JPH0764318A - Toner and developer for developing electrostatic charge image - Google Patents
Toner and developer for developing electrostatic charge imageInfo
- Publication number
- JPH0764318A JPH0764318A JP5213010A JP21301093A JPH0764318A JP H0764318 A JPH0764318 A JP H0764318A JP 5213010 A JP5213010 A JP 5213010A JP 21301093 A JP21301093 A JP 21301093A JP H0764318 A JPH0764318 A JP H0764318A
- Authority
- JP
- Japan
- Prior art keywords
- hydrophobic silica
- developing
- toner
- magnetic
- electrostatic charge
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Dry Development In Electrophotography (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、静電荷像現像用トナー
及び現像剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing toner and a developer.
【０００２】[0002]
【従来の技術】従来、トナー及び現像剤に外添するため
の微粒子シリカとして、疎水性シリカ自体は公知のもの
である。すなわち、疎水性シリカは特開昭55-159450、
同58-80651、同59-52255等の公報に記載されているごと
く、親水性シリカに各種カップリング剤処理を行なうこ
とにより得ることができる。しかし、各種カップリング
剤を使用して親水性シリカ表面を疎水化する方法は容易
に疎水化することができる反面、カップリング剤は親水
性シリカ表面の水酸基と反応して副産物として塩酸やア
ンモニア等の揮発性成分を生成する。2. Description of the Related Art Conventionally, hydrophobic silica itself has been known as fine particle silica for external addition to toners and developers. That is, hydrophobic silica is disclosed in JP-A-55-159450,
As described in JP-A-58-80651 and JP-A-59-52255, it can be obtained by treating hydrophilic silica with various coupling agents. However, the method of hydrophobizing the hydrophilic silica surface using various coupling agents can easily hydrophobize it, while the coupling agent reacts with the hydroxyl groups on the hydrophilic silica surface to produce hydrochloric acid, ammonia, etc. as by-products. To produce volatile components of.
【０００３】また、シリカ自体の一次粒子径は一般的に
5〜100nm程度の粒径と細かく、表面積も100m2/g程度と
大きいために揮発成分自体が粒子表面に吸着された状態
となっている。このため、使用にあたってはこれら揮発
性副産物が経時で遊離し現像用キャリアに対する汚染や
現像スリーブに対する汚染、さらにはトナー自体の帯電
量を変動させるという問題を有している。すなわち、揮
発成分の存在によって、いわゆる帯電量の増加あるいは
減少といった問題を起こし、特に薄層形成方式の現像に
於いては外添剤の帯電性が支配因子となりうるために画
像濃度の減少やカブリの発生等の問題を起こす。The primary particle size of silica itself is generally
Since the particle size is as small as 5 to 100 nm and the surface area is as large as 100 m 2 / g, the volatile component itself is adsorbed on the particle surface. Therefore, upon use, these volatile by-products are liberated over time, which causes a problem that the carrier for development is contaminated, the developing sleeve is contaminated, and the charge amount of the toner itself is changed. That is, the presence of the volatile component causes a problem of so-called increase or decrease of the charge amount, and particularly in the development of the thin layer forming method, the chargeability of the external additive may become a controlling factor, so that the image density is reduced or the fog is reduced. Cause problems such as occurrence of.
【０００４】しかし、従来はこれらに対する問題意識が
無く、有効な対策も見いだされていなかった。However, conventionally, there is no awareness of these problems and no effective countermeasure has been found.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、使用
にあたって現像用キャリアに対する汚染や現像スリーブ
に対する汚染、さらにはトナー自体の帯電量を変動させ
るという問題を有しない疎水性シリカ及び疎水性シリカ
を添加した現像剤の開発にある。本発明は遊離した副産
物を除去することによって、上記問題を解決することが
できることを見いだした結果によるものである。DISCLOSURE OF THE INVENTION An object of the present invention is to provide a hydrophobic silica and a hydrophobic silica which are free from the problems of contamination of a developing carrier, contamination of a developing sleeve, and fluctuation of the charge amount of the toner itself in use. It is in the development of the developer which added. The present invention is based on the finding that the above problems can be solved by removing free byproducts.
【０００６】[0006]
【課題を解決するための手段】上記問題を解決するため
に鋭意検討した結果、疎水性シリカに含まれる揮発成分
の残留によるpＨ値の変動が少ない疎水性シリカを使用
することによって上記問題を解決出来ることを見いだし
たものである。すなわち、環境による変動及び使用条件
に於ける変動を防止するためには、機内温度及び使用環
境の変動があっても外添剤が変化しないことが重要であ
る。Means for Solving the Problems As a result of intensive studies to solve the above problems, the above problems can be solved by using hydrophobic silica in which the fluctuation of the pH value due to the residual volatile components contained in the hydrophobic silica is small. It is a finding of what can be done. That is, in order to prevent the fluctuation due to the environment and the fluctuation in the usage conditions, it is important that the external additive does not change even if the temperature inside the machine and the usage environment change.
【０００７】このためには、機内温度の上昇による揮発
成分の変化を防止することが必要であり、高温環境に於
いて、機内の温度、特に現像器内部の温度が50℃程度ま
で上昇する可能性があり、この条件下でpＨ値が変動し
ないことが性能変動の少ない現像剤を提供することにな
るのである。To this end, it is necessary to prevent changes in volatile components due to an increase in the temperature inside the machine, and in a high temperature environment, the temperature inside the machine, especially the temperature inside the developing device, can rise to about 50 ° C. That is, the fact that the pH value does not fluctuate under these conditions provides a developer with less performance fluctuation.
【０００８】すなわち、少なくとも着色剤と樹脂とから
なる着色粒子に疎水性シリカを添加混合してなる静電荷
像現像用トナーに於いて、該疎水性シリカが50℃、相対
湿度50％の条件下において24時間放置前のpＨと放置後
のpＨの値の変化が1.0以下の疎水性シリカであることを
特徴とする静電荷像現像用トナー。That is, in a toner for developing an electrostatic image, wherein hydrophobic silica is added to and mixed with colored particles composed of at least a colorant and a resin, the hydrophobic silica is at a temperature of 50 ° C. and a relative humidity of 50%. 2. A toner for developing an electrostatic charge image, which comprises hydrophobic silica having a pH value change of 1.0 or less after being left for 24 hours and after being left for 24 hours.
【０００９】又、 少なくとも樹脂と着色剤とからなる
着色粒子に疎水性シリカを添加混合してなる静電荷像現
像用トナーとキャリアからなる二成分現像剤を20〜500
μmの層厚で現像領域へ搬送し感光体上の静電潜像を現
像する現像方法に用いられる現像剤に於いて、該疎水性
シリカが50℃、相対湿度50％の条件下において24時間放
置前のpＨと放置後のpＨの値の変化が1.0以下の疎水性
シリカであることを特徴とする静電荷像現像用二成分現
像剤。Further, a two-component developer comprising a toner for developing an electrostatic image and a carrier prepared by adding and mixing hydrophobic silica to colored particles comprising at least a resin and a colorant is used in an amount of 20 to 500.
In a developer used in a developing method for developing an electrostatic latent image on a photoconductor by transporting it to a developing area with a layer thickness of μm, the hydrophobic silica is 24 hours under the condition of 50 ° C. and relative humidity of 50%. A two-component developer for developing an electrostatic charge image, which is a hydrophobic silica having a pH value change of 1.0 or less before and after being left.
【００１０】少なくとも樹脂と磁性粒子粉とからなる着
色粒子に疎水性シリカを添加混合した磁性一成分現像剤
を20〜500μmの層厚で現像領域へ搬送し感光体上の静電
潜像を現像する現像方法に用いられる現像剤に於いて、
該疎水性シリカが50℃、相対湿度50％の条件下において
24時間放置前のpＨと放置後のpＨの値の変化が1.0以下
の疎水性シリカであることを特徴とする静電荷像現像用
磁性一成分現像剤。A magnetic one-component developer in which hydrophobic silica is added to and mixed with colored particles composed of at least a resin and magnetic particle powder is conveyed to a development area in a layer thickness of 20 to 500 μm to develop an electrostatic latent image on a photoreceptor. In the developer used in the developing method,
When the hydrophobic silica is at 50 ° C and relative humidity of 50%,
A magnetic one-component developer for developing an electrostatic charge image, which is a hydrophobic silica having a pH value change of 1.0 or less before and after being left for 24 hours.
【００１１】少なくとも樹脂と着色剤とからなる着色粒
子に疎水性シリカを添加混合した非磁性一成分現像剤を
20〜500μmの層厚で現像領域へ搬送し感光体上の静電潜
像を現像する現像方法に用いられる現像剤に於いて、該
疎水性シリカが50℃、相対湿度50％の条件下において24
時間放置前のpＨと放置後のpＨの値の変化が1.0以下の
疎水性シリカであることを特徴とする静電荷像現像用非
磁性一成分現像剤によって、本発明の目的は達成され
る。A non-magnetic one-component developer in which hydrophobic silica is added to and mixed with colored particles composed of at least a resin and a colorant
In a developer used in a developing method for developing an electrostatic latent image on a photoconductor by transporting it to a developing region with a layer thickness of 20 to 500 μm, the hydrophobic silica is at 50 ° C. under a relative humidity of 50%. twenty four
The object of the present invention is achieved by a non-magnetic one-component developer for developing an electrostatic charge image, which is characterized in that the hydrophobic silica has a pH value change before and after standing for 1 hour and a pH value after standing time is 1.0 or less.
【００１２】上記のごとき50℃相対湿度50％の条件下に
おいて24時間放置前のpＨと放置後のpＨの変化が1.0以
下の疎水性シリカは、いわゆる疎水化のためのカップリ
ング剤によって親水性シリカを処理し、ついで、30〜10
0℃の温度条件下で乾燥させ揮発成分を除去し、pＨが安
定した状態とすることによって得ることができる。Hydrophobic silica having a pH before and after being left for 24 hours under a condition of 50 ° C. and a relative humidity of 50% as described above is 1.0 or less, so that the hydrophobic silica is hydrophilic by a so-called coupling agent for hydrophobization. Treat the silica, then 30 to 10
It can be obtained by drying under a temperature condition of 0 ° C. to remove volatile components and stabilizing the pH.
【００１３】また、30〜100℃の温度条件下で減圧工程
を使用して揮発成分を除去する方法でもよい。この場
合、減圧条件としては1〜100mmHgの条件が好ましい。上
記方法に於いて、100℃以上の高い温度条件では、未反
応のカプリング剤が反応したりさらにはシリカ表面が変
質等の問題を生じるため、好ましくない。また、30℃以
下の温度条件が低くすぎる場合には揮発成分が除去でき
ず、経時変化を防止することができない。Alternatively, a method of removing volatile components by using a depressurizing step under a temperature condition of 30 to 100 ° C. may be used. In this case, the reduced pressure condition is preferably 1 to 100 mmHg. In the above method, under a high temperature condition of 100 ° C. or higher, unreacted coupling agent reacts, and further, the silica surface causes problems such as alteration, which is not preferable. Further, if the temperature condition of 30 ° C. or lower is too low, the volatile components cannot be removed and it is impossible to prevent the change with time.
【００１４】カップリング剤の例としては、ヘキサメチ
ルジシラザン、ジクロロジメチルシラン、3-アミノプロ
ピルトリエトキシシラン、アルキルトリアルコキシシラ
ン等のシランカップリング剤が使用されるが、pＨの変
動は特に塩酸やアンモニアが脱離するヘキサメチルジシ
ラザンやジクロロジメチルシランで顕著である。As an example of the coupling agent, a silane coupling agent such as hexamethyldisilazane, dichlorodimethylsilane, 3-aminopropyltriethoxysilane, alkyltrialkoxysilane or the like is used. Hexamethyldisilazane and dichlorodimethylsilane, which release ammonia and ammonia, are remarkable.
【００１５】一方、シリカの例としては、一次粒径が５
〜500nmのものが使用される。特に一次粒径が７〜100nm
のものが流動性付与及び帯電性付与の観点で好適であ
る。この一次粒径は走査型電子顕微鏡により観察して画
像解析によって測定される個数規準の平均粒径を示す。On the other hand, as an example of silica, the primary particle size is 5
A ~ 500 nm one is used. Especially the primary particle size is 7-100nm
The ones are preferable from the viewpoint of imparting fluidity and charging property. This primary particle size indicates a number-based average particle size measured by image analysis by observing with a scanning electron microscope.
【００１６】[0016]
〈薄層形成の定義〉本発明における薄層形成方式とは現
像スリーブ表面に現像領域で20〜500μmのトナー層を形
成する方式を示す。この薄層形成を行う場合には磁気の
力を使用する磁性ブレードや現像スリーブ表面にトナー
層規制棒を押圧する方式等がある。さらに、ウレタンブ
レードや燐青銅板等を現像スリーブ表面に接触させトナ
ー層を規制する方法もある。<Definition of thin layer formation> The thin layer formation method in the present invention means a method of forming a toner layer of 20 to 500 μm on the surface of the developing sleeve in the developing region. When forming this thin layer, there is a method of pressing a toner layer regulating rod against the surface of a developing blade or a magnetic blade that uses magnetic force. Further, there is also a method of contacting a urethane blade, a phosphor bronze plate, or the like with the surface of the developing sleeve to regulate the toner layer.
【００１７】現像スリーブと感光体表面の間隙はトナー
層よりも大きくても小さくても良い。さらに、現像バイ
アスとしてDC成分のみ付与する方式でも良いし、ACバイ
アスを印加する方式のいずれでも良い。The gap between the developing sleeve and the surface of the photoreceptor may be larger or smaller than the toner layer. Further, either the method of applying only the DC component as the developing bias or the method of applying the AC bias may be used.
【００１８】本発明の現像剤は特に上記薄層形成方式に
好適に使用される。この場合、トナーとキャリアを混合
したいわゆる二成分現像方式及び微粒子の磁性粉を含有
する磁性トナーのみより構成される一成分磁性現像方式
や磁性粉を含有しない非磁性トナーのみにより構成され
る非磁性一成分現像方式に好適に使用することができ
る。The developer of the present invention is particularly preferably used in the above thin layer forming system. In this case, a so-called two-component development method in which toner and carrier are mixed, a one-component magnetic development method composed only of magnetic toner containing fine magnetic powder, and a non-magnetic composition composed only of non-magnetic toner containing no magnetic powder It can be suitably used for a one-component developing system.
【００１９】薄層形成のための押圧規制部材の押圧力
は、１〜15gf／mmがよく、押圧力が小さい場合には規制
力が不足するために搬送が不安定になる。一方、押圧力
が大きい場合には現像剤に対するストレスが大きくなる
ため、現像剤の耐久性が低下する。本発明に用いられる
薄層形成方式において、特に好ましい範囲は３〜10gf／
mmである。The pressing force of the pressing regulating member for forming the thin layer is preferably 1 to 15 gf / mm, and when the pressing force is small, the regulation force is insufficient and the conveyance becomes unstable. On the other hand, when the pressing force is large, the stress on the developer increases, so that the durability of the developer decreases. In the thin layer forming method used in the present invention, a particularly preferable range is 3 to 10 gf /
mm.
【００２０】〈現像剤の構成〉着色粒子（トナー)は結
着樹脂と着色剤と必要に応じて使用されるその他の添加
剤とを含有してなり、その平均粒径は体積平均粒径で通
常１〜30μm、好ましくは５〜20μmである。トナーを構
成する結着樹脂としては特に限定されず、従来公知の種
々の樹脂が用いられる。例えば、スチレン系樹脂、アク
リル系樹脂、スチレンーアクリル系樹脂、ポリエステル
樹脂等があげられる。<Structure of Developer> The colored particles (toner) contain a binder resin, a colorant, and other additives used as necessary, and the average particle size is a volume average particle size. It is usually 1 to 30 μm, preferably 5 to 20 μm. The binder resin that constitutes the toner is not particularly limited, and various conventionally known resins can be used. For example, styrene resin, acrylic resin, styrene-acrylic resin, polyester resin, etc. may be mentioned.
【００２１】トナーを構成する着色剤としては特に限定
されず、従来公知の種々の材料が使用可能である。例え
ばカーボンブラック、ニグロシン染料、アニリンブル
ー、カルコイルブルー、クロムイエロー、ウルトラマリ
ンブルー、デュポンオイルレッド、キノリンイエロー、
メチレンブルークロライド、フタロシアニンブルー、マ
ラカイトグリーンオクサレート、ローズベンガル等が挙
げられる。The colorant constituting the toner is not particularly limited, and various conventionally known materials can be used. For example, carbon black, nigrosine dye, aniline blue, calcoil blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow,
Examples thereof include methylene blue chloride, phthalocyanine blue, malachite green oxalate, and rose bengal.
【００２２】その他の添加剤としては例えばサリチル酸
誘導体、アゾ系金属錯体等の荷電制御剤、低分子量ポリ
オレフィン、カルナウバワックス等の定着性改良剤等が
挙げられる。Examples of other additives include salicylic acid derivatives, charge control agents such as azo metal complexes, low molecular weight polyolefins, and fixability improving agents such as carnauba wax.
【００２３】また、一成分磁性トナーを得る場合には着
色粒子に添加剤として磁性体粒子が含有される。磁性体
粒子としては数平均一次粒子径が0.1〜2.0μmのフェラ
イトやマグネタイト等の磁性粒子が用いられる。磁性体
粒子の添加量は着色粒子中の20〜70重量％である。When a one-component magnetic toner is obtained, the colored particles contain magnetic particles as an additive. As the magnetic particles, magnetic particles such as ferrite and magnetite having a number average primary particle diameter of 0.1 to 2.0 μm are used. The amount of the magnetic particles added is 20 to 70% by weight of the colored particles.
【００２４】また、トナーには上記疎水性シリカ以外
に、クリーニング助剤として数平均粒径が0.1〜2.0μm
のスチレン-アクリル樹脂微粒子やステアリン酸亜鉛の
様な高級脂肪酸金属塩を添加してもよい。In addition to the above hydrophobic silica, the toner has a number average particle size of 0.1 to 2.0 μm as a cleaning aid.
Styrene-acrylic resin fine particles, or higher fatty acid metal salt such as zinc stearate may be added.
【００２５】本発明に於ける現像剤は、トナーとキャリ
アとを混合して、二成分現像剤として使用されるか、あ
るいは磁性トナーである場合は当該磁性トナーのみによ
り一成分現像剤として使用される。さらに、上記トナー
のみで非磁性一成分現像剤として使用しても良い。The developer in the present invention is used as a two-component developer by mixing a toner and a carrier, or when it is a magnetic toner, it is used as a one-component developer only with the magnetic toner. It Further, the toner alone may be used as a non-magnetic one-component developer.
【００２６】二成分現像剤を構成するキャリアとしては
鉄・フェライト等の磁性材料粒子のみで構成される非被
覆キャリア、磁性材料粒子表面を樹脂等によって被覆し
た樹脂被覆キャリアあるいは、樹脂と磁性粉とを混合し
て得られる樹脂分散型キャリアのいずれを使用してもよ
い。このキャリアの平均粒径は体積平均粒径で30〜150
μmが好ましい。The carrier constituting the two-component developer is an uncoated carrier composed only of magnetic material particles such as iron and ferrite, a resin coated carrier in which the surface of the magnetic material particles is coated with resin, or a resin and magnetic powder. Any of the resin dispersion type carriers obtained by mixing the above may be used. The average particle size of this carrier is 30 to 150 in terms of volume average particle size.
μm is preferred.
【００２７】〈揮発成分除去工程の具体的例〉揮発成分
の除去は、30〜100℃の条件に設定した乾燥器中で乾燥
させる方法や、上記乾燥時に同時に減圧し、乾燥を促進
してもよい。本明細書に記載されているように、乾燥直
後にpＨを測定し、ついで50℃相対湿度50％環境下に24
時間放置し、pＨを測定する。この両者のpＨ値の差が本
発明範囲内になるまで乾燥を継続する。<Specific Example of Volatile Component Removal Step> The volatile component can be removed by a method of drying in a dryer set to a condition of 30 to 100 ° C., or by reducing the pressure at the same time during the drying to accelerate the drying. Good. The pH was measured immediately after drying as described herein, and then measured at 50 ° C. and 50% relative humidity in an environment of 24%.
Let stand for a time and measure pH. Drying is continued until the difference between the pH values of the both falls within the range of the present invention.
【００２８】〈pＨ値測定法〉疎水性シリカのpＨ測定方
法は、疎水性シリカ10gを水：メタノール＝１：１溶液1
00mlに添加混合し、分散させる。ついで、pＨメーター
により上記分散液のpＨを測定する方法である。<Method of measuring pH value> The pH of hydrophobic silica is measured by adding 10 g of hydrophobic silica to a solution of water: methanol = 1: 1.
Add to 00 ml, mix and disperse. Next, it is a method of measuring the pH of the above dispersion liquid with a pH meter.
【００２９】[0029]
【実施例】以下、実施例を挙げて本発明を詳細に説明す
るが、本発明の態様はこれに限定されない。なお、本実
施例中に記載された部とは、重量部を示す。The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto. In addition, the part described in this example shows a weight part.
【００３０】＜疎水性シリカ作製例＞作製例１：一次粒
径が17nmの親水性シリカに対してジメチルジクロロシラ
ン処理し、疎水性シリカを得た。このものの調整直後の
pＨ値は4.0であった。このものを50℃の乾燥器に投入し
て48時間乾燥させた。乾燥後のpＨは5.1であった。つい
で、50℃相対湿度50％の条件に調整した乾燥器へ投入し
て24時間乾燥させた。乾燥後のpＨは5.4であった。これ
を「疎水性シリカ１」とする。<Preparation Example of Hydrophobic Silica> Preparation Example 1: Hydrophilic silica having a primary particle size of 17 nm was treated with dimethyldichlorosilane to obtain hydrophobic silica. Immediately after adjustment of this thing
The pH value was 4.0. This was placed in a dryer at 50 ° C. and dried for 48 hours. The pH after drying was 5.1. Then, it was placed in a dryer adjusted to 50 ° C. and 50% relative humidity and dried for 24 hours. The pH after drying was 5.4. This is designated as "hydrophobic silica 1".
【００３１】作製例２：一次粒径が12nmの親水性シリカ
に対してヘキサメチルジシラザン処理し、疎水性シリカ
を得た。このものの調整直後のpＨは7.6であった。この
ものを、60℃の乾燥器に投入して100時間乾燥させた。
乾燥後のpＨは6.0であった。ついで、50℃相対湿度50％
の条件に調整した乾燥器へ投入して24時間乾燥させた。
乾燥後のpＨは5.9であった。これを「疎水性シリカ2」とす
る。Preparation Example 2: Hydrophilic silica having a primary particle size of 12 nm was treated with hexamethyldisilazane to obtain hydrophobic silica. The pH of this product immediately after adjustment was 7.6. This was placed in a dryer at 60 ° C. and dried for 100 hours.
The pH after drying was 6.0. Then, 50 ℃ relative humidity 50%
It was put into a dryer adjusted to the conditions of and dried for 24 hours.
The pH after drying was 5.9. This is designated as "hydrophobic silica 2".
【００３２】作製例３：作製例２に於いて60℃の乾燥器
で乾燥させた代わりに60℃の温度条件下10mmHgの減圧下
24時間乾燥させた。乾燥後のpＨは5.9であった。つい
で、50℃相対湿度50％の条件に調整した乾燥器へ投入し
て24時間乾燥させた。乾燥後のpＨは5.8であった。これ
を「疎水性シリカ3」とする。Preparation Example 3: Instead of drying with a dryer at 60 ° C. in Preparation Example 2, under a reduced pressure of 10 mmHg under a temperature condition of 60 ° C.
It was dried for 24 hours. The pH after drying was 5.9. Then, it was placed in a dryer adjusted to 50 ° C. and 50% relative humidity and dried for 24 hours. The pH after drying was 5.8. This is designated as "hydrophobic silica 3".
【００３３】＜トナー作製例＞ 非磁性トナー作製例：ポリエステル樹脂100部とカーボ
ンブラック８部とを混合し、通常の条件に従って練肉・
粉砕・分級して体積平均粒径が10μの非磁性着色粒子を
得た。このものに、上記本発明の疎水性シリカを0.4重
量％添加して本発明のトナーを得たこれを「トナー１」
〜「トナー３」とする。一方、比較用として上記疎水性
シリカ作製例１及び２で作製した処理直後のシリカを乾
燥工程を経ずに添加して比較用トナーを作製した。これを
「比較トナー１」「比較トナー２」とする。なお、この
乾燥工程を経ない疎水性シリカの50℃相対湿度50％下に
24時間放置後のpＨは作製例１では5.4であり、作製例２
では6.5であった。<Preparation example of toner> Preparation example of non-magnetic toner: 100 parts of polyester resin and 8 parts of carbon black are mixed and kneaded according to the usual conditions.
The particles were pulverized and classified to obtain non-magnetic colored particles having a volume average particle diameter of 10μ. The toner of the present invention was obtained by adding 0.4% by weight of the above hydrophobic silica of the present invention to this toner.
~ "Toner 3". On the other hand, for comparison, the silica immediately after the treatment prepared in the above-mentioned hydrophobic silica preparation examples 1 and 2 was added without a drying step to prepare a comparative toner. These will be referred to as “comparative toner 1” and “comparative toner 2”. It should be noted that the hydrophobic silica that has not undergone this drying process is kept at 50 ° C and 50% relative humidity.
The pH after leaving for 24 hours was 5.4 in Preparation Example 1, and
Was 6.5.
【００３４】磁性トナー作製例：ポリエステル樹脂100
部と磁性粉（マグネタイト）50部と荷電制御剤（サリチ
ル酸誘導体の金属錯体）１部とを混合し、通常の条件に
従って練肉・粉砕・分級し体積平均粒径が11μの磁性着
色粒子を得た。この磁性着色粒子に、上記本発明の疎水
性シリカを0.4重量％添加して本発明のトナーを得た。
これを「トナー４」〜「トナー６」とする。一方、比較
用として上記疎水性シリカ作製例１〜２で作製した処理
直後のシリカを乾燥工程を経ずに添加して比較用トナー
を作製した。これを「比較トナー３」「比較トナー４」
とする。Magnetic toner preparation example: polyester resin 100
And 50 parts of magnetic powder (magnetite) and 1 part of a charge control agent (metal complex of salicylic acid derivative) are mixed, and the mixture is kneaded, crushed and classified according to ordinary conditions to obtain magnetic colored particles having a volume average particle diameter of 11μ. It was 0.4% by weight of the hydrophobic silica of the present invention was added to the magnetic colored particles to obtain a toner of the present invention.
These are designated as "toner 4" to "toner 6". On the other hand, for comparison, silica immediately after the treatment prepared in the above-mentioned hydrophobic silica preparation examples 1 and 2 was added without a drying step to prepare a comparative toner. This is "Comparative Toner 3" and "Comparative Toner 4".
And
【００３５】二成分現像剤調整例：体積平均粒径80μm
のフェライト粒子にスチレン・アクリル樹脂を被覆した
樹脂被覆キャリア100部と上記「トナー１」〜「トナー
３」及び「比較トナー１」「比較トナー２」5部を混合
して二成分系現像剤を得た。Preparation example of two-component developer: volume average particle size 80 μm
100 parts of a resin-coated carrier obtained by coating ferrite particles of styrene / acrylic resin with 5 parts of the above-mentioned "toner 1" to "toner 3" and "comparative toner 1""comparative toner 2" are mixed to prepare a two-component developer. Obtained.
【００３６】磁性一成分現像剤調整例：磁性一成分現像
剤は、上記「トナー４」〜「トナー６」及び「比較トナ
ー３」「比較トナー４」をそのまま使用した。Magnetic One-Component Developer Preparation Example: As the magnetic one-component developer, the above-mentioned "Toner 4" to "Toner 6" and "Comparative Toner 3" and "Comparative Toner 4" were used as they were.
【００３７】非磁性一成分現像剤調整例：非磁性一成分
現像剤は、上記「トナー１」〜「トナー３」及び「比較
トナー１」「比較トナー２」をそのまま使用した。Nonmagnetic One-Component Developer Preparation Example: As the nonmagnetic one-component developer, the above-mentioned "toner 1" to "toner 3" and "comparative toner 1" and "comparative toner 2" were used as they were.
【００３８】＜現像剤評価方法＞上記で調整した現像剤
は下記評価方法に従って評価を実施した。<Developer Evaluation Method> The developer prepared above was evaluated according to the following evaluation method.
【００３９】・二成分現像剤評価条件 コニカ社製のKonica9028を改造して使用した。現像条件
は下記に示す条件である。なお、感光体としては積層型
有機感光体を使用した。Two-component developer evaluation conditions Konica 9028 manufactured by Konica Corporation was modified and used. The developing conditions are as shown below. A laminated organic photoconductor was used as the photoconductor.
【００４０】感光体表面電位＝−550V DCバイアス ＝−250V ACバイアス ＝Vp-p:-50〜-450V 現像領域間隙：Dsd =300μm 押圧規制力 ＝10gf／mm 押圧規制棒 ＝SUS416(磁性ステンレス製)／直径３mm 現像スリーブ ＝20mm ・磁性一成分現像(非接触系)評価方法 評価はコニカ社製レーザープリンタを20枚／分とし、６
極の固定磁石を内臓した直径25mmの磁性ステンレス製の
現像スリーブを有し、現像領域間隙:Ｄsd=0.2mmとし、
現像領域に於ける現像器表面に於けるトナー層を0.15mm
とした非接触方式に改造した。感光体は積層型有機感光
体を使用して現像部電位を−500Ｖとし、現像バイアス
をＶp-p（ピークツウピーク）で−50〜−550ＶのACバイ
アス（周波数２ｋHz）及び−250ＶのDCバイアスを印加
した。Photoconductor surface potential = -550V DC bias = -250V AC bias = Vp-p: -50 to -450V Development area gap: Dsd = 300μm Pressing control force = 10gf / mm Pressing control rod = SUS416 (magnetic stainless steel) ) / Diameter 3 mm Development sleeve = 20 mm ・ Magnetic one-component development (non-contact system) Evaluation method Evaluation was made with a Konica laser printer at 20 sheets / minute and 6
It has a developing sleeve made of magnetic stainless steel with a diameter of 25 mm that incorporates a fixed magnet of the pole, and the developing area gap: Dsd = 0.2 mm,
0.15mm toner layer on the surface of the developing device in the developing area
It was modified to the non-contact method. The photosensitive member is a laminated organic photosensitive member, the developing portion potential is -500V, the developing bias is Vp-p (peak-to-peak), AC bias of -50 to -550V (frequency 2kHz) and DC bias of -250V. Was applied.
【００４１】・非磁性一成分現像評価条件 コニカ社製LP-3110を改造し、現像スリーブとして直径1
8mmのシリコンゴムローラーで形成された弾性スリーブ
を使用し、ウレタンゴムで形成されたトナー層規制部材
を現像スリーブ表面に接触させてトナー層を規制した。
また、感光体と現像スリーブ表面は接触しており、ニッ
プ幅が約２mmとなるように接触している。なお、感光体
は積層型有機感光体を使用している。現像条件は感光体
表面電位を−550Ｖとし、DCバイアスを-450Ｖとして反
転現像した。Non-magnetic one-component development evaluation condition Konica LP-3110 was modified to have a development sleeve with a diameter of 1
An elastic sleeve formed of an 8 mm silicon rubber roller was used, and a toner layer regulating member formed of urethane rubber was brought into contact with the surface of the developing sleeve to regulate the toner layer.
Further, the photosensitive member and the surface of the developing sleeve are in contact with each other so that the nip width is about 2 mm. As the photoconductor, a laminated organic photoconductor is used. The developing conditions were reversal development with the surface potential of the photosensitive member set at -550V and the DC bias set at -450V.
【００４２】（評価項目）上記評価条件を用いて前述の
各現像剤を評価した。評価は高温高湿環境(33℃／相対
湿度80％)下で10万枚の印字をおこない、画像濃度の変
化及びカブリ濃度の変化を測定した。なお、画像濃度は
ベタ黒画像の12箇所を測定し平均化したものである。ま
た、この12箇所測定に於ける最大濃度と最少濃度の差を
測定し、濃度ムラの評価を実施した。これら濃度の測定
は、マクベス社製の反射濃度測定器RD-918を使用し、絶
対反射濃度を測定した。カブリ濃度に関しては紙の濃度
を０とした相対濃度である。実際には、カブリ濃度はベ
タ白画像を印字し、その12箇所の濃度を測定し、平均化
したものである。(Evaluation Item) Each of the above-mentioned developers was evaluated under the above evaluation conditions. The evaluation was performed by printing 100,000 sheets under a high temperature and high humidity environment (33 ° C./80% relative humidity) and measuring the change in image density and the change in fog density. The image density is obtained by measuring 12 points of a solid black image and averaging them. Further, the difference between the maximum density and the minimum density in these 12 measurement points was measured, and the density unevenness was evaluated. For the measurement of these densities, a reflection density measuring device RD-918 manufactured by Macbeth was used to measure absolute reflection densities. The fog density is a relative density when the density of the paper is 0. Actually, the fog density is a value obtained by printing a solid white image, measuring the densities at the 12 points, and averaging.
【００４３】結果を下記表１〜３に示す。The results are shown in Tables 1 to 3 below.
【００４４】[0044]
【表１】 [Table 1]
【００４５】[0045]
【表２】 [Table 2]
【００４６】[0046]
【表３】 [Table 3]
【００４７】以上の結果に示す様に、本発明の疎水性シ
リカを使用した現像剤では高温多湿環境下での現像性の
変化が無く、良好な結果を示した。As shown in the above results, the developer using the hydrophobic silica of the present invention showed no change in developability under a high temperature and high humidity environment and showed good results.
【００４８】[0048]
【発明の効果】本発明により、疎水性シリカを添加した
トナー及び現像剤を用いても、温度、湿度の変動等外部
環境変化による影響を受けにくく、安定性が向上する。According to the present invention, even when a toner and a developer to which hydrophobic silica is added are used, they are hardly affected by changes in the external environment such as changes in temperature and humidity, and the stability is improved.
【００４９】特に薄層形成方式に於いて、相互摩擦性を
安定化し画像濃度が向上しカブリ及び静電オフセットの
発生が防止される。Particularly in the thin layer forming method, mutual friction is stabilized, image density is improved, and fog and electrostatic offset are prevented from occurring.
Claims (5)
粒子に疎水性シリカを添加混合してなる静電荷像現像用
トナーに於いて、該疎水性シリカが50℃、相対湿度50％
の条件下において24時間放置前のpＨと放置後のpＨの値
の変化が1.0以下の疎水性シリカであることを特徴とす
る静電荷像現像用トナー。1. A toner for developing an electrostatic charge image, wherein hydrophobic silica is added to and mixed with colored particles comprising at least a colorant and a resin, wherein the hydrophobic silica is 50 ° C. and relative humidity is 50%.
A toner for developing an electrostatic charge image, which is a hydrophobic silica having a pH value change before and after being left for 24 hours and a pH value after being left for 1.0 hour or less.
粒子に疎水性シリカを添加混合してなる静電荷像現像用
トナーに於いて、疎水性シリカを30〜100℃の温度条件
下で乾燥させ揮発成分を除去したものと、更に50℃相対
湿度50％の条件下で24時間放置したものとのpＨの値の
変化が1.0以下であることを特徴とする静電荷像現像用
トナー。2. A toner for developing an electrostatic charge image, which comprises mixing and mixing hydrophobic silica with colored particles comprising at least a colorant and a resin, wherein the hydrophobic silica is dried under a temperature condition of 30 to 100 ° C. A toner for developing an electrostatic charge image, characterized in that a change in pH value between the one from which volatile components have been removed and the one left to stand under the condition of 50 ° C. and 50% relative humidity for 24 hours is 1.0 or less.
粒子に疎水性シリカを添加混合してなる静電荷像現像用
トナーとキャリアからなる二成分現像剤を20〜500μmの
層厚で現像領域へ搬送し感光体上の静電荷潜像を現像す
る現像方法に用いられる現像剤に於いて、該疎水性シリ
カが50℃、相対湿度50％の条件下において24時間放置前
のpＨと放置後のpＨの値の変化が1.0以下の疎水性シリ
カであることを特徴とする静電荷像現像用二成分現像
剤。3. A two-component developer comprising a toner for electrostatic image development and a carrier, which is obtained by adding and mixing hydrophobic silica to colored particles comprising at least a resin and a colorant, to a developing region in a layer thickness of 20 to 500 μm. A developer used in a developing method for carrying and developing an electrostatic latent image on a photoconductor, wherein the hydrophobic silica is at a pH of 50 ° C. and a relative humidity of 50% for 24 hours before being left and after being left for 24 hours. A two-component developer for developing an electrostatic charge image, which is a hydrophobic silica having a pH value change of 1.0 or less.
着色粒子に疎水性シリカを添加混合した磁性一成分現像
剤を20〜500μmの層厚で現像領域へ搬送し感光体上の静
電潜像を現像する現像方法に用いられる現像剤に於い
て、該疎水性シリカが50℃、相対湿度50％の条件下にお
いて24時間放置前のpＨと放置後のpＨの値の変化が1.0
以下の疎水性シリカであることを特徴とする静電荷像現
像用磁性一成分現像剤。4. An electrostatic latent image on a photoconductor is obtained by transporting a magnetic one-component developer, in which hydrophobic silica is added to and mixed with colored particles composed of at least a resin and magnetic particle powder, to a developing area in a layer thickness of 20 to 500 μm. In the developer used in the developing method for developing the above, the hydrophobic silica has a pH change before and after leaving for 24 hours of 1.0 at a temperature of 50 ° C. and a relative humidity of 50%.
A magnetic one-component developer for developing an electrostatic charge image, comprising the following hydrophobic silica.
粒子に疎水性シリカを添加混合した非磁性一成分現像剤
を20〜500μmの層厚で現像領域へ搬送し感光体上の静電
潜像を現像する現像方法に用いられる現像剤に於いて、
該疎水性シリカが50℃、相対湿度50％の条件下において
24時間放置前のpＨと放置後のpＨの値の変化が1.0以下
の疎水性シリカであることを特徴とする静電荷像現像用
非磁性一成分現像剤。5. A non-magnetic one-component developer obtained by adding hydrophobic silica to colored particles comprising at least a resin and a colorant and mixing the particles with a layer thickness of 20 to 500 .mu.m to a developing area to form an electrostatic latent image on a photoreceptor. In the developer used in the developing method for developing
When the hydrophobic silica is at 50 ° C and relative humidity of 50%,
A non-magnetic one-component developer for developing an electrostatic charge image, which is a hydrophobic silica having a pH value change of 1.0 or less after being left for 24 hours and after being left for 24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5213010A JPH0764318A (en) | 1993-08-27 | 1993-08-27 | Toner and developer for developing electrostatic charge image |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5213010A JPH0764318A (en) | 1993-08-27 | 1993-08-27 | Toner and developer for developing electrostatic charge image |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0764318A true JPH0764318A (en) | 1995-03-10 |
Family
ID=16632006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5213010A Pending JPH0764318A (en) | 1993-08-27 | 1993-08-27 | Toner and developer for developing electrostatic charge image |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764318A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8168360B2 (en) | 2007-07-20 | 2012-05-01 | Sharp Kabushiki Kaisha | External additive, toner, and image forming apparatus |
| WO2016027674A1 (en) * | 2014-08-18 | 2016-02-25 | 日本ゼオン株式会社 | Toner for developing electrostatic images |
| US10407571B2 (en) | 2006-09-15 | 2019-09-10 | Cabot Corporation | Hydrophobic-treated metal oxide |
-
1993
- 1993-08-27 JP JP5213010A patent/JPH0764318A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10407571B2 (en) | 2006-09-15 | 2019-09-10 | Cabot Corporation | Hydrophobic-treated metal oxide |
| US8168360B2 (en) | 2007-07-20 | 2012-05-01 | Sharp Kabushiki Kaisha | External additive, toner, and image forming apparatus |
| WO2016027674A1 (en) * | 2014-08-18 | 2016-02-25 | 日本ゼオン株式会社 | Toner for developing electrostatic images |
| CN106575091A (en) * | 2014-08-18 | 2017-04-19 | 日本瑞翁株式会社 | Toner for developing electrostatic images |
| JPWO2016027674A1 (en) * | 2014-08-18 | 2017-06-15 | 日本ゼオン株式会社 | Toner for electrostatic image development |
| US10539894B2 (en) | 2014-08-18 | 2020-01-21 | Zeon Corporation | Toner for developing electrostatic images |
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