JP3990507B2 - Electrophotographic carrier - Google Patents

Electrophotographic carrier Download PDF

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JP3990507B2
JP3990507B2 JP11140499A JP11140499A JP3990507B2 JP 3990507 B2 JP3990507 B2 JP 3990507B2 JP 11140499 A JP11140499 A JP 11140499A JP 11140499 A JP11140499 A JP 11140499A JP 3990507 B2 JP3990507 B2 JP 3990507B2
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Japan
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control agent
charge control
toner
chargeable charge
carrier
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JP2000305322A (en
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隆之 佐野
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Tomoegawa Co Ltd
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Tomoegawa Paper Co Ltd
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Description

【0001】
【発明の属する技術分野】
本発明は複写機やプリンター等に用いられる電子写真用キャリアに関する。
【0002】
【従来の技術】
従来より広く使用されている電子写真用現像剤は、一成分系現像剤と、二成分系現像剤とに大別することができる。
上記一成分系現像剤はトナーのみで構成されており、トナー自体が電荷を有している。上記二成分系現像剤は、トナーとキャリアとから構成されている。
近年、二成分系現像剤を用いる複写機やプリンターは多種多様なものが製造され、例えばプリント速度が3〜100枚/分程度の広い範囲の複写機やプリンターが上市されている。
このような複写機やプリンターに使用される二成分系現像剤は、そのプリント速度に合わせて適正な摩擦帯電量を維持するように処方設計される。プリント速度が異なる複写機やプリンターでは、使用される二成分系現像剤の適切な摩擦帯電量が異なり、適切な摩擦帯電量を有しない二成分系現像剤では摩擦帯電量が高い場合では画像濃度が低下し画質が悪くなり、摩擦帯電量が低い場合では地カブリの発生が問題となる。
従来、二成分系現像剤の摩擦帯電量の調整は、▲1▼トナー及びキャリアの電気抵抗による調整、▲2▼トナーの表面に外添する外添剤による調整、▲3▼トナー中の電荷制御剤量による調整、が行われていた。
しかし、上記▲1▼による調整はトナー及びキャリアの電気抵抗を安定してコントロールすることが難しく、トナー及びキャリアの抵抗が低すぎると現像剤の放置後に摩擦帯電量が著しく低下し地カブリが発生し、高すぎると低温低湿環境下において摩擦帯電量が上昇して画像濃度低下の問題が発生していた。また、上記▲2▼による調整は外添剤が多数枚プリントの過程でトナー表面に埋没しやすいために初期の摩擦帯電量を多数枚プリント後まで維持することが困難であり、したがって多数枚プリント時における画像濃度低下や地カブリの発生等の問題を有していた。また、上記▲3▼による調整はトナー中への電荷制御剤の分散が不均一に行われるために十分に電荷制御剤が含有していないトナー粒子が生じやすく、未帯電トナー粒子の発生により地カブリが生じやすいという問題を有していた。
【0003】
【発明が解決しようとする課題】
本発明は、摩擦帯電量を適切に調整することができる二成分系現像剤用の電子写真用キャリアを提供することを目的とする。
【0004】
【課題を解決するための手段】
本発明にかかる電子写真用キャリアは、負帯電性の電荷制御剤及び正帯電性の電荷制御剤を含有した樹脂コート剤で被覆された電子写真用キャリアであって、前記負帯電性の電荷制御剤と正帯電性の電荷制御剤の含有量が重量比率で3:97〜97:3であることにより前記目的を達成した。
【0005】
【発明の実施の形態】
以下、本発明の電子写真用キャリアについて詳細に説明する。
電子写真用キャリアの樹脂コート剤で被覆されるコア粒子としては、鉄粉、マグネタイト、フェライト等の磁性体を使用することができるが、特にフェライトが好ましい。該フェライトからなるコア粒子は、下記一般式で示される3価の鉄酸化物と、金属酸化物との焼結体である。
【数1】
(MO)X(Fe23Y
(ただし、上記式中、Mは銅、亜鉛、マンガン、マグネシウム、ニッケル、バリウム、リチウム、バナジウム、カルシウム、クロム、コバルト、および鉄等からなる群から選択される1種類、もしくは2種類以上の金属を示す。XおよびYはモル比を示し、磁気特性等の要求される特性により適宜決定される。)
上記フェライトは、従来より実施されている一般的な方法により得ることができる。例えば、上記一般式を有するフェライトの原料である3価の鉄酸化物と金属酸化物を湿式で充分混合してスラリー状にする。得られたスラリー状の原料をスプレードライ法により造粒、乾燥する。この乾燥粒を焼成した後、解砕し、ふるい分けすることにより得ることができる。
【0006】
樹脂コート剤を構成する樹脂としては、シリコーン樹脂、シリコーングラフト樹脂、アクリル系樹脂、スチレン系樹脂、ウレタン系樹脂、およびフッ素系樹脂等が挙げられる。特にシリコーン樹脂はキャリア表面へのトナー融着現象(スペント)が生じにくいので好適に使用できる。
【0007】
樹脂コート剤に含有させる負帯電性の電荷制御剤及び正帯電性の電荷制御剤としては次のものが挙げられる。
負帯電性の電荷制御剤としては、例えば、オリエント化学工業社の商品名:ボントロンS−31、ボントロンS−32、ボントロンS−34、保土谷化学工業社の商品名:TRH等の含金属アゾ染料、オリエント化学工業社の商品名:ボントロンE−82、ボントロンE−84等のサリチル酸の金属錯体化合物、藤倉化成社製の商品名:FCA1001N等の樹脂系電荷制御剤、日本カーリット社製の商品名:LR−147等のボロン化合物を挙げることができる。
また、正帯電性の電荷制御剤としては、例えば、オリエント化学工業社の商品名:ボントロンP−51等の第4級アンモニウム塩、オリエント化学工業社の商品名:ボントロンN−01、ボントロンN−02、ボントロンN−03、ボントロンN−04、ボントロンN−05、ボントロンN−07、ボントロンN−09、ボントロンN−11等のアジン化合物、オリエント化学工業社の商品名:オイルブラックBS等のニグロシン系染料、オリエント化学工業社の商品名:ボントロンAFP−B等のポリアニリン系樹脂、ヘキスト社の商品名:コピーブルーPR等を挙げることができる。
この中でも特に含金属アゾ染料とアジン化合物とを組み合わせて用いることが良好な摩擦帯電性を有するので好ましい。
前記負帯電性の電荷制御剤と正帯電性の電荷制御剤との組み合わせは、各々1種類とは限らず2種類以上を適宜要求する特性に応じて用いればよい。
【0008】
上記負帯電性の電荷制御剤と正帯電性の電荷制御剤の含有量は、重量比率で3:97〜97:3でなければならない。負帯電性の電荷制御剤又は正帯電性の電荷制御剤の比率が3未満ではトナーと摩擦帯電させた場合に未帯電のトナー粒子が発生しやすいために画像に地カブリが生じ本発明の目的を達成することができない。
また、負帯電性の電荷制御剤及び正帯電性の電荷制御剤の総含有量が樹脂コート剤中の樹脂100重量部に対して0.5〜30重量部であることが好ましい。0.5重量部未満では樹脂コート剤中で負帯電性の電荷制御剤及び正帯電性の電荷制御剤の分散にムラが生じやすく個々の電子写真用キャリアの摩擦帯電性にバラツキが生じて地カブリやトナー飛散等の問題をおこしやすい。また、30重量部より多い場合では多数枚プリント時に電子写真用キャリアの抵抗が低下しやすく、地カブリの発生やトナー消費量の増加等の問題をおこしやすい。
【0009】
樹脂コート剤は、例えば溶剤に溶かした樹脂に前記負帯電性の電荷制御剤及び正帯電性の電荷制御剤を添加してヘンシェルミキサーやスーパーミキサー等の撹拌機で混合撹拌すれば得ることができる。
そして次に、通常の方法により前記コア粒子表面に上記樹脂コート剤を被覆することにより本発明の電子写真用キャリアを得ることができる。例えば流動床法を使用する製造方法では、流動層の下方から気流を吹き上げ、フェライト等のコア粒子群を浮遊懸濁状態に保ちつつ、ついで流動化した粒子に樹脂コート剤を噴霧してコア粒子の表面に付着させる。ついで上記樹脂コート剤からなる膜をコア粒子に焼付けることにより該樹脂を熱硬化させ、ふるい分けをして所望の粒子径を有する本発明の電子写真用キャリアを得る。
【0010】
本発明の電子写真用キャリアは、樹脂コート剤に負帯電性の電荷制御剤及び正帯電性の電荷制御剤を含有する。そして、該負帯電性の電荷制御剤と正帯電性の電荷制御剤との含有比率と総含有量を調整することによりトナーの摩擦帯電性を制御することが可能となった。
例えば負帯電性トナーにおいて、摩擦帯電量を低下させたい場合は、従来技術では該トナー中に含有させる電荷制御剤の含有量を少なくしていた。しかし、電荷制御剤の含有量が少ないとトナー粒子表面上に存在する電荷制御剤の量が個々のトナー粒子により差ができやすくなり、未帯電のトナー粒子が生じて地カブリやトナー飛散の原因となっていた。
そこで、負帯電性トナーにおいて電荷制御剤の含有量を減らさないで、樹脂コート剤に負帯電性の電荷制御剤を多く含有させた本発明の電子写真用キャリアを該負帯電性トナーと組み合わせて用いることにより、該電子写真用キャリアによって摩擦帯電性を調整して負帯電性トナーの摩擦帯電性を低下させることが可能となる。この結果、個々のトナー粒子の電荷制御剤の量を十分に保ちつつ、摩擦帯電性を維持し、一方本発明の電子写真用キャリアによって摩擦帯電量を下げることが可能となるので良好な現像特性を得ることができる。
正帯電性トナーの場合では、上記とは逆にトナー中の電荷制御剤で摩擦帯電性を維持しつつ、電子写真用キャリアの樹脂コート剤の正帯電性の電荷制御剤でトナー粒子の摩擦帯電量を下げることが可能となる。
【0011】
【実施例】
以下、実施例に基づき本発明をより詳しく説明する。なお、下記において「部」とは「重量部」を示す。
(実施例1)
シリコーン樹脂 100部、負帯電性の電荷制御剤(保土谷化学工業社の商品名:TRH)7部及び正帯電性の電荷制御剤(ヘキスト社の商品名:コピーブルーPR)3部をトルエン500部に溶解し、スーパーミキサーにより混合撹拌して樹脂コート剤を得た。
次に、流動床法に基づく装置を用いて該装置を構成する流動層に上記樹脂コート剤1部を敷き、市販のノンコートのフェライトキャリア100部を配置する。ついで気流中でフェライトキャリアを浮遊状態に保ち、樹脂を噴霧してフェライト粒子の表面に樹脂コート剤を付着させて樹脂被覆されたキャリアコアを得た。ついでこのキャリアコアを60℃で24時間加熱して、樹脂を硬化させて本発明の電子写真用キャリアを得た。
【0012】
(実施例2)
アクリル樹脂 100部、負帯電性の電荷制御剤(オリエント化学工業社の商品名:ボントロンS−34)3部、正帯電性の電荷制御剤(オリエント化学工業社の商品名:ボントロンN−04)7部をトルエン500部に溶解し、スーパーミキサーにより混合撹拌して樹脂コート剤を得た。
次に、流動床法に基づく装置を用いて該装置を構成する流動層に上記樹脂コート剤1部を敷き、市販のノンコートのマグネタイトキャリア100部を配置する。ついで気流中でマグネタイトキャリアを浮遊状態に保ち、樹脂を噴霧してマグネタイト粒子の表面に樹脂コート剤を付着させて樹脂被覆されたキャリアコアを得た。ついでこのキャリアコアを60℃で24時間加熱して、樹脂を硬化させて本発明の電子写真用キャリアを得た。
【0013】
(比較例1)
実施例1において、負帯電性の電荷制御剤及び正帯電性の電荷制御剤を含有させないで樹脂コート剤を作製し、その他は同様にして比較用の電子写真用キャリアを得た。
【0014】
(比較例2)
実施例1において、負帯電性の電荷制御剤の含有量を9.75部及び正帯電性の電荷制御剤の含有量を0.25部にした以外は同様にして電子写真用キャリアを得た。
【0015】
(比較例3)
実施例2において、負帯電性の電荷制御剤の含有量を0.25部及び正帯電性の電荷制御剤の含有量を9.75部にした以外は同様にして電子写真用キャリアを得た。
【0016】
次に下記原料に基づいて負帯電性トナー及び正帯電性トナーを得た。
トナーの製造方法は各々下記原料をスーパーミキサーで混合し、二軸混練機で熱溶融混練後、ジェットミルで粉砕し、その後乾式気流分級機で分級して体積平均粒子径が8μmの粒子を得、該粒子100部対して負帯電性トナーでは疎水性シリカ(日本アエロジル社製 商品名:R972)0.8部をヘンシェルミキサーで5分間撹拌し、正帯電性トナーでは疎水性シリカ(ヘキスト社製 商品名:HVK2115)0.8部をヘンシェルミキサーで5分間撹拌してトナー得た。
【0017】
(負帯電性トナーの原料)
・スチレン−アクリル酸エステル共重合体樹脂 88.8部
(三井化学社製 商品名:CPR−100)
・負帯電性の電荷制御剤 1.2部
(保土谷化学工業社の商品名:TRH)
・カーボンブラック 8部
(三菱化学社製、商品名:MA−100)
・低分子量ポリプロピレン 2部
(三洋化成工業社製、商品名:ビスコール330P)
【0018】
(正帯電性トナーの原料)
・スチレン−アクリル酸エステル共重合体樹脂 88.5部
(三井化学社製 商品名:CPR−100)
・正帯電性の電荷制御剤 1.5部
(ヘキスト社の商品名:コピーブルーPR)
・カーボンブラック 8部
(三菱化学社製、商品名:#40)
・低分子量ポリプロピレン 2部
(三洋化成工業社製、商品名:ビスコール550P)
【0019】
次に前記実施例1〜2及び比較例1〜3のキャリアを表1に示すトナーと組み合わせて二成分系現像剤を作製し100000枚まで連続コピー試験を行った。その結果は表1に示す通りであった。
なお、正帯電性トナーを用いた現像剤はシャープ社製の複写機 商品名:SD−2060により試験を行い、負帯電性トナーを用いた現像剤はシャープ社製の複写機 商品名:SF−9800により試験を行った。
なお、各特性の評価方法に使用した装置は次の通りである。
(1)摩擦帯電性(Q/M):東芝ケミカル社製のブローオフ摩擦帯電量測定装置TB−200を用いてトナーの摩擦帯電量を記した。
(2)画像濃度(ID):マクベス社製の反射濃度計RD−914(実用上必要な値は1.30以上である。)
(3)地カブリ(BG):日本電色工業社製の測色色差計ZE−2000(実用上必要な値は1.00以下である。)
(4)感光体カブリ(PCBG)は転写紙に転写されていない感光体上に現像された非画像部上のトナー粒子を透明な粘着テープに貼着し、該テープを白紙に貼り付けて透明粘着テープ面から前記反射濃度計で画像濃度を測定した値である。(実用上必要な値は0.03以下である。)
(5)トナー飛散:現像器周辺を目視で確認し、トナー飛散が発生しないで実用上問題がないものを○、トナー飛散が発生して実用上問題があるものを×とした。
【0020】
【表1】

Figure 0003990507
【0021】
表1から明らかなように、実施例1及び2で得られた電子写真用キャリアによる画像は、100000枚コピーした後も安定した画像特性を有していた。つまり、地カブリ及び感光体カブリは実用上問題なく画質濃度も安定していた。また、トナー飛散も発生していなかった。
一方、比較例1で得られた電子写真用キャリアによる画像は、100000枚において画像濃度が低く実用上問題を生じた。
また、比較例2及び3で得られた電子写真用キャリアによる画像は、100000枚において地カブリ及び感光体カブリが多く、トナー飛散が発生し実用上問題があることを確認した。
【0022】
【発明の効果】
本発明の電子写真用キャリアは、トナーの摩擦帯電量を適切に調整することができる。その結果、画像濃度が十分あり、地カブリやトナー飛散のない画像特性を多数枚得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotographic carrier used for a copying machine, a printer, or the like.
[0002]
[Prior art]
Electrophotographic developers that have been widely used in the past can be broadly divided into one-component developers and two-component developers.
The one-component developer is composed only of toner, and the toner itself has a charge. The two-component developer is composed of a toner and a carrier.
In recent years, a wide variety of copiers and printers using a two-component developer have been manufactured, and for example, a wide range of copiers and printers with a printing speed of about 3 to 100 sheets / min are on the market.
The two-component developer used in such a copying machine or printer is formulated and designed so as to maintain an appropriate triboelectric charge amount according to the printing speed. For copiers and printers with different printing speeds, the appropriate triboelectric charge amount of the two-component developer used is different, and for two-component developers that do not have the appropriate triboelectric charge amount, the image density is high when the triboelectric charge amount is high. When the frictional charge amount is low, the occurrence of background fog becomes a problem.
Conventionally, the adjustment of the triboelectric charge amount of the two-component developer is (1) adjustment by the electric resistance of the toner and carrier, (2) adjustment by an external additive externally added to the toner surface, and (3) the charge in the toner. Adjustment by the amount of control agent was performed.
However, it is difficult to control the electrical resistance of the toner and the carrier stably with the adjustment of the above (1). If the resistance of the toner and the carrier is too low, the triboelectric charge is remarkably lowered after the developer is left and the fogging occurs. However, if it is too high, the triboelectric charge amount increases in a low-temperature and low-humidity environment, causing a problem of image density reduction. Further, in the adjustment by the above (2), it is difficult to maintain the initial triboelectric charge amount after the printing of a large number of sheets because the external additive is easily embedded in the toner surface in the process of printing a large number of sheets. There were problems such as image density reduction and generation of ground fog. In addition, the adjustment according to the above (3) tends to generate toner particles that do not contain the charge control agent sufficiently because the charge control agent is not uniformly dispersed in the toner. There was a problem that fog was likely to occur.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide an electrophotographic carrier for a two-component developer capable of appropriately adjusting the triboelectric charge amount.
[0004]
[Means for Solving the Problems]
The electrophotographic carrier according to the present invention is an electrophotographic carrier coated with a resin coating agent containing a negatively chargeable charge control agent and a positively chargeable charge control agent, and the negatively chargeable charge control agent. The above object was achieved when the weight ratio of the agent and the positively chargeable charge control agent was 3:97 to 97: 3.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The electrophotographic carrier of the present invention will be described in detail below.
As the core particles to be coated with the resin coating agent of the electrophotographic carrier, a magnetic material such as iron powder, magnetite or ferrite can be used, and ferrite is particularly preferable. The core particle made of ferrite is a sintered body of a trivalent iron oxide represented by the following general formula and a metal oxide.
[Expression 1]
(MO) X (Fe 2 O 3 ) Y
(Wherein, M is one or more metals selected from the group consisting of copper, zinc, manganese, magnesium, nickel, barium, lithium, vanadium, calcium, chromium, cobalt, iron, etc.) X and Y represent molar ratios, which are determined as appropriate according to required properties such as magnetic properties.)
The ferrite can be obtained by a general method that has been conventionally performed. For example, a trivalent iron oxide, which is a raw material for ferrite having the above general formula, and a metal oxide are sufficiently mixed in a wet state to form a slurry. The obtained slurry-like raw material is granulated and dried by a spray drying method. After the dried grains are fired, they can be obtained by crushing and sieving.
[0006]
Examples of the resin constituting the resin coating agent include silicone resins, silicone graft resins, acrylic resins, styrene resins, urethane resins, and fluorine resins. In particular, a silicone resin can be suitably used because it hardly causes a toner fusion phenomenon (spent) on the carrier surface.
[0007]
Examples of the negatively chargeable charge control agent and the positively chargeable charge control agent contained in the resin coating agent include the following.
Examples of the negatively chargeable charge control agent include, for example, trade names of Orient Chemical Industry: Bontron S-31, Bontron S-32, Bontron S-34, trade names of Hodogaya Chemical Co., Ltd .: metal-containing azo such as TRH Dye, product name of Orient Chemical Industries: Metal complex compounds of salicylic acid such as Bontron E-82 and Bontron E-84, product name manufactured by Fujikura Kasei Co., Ltd .: resin charge control agent such as FCA1001N; Name: Boron compounds such as LR-147.
Examples of the positively chargeable charge control agent include, for example, quaternary ammonium salts such as Orient Chemical Industry's trade name: Bontron P-51, Orient Chemical Industry's trade names: Bontron N-01, Bontron N- 02, Bontron N-03, Bontron N-04, Bontron N-05, Bontron N-07, Bontron N-09, Bontron N-11 and other azine compounds, product names of Orient Chemical Industries: Nigrosine such as Oil Black BS And dyes, Polyaniline resins such as Bontron AFP-B, trade names of Orient Chemical Industries, Co., Ltd., and Copy Blue PR, trade names of Hoechst.
Among these, it is particularly preferable to use a combination of a metal-containing azo dye and an azine compound because of good triboelectric chargeability.
The combination of the negatively chargeable charge control agent and the positively chargeable charge control agent is not limited to one type, and may be used according to the characteristics that require two or more types as appropriate.
[0008]
The content of the negatively chargeable charge control agent and the positively chargeable charge control agent must be 3:97 to 97: 3 by weight. If the ratio of the negatively chargeable charge control agent or the positively chargeable charge control agent is less than 3, uncharged toner particles are likely to be generated when the toner and the toner are triboelectrically charged. Cannot be achieved.
The total content of the negatively chargeable charge control agent and the positively chargeable charge control agent is preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of the resin in the resin coating agent. If the amount is less than 0.5 part by weight, the dispersion of the negatively chargeable charge control agent and the positively chargeable charge control agent tends to be uneven in the resin coating agent, resulting in variations in the triboelectric chargeability of individual electrophotographic carriers. Problems such as fogging and toner scattering are likely to occur. On the other hand, when the amount is more than 30 parts by weight, the resistance of the electrophotographic carrier tends to be lowered when printing a large number of sheets, and problems such as generation of background fogging and increase in toner consumption are likely to occur.
[0009]
The resin coating agent can be obtained, for example, by adding the negatively chargeable charge control agent and the positively chargeable charge control agent to a resin dissolved in a solvent and mixing and stirring with a stirrer such as a Henschel mixer or a supermixer. .
Then, the electrophotographic carrier of the present invention can be obtained by coating the surface of the core particles with the resin coating agent by a usual method. For example, in the production method using the fluidized bed method, an air stream is blown from below the fluidized bed, and the core particles such as ferrite are kept in a suspended state, and then the resin particles are sprayed onto the fluidized particles. Adhere to the surface. Subsequently, the film made of the resin coating agent is baked onto the core particles to thermally cure the resin, and sieved to obtain the electrophotographic carrier of the present invention having a desired particle size.
[0010]
The electrophotographic carrier of the present invention contains a negatively chargeable charge control agent and a positively chargeable charge control agent in the resin coating agent. Further, the triboelectric chargeability of the toner can be controlled by adjusting the content ratio and the total content of the negatively chargeable charge control agent and the positively chargeable charge control agent.
For example, in the case of a negatively chargeable toner, when it is desired to reduce the triboelectric charge amount, the prior art has reduced the content of the charge control agent contained in the toner. However, if the content of the charge control agent is small, the amount of the charge control agent present on the toner particle surface tends to be different depending on the individual toner particles, and uncharged toner particles are generated, causing ground fogging and toner scattering. It was.
Accordingly, the electrophotographic carrier of the present invention in which the resin coating agent contains a large amount of the negatively chargeable charge control agent without reducing the content of the charge control agent in the negatively chargeable toner is combined with the negatively chargeable toner. By using the electrophotographic carrier, the triboelectric chargeability can be adjusted by the electrophotographic carrier, and the triboelectric chargeability of the negatively chargeable toner can be lowered. As a result, it is possible to maintain the triboelectric chargeability while maintaining a sufficient amount of the charge control agent of the individual toner particles, and on the other hand, the triboelectric charge amount can be lowered by the electrophotographic carrier of the present invention. Can be obtained.
In the case of a positively chargeable toner, contrary to the above, the triboelectric charge of the toner particles is maintained with the positively chargeable charge control agent of the resin coating agent of the electrophotographic carrier while maintaining the triboelectric charge property with the charge control agent in the toner. The amount can be reduced.
[0011]
【Example】
Hereinafter, the present invention will be described in more detail based on examples. In the following, “part” means “part by weight”.
Example 1
100 parts of a silicone resin, 7 parts of a negatively chargeable charge control agent (trade name: Hodogaya Chemical Co., Ltd .: TRH) and 3 parts of a positively chargeable charge control agent (trade name of Hoechst: Copy Blue PR) are added to toluene 500 The resin coating agent was obtained by mixing and stirring with a super mixer.
Next, using the apparatus based on the fluidized bed method, 1 part of the resin coating agent is laid on the fluidized bed constituting the apparatus, and 100 parts of a commercially available non-coated ferrite carrier is placed. Next, the ferrite carrier was kept in a floating state in an air stream, and the resin was sprayed to attach a resin coating agent to the surface of the ferrite particles to obtain a resin-coated carrier core. Subsequently, this carrier core was heated at 60 ° C. for 24 hours to cure the resin, thereby obtaining the electrophotographic carrier of the present invention.
[0012]
(Example 2)
100 parts of an acrylic resin, 3 parts of a negatively chargeable charge control agent (trade name of Orient Chemical Industry: Bontron S-34), a charge control agent of positive charge (trade name of Orient Chemical Industry: Bontron N-04) 7 parts were dissolved in 500 parts of toluene and mixed and stirred with a super mixer to obtain a resin coating agent.
Next, using the apparatus based on the fluidized bed method, 1 part of the resin coating agent is laid on the fluidized bed constituting the apparatus, and 100 parts of a commercially available non-coated magnetite carrier is placed. Next, the magnetite carrier was kept in a floating state in an air stream, and a resin coating agent was adhered to the surface of the magnetite particles by spraying the resin to obtain a resin-coated carrier core. Subsequently, this carrier core was heated at 60 ° C. for 24 hours to cure the resin, thereby obtaining the electrophotographic carrier of the present invention.
[0013]
(Comparative Example 1)
In Example 1, a resin coating agent was prepared without containing a negatively chargeable charge control agent and a positively chargeable charge control agent, and the rest was similarly obtained a comparative electrophotographic carrier.
[0014]
(Comparative Example 2)
An electrophotographic carrier was obtained in the same manner as in Example 1 except that the content of the negatively chargeable charge control agent was 9.75 parts and the content of the positively chargeable charge control agent was 0.25 parts. .
[0015]
(Comparative Example 3)
In Example 2, an electrophotographic carrier was obtained in the same manner except that the content of the negatively chargeable charge control agent was 0.25 part and the content of the positively chargeable charge control agent was 9.75 parts. .
[0016]
Next, a negatively chargeable toner and a positively chargeable toner were obtained based on the following raw materials.
The toner is produced by mixing the following raw materials with a super mixer, hot melt kneading with a biaxial kneader, pulverizing with a jet mill, and then classifying with a dry air classifier to obtain particles having a volume average particle size of 8 μm. For 100 parts of the particles, 0.8 part of hydrophobic silica (trade name: R972, manufactured by Nippon Aerosil Co., Ltd.) is stirred for 5 minutes with a Henschel mixer, and hydrophobic silica (manufactured by Hoechst) is used for the positively charged toner. A product name: HVK2115) 0.8 part was stirred with a Henschel mixer for 5 minutes to obtain a toner.
[0017]
(Raw material for negatively chargeable toner)
・ Styrene-acrylic acid ester copolymer resin 88.8 parts (trade name: CPR-100, manufactured by Mitsui Chemicals, Inc.)
・ Negatively charge control agent 1.2 parts (trade name of Hodogaya Chemical Co., Ltd .: TRH)
-Carbon black 8 parts (Mitsubishi Chemical Corporation, trade name: MA-100)
・ 2 parts low molecular weight polypropylene (manufactured by Sanyo Chemical Industries, trade name: Biscol 330P)
[0018]
(Raw material for positively chargeable toner)
-Styrene-acrylic acid ester copolymer resin 88.5 parts (trade name: CPR-100, manufactured by Mitsui Chemicals, Inc.)
・ 1.5 parts of positively chargeable charge control agent (trade name of Hoechst: Copy Blue PR)
・ 8 parts carbon black (Mitsubishi Chemical Corporation, trade name: # 40)
・ 2 parts of low molecular weight polypropylene (manufactured by Sanyo Chemical Industries, trade name: Viscol 550P)
[0019]
Next, a two-component developer was prepared by combining the carriers of Examples 1-2 and Comparative Examples 1-3 with the toner shown in Table 1, and a continuous copy test was conducted up to 100,000 sheets. The results were as shown in Table 1.
The developer using a positively chargeable toner was tested by a Sharp Copier product name: SD-2060, and the developer using a negatively charged toner was a Sharp copier product name: SF- Tested according to 9800.
In addition, the apparatus used for the evaluation method of each characteristic is as follows.
(1) Triboelectric chargeability (Q / M): The triboelectric charge amount of the toner was recorded using a blow-off triboelectric charge measuring device TB-200 manufactured by Toshiba Chemical Corporation.
(2) Image density (ID): reflection densitometer RD-914 manufactured by Macbeth (practically necessary value is 1.30 or more)
(3) Ground fog (BG): Colorimetric color difference meter ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. (A practically necessary value is 1.00 or less.)
(4) Photoresist fog (PCBG) is a transparent adhesive tape in which toner particles on a non-image area developed on a photoreceptor not transferred to a transfer paper are adhered to a transparent adhesive tape. It is a value obtained by measuring the image density with the reflection densitometer from the adhesive tape surface. (A practically necessary value is 0.03 or less.)
(5) Toner scattering: The periphery of the developing device was visually confirmed, and the case where no toner scattering occurred and there was no practical problem was marked with ◯, and the toner scattering occurred where there was a practical problem.
[0020]
[Table 1]
Figure 0003990507
[0021]
As is apparent from Table 1, the images obtained by the electrophotographic carriers obtained in Examples 1 and 2 had stable image characteristics even after 100000 copies were made. In other words, the background fog and the photoreceptor fog were stable in image quality without any practical problem. Further, toner scattering did not occur.
On the other hand, the image obtained with the carrier for electrophotography obtained in Comparative Example 1 had a practical problem due to low image density on 100,000 sheets.
In addition, it was confirmed that the images using the electrophotographic carrier obtained in Comparative Examples 2 and 3 had a lot of ground fog and photoreceptor fog on 100,000 sheets, causing toner scattering and causing a problem in practical use.
[0022]
【The invention's effect】
The electrophotographic carrier of the present invention can appropriately adjust the triboelectric charge amount of the toner. As a result, it is possible to obtain a large number of image characteristics having sufficient image density and free from background fogging and toner scattering.

Claims (2)

負帯電性の電荷制御剤及び正帯電性の電荷制御剤を含有した樹脂コート剤で被覆された電子写真用キャリアであって、前記負帯電性の電荷制御剤と正帯電性の電荷制御剤の含有量が重量比率で3:97〜97:3であることを特徴とする電子写真用キャリア。An electrophotographic carrier coated with a resin coating agent containing a negatively chargeable charge control agent and a positively chargeable charge control agent, comprising the negatively chargeable charge control agent and the positively chargeable charge control agent. The electrophotographic carrier, wherein the content is from 3:97 to 97: 3 by weight. 負帯電性の電荷制御剤及び正帯電性の電荷制御剤の総含有量が樹脂コート剤中の樹脂100重量部に対して0.5〜30重量部であることを特徴とする請求項1記載の電子写真用キャリア。The total content of the negatively chargeable charge control agent and the positively chargeable charge control agent is 0.5 to 30 parts by weight with respect to 100 parts by weight of the resin in the resin coating agent. Carrier for electrophotography.
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