the entire silica particles contained in the external additive is 15% or more and 50% or less, more preferably 16% or more and 45% or less, and further preferably 18% or more and 40% or less. is there.
When the strong adhesion ratio in the entire silica particles is less than 15%, the silica particles are likely to adhere and film on the surface of the photoreceptor, which may cause image defects such as streaks, and the initial developability is improved. However, if the silica particles are detached and the number of printed sheets is increased, the developability is lowered and the decrease in the image density cannot be sufficiently suppressed.
A strong adhesion ratio exceeding 50% is not preferable because the number of silica particles embedded in the toner increases, the chargeability and fluidity deteriorate, and the image density decreases.
なお、外添剤に含まれるシリカ粒子全体の強付着割合は、以下に示す方法で測定できる。
１００ｍｌのビーカーの０．２％界面活性剤水溶液４０ｍｌ中にトナー母粒子２ｇを添加し、無機粒子を外添処理したトナー母粒子が水溶液に濡れるよう充分に分散させる。具体的には１００ｍｌビーカーにポリオキシエチレンオクチルフェニルエーテルの０．２質量％水溶液を４０ｍｌとり、その中にトナーを２ｇ入れて分散させた後、超音波ホモジナイザーにて周波数２０ｋＨｚ、出力６０Ｗで３０分間振動を与える。
次に、分散液を３０００ｒｐｍ、２分間遠心分離機にかけ、上澄み液は除去し、沈殿した母粒子のみを取り出す。沈殿したトナー母粒子を５Ｃのろ紙にてろ過し、ろ紙上に残ったトナー母粒子と、外添処理したトナー母粒子とのシリカ粒子量を蛍光Ｘ線にてＳｉの強度を測定し、下記式（１）により、強付着成分を測定することができる。
In addition, the strong adhesion rate of the whole silica particle contained in an external additive can be measured by the method shown below.
2 g of toner base particles are added to 40 ml of a 0.2% surfactant aqueous solution in a 100 ml beaker, and the toner base particles externally treated with inorganic particles are sufficiently dispersed so as to get wet with the aqueous solution. Specifically, 40 ml of a 0.2% by mass aqueous solution of polyoxyethylene octylphenyl ether is placed in a 100 ml beaker, and 2 g of toner is placed therein and dispersed, and then an ultrasonic homogenizer is used at a frequency of 20 kHz and an output of 60 W for 30 minutes. Give vibration.
Next, the dispersion is centrifuged at 3000 rpm for 2 minutes, the supernatant is removed, and only the precipitated mother particles are taken out. The precipitated toner base particles are filtered with a 5C filter paper, and the amount of silica particles of the toner base particles remaining on the filter paper and the externally treated toner base particles is measured by fluorescent X-ray to measure the Si intensity. The strongly adhered component can be measured by the equation (1).
式（１）： （シリカ強付着成分）＝［（超音波処理前のトナー粒子のＳｉ強度）−（ろ紙上に残ったトナー母粒子のＳｉ強度）］／（超音波処理前のトナー粒子のＳｉ強度） Formula (1): (Silicon strongly adhering component) = [(Si strength of toner particles before ultrasonic treatment) − (Si strength of toner mother particles remaining on the filter paper)] / (of toner particles before ultrasonic treatment) Si strength)
但し、外添していないトナー母粒子中に磁性体等の材料に起因したＳｉ成分が含まれる場合には、未外添トナーのＳｉ強度で補正をおこなう。すなわち、下記式（２）によって求めることができる。 However, if the toner base particles that are not externally added contain Si components due to the material such as a magnetic material, correction is performed with the Si intensity of the unexternally added toner. That is, it can be obtained by the following equation (2).
式（２）： （シリカ強付着成分）＝［（超音波処理前のトナー粒子のＳｉ強度）−（ろ紙上に残ったトナー母粒子のＳｉ強度）］／［（超音波処理前のトナー粒子のＳｉ強度）−（未外添トナー粒子のＳｉ強度）］ Formula (2): (Strongly adhering component of silica) = [(Si strength of toner particles before ultrasonic treatment) − (Si strength of toner mother particles remaining on the filter paper)] / [(toner particles before ultrasonic treatment) Si strength)-(Si strength of non-externally added toner particles)]
一般的に１次粒径の大きなシリカ粒子はトナー表面に付着しがたく、また、大粒径のシリカ粒子がトナー表面に存在する場合には、大粒径のシリカ粒子が小粒径のシリカ粒子のトナー表面への付着を阻害する。
そのため、通常使用されている外添剤に含まれるシリカ粒子では、その強付着割合は１５％未満である。
In general, silica particles having a large primary particle size are difficult to adhere to the toner surface, and when silica particles having a large particle size are present on the toner surface, the silica particles having a large particle size are reduced to silica particles having a small particle size. Inhibits adhesion of particles to the toner surface.
For this reason, the silica particles contained in commonly used external additives have a strong adhesion ratio of less than 15%.
本発明は以下で述べるようにして、第１のシリカ粒子群のシリカ粒子と第２のシリカ粒子群のシリカ粒子を用い、シリカ粒子全体の強付着割合を１５％以上５０％以下に調整することで、プリントの初期からトナー使い切りまで、ゴーストの発生を抑制し、充分な画像濃度を得ることができる。 As described below, the present invention uses the silica particles of the first silica particle group and the silica particles of the second silica particle group, and adjusts the strong adhesion ratio of the entire silica particles to 15% or more and 50% or less. Thus, it is possible to suppress the generation of a ghost and obtain a sufficient image density from the initial printing to the time when the toner is used up.
そのメカニズムは、明確でないものの、以下のように推定できる。
プリント枚数が増えるにつれ画像濃度が低下する原因として、トナー表面の外添剤がトナーから脱離する或いはトナー内部に埋まり込むことにより、トナー表面の構造が変化し、トナーと現像剤担持体の付着性が高くなったり、帯電性が低下したりするために起こると考えられる。
ここで、２種類の粒径の異なるシリカ粒子を用いて、更に強付着量を調整することにより、現像器内でストレスを受けても、大粒径のシリカによって小粒径シリカのトナー内部への埋まり込みを防ぐことができ、また、シリカ粒子全体の１５％以上が強付着であるため、脱離する外添剤の割合は大幅に少なくなる。
その結果、トナー表面のシリカ粒子が形成する凹凸は、現像機内でストレスが加わってもその構造変化が小さく、トナーと現像剤担持体の付着性が小さいまま維持できるとともに、帯電性の低下も極めて小さくなるため、安定した高濃度の画像が得られるものと考えられる。
Although the mechanism is not clear, it can be estimated as follows.
The cause of the decrease in image density as the number of printed sheets increases is that the external surface additive on the toner surface is detached from the toner or embedded in the toner, so that the structure of the toner surface changes and the toner adheres to the developer carrier. This is considered to occur due to a decrease in chargeability or a decrease in chargeability.
Here, two types of silica particles having different particle diameters are used to further adjust the amount of strong adhesion, so that even if stress is applied in the developing device, the large particle diameter silica allows the small particle diameter silica to enter the toner. In addition, since 15% or more of the entire silica particles are strongly adhered, the ratio of the external additive to be detached is greatly reduced.
As a result, the irregularities formed by the silica particles on the toner surface are small in structural change even when stress is applied in the developing machine, and the adhesion between the toner and the developer carrying member can be kept small, and the charging property is extremely reduced. Therefore, it is considered that a stable high-density image can be obtained.
このような効果を発揮するためには、シリカ粒子全体の強付着割合を１５％以上５０％以下とする必要がある。そのためには、第１のシリカ粒子群のシリカ粒子を第２のシリカ粒子群のシリカ粒子と同程度かそれ以上に強付着化することが好ましい。 In order to exhibit such an effect, it is necessary to make the strong adhesion ratio of the entire silica particles 15% or more and 50% or less. For that purpose, it is preferable to make the silica particles of the first silica particle group strongly adhere to the same degree or more as the silica particles of the second silica particle group.
すなわち、トナー表面から脱離しやすい第１のシリカ粒子群のシリカ粒子について、より強付着化することにより、トナー表面からの脱離が少なくなり、トナー表面の形状の変化が抑えられる。その結果、経時的に安定な高濃度の画像を得ることができる。
一方、第２のシリカ粒子群のシリカ粒子は、第１のシリカ粒子群のシリカ粒子に比べて強付着割合が少ないか、或いは同程度であるため、初期から高い流動性と帯電性を付与され、かつ第１のシリカ粒子により現像器内ストレスが緩和されるため、ストレスによる強付着割合の変化を低減することができ、帯電性、流動性を維持させることができる。
In other words, the silica particles of the first silica particle group that are easily detached from the toner surface are more strongly adhered, so that the separation from the toner surface is reduced and the change in the shape of the toner surface is suppressed. As a result, a high-density image that is stable over time can be obtained.
On the other hand, since the silica particles of the second silica particle group have a low adhesion ratio or the same degree as the silica particles of the first silica particle group, high fluidity and chargeability are imparted from the beginning. In addition, since the stress in the developing device is relieved by the first silica particles, the change in the strong adhesion ratio due to the stress can be reduced, and the chargeability and fluidity can be maintained.
強付着割合を１５％以上５０％以下とするためには、例えばトナーにシリカ粒子を外添混合する際に、まずミキサーを高回転で回転数させトナーに第１のシリカ粒子群のシリカ粒子を付着させた後に、比較的低回転数で回転させ第２のシリカ粒子群のシリカ粒子を付着させるなどの方法をとり、調整することも可能である。
しかし、この方法では、非常に高回転としたり長時間の混合が必要となり、製造上困難となる場合が多い。
In order to set the strong adhesion ratio to 15% or more and 50% or less, for example, when silica particles are externally added to the toner, the mixer is first rotated at a high rotation speed so that the silica particles of the first silica particle group are added to the toner. After adhering, it is possible to adjust by taking a method such as rotating at a relatively low rotational speed to adhere the silica particles of the second silica particle group.
However, this method often requires a very high rotation speed or mixing for a long time, which is often difficult to manufacture.
そこで、シリカ粒子を強付着化する方法として、シリカ粒子を酸化アルミニウム又は酸化チタンで被覆することが好ましい。
特に、上述のように、第１のシリカ粒子群のシリカ粒子は、第２のシリカ粒子群のシリカ粒子よりも強付着化することが好ましいため、本発明では第１のシリカ粒子群のシリカ粒子を酸化アルミニウム又は酸化チタンで被覆する。
Therefore, as a method for strengthening the silica particles, it is preferable to coat the silica particles with aluminum oxide or titanium oxide.
In particular, as described above, since the silica particles of the first silica particle group preferably adhere more strongly than the silica particles of the second silica particle group, the silica particles of the first silica particle group are used in the present invention. It coated with aluminum oxide or titanium oxide.
酸化アルミニウム又は酸化チタンで被覆されたシリカを用いると、酸化アルミニウム又は酸化チタンで被覆されていないシリカ粒子に比べ、トナーに強く付着させることができる。
したがって、酸化アルミニウム又は酸化チタンで被覆されたシリカと被覆されていないシリカとの添加量の割合、被覆する被覆量、等を調整し、さらに外添混合の条件を微調整することで、容易に外添剤に含まれるのシリカ粒子全体の強付着割合を制御することが可能となる。
When silica coated with aluminum oxide or titanium oxide is used, it can adhere to the toner more strongly than silica particles not coated with aluminum oxide or titanium oxide.
Therefore, it is easy to adjust the ratio of the addition amount of silica coated with aluminum oxide or titanium oxide and uncoated silica, the coating amount to be coated, etc., and further finely adjust the conditions of external addition mixing. It becomes possible to control the strong adhesion ratio of the entire silica particles contained in the external additive.
酸化アルミニウム又は酸化チタンで被覆されたシリカが酸化アルミニウム又は酸化チタンで被覆されていないシリカ粒子に比べ強付着となる理由は明確ではないが、酸化アルミニウム又は酸化チタンの均一層がつくるミクロな凹凸が、シリカ粒子とトナーの結着樹脂とを付着させ、ある種の糊のような効果を与えていることによるものと推定される。 The reason why silica coated with aluminum oxide or titanium oxide is more strongly adhered than silica particles not coated with aluminum oxide or titanium oxide is not clear, but there are micro unevenness formed by a uniform layer of aluminum oxide or titanium oxide. It is presumed that the silica particles and the binder resin of the toner are adhered to each other to give an effect like a certain kind of glue.
酸化アルミニウム又は酸化チタンで被覆されたシリカ粒子は、例えば以下のような方法で得ることができる。
すなわち、表面処理を施していない親水性のシリカ粒子を、水中に分散してスラリーとし、アルミニウム又はチタンを含有する溶液を加え、シリカ表面を被覆処理し、アルカリで中和し、ろ過、洗浄、乾燥及び粉砕を行い、目的の粒子を得ることができる。
アルミニウム又はチタンを含有する溶液として具体的には、アルミニウムであれば硫酸アルミニウム、アルミン酸ナトリウム等、チタンであれば硫酸チタン、四塩化チタン等を用いることができる。
Silica particles coated with aluminum oxide or titanium oxide can be obtained, for example, by the following method.
That is, hydrophilic silica particles that have not been surface-treated are dispersed in water to form a slurry, a solution containing aluminum or titanium is added, the silica surface is coated, neutralized with an alkali, filtered, washed, Desired particles can be obtained by drying and grinding.
Specifically, as the solution containing aluminum or titanium, aluminum sulfate, sodium aluminate, or the like can be used for aluminum, and titanium sulfate, titanium tetrachloride, or the like can be used for titanium.
酸化アルミニウム又は酸化チタンでの被覆量は、シリカ粒子表面の４０％〜１００％を被覆する量が好ましく、より好ましくは、６０％〜１００％であり、シリカ粒子表面を単分子層で被覆する程度の場合が、特に好ましい。
このような被覆量として、シリカ母粒子１００重量部に対し、酸化アルミニウム又は酸化チタンを１重量部以上２０重量部以下で被覆することが好ましい。１重量部未満では、シリカ粒子を強付着化するのに充分でなく、２０重量部より多い場合にはシリカ粒子の抵抗が低下し転写性が悪化する場合があり好ましくない。
The coating amount with aluminum oxide or titanium oxide is preferably an amount covering 40% to 100% of the surface of the silica particles, more preferably 60% to 100%, and the degree of covering the silica particle surface with a monomolecular layer. This is particularly preferable.
As such a coating amount, it is preferable to coat aluminum oxide or titanium oxide with 1 to 20 parts by weight with respect to 100 parts by weight of silica mother particles. If it is less than 1 part by weight, it is not sufficient for strongly adhering the silica particles, and if it is more than 20 parts by weight, the resistance of the silica particles is lowered and transferability may be deteriorated.
さらに、酸化アルミニウム又は酸化チタンで被覆した後、疎水化処理を行ってもよい。 Furthermore, after coating with aluminum oxide or titanium oxide, a hydrophobic treatment may be performed.
疎水化剤としては、シラン系カップリング剤、チタネート系カップリング剤、アルミネート系カップリング剤、ジルコニウム系カップリング剤等のカップリング剤、シリコーンオイルやポリマーコーティング処理などが挙げられる。これらの疎水化剤を単独又は組み合わせて用いることができる。 Examples of hydrophobizing agents include silane coupling agents, titanate coupling agents, aluminate coupling agents, coupling agents such as zirconium coupling agents, silicone oils, and polymer coating treatments. These hydrophobizing agents can be used alone or in combination.
これらの中でも、シラン系カップリング剤とシリコーンオイルを好ましく用いることができる。
シラン系カップリング剤としては、クロロシラン、アルコキシシラン、シラザン、特殊シリル化剤等いずれのタイプも使用することができ、その具体例としては、メチルトリクロロシラン、ジメチルジクロロシラン、トリメチルクロロシラン、フェニルトリクロロシラン、ジフェニルジクロロシラン、テトラメトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、エチルトリメトキシシラン、プロピルトリメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、テトラエトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、エチルトリエトキシシラン、プロピルトリエトキシシラン、フェニルトリエトキシシラン、ジフェニルジエトキシシラン、ブチルトリメトキシシラン、ブチルトリエトキシシラン、イソブチルトリメトキシシラン、ヘキシルトリメトキシシラン、オクチルトリメトキシシラン、デシルトリメトキシシラン、ヘキサデシルトリメトキシシラン、トリメチルトリメトキシシラン、ヘキサメチルジシラザン、Ｎ，Ｏ−（ビストリメチルシリル）アセトアミド、Ｎ，Ｎ−ビス（トリメチルシリル）ウレア、ｔｅｒｔ−ブチルジメチルクロロシラン、ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリアセトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、β−（３．４エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン等や、それらの一部の水素原子をフッ素原子に変えた、トリフルオロプロピルトリメトキシシラン、トリデカフルオロオクチルトリメトキシシラン、ヘプタデカフルオロデシルトリメトキシシラン、ヘプタデカフルオロデシルメチルジメトキシシラン、トリデカフルオロ−１，１，２，２−テトラヒドロオクチルトリエトキシシラン、３，３，３−トリフルオロプロピルトリメトキシシラン、ヘプタデカフルオロ−１，１，２，２−テトラヒドロデシルトリエトキシシラン、３−ヘプタフルオロイソプロポキシプロピルトリエトキシシランなどのフッ素系シラン化合物、水素原子の一部をアミノ基で置換したアミノ系シラン化合物等を挙げることができるが、これらに限定されるものではない。
Among these, a silane coupling agent and silicone oil can be preferably used.
As the silane coupling agent, any type such as chlorosilane, alkoxysilane, silazane, and special silylating agent can be used. Specific examples thereof include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, and phenyltrichlorosilane. , Diphenyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane , Ethyltriethoxysilane, propyltriethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, butyltrimethoxysilane, Rutriethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, hexadecyltrimethoxysilane, trimethyltrimethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) acetamide, N, N-bis (trimethylsilyl) urea, tert-butyldimethylchlorosilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3.4 Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyl Tildiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, etc., and trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxy in which some hydrogen atoms are changed to fluorine atoms Silane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, hepta Fluorine-based silane compounds such as decafluoro-1,1,2,2-tetrahydrodecyltriethoxysilane, 3-heptafluoroisopropoxypropyltriethoxysilane, and amino-based silane compounds in which some of the hydrogen atoms are substituted with amino groups It can be exemplified, but the invention is not limited thereto.
また、シリコーンオイルとしては、ジメチルシリコーンオイル、メチルハイドロジェンシリコーンオイル、メチルフェニルシリコーンオイル、環状ジメチルシリコーンオイル、エポキシ変性シリコーンオイル、カルボキシル変性シリコーンオイル、カルビノール変性シリコーンオイル、メタクリル変性シリコーンオイル、メルカプト変性シリコーンオイル、ポリエーテル変性シリコーンオイル、メチルスチリル変性シリコーンオイル、アルキル変性シリコーンオイル、アミノ変性シリコーンオイル、フッ素変性シリコーンオイル等を用いることができるが、これらに限定されるものではない。 Silicone oils include dimethyl silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, cyclic dimethyl silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, carbinol-modified silicone oil, methacryl-modified silicone oil, and mercapto-modified. Silicone oil, polyether-modified silicone oil, methylstyryl-modified silicone oil, alkyl-modified silicone oil, amino-modified silicone oil, fluorine-modified silicone oil, and the like can be used, but are not limited thereto.
母体となる未処理のシリカの製法は問わず、湿式法あるいは気相法で製造されたいずれの粒子を使用しても良く、例えば特開２０００−２５８９７４号公報に開示されている方法により、所望の平均１次粒径をもつシリカ粒子を得ることができる。 Regardless of the method for producing the raw untreated silica, any particle produced by a wet method or a gas phase method may be used. For example, a desired method can be used by the method disclosed in JP-A-2000-258974. Silica particles having an average primary particle size of can be obtained.
第２のシリカ粒子群のシリカ粒子は、上記疎水化剤で疎水化処理されることが好ましい。疎水化処理されることにより、流動性や帯電安定性に優れ、環境依存性も小さくすることができる。 The silica particles of the second silica particle group are preferably hydrophobized with the above hydrophobizing agent. By being hydrophobized, it is excellent in fluidity and charging stability, and the environment dependency can be reduced.
特に疎水化処理は、流動性、帯電性の観点からシリコーンオイル処理又はヘキサメチルジシラザン処理であることが好ましい。 In particular, the hydrophobizing treatment is preferably a silicone oil treatment or a hexamethyldisilazane treatment from the viewpoint of fluidity and chargeability.
さらに、本発明では、第１のシリカ粒子群、第２のシリカ粒子群以外のシリカを併用してもよい。 Further, in the present invention, silica other than the first silica particle group and the second silica particle group may be used in combination.
またシリカ以外の外添剤としては、通常、トナーの外添剤として用いられている公知の材料であれば特に制限なく利用でき、例えば、酸化アルミニウム、酸化チタン、チタン酸バリウム、チタン酸マグネシウム、チタン酸カルシウム、チタン酸ストロンチウム、酸化亜鉛、ケイ砂、クレー、雲母、ケイ灰石、ケイソウ土、塩化セリウム、ベンガラ、酸化クロム、酸化セリウム、三酸化アンチモン、酸化マグネシウム、炭酸マグネシウム、酸化ジルコニウム、炭化ケイ素、窒化ケイ素、炭酸カルシウム、硫酸バリウムなどの金属酸化物やセラミック粒子などを併用しても良い。 As the external additive other than silica, any known material that is usually used as an external additive for a toner can be used without particular limitation. For example, aluminum oxide, titanium oxide, barium titanate, magnesium titanate, Calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, cerium chloride, bengara, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, magnesium carbonate, zirconium oxide, carbonized Metal oxides such as silicon, silicon nitride, calcium carbonate, barium sulfate or ceramic particles may be used in combination.
さらに、外添剤として、上記無機系粒子に加え、有機系粒子を添加してもよい。
有機粒子としては、例えば、スチレン系重合体、（メタ）アクリル系重合体、エチレン系重合体などのビニル系重合体や、エステル系、メラミン系、アミド系、アリルフタレート系などの各種重合体、フッ化ビニリデンなどのフッ素系重合体、ユニリンなどの高級アルコールからなる粒子などを挙げる事ができ、一次粒径で０．０５〜７．０μｍのものが好ましく用いられる。前記有機粒子は、一般にクリーニング性や転写性を向上させる目的で添加される。
Furthermore, as external additives, organic particles may be added in addition to the inorganic particles.
Examples of the organic particles include vinyl polymers such as styrene polymers, (meth) acrylic polymers, and ethylene polymers, and various polymers such as ester, melamine, amide, and allyl phthalate. Fluorine polymers such as vinylidene fluoride and particles made of higher alcohols such as unilin can be used, and those having a primary particle size of 0.05 to 7.0 μm are preferably used. The organic particles are generally added for the purpose of improving cleaning properties and transferability.
前記トナーに添加される粒子は、トナー粒子と共にサンプルミルやヘンシェルミキサーなどで機械的衝撃力を加えられてトナー粒子表面に付着又は固着させられる。 The particles added to the toner are adhered or fixed to the surface of the toner particles by applying a mechanical impact force together with the toner particles by a sample mill or a Henschel mixer.
本発明に用いる結着樹脂としては、スチレン、クロロスチレンなどのスチレン類、エチレン、プロピレン、ブチレン、イソブチレンなどのモノオレフィン類、酢酸ビニル、プロピオン酸ビニル、安息香酸ビニル、酪酸ビニルなど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、アクリル酸ブチル、アクリル酸オクチル、アクリル酸ドデシル、アクリル酸フェニル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸ドデシル、などのα−メチレン脂肪族モノカルボン酸のエステル類、ビニルメチルエーテル、ビニルエチルエーテル、ビニルブチルエーテルなどのビニルエーテル類、ビニルメチルケトン、ビニルヘキシルケトン、ビニルイソプロペニルケトンなどのビニルケトン類、などの単独重合体および共重合体を例示することができる。 Examples of the binder resin used in the present invention include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene, and isobutylene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyrate. Α-methylene aliphatic monocarboxylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Homopolymers of acid esters, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone It can be exemplified and copolymers.
特に代表的な結着樹脂としてはポリスチレン、スチレン−アクリル酸アルキル共重合体、スチレン−メタクリル酸アルキル共重合体、スチレン−アクリロニトリル共重合体、スチレン−ブタジエン共重合体、スチレン−無水マレイン酸共重合体、ポリエチレン、ポリプロピレン、を挙げることができる。
さらに、ポリエステル、ポリウレタン、エポキシ樹脂、シリコーン樹脂、ポリアミド、変性ロジンなどを挙げることができる。
これらの中でも、スチレン−（メタ）アクリル酸エステル共重合樹脂とポリエステル樹脂が好ましく用いられる。
特に低温定着性の観点からポリエステル樹脂が好ましく用いられる。
Typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. And coalesced polyethylene, polypropylene and the like.
Further examples include polyester, polyurethane, epoxy resin, silicone resin, polyamide, and modified rosin.
Among these, styrene- (meth) acrylic acid ester copolymer resins and polyester resins are preferably used.
In particular, a polyester resin is preferably used from the viewpoint of low-temperature fixability.
本発明に用いられる磁性粉末としては公知の磁性体、例えば、鉄、コバルト、ニッケル等の金属及びこれらの合金、Ｆｅ3Ｏ4，γ−Ｆｅ2Ｏ3，コバルト添加酸化鉄等の金属酸化物、ＭｎＺｎフェライト、ＮｉＺｎフェライト等の各種フェライト、マグネタイト、ヘマタイト等が使用でき、更にそれらの表面をシランカップリング剤、チタネートカップリング剤等の表面処理剤で処理したもの、珪素系化合物やアルミニウム系化合物など無機系材料でコーティングしたもの、あるいはポリマーコーテイングしたもの等でも良い。 Examples of the magnetic powder used in the present invention include known magnetic materials, for example, metals such as iron, cobalt, nickel, and alloys thereof, and metal oxides such as Fe 3 O 4 , γ-Fe 2 O 3 , and cobalt-added iron oxide. , MnZn ferrite, NiZn ferrite and other various ferrites, magnetite, hematite, etc. can be used, and their surfaces are treated with surface treatment agents such as silane coupling agents and titanate coupling agents, silicon compounds and aluminum compounds For example, a material coated with an inorganic material or a polymer coated material may be used.
磁性粉末の混合割合は、トナー粒子全体に対して３５〜５５質量％の範囲が好ましく、より好ましくは４０〜５０質量％の範囲である。磁性粉末が３５質量％より少ない場合は、トナー担持体のマグネットによるトナーの拘束力が低下し、トナー飛散、カブリの問題が発生する。一方５５質量％を越える場合は画像濃度が低下するという問題がある。 The mixing ratio of the magnetic powder is preferably in the range of 35 to 55% by mass, more preferably in the range of 40 to 50% by mass with respect to the entire toner particles. When the amount of magnetic powder is less than 35% by mass, the toner binding force by the magnet of the toner carrier is reduced, causing problems of toner scattering and fogging. On the other hand, when it exceeds 55% by mass, there is a problem that the image density is lowered.
これらの磁性粉の数平均粒径は０．０５μｍ〜０．３５μｍ程度のものが結着樹脂への分散性の観点で好ましく用いられ、より好ましくは０．１０μｍ〜０．３０μｍ程度である。 The number average particle diameter of these magnetic powders is preferably about 0.05 μm to 0.35 μm from the viewpoint of dispersibility in the binder resin, and more preferably about 0.10 μm to 0.30 μm.
本発明のトナーには、耐オフセット性を向上させる目的でワックスを含有する。
本発明に用いられるワックスとしては、例えば、低分子量ポリプロピレンや低分子量ポリエチレン等の炭化水素系ワックス、マイクロクリスタリンワックス、シリコーン樹脂、ロジン類、エステル系ワックス、ライスワックス、カルナバワックス、フィッシャートロプシュワックス、モンタンワックス、キャンデリラワックスなどが挙げられる。
The toner of the present invention contains a wax for the purpose of improving offset resistance.
Examples of the wax used in the present invention include hydrocarbon waxes such as low molecular weight polypropylene and low molecular weight polyethylene, microcrystalline wax, silicone resin, rosins, ester wax, rice wax, carnauba wax, Fischer-Tropsch wax, and Montan. Examples thereof include wax and candelilla wax.
ワックスの割合はトナーの粒子全体に対して０．１〜１０質量％の範囲内であることが好ましく、より好ましくは１〜８質量％の範囲内である。
離型剤の含有量が、上記下限値より少ないと、トナーの離型性能が低下しオフセットが発生する場合があり、一方、上記上限値を越えると、トナーの帯電性能の低下や熱保管性能の低下が発生する場合があり、それぞれ好ましくない。
The ratio of the wax is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 1 to 8% by mass with respect to the whole toner particles.
If the content of the release agent is less than the above lower limit value, the toner release performance may be reduced and offset may occur. On the other hand, if the content exceeds the upper limit value, the toner charging performance is deteriorated or the heat storage performance is increased. May occur, which is not preferable.
また、本発明のトナーには、色調を調整するために着色剤を含有させても良い。
着色剤としては、特に制限はなく、それ自体公知の着色剤を挙げることができ、目的に応じて適宜選択することができる。
The toner of the present invention may contain a colorant in order to adjust the color tone.
There is no restriction | limiting in particular as a coloring agent, The coloring agent known per se can be mentioned, According to the objective, it can select suitably.
例えば、カーボンブラック、ランプブラックや、デュポンオイルレッド、オリエントオイルレッド、ローズベンガル、Ｃ．Ｉ．ピグメントレッドの５、１１２、１２３、１３９、１４４、１４９、１６６、１７７、１７８、２２２、４８：１、４８：２、４８：３、５３：１、５７：１、８１：１や、Ｃ．Ｉ．ピグメントオレンジの３１、４３や、キノリンイエロー、クロームイエロー、Ｃ．Ｉ．ピグメントイエローの１２、１４、１７、９３、９４、９７、１３８、１７４、１８０、１８８や、ウルトラマリンブルー、アニリンブルー、カルコイルブルー、メチレンブルークロライド、銅フタロシアニン、Ｃ．Ｉ．ピグメントブルーの１５、６０、１５：１、１５：２、１５：３や、Ｃ．Ｉ．ピグメントグリーンの７や、マラカイトグリーンオキサレート、ニグロシン染料などが挙げられ、これらを単独又は複数組み合わせて用いることも可能である。これらはあらかじめフラッシング分散処理されたものであってもよい。
For example, carbon black, lamp black, Dupont Oil Red, Orient Oil Red, Rose Bengal, C.I. I.
また、帯電制御を目的として、種々の物質を添加することができる。
例えば、フッ素系界面活性剤、サリチル酸系錯体、鉄錯体のような鉄系染料、クロム錯体のようなクロム系染料、マレイン酸を単量体成分として含む共重合体のごとき高分子酸、４級アンモニウム塩、ニグロシンなどのアジン系染料などを０．１〜１０．０質量％の範囲で添加しても良い。
Various substances can be added for the purpose of charge control.
For example, high molecular acids such as fluorosurfactants, salicylic acid complexes, iron dyes such as iron complexes, chromium dyes such as chromium complexes, and copolymers containing maleic acid as a monomer component, quaternary Azine dyes such as ammonium salts and nigrosine may be added in the range of 0.1 to 10.0% by mass.
本発明に用いられるトナーは、公知の製造方法に従って製造することができる。前記製造方法としては、特に制限はなく、目的に応じて適宜決定することができる。
例えば、混練粉砕法、混練冷凍粉砕法、液中乾燥法、溶融トナーを不溶解性液体中で剪断撹拌して微粒子化する方法、結着樹脂と着色剤を溶剤に分散させジェット噴霧により微粒子化する方法、あるいは、乳化重合法による樹脂をもちいた乳化凝集法、懸濁重合法、溶解懸濁法などが挙げられる。トナーの体積平均粒径は５〜１５μｍ程度であることが好ましく、より好ましくは５．５〜１０μｍ程度である。
The toner used in the present invention can be produced according to a known production method. There is no restriction | limiting in particular as said manufacturing method, According to the objective, it can determine suitably.
For example, kneading pulverization method, kneading freezing pulverization method, submerged drying method, a method in which molten toner is sheared and stirred in an insoluble liquid to form fine particles, a binder resin and a colorant are dispersed in a solvent, and fine particles are formed by jet spraying. Or an emulsion aggregation method using a resin by an emulsion polymerization method, a suspension polymerization method, a dissolution suspension method, and the like. The volume average particle diameter of the toner is preferably about 5 to 15 μm, more preferably about 5.5 to 10 μm.
次に、本発明の画像形成方法について説明する。本発明の画像形成方法は、本発明のトナーを用いたものであれば特に限定されないが、具体的には以下のような画像形成方法であることが好ましい。
すなわち、本発明の画像形成方法は、少なくとも、静電担持体上に静電潜像を形成する工程と、前記静電潜像を現像剤により現像してトナー像を前記静電担持体上に形成する工程と、前記トナー像を前記静電担持体から転写体上に転写する工程と、前記転写体上に転写された前記トナー像を熱定着ロールと該熱定着ロールに圧着される圧力部材とにより前記転写体に定着させる工程と、を含む画像形成方法であって、前記現像剤が、上記に説明した磁性一成分現像剤であることを特徴とする。
Next, the image forming method of the present invention will be described. The image forming method of the present invention is not particularly limited as long as the toner of the present invention is used, but specifically, the following image forming method is preferable.
That is, the image forming method of the present invention includes at least a step of forming an electrostatic latent image on an electrostatic carrier, and developing the electrostatic latent image with a developer to form a toner image on the electrostatic carrier. A step of forming, a step of transferring the toner image from the electrostatic carrier onto a transfer body, a heat fixing roll, and a pressure member that press-bonds the toner image transferred onto the transfer body to the heat fixing roll. And the step of fixing to the transfer body by the method, wherein the developer is the magnetic one-component developer described above.
上述の各工程は、いずれも従来の画像形成方法で採用されている公知の方法により行なうことができる。
また、本発明の画像形成方法は、例えば、潜像担持体表面をクリーニングするクリーニング工程等、上記した工程以外の工程を含むものであってもよい。
さらに、定着工程においては、フラッシュ定着方式、赤外線照射定着方式等の公知の光定着方式を利用することもできる。
Each of the above steps can be performed by a known method employed in a conventional image forming method.
Further, the image forming method of the present invention may include processes other than the above-described processes such as a cleaning process for cleaning the surface of the latent image carrier.
Furthermore, in the fixing step, a known light fixing method such as a flash fixing method or an infrared irradiation fixing method can be used.
なお、本発明のトナーは、画像濃度維持に優れるため、かかるトナーを用いた画像形成方法は、プリントの初期からトナー使い切りまで、充分な画像濃度を有する高画質なプリントを可能とする画像形成方法である。 Since the toner of the present invention is excellent in maintaining the image density, the image forming method using such toner enables an image forming method capable of high-quality printing having a sufficient image density from the initial printing to the time when the toner is used up. It is.
本発明の画像形成方法による画像の形成は、潜像担持体として電子写真感光体を利用した場合、例えば、以下のようにして行うことができる。
まず、電子写真感光体の表面を、コロトロン帯電器、接触帯電器等により一様に帯電した後、露光し、静電潜像を形成する。次いで、表面に現像剤層を形成させた現像ロールと接触若しくは近接させて、静電潜像にトナーの粒子を付着させ、電子写真感光体上にトナー像を形成する。形成されたトナー像は、コロトロン帯電器等を利用して紙等の被転写体表面に転写される。さらに、被転写体表面に転写されたトナー像は、光定着器あるいは熱定着器により光定着又は熱定着され、記録媒体上に画像が形成される。
Image formation by the image forming method of the present invention can be performed, for example, as follows when an electrophotographic photosensitive member is used as a latent image carrier.
First, the surface of the electrophotographic photosensitive member is uniformly charged by a corotron charger, a contact charger or the like and then exposed to form an electrostatic latent image. Next, the toner particles are adhered to the electrostatic latent image by contacting or approaching with a developing roll having a developer layer formed on the surface, thereby forming a toner image on the electrophotographic photosensitive member. The formed toner image is transferred onto the surface of a transfer medium such as paper using a corotron charger or the like. Further, the toner image transferred to the surface of the transfer medium is light-fixed or heat-fixed by a light fixing device or a heat fixing device, and an image is formed on the recording medium.
本発明の画像形成方法では、少なくとも１種の本発明のトナーが必ず用いられるが、２種類以上のトナーを用いる場合には、少なくとも１種が本発明のトナーであればよい。例えば、シアン、マゼンタ、イエロー、ブラックの４色のカラートナーを用いて、カラー画像（可視画像）を形成する場合には、４色のカラートナーのうち、ブラックトナーに本発明のトナーを用いることができる In the image forming method of the present invention, at least one type of toner of the present invention is used without fail, but when two or more types of toner are used, at least one type of toner may be used. For example, when a color image (visible image) is formed using four color toners of cyan, magenta, yellow, and black, the toner of the present invention is used as the black toner among the four color toners. Can
また、本発明の画像形成装置は、少なくとも、静電担持体と、前記静電担持体を帯電させる帯電装置と、帯電した前記静電担持体を露光して静電潜像を形成させる露光装置と、前記静電潜像を現像剤により現像してトナー像を形成させる現像装置と、前記トナー像を前記静電担持体から転写体に転写する転写装置と、を備え、
前記現像装置に含有される前記現像剤が、上述の磁性一成分現像剤であることを特徴とする。
The image forming apparatus of the present invention includes at least an electrostatic carrier, a charging device that charges the electrostatic carrier, and an exposure device that exposes the charged electrostatic carrier to form an electrostatic latent image. A developing device that develops the electrostatic latent image with a developer to form a toner image, and a transfer device that transfers the toner image from the electrostatic carrier to a transfer body,
The developer contained in the developing device is the magnetic one-component developer described above.
図１は、本発明の画像形成装置の好適な一実施形態の基本構成を概略的に示す断面図である。図１に示す画像形成装置１００は、電子写真感光体１０７と、電子写真感光体１０７を帯電させるコロトロンやスコロトロンなどの帯電装置１０８と、帯電装置１０８に接続された電源１０９と、帯電装置１０８により帯電される電子写真感光体１０７を露光して静電潜像を形成する露光装置１１０と、露光装置１１０により形成された静電潜像をトナーにより現像してトナー像を形成する現像装置１１１と、現像装置１１１により形成されたトナー像を被転写媒体５００に転写する転写装置１１２と、転写後に電子写真感光体１０７に残留しているトナーを除去するクリーニング装置１１３と、除電器１１４と、定着装置１１５とを備える。
FIG. 1 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of an image forming apparatus of the present invention. An
画像形成装置１００における各装置は、いずれも従来の画像形成装置で採用されているものを適用できる。
なお、本発明においては、除電器１１４が設けられていない画像形成装置であってもよい。また、図１では、帯電装置１０８は接触型の帯電装置を示しているが、コロトロン帯電器のような非接触型の帯電装置であってもよい。
As each device in the
In the present invention, an image forming apparatus in which the
以下、本発明の実施例を説明するが、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
〔シリカ粒子１の作製〕
気相法シリカ粒子（アエロジルＯＸ５０、基体シリカの比表面積５０ｍ2／ｇ、日本アエロジル製）１００ｇを２Ｌの水に分散し、液温を７０℃に加温し、Ａｌ2Ｏ3として１００ｇ／Ｌのアルミン酸ナトリウム溶液５０ｍＬと５Ｎ水酸化ナトリウム水溶液をｐＨが６．０となるように同時に滴下した。滴下終了後、液温を４０℃まで冷却し、ｐＨを５．０に調整した後、引き続いてｎ−ヘキシルトリメトキシシラン２０ｇを添加した。４時間撹拌保持後、２Ｎ水酸化ナトリウム水溶液を加えてｐＨを６．５に調整し、更に２時間撹拌保持した後、ろ過、水洗を行った。ろ過、水洗済ケーキは１３０℃で乾燥した後、エアジェット方式による微粉砕機で微粉砕し、シリカ粒子１を得た。
１次粒子の数平均粒径は４０ｎｍ、ＢＥＴ比表面積は、５２ｍ2／ｇであった。
[Preparation of Silica Particle 1]
Gas phase method silica particles (Aerosil OX50, specific surface area of base silica 50 m 2 / g, manufactured by Nippon Aerosil) are dispersed in 2 L of water, the liquid temperature is heated to 70 ° C., and Al 2 O 3 is 100 g / L. 50 mL of sodium aluminate solution and 5N aqueous sodium hydroxide solution were simultaneously added dropwise so that the pH was 6.0. After completion of the dropwise addition, the liquid temperature was cooled to 40 ° C., the pH was adjusted to 5.0, and then 20 g of n-hexyltrimethoxysilane was added. After stirring and holding for 4 hours, 2N aqueous sodium hydroxide solution was added to adjust the pH to 6.5, and after stirring and holding for 2 hours, filtration and washing were performed. The filtered and washed cake was dried at 130 ° C. and then finely pulverized by an air jet type fine pulverizer to obtain silica particles 1.
The number average particle diameter of the primary particles was 40 nm, and the BET specific surface area was 52 m 2 / g.
〔シリカ粒子２の作製〕
シリカ粒子１の作製においてアルミン酸ナトリウム溶液の添加量を８０ｍＬとした以外は同様にして、シリカ粒子２を得た。
ＢＥＴ比表面積は、５６ｍ2／ｇであった。
[Preparation of silica particles 2]
Silica particles 2 were obtained in the same manner except that the amount of sodium aluminate solution added was 80 mL in the production of silica particles 1.
The BET specific surface area was 56 m 2 / g.
〔シリカ粒子３の作製〕
気相法シリカ粒子（アエロジルＯＸ５０、基体シリカの比表面積５０ｍ2／ｇ、日本アエロジル製）１００ｇを２Ｌの水に分散し、液温を７０℃に加温し、ＴｉＯ2として１００ｇ／Ｌの硫酸チタン溶液３０ｍＬと５Ｎ水酸化ナトリウム水溶液をｐＨが６．０となるように同時に滴下した。滴下終了後、液温を４０℃まで冷却し、ｐＨを５．０に調整した後、引き続いてｎ−ヘキシルトリメトキシシラン２０ｇを添加した。４時間撹拌保持後、２Ｎ水酸化ナトリウム水溶液を加えてｐＨを６．５に調整し、更に２時間撹拌保持した後、ろ過、水洗を行った。ろ過、水洗済ケーキは１３０℃で乾燥した後、エアジェット方式による微粉砕機で微粉砕し、シリカ粒子３を得た。
１次粒子の数平均粒径は４０ｎｍ、ＢＥＴ比表面積は、５５ｍ2／ｇであった。
[Preparation of Silica Particle 3]
100 g of vapor phase silica particles (Aerosil OX50, specific surface area of base silica 50 m 2 / g, manufactured by Nippon Aerosil) are dispersed in 2 L of water, the liquid temperature is heated to 70 ° C., and TiO 2 is 100 g / L of sulfuric acid. Titanium solution (30 mL) and 5N aqueous sodium hydroxide solution were simultaneously added dropwise so that the pH was 6.0. After completion of the dropwise addition, the liquid temperature was cooled to 40 ° C., the pH was adjusted to 5.0, and then 20 g of n-hexyltrimethoxysilane was added. After stirring and holding for 4 hours, 2N aqueous sodium hydroxide solution was added to adjust the pH to 6.5, and after stirring and holding for 2 hours, filtration and washing were performed. The filtered and washed cake was dried at 130 ° C. and then finely pulverized by an air jet type fine pulverizer to obtain silica particles 3.
The number average particle diameter of the primary particles was 40 nm, and the BET specific surface area was 55 m 2 / g.
〔シリカ粒子４の作製〕
蒸留精製したメチルトリメトキシシランを加熱し、窒素ガスをバブリングし、メチルトリメトキシシランを窒素ガスで気流伴流して酸水素火炎バーナーに導入し、この酸水素火炎中で燃焼分解させた。メチルトリメトキシシラン、酸素ガス、水素ガス、窒素ガスの量を調整し、１次粒子の数平均粒径が２００ｎｍのシリカ粒子Ａを得た。
[Preparation of Silica Particle 4]
Distilled and purified methyltrimethoxysilane was heated, nitrogen gas was bubbled, and methyltrimethoxysilane was introduced into an oxyhydrogen flame burner with a stream of nitrogen gas, and burned and decomposed in the oxyhydrogen flame. The amount of methyltrimethoxysilane, oxygen gas, hydrogen gas and nitrogen gas was adjusted to obtain silica particles A having a primary particle number average particle size of 200 nm.
得られたシリカ粒子Ａの１００ｇを用いて、シリカ粒子１の作製において、アルミン酸ナトリウム水溶液の添加量を２５ｍＬとした以外は同様の方法で、Ａｌ2Ｏ3の被覆を行いシリカ粒子４を得た。ＢＥＴ比表面積は、２２ｍ2／ｇであった。 Using 100 g of the obtained silica particles A, silica particles 4 were obtained by coating Al 2 O 3 in the same manner as in the preparation of silica particles 1 except that the amount of sodium aluminate aqueous solution added was 25 mL. It was. The BET specific surface area was 22 m 2 / g.
〔シリカ粒子５の作製〕
気相法シリカ粒子（アエロジルＯＸ５０、基体シリカの比表面積５０ｍ2／ｇ、日本アエロジル製）８０重量部を、ジメチルシリコーンオイル（ＫＦ−９６；信越化学工業社製）２０重量部で処理を行い、シリカ粒子５を得た。
１次粒子の数平均粒径は４０ｎｍ、ＢＥＴ比表面積は、３５ｍ2／ｇであった。
[Preparation of silica particles 5]
80 parts by weight of vapor phase method silica particles (Aerosil OX50, specific surface area of base silica 50 m 2 / g, manufactured by Nippon Aerosil) are treated with 20 parts by weight of dimethyl silicone oil (KF-96; manufactured by Shin-Etsu Chemical Co., Ltd.) Silica particles 5 were obtained.
The number average particle diameter of the primary particles was 40 nm, and the BET specific surface area was 35 m 2 / g.
〔シリカ粒子６の作製〕
気相法シリカ粒子（アエロジル１３０、基体シリカの比表面積１３０ｍ2／ｇ、日本アエロジル製）８０重量部を、ジメチルシリコーンオイル（ＫＦ−９６；信越化学工業社製）２０重量部で処理を行い、シリカ粒子６を得た。
１次粒子の数平均粒径は１６ｎｍ、ＢＥＴ比表面積は、１０５ｍ2／ｇであった。
[Preparation of Silica Particle 6]
80 parts by weight of vapor phase silica particles (Aerosil 130, specific surface area of base silica 130 m 2 / g, manufactured by Nippon Aerosil) are treated with 20 parts by weight of dimethyl silicone oil (KF-96; manufactured by Shin-Etsu Chemical Co., Ltd.) Silica particles 6 were obtained.
The number average particle diameter of the primary particles was 16 nm, and the BET specific surface area was 105 m 2 / g.
〔シリカ粒子７の作製〕
気相法シリカ粒子（アエロジル２００、基体シリカの比表面積２００ｍ2／ｇ、日本アエロジル製）７０重量部を、ジメチルシリコーンオイル（ＫＦ−９６；信越化学工業社製）３０重量部で処理を行い、シリカ粒子７を得た。
１次粒子の数平均粒径は１２ｎｍ、ＢＥＴ比表面積は、１６０ｍ2／ｇであった。
[Preparation of silica particles 7]
70 parts by weight of vapor phase method silica particles (Aerosil 200, specific surface area of base silica 200 m 2 / g, manufactured by Nippon Aerosil) are treated with 30 parts by weight of dimethyl silicone oil (KF-96; manufactured by Shin-Etsu Chemical Co., Ltd.) Silica particles 7 were obtained.
The number average particle diameter of the primary particles was 12 nm, and the BET specific surface area was 160 m 2 / g.
〔シリカ粒子８の作製〕
気相法シリカ粒子（アエロジル１３０、基体シリカの比表面積１３０ｍ2／ｇ、日本アエロジル製）８０重量部を、ヘキサメチルジシラザン２０重量部で処理を行い、シリカ粒子８を得た。
１次粒子の数平均粒径は１６ｎｍ、ＢＥＴ比表面積は、１１５ｍ2／ｇであった。
[Preparation of silica particles 8]
80 parts by weight of vapor-phase method silica particles (Aerosil 130, specific surface area of base silica 130 m 2 / g, manufactured by Nippon Aerosil) were treated with 20 parts by weight of hexamethyldisilazane to obtain silica particles 8.
The number average particle diameter of the primary particles was 16 nm, and the BET specific surface area was 115 m 2 / g.
〔シリカ粒子９の作製〕
蒸留精製したメチルトリメトキシシランを加熱し、窒素ガスをバブリングし、メチルトリメトキシシランを窒素ガスで気流伴流して酸水素火炎バーナーに導入し、この酸水素火炎中で燃焼分解させた。メチルトリメトキシシラン、酸素ガス、水素ガス、窒素ガスの量を調整し、１次粒子の数平均粒径が２３ｎｍのシリカ粒子Ｂを得た。
[Preparation of Silica Particles 9]
Distilled and purified methyltrimethoxysilane was heated, nitrogen gas was bubbled, and methyltrimethoxysilane was introduced into an oxyhydrogen flame burner with a stream of nitrogen gas, and burned and decomposed in the oxyhydrogen flame. The amount of methyltrimethoxysilane, oxygen gas, hydrogen gas, and nitrogen gas was adjusted to obtain silica particles B having a primary particle number average particle size of 23 nm.
得られたシリカ粒子Ｂの１００ｇを用いて、シリカ粒子１の作製において、アルミン酸ナトリウム水溶液の添加量を１１０ｍＬとした以外は同様の方法で、Ａｌ2Ｏ3の被覆を行いシリカ粒子９を得た。ＢＥＴ比表面積は、１０７ｍ2／ｇであった。 Using 100 g of the obtained silica particles B, silica particles 9 were obtained by coating Al 2 O 3 in the same manner except that the amount of sodium aluminate aqueous solution was changed to 110 mL in the production of silica particles 1. It was. The BET specific surface area was 107 m 2 / g.
〔シリカ粒子１０の作製〕
シリカ粒子９の作製において得られたシリカ粒子Ａの８０重量部を、ジメチルシリコーンオイル２０重量部で処理を行い、シリカ粒子１０を得た。
１次粒子の数平均粒径は２３ｎｍ、ＢＥＴ比表面積は、９６ｍ2／ｇであった。
[Preparation of Silica Particle 10]
80 parts by weight of silica particles A obtained in the production of silica particles 9 were treated with 20 parts by weight of dimethyl silicone oil to obtain silica particles 10.
The number average particle diameter of the primary particles was 23 nm, and the BET specific surface area was 96 m 2 / g.
［実施例１］
ポリエステル樹脂（ビスフェノールＡプロピレンオキサイド付加物・テレフタル酸を主体とする架橋ポリエステル、ＴＨＦ不溶分２０％、ＭＩ＝５．０、酸価＝１２．０、水酸基化＝１５．０、Ｔｇ＝５９℃）５１．２５重量部、マグネタイト（飽和磁化８２Ａｍ2／ｋｇ、残留磁化５．５Ａｍ2／ｋｇ、保磁力４．８ｋＡ／ｍ、３９８ｋＡ／ｍ）４５．０重量部、ポリプロピレンワックス（重量平均分子量３０００）３．０重量部、帯電制御剤（商品名Ｔ−７７、保土ヶ谷化学（株）製）０．７５重量部とを、ヘンシェルミキサーにより粉体混合し、これを設定温度１６０℃のエクストルーダーにより熱混練した。冷却後、粉砕分級し、得られたトナー分級品Ａを得た。
トナー分級品Ａ１００重量部に対して、シリカ粒子１を０．８重量部、シリカ粒子６を１．４重量部添加しヘンシェルミキサーで外添混合し、体積平均粒度６．８μｍの磁性一成分現像剤１を得た。
現像剤１におけるシリカ粒子の強付着割合を、上述の方法によって、式（１）又は式（２）により求めたところ、２８％であった。
[Example 1]
Polyester resin (Bisphenol A propylene oxide adduct / crosslinked polyester mainly composed of terephthalic acid, THF insoluble content 20%, MI = 5.0, acid value = 12.0, hydroxylation = 15.0, Tg = 59 ° C.) 51.25 parts by weight, magnetite (saturation magnetization 82 Am 2 / kg, residual magnetization 5.5 Am 2 / kg, coercive force 4.8 kA / m, 398 kA / m) 45.0 parts by weight, polypropylene wax (weight average molecular weight 3000) 3.0 parts by weight and 0.75 parts by weight of a charge control agent (trade name T-77, manufactured by Hodogaya Chemical Co., Ltd.) are mixed with powder using a Henschel mixer and heated with an extruder at a set temperature of 160 ° C. Kneaded. After cooling, pulverization and classification were performed, and the resulting toner classification product A was obtained.
0.8 parts by weight of silica particles 1 and 1.4 parts by weight of silica particles 6 are added to 100 parts by weight of toner classification product A, and externally added and mixed with a Henschel mixer to develop a magnetic one-component development having a volume average particle size of 6.8 μm. Agent 1 was obtained.
When the strong adhesion ratio of the silica particles in the developer 1 was determined by the formula (1) or the formula (2) by the above-described method, it was 28%.
尚、トナーの粒度は、コールターカウンター社製粒度測定機ＴＡ−ＩＩによりアパーチャー径１００μｍで測定した。 The particle size of the toner was measured with a particle size measuring device TA-II manufactured by Coulter Counter with an aperture diameter of 100 μm.
このように作製された磁性一成分現像剤１を、富士ゼロックス社製レーザープリンターＤｏｃｕＰｒｉｎｔ３４０Ａトナーカートリッジに充填し、該機械にセットし、画像濃度をＸ−ｒｉｔｅ濃度計によって測定した。
ここで、画像濃度は、初期画像濃度と画像濃度維持性を求めるため、以下の条件で行った。
The magnetic one-component developer 1 produced in this way was filled in a laser printer DocuPrint340A toner cartridge manufactured by Fuji Xerox Co., Ltd., set in the machine, and the image density was measured with an X-rite densitometer.
Here, the image density was determined under the following conditions in order to obtain the initial image density and the image density maintainability.
初期画像濃度は、２３℃、６０％ＲＨで測定を行った。画像濃度が１．４０以上を○とし、１．４０未満を×とした。 The initial image density was measured at 23 ° C. and 60% RH. An image density of 1.40 or more was rated as ◯, and an image density less than 1.40 was rated as x.
画像濃度維持性は、３０℃９０％ＲＨの高温高湿（Ｈ−Ｈ）条件、及び１０℃１５％ＲＨの低温低湿（Ｌ−Ｌ）条件において、初期画像濃度と、Ａ４で画像密度３％で１５０００枚プリント後の画像濃度を測定した。この測定値を元に、初期画像濃度を１００％とした時の１５０００枚プリント後の画像濃度（画像濃度変化率）を求めた。
なお、表１に示す評価基準は以下の通りである。
The image density maintainability is 30% 90% RH high temperature and high humidity (H-H) condition and 10 ° C. 15% RH low temperature and low humidity (L-L) condition. The image density after printing 15000 sheets was measured. Based on this measurement value, the image density (image density change rate) after printing 15000 sheets when the initial image density is 100% was obtained.
The evaluation criteria shown in Table 1 are as follows.
◎：画像濃度変化率の値が９６％以上であり、濃度維持性に非常に優れている。
○：画像濃度変化率の値が９３％以上９６％未満であり、実用上全く問題無いレベルである。
△：画像濃度変化率の値が９０％以上９３％未満であり、濃度変化はあるものの実用上の問題は非常に小さいレベルである。
×：画像濃度変化率の値が９０％未満であり、実用上問題となるレベルである。
A: Image density change rate value is 96% or more, and density maintenance is very good.
◯: The value of the image density change rate is 93% or more and less than 96%, which is a level that causes no problem in practical use.
Δ: The value of the image density change rate is 90% or more and less than 93%, and although there is a density change, the practical problem is a very small level.
X: The image density change rate is less than 90%, which is a practically problematic level.
また初期及び１５０００枚後のプリント画像を目視で観察し、濃度ムラ、白筋、白点、黒点などの画質欠陥の有無を評価した。 In addition, the printed images after the initial and 15,000 sheets were visually observed to evaluate the presence or absence of image quality defects such as density unevenness, white streaks, white spots, black spots, and the like.
○：画像欠陥が全くなく、問題ないレベルである。
△：非常に軽微な画質欠陥があるが、実用上問題ないレベルである
×：画質欠陥が見られ、実用上問題となるレベルである
◯: There is no image defect at all and there is no problem.
Δ: Although there is a very slight image quality defect, it is a level that does not cause a problem in practical use.
［実施例２］
トナー分級品Ａ１００重量部に対して、シリカ粒子２を０．７重量部、シリカ粒子６を１．４重量部添加しヘンシェルミキサーで外添混合し、磁性一成分現像剤２を得て、実施例１と同様に評価を行った。
なお、現像剤２におけるシリカ粒子の強付着割合は３１％であった。
[Example 2]
0.7 parts by weight of silica particles 2 and 1.4 parts by weight of silica particles 6 are added to 100 parts by weight of toner classification product A, and externally added and mixed with a Henschel mixer to obtain a magnetic one-component developer 2. Evaluation was performed in the same manner as in Example 1.
The strong adhesion ratio of silica particles in Developer 2 was 31%.
［実施例３］
トナー分級品Ａ１００重量部に対して、シリカ粒子３を０．９重量部、シリカ粒子６を１．４重量部添加しヘンシェルミキサーで外添混合し、磁性一成分現像剤３を得て、実施例１と同様に評価を行った。
なお、現像剤３におけるシリカ粒子の強付着割合は２５％であった。
[Example 3]
0.9 parts by weight of silica particles 3 and 1.4 parts by weight of silica particles 6 are added to 100 parts by weight of toner classification product A, and externally mixed with a Henschel mixer to obtain a magnetic one-component developer 3. Evaluation was performed in the same manner as in Example 1.
The strong adhesion ratio of silica particles in Developer 3 was 25%.
［実施例４］
トナー分級品Ａ１００重量部に対して、シリカ粒子１を１．６重量部、シリカ粒子７を１．０重量部添加しヘンシェルミキサーで外添混合し、磁性一成分現像剤４を得て、実施例１と同様に評価を行った。
なお、現像剤４におけるシリカ粒子の強付着割合は３７％であった。
[Example 4]
1.6 parts by weight of silica particles 1 and 1.0 parts by weight of silica particles 7 are added to 100 parts by weight of toner classification product A, and externally mixed with a Henschel mixer to obtain a magnetic one-component developer 4. Evaluation was performed in the same manner as in Example 1.
The strong adhesion ratio of silica particles in developer 4 was 37%.
［実施例５］
トナー分級品Ａ１００重量部に対して、シリカ粒子１を０．３重量部、シリカ粒子８を１．１重量部添加しヘンシェルミキサーで外添混合し、磁性一成分現像剤５を得て、実施例１と同様に評価を行った。
なお、現像剤５におけるシリカ粒子の強付着割合は２１％であった。
[Example 5]
With respect to 100 parts by weight of toner classification product A, 0.3 part by weight of silica particles 1 and 1.1 parts by weight of silica particles 8 are added and externally mixed with a Henschel mixer to obtain a magnetic one-component developer 5. Evaluation was performed in the same manner as in Example 1.
In addition, the strong adhesion ratio of the silica particles in the developer 5 was 21%.
［実施例６（参考例）］
トナー分級品Ａ１００重量部に対して、シリカ粒子１を２．２重量部、シリカ粒子６を１．４重量部添加しヘンシェルミキサーで外添混合し、磁性一成分現像剤６を得て、実施例１と同様に評価を行った。
なお、現像剤６におけるシリカ粒子の強付着割合は４４％であった。
[Example 6 (reference example) ]
With respect to 100 parts by weight of toner classification product A, 2.2 parts by weight of silica particles 1 and 1.4 parts by weight of silica particles 6 are added and externally mixed with a Henschel mixer to obtain a magnetic one-component developer 6. Evaluation was performed in the same manner as in Example 1.
The strong adhesion ratio of silica particles in the developer 6 was 44%.
［実施例７（参考例）］
トナー分級品Ａ１００重量部に対して、シリカ粒子１を０．０８重量部、シリカ粒子６を１．４重量部添加しヘンシェルミキサーで外添混合し、磁性一成分現像剤７を得て、実施例１と同様に評価を行った。
なお、現像剤７におけるシリカ粒子の強付着割合は１７％であった。
[Example 7 (reference example) ]
0.08 parts by weight of silica particles 1 and 1.4 parts by weight of silica particles 6 are added to 100 parts by weight of toner classification product A, and externally mixed with a Henschel mixer to obtain a magnetic one-component developer 7. Evaluation was performed in the same manner as in Example 1.
The strong adhesion ratio of silica particles in developer 7 was 17%.
［実施例８］
トナー分級品Ａ１００重量部に対して、シリカ粒子１を０．８重量部、シリカ粒子６を０．６重量部、シリカ粒子８を０．６重量部添加しヘンシェルミキサーで外添混合し、磁性一成分現像剤８を得て、実施例１と同様に評価を行った。
なお、現像剤８におけるシリカ粒子の強付着割合は３０％であった。
[Example 8]
To 100 parts by weight of toner classification product A, 0.8 parts by weight of silica particles 1, 0.6 parts by weight of silica particles 6 and 0.6 parts by weight of silica particles 8 are added and externally mixed with a Henschel mixer, and magnetically added. A one-component developer 8 was obtained and evaluated in the same manner as in Example 1.
The strong adhesion ratio of silica particles in the developer 8 was 30%.
［実施例９］
トナー分級品Ａ１００重量部に対して、シリカ粒子４を０．８重量部、シリカ粒子６を１．４重量部添加しヘンシェルミキサーで外添混合し、磁性一成分現像剤９を得て、実施例１と同様に評価を行った。
なお、現像剤９におけるシリカ粒子の強付着割合は、１９％であった。
[Example 9]
0.8 parts by weight of silica particles 4 and 1.4 parts by weight of silica particles 6 are added to 100 parts by weight of toner classification product A, and externally added and mixed with a Henschel mixer to obtain a magnetic one-component developer 9. Evaluation was performed in the same manner as in Example 1.
The strong adhesion ratio of silica particles in developer 9 was 19%.
［比較例１］
トナー分級品Ａ１００重量部に対して、シリカ粒子６を１．４重量部添加しヘンシェルミキサーで外添混合し、磁性一成分現像剤１０を得て、実施例１と同様に評価を行った。
なお、現像剤９におけるシリカ粒子の強付着割合８％であった。
[Comparative Example 1]
1.4 parts by weight of silica particles 6 was added to 100 parts by weight of toner classification product A, and externally added and mixed with a Henschel mixer to obtain a magnetic one-component developer 10, which was evaluated in the same manner as in Example 1.
The strong adhesion ratio of silica particles in the developer 9 was 8%.
［比較例２］
実施例１においてシリカ粒子１をシリカ粒子５に変更した以外は同様にして、磁性一成分現像剤１１を得て、実施例１と同様に評価を行った。
なお、現像剤１１におけるシリカ粒子の強付着割合６％であった。
[Comparative Example 2]
A magnetic one-component developer 11 was obtained in the same manner as in Example 1 except that the silica particles 1 were changed to the silica particles 5 and evaluated in the same manner as in Example 1.
The strong adhesion ratio of silica particles in the developer 11 was 6%.
［比較例３］
トナー分級品Ａ１００重量部に対して、シリカ粒子１を１．７重量部、シリカ粒子６を０．７重量部添加しヘンシェルミキサーで外添混合し、磁性一成分現像剤１２を得て、実施例１と同様に評価を行った。
なお、現像剤１２におけるシリカ粒子の強付着割合は５４％であった。
[Comparative Example 3]
With respect to 100 parts by weight of the toner classified product A, 1.7 parts by weight of silica particles 1 and 0.7 parts by weight of silica particles 6 are added and externally mixed with a Henschel mixer to obtain a magnetic one-component developer 12. Evaluation was performed in the same manner as in Example 1.
The strong adhesion ratio of silica particles in the developer 12 was 54%.
［比較例４］
トナー分級品Ａ１００重量部に対して、シリカ粒子１を０．８重量部、シリカ粒子１０を１．４重量部添加しヘンシェルミキサーで外添混合し、磁性一成分現像剤１３を得て、実施例１と同様に評価を行った。
なお、現像剤１３におけるシリカ粒子の強付着割合は２３％であった。
[Comparative Example 4]
0.8 parts by weight of silica particles 1 and 1.4 parts by weight of silica particles 10 are added to 100 parts by weight of toner classification product A, and externally added and mixed with a Henschel mixer to obtain a magnetic one-component developer 13. Evaluation was performed in the same manner as in Example 1.
The strong adhesion ratio of silica particles in the developer 13 was 23%.
［比較例５］
トナー分級品Ａ１００重量部に対して、シリカ粒子９を０．８重量部、シリカ粒子６を１．４重量部添加しヘンシェルミキサーで外添混合し、磁性一成分現像剤１４を得て、実施例１と同様に評価を行った。
なお、現像剤１４におけるシリカ粒子の強付着割合は３８％であった。
[Comparative Example 5]
0.8 parts by weight of silica particles 9 and 1.4 parts by weight of silica particles 6 are added to 100 parts by weight of toner classification product A, and externally mixed with a Henschel mixer to obtain a magnetic one-component developer 14. Evaluation was performed in the same manner as in Example 1.
The strong adhesion ratio of silica particles in the developer 14 was 38%.
評価結果を表１に示す。 The evaluation results are shown in Table 1.
表１に示す通り、外添剤が１次粒径の異なる少なくとも２種類のシリカ粒子群を含み、第１のシリカ粒子群は、１次粒子の数平均粒径が２５ｎｍ以上５００ｎｍ以下であり、第２のシリカ粒子群は、１次粒子の数平均粒径が５ｎｍ以上２０ｎｍ以下であって、外添剤に含まれるシリカ粒子全体の強付着割合が、１５％以上５０％以下の場合に、画像濃度および画像濃度維持性に優れ、画質欠陥の少ない優れた画像を安定的に得られることが分かった。 As shown in Table 1, the external additive includes at least two types of silica particle groups having different primary particle sizes, and the first silica particle group has a number average particle size of primary particles of 25 nm or more and 500 nm or less, The second silica particle group has a number average particle size of primary particles of 5 nm to 20 nm, and the strong adhesion ratio of the entire silica particles contained in the external additive is 15% to 50%. It was found that an excellent image having excellent image density and image density maintenance and having few image quality defects can be stably obtained.
１００…画像形成装置
１０７…電子写真感光体
１０８…帯電装置
１０９…電源
１１０…露光装置
１１１…現像装置
１１２…転写装置
１１３…クリーニング装置
１１４…除電器
１１５…定着装置
５００…転写体
DESCRIPTION OF
Claims (3)
前記外添剤は、１次粒径の異なる少なくとも２種のシリカ粒子群からなるシリカ粒子を含み、
第１のシリカ粒子群は、Ａｌ ２ Ｏ ３ 又はＴｉＯ ２ にて被覆され且つその表面がシランカップリング剤で処理され、１次粒子の数平均粒径が４０ｎｍ以上２００ｎｍ以下であり、前記トナー粒子１００重量部に対し０．１重量部以上２重量部以下含有され、
第２のシリカ粒子群は、ジメチルシリコーンオイル又はヘキサメチルシラザンで処理され、１次粒子の数平均粒径が１２ｎｍ以上１６ｎｍ以下であり、前記トナー粒子１００重量部に対し０．５重量部以上５重量部以下含有され、
前記外添剤に含まれるシリカ粒子全体の強付着割合が、１５％以上５０％以下であることを特徴とする磁性一成分現像剤。 A binder resin, a magnetic one-component developer containing the toner particles and an external additive comprising a magnetic substance and a wax,
The external additive includes silica particles composed of at least two types of silica particles having different primary particle sizes,
The first silica particles are coated and the surface at Al 2 O 3 or TiO 2 is treated with a silane coupling agent, and the number average particle size of the primary particles is 40 nm or more size less than 200 nm, the 0.1 to 2 parts by weight with respect to 100 parts by weight of toner particles,
The second silica particle group is treated with dimethyl silicone oil or hexamethylsilazane, and the number average particle diameter of the primary particles is 12 nm or more and 16 nm or less, and 0.5 parts by weight with respect to 100 parts by weight of the toner particles. More than 5 parts by weight,
A magnetic one-component developer, wherein the ratio of strong adhesion of the entire silica particles contained in the external additive is 15% or more and 50% or less.
前記現像剤が、請求項１に記載の磁性一成分現像剤であることを特徴とする画像形成方法。 At least a step of forming an electrostatic latent image on the electrostatic carrier, a step of developing the electrostatic latent image with a developer to form a toner image on the electrostatic carrier, and A step of transferring from an electrostatic carrier onto a transfer member, and a step of fixing the toner image transferred onto the transfer member onto the transfer member by a heat fixing roll and a pressure member pressed against the heat fixing roll; An image forming method comprising:
The image forming method according to claim 1, wherein the developer is a magnetic one-component developer according to claim 1.
前記現像装置に含有される前記現像剤が、請求項１に記載の磁性一成分現像剤であることを特徴とする画像形成装置。 At least an electrostatic carrier, a charging device for charging the electrostatic carrier, an exposure device for exposing the charged electrostatic carrier to form an electrostatic latent image, and developing the electrostatic latent image with a developer A developing device that forms a toner image by developing the toner image, and a transfer device that transfers the toner image from the electrostatic carrier to a transfer body,
The image forming apparatus according to claim 1, wherein the developer contained in the developing device is the magnetic one-component developer according to claim 1.
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| JP6287272B2 (en) * | 2013-03-25 | 2018-03-07 | 三菱ケミカル株式会社 | Magnetic toner and electrophotographic cartridge |
| US9304422B2 (en) * | 2013-12-26 | 2016-04-05 | Canon Kabushiki Kaisha | Magnetic toner |
| JP6335656B2 (en) * | 2014-05-30 | 2018-05-30 | キヤノン株式会社 | Magnetic toner |
| JP6520471B2 (en) | 2015-06-29 | 2019-05-29 | 株式会社リコー | Toner, developer, developer containing unit and image forming apparatus |
| JP6915449B2 (en) * | 2017-08-21 | 2021-08-04 | コニカミノルタ株式会社 | Toner for electrostatic latent image development and two-component developer |
| JP7396921B2 (en) * | 2020-02-13 | 2023-12-12 | シャープ株式会社 | Toner and its manufacturing method, and developer containing the same |
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| JPH08272136A (en) * | 1995-03-29 | 1996-10-18 | Canon Inc | Toner and image forming method |
| JPH1097098A (en) * | 1996-07-31 | 1998-04-14 | Canon Inc | Magnetic black toner for developing electrostatic latent image and multicolor or full-color image forming method |
| JPH1124301A (en) * | 1997-07-01 | 1999-01-29 | Fuji Xerox Co Ltd | One-component developing toner and one-component developing device using the same |
| JPH11143115A (en) * | 1997-11-10 | 1999-05-28 | Fuji Xerox Co Ltd | Electrophotographic developer |
| JP2001005220A (en) * | 1999-06-22 | 2001-01-12 | Matsushita Electric Ind Co Ltd | Color toner and color electrophotographic method |
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| JPH08272136A (en) * | 1995-03-29 | 1996-10-18 | Canon Inc | Toner and image forming method |
| JPH1097098A (en) * | 1996-07-31 | 1998-04-14 | Canon Inc | Magnetic black toner for developing electrostatic latent image and multicolor or full-color image forming method |
| JPH1124301A (en) * | 1997-07-01 | 1999-01-29 | Fuji Xerox Co Ltd | One-component developing toner and one-component developing device using the same |
| JPH11143115A (en) * | 1997-11-10 | 1999-05-28 | Fuji Xerox Co Ltd | Electrophotographic developer |
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