JP2004191598A - Toner, two-component developer, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for contriving oilless fixing preventing off-set property while maintaining a high OHP translucency and a long life without having a spent of toner component to a carrier, and to provide a two-component developer and an image forming apparatus. <P>SOLUTION: The toner containing at least a binding resin, a coloring resin and a wax contains 5-20 pt.wt. of the wax of which heat absorption peak temperature by a DSC method is 60-120°C to 100 pt.wt. of the binding resin. The toner blends coarse particles having a volume average particle diameter of 2-6 times the volume average particle diameter of toner base particles. Furthermore, the two-component developer combines fluorine modified silicone resin containing an aminosilane coupling agent with the carrier which is a coated resin. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【０１２０】
３価以上のアルコール成分としては、ソルビトール、１，２，３，６−ヘキサンテトロール、１，４−ソルビタン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、１，２，４−ブタントリオール、１，２，５−ペンタントリオール、グリセロール、２−メチルプロパントリオール、２−メチル−１，２，４−ブタントリオール、トリメチロールエタン、トリメチロールプロパン、１，３，５−トリヒドロキシメチルベンゼン等が挙げられる。
【０１２１】
重合は公知の重縮合、溶液重縮合等を用いることが出来る。これによって耐塩ビマット性やカラートナーの色材の色を損なうこトナーしに、良好なトナーを得ることができる。
【０１２２】
多価カルボン酸と多価アルコールの使用割合は通常、カルボキシル基数に対する水酸基数の割合（ＯＨ／ＣＯＯＨ）で０．８〜１．４が一般的である。
【０１２３】
樹脂、ワックス及びトナーの分子量は、数種の単分散ポリスチレンを標準サンプルとするゲル浸透クロマトグラフィー（ＧＰＣ）によって測定された値である。
【０１２４】
装置は、東ソー社製ＨＰＬＣ８１２０シリーズ、カラムはＴＳＫｇｅｌ ｓｕｐｅｒＨＭ−Ｈ Ｈ４０００／Ｈ３０００／Ｈ２０００（７．８ｍｍ径、１５０ｍｍ×３）、溶離液ＴＨＦ（テトラヒドロフラン）、流量０．６ｍｌ／ｍｉｎ、試料濃度０．１％、注入量２０μＬ、検出器ＲＩ、測定温度４０℃、測定前処理は試料をＴＨＦに溶解後０．４５μｍのフィルターでろ過しシリカ等の添加剤を除去した樹脂成分を測定する。測定条件は、対象試料の分子量分布が、数種の単分散ポリスチレン標準試料により得られる検量線における分子量の対数とカウント数が直線トナーる範囲内に包含される条件である。
【０１２５】
また炭素数５〜１００の長鎖アルキルアルコール、不飽和多価カルボン酸又はその無水物及び不飽和炭化水素系ワックスとの反応により得られるワックスの測定は、装置はＷＡＴＥＲＳ製ＧＰＣ−１５０Ｃ、カラムはＳｈｏｄｅｘ ＨＴ−８０６Ｍ（８．０ｍｍＩ．Ｄ．−３０ｃｍ×２）、溶離液はｏ−ジクロロベンゼン、流量は１．０ｍＬ／ｍｉｎ、試料濃度は０．３％、注入量は２００μＬ、検出器はＲＩ、測定温度は１３０℃、測定前処理は試料を溶媒に溶解後０．５μｍの金属焼結フィルターでろ過処理した。測定条件は、対象試料の分子量分布が、数種の単分散ポリスチレン標準試料により得られる検量線における分子量の対数とカウント数が直線トナーる範囲内に包含される条件である。
【０１２６】
また、結着樹脂の軟化点は、島津製作所の定荷重押出し形細管式レオメータフローテスタ（ＣＦＴ５００）により、１ｃｍ^３の試料を昇温速度６℃／分で加熱しながらプランジャーにより約９．８×１０^５Ｎ／ｍ^２ の荷重を与え、直径１ｍｍ、長さ１ｍｍのダイから押し出して、このプランジャーのピストンストロークと温度との関係における昇温温度特性との関係から、ピストンストロークが立上がり始める温度が流出開始温度（Ｔｆｂ）、曲線の最低値と流出終了点の差の１／２を求め、それと曲線の最低値を加えた点の位置における温度を１／２法における溶融温度（軟化点Ｔｍ）トナーる。
【０１２７】
また樹脂のガラス転移点は示差走査熱量計を用い、１００℃まで昇温し、その温度にて３分間放置した後、降温速度１０℃／ｍｉｎで室温まで冷却したサンプルを、昇温速度１０℃／ｍｉｎで昇温して熱履歴を測定した際に、ガラス転移点以下のベースラインの延長線とピークの立上がり部分からピークの頂点までの間での最大傾斜を示す接線との交点の温度をいう。
【０１２８】
ＤＳＣによる吸熱ピークの融点は、島津製作所の示差熱量分析計ＤＳＣ−５０を使用した。５℃／ｍｉｎで２００℃まで昇温し、５分間保温１０℃まで急冷後、１５分間放置後５℃／ｍｉｎで昇温させ、吸熱（融解）ピークから求めた。セルに投入するサンプル量は１０ｍｇ±２ｍｇとした。
【０１２９】
本実施形態に好適に使用される結着樹脂には、各種ビニル系モノマーによる単独重合体または共重合体も好適に使用できる。例えば、スチレン、Ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ｐ―エチルスチレン、２，４−ジメチルスチレン、ｐ−ｎブチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ヘキシルスチレン、Ｐ−クロルスチレンなどのスチレンのおよびその誘導体があげられ、とくにスチレンが好ましい。
【０１３０】
またアクリル単量体としては、アクリル酸、メタクリル酸、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−２−エチルヘキシル、アクリル酸シクロヘキシル、アクリル酸フェニル、メタクリル酸メチル、メタクリル酸ヘキシル、メタクリル酸−２−エチルヘキシル、β−ヒドロキシアクリル酸エチル、γ−ヒドロキシアクリル酸プロピルα−ヒドロキシアクリル酸ブチル、β−ヒドロキシメタクリル酸エチル、γ−アミノアクリル酸プロピル、γ−Ｎ，Ｎ−ジエチルアミノアクリル酸プロピル、エチレングリコールジメタクリル酸エステル、テトラエチレングリコールジメタクリル酸エステル等を挙げることができる。本発明の目的に好適なスチレンーアクリル系共重合体としては、スチレン／ブチルアクリレート共重合体であり、特にスチレンを７５〜８５重量％、ブチルアクリレートを１５〜２５重量％含有するものが好適に使用される。
（４）電荷制御剤
本実施形態ではトナーの電荷制御の目的、及びオイルレス定着をより強固なものとするために、電荷制御剤が添加される。好ましい材料としては、アクリルスルホン酸系の重合体で、スチレン系モノマーと極性基としてスルホン酸基を有するアクリル酸系モノマーとのビニル共重合体が好ましい。特にはアクリルアミド−２−メチルプロパンスルホン酸との共重合体が好ましい特性を発揮できる。前記したキャリアと組合わせて使用することにより、現像器内でのハンドリング性を向上し、トナー濃度の均一性が向上する。さらに現像メモリーの発生を抑制できる。また、好ましい材料としては下記化学式（化２）に示すサリチル酸誘導体の金属塩が用いられる。
【０１３１】
【化２】

【０１３２】
また、好ましい材料としては下記化学式（化３）に示すベンジル酸誘導体の金属塩が用いられる。
【０１３３】
【化３】

【０１３４】
この構成により、オイルレス定着において広範囲の非オフセット温度域を確保できると共に、定着時での帯電作用による画像乱れを防止できる。これはワックスのもつ酸価を有する官能基と金属塩の帯電極性の効果と思われる。また連続使用時での帯電量の低下を防止できる。
【０１３５】
添加量は結着樹脂１００重量部に対し、０．５〜５重量部が好ましい。より好ましくは１〜４重量部、さらに好ましくは３〜４重量部である。０．５重量部よりも少ないと、帯電作用効果が無くなる。５重量部よりも多くなるとカラー画像での色濁りが目立ってくる。
（５）顔料
また、本実施形態に使用される顔料としては、カーボンブラック、鉄黒、グラファイト、ニグロシン、アゾ染料の金属錯体、Ｃ．Ｉ．ピグメント・イエロー１，３，７４，９７，９８等のアセト酢酸アリールアミド系モノアゾ黄色顔料、Ｃ．Ｉ．ピグメント・イエロー１２，１３，１４，１７等のアセト酢酸アリールアミド系ジスアゾ黄色顔料、Ｃ．Ｉ．ソルベントイエロー１９，７７，７９、Ｃ．Ｉ．ディスパース・イエロー１６４が配合され、特に好ましくはＣ．Ｉ．ピグメント・イエロー９３，１８０，１８５のベンズイミダゾロン系が感光体フィルミングに対して効果がある。
【０１３６】
Ｃ．Ｉ．ピグメント・レッド４８，４９：１，５３：１，５７，５７：１，８１，１２２，５等の赤色顔料、Ｃ．Ｉ．ソルベント・レッド４９，５２，５８，８等の赤色染料、Ｃ．Ｉ．ピグネント・ブルー１５：３等のフタロシアニン及びその誘導体の青色染顔料が１種又は２種類以上で配合される。添加量は結着樹脂１００重量部に対し、３〜８重量部が好ましい。
（６）外添剤
また本実施形態では外添剤として、シリカ、アルミナ、酸化チタン、ジルコニア、マグネシア、フェライト、マグネタイト等の金属酸化物微粉末、チタン酸バリウム、チタン酸カルシウム、チタン酸ストロンチウム等のチタン酸塩、ジルコン酸バリウム、ジルコン酸カルシウム、ジルコン酸ストロンチウム等のジルコン酸塩あるいはこれらの混合物が用いられる。外添剤は必要に応じて疎水化処理される。
【０１３７】
シリカに処理されるシリコーンオイル系の材料としては、下記化学式（化４）に示されるものが好ましい。
【０１３８】
【化４】

【０１３９】
例えば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、フッ素変性シリコーンオイル、アミノ変性シリコーンオイル、クロルフェニル変成シリコーンオイルのうちの少なくとも１種類以上で処理されるシリカが好適に使用される。例えば東レダウコーニングシリコーン社のＳＨ２００、ＳＨ５１０、ＳＦ２３０、ＳＨ２０３、ＢＹ１６―８２３、ＢＹ１６―８５５Ｂ等が挙げられる。処理は無機微粉末とシリコーンオイル等の材料とをヘンシェルミキサ等の混合機により混合する方法や、シリカへシリコーンオイル系の材料を噴霧する方法、溶剤にシリコーンオイル系の材料を溶解或いは分散させた後、シリカ微粉末と混合した後、溶剤を除去して作成する方法等がある。無機微粉末１００重量部に対して、シリコーンオイル系の材料は１〜２０重量部配合されるのが好ましい。
【０１４０】
シランカップリング剤としては、ジメチルジクロロシラン、トリメチルクロルシラン、アリルジメチルクロルシラン、ヘキサメチルジシラザン、アリルフェニルジクロルシラン、ベンジルメチルクロルシラン、ビニルトリエトキシシラン、γ−メタクリルオキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、ジビニルクロルシラン、ジメチルビニルクロルシラン等がある。シランカップリング剤処理は、微粉体を攪拌等によりクラウド状としたものに気化したシランカップリング剤を反応させる乾式処理又は、微粉体を溶媒中に分散させたシランカップリング剤を滴下反応させる湿式法等により処理される。
【０１４１】
またシランカップリング処理した後にシリコーンオイル系の材料を処理することも好ましい。
【０１４２】
正極帯電性を有する無機微粉末はアミノシランや下記化学式（化５）に示されるアミノ変性シリコーンオイル、エポキシ変性シリコーンオイルで処理される。
【０１４３】
【化５】

【０１４４】
また、疎水性処理を高めるため、ヘキサメチルジシラザンやジメチルジクロロシラン、他のシリコーンオイルによる処理の併用も好ましい。例えば、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、アルキル変性シリコーンオイルのうちの少なくとも１種類以上で処理することが好ましい。
【０１４５】
また、脂肪酸エステル、脂肪酸アミド、脂肪酸金属塩により無機微粉末の表面を処理することも好ましい。いずれか１種または２種以上を表面処理したシリカ又は酸化チタン微粉末がより好ましい。
【０１４６】
脂肪酸、脂肪酸金属塩としては、カプリル酸、カプリン酸、ウンデシル酸、ラウリル酸、ミスチリン酸、パリミチン酸、ステアリン酸、ベヘン酸、モンタン酸、ラクセル酸、オレイン酸、エルカ酸、ソルビン酸、リノール酸等が挙げられる。中でも炭素数１５〜２０の脂肪酸が好ましい。
【０１４７】
また脂肪酸金属塩を構成する金属としては、アルミニウム、亜鉛、カルシウム、マグネシウム、リチウム、ナトリウム、鉛、バリウムが挙げられ、中でもアルミニウム、亜鉛、ナトリウムが好ましい。特に好ましくはジステアリン酸アルミニウム（Ａｌ（ＯＨ）（Ｃ_１７Ｈ_３５ＣＯＯ）_２）、またはモノステアリン酸アルミニウム（Ａｌ（ＯＨ）_２（Ｃ_１７Ｈ_３５ＣＯＯ））、等のジ脂肪酸アルミニウム、モノ脂肪酸アルミニウムが好ましい。ＯＨ基を有することが過帯電を防止し、転写不良を抑えることができる。また処理時にシリカ等の無機微粉末との処理性が向上するものと考えられる。
【０１４８】
また、小粒径トナーのハンドリング性を向上でき、現像、転写において高画質化と転写性向上の両立を図ることができる。現像においては潜像をより忠実に再現できる。そして転写の際のトナー粒子の転写率を悪化させるこトナーく転写できる。またタンデム転写においても再転写を防止でき、中抜けの発生の抑制が可能トナーる。さらには現像量を少なくしても高画像濃度を得ることができる。また後述するキャリアと組合わせた使用により、耐スペント性をより向上でき、現像器内でのハンドリング性を向上させトナー濃度の均一性を上げることが出きる。また現像メモリー発生を抑制できる。
【０１４９】
平均粒子径６ｎｍ〜２００ｎｍである無機微粉末をトナー母体粒子１００重量部に対し１．５〜５．５重量部外添処理する構成が好ましい。平均粒子径６ｎｍよりも小さいと、シリカ浮遊や感光体へのフィルミングが生じ易い。転写時の逆転写の発生を抑さえ切れない。２００ｎｍよりも大きくなると、トナーの流動性が悪化する。１．５重量部よりも少ないとトナーの流動性が悪化する。転写時の逆転写の発生を抑さえ切れない。５．５重量部よりも多いとシリカ浮遊や感光体へのフィルミングが生じ易い。高温オフセット性を悪化される。
【０１５０】
さらには、平均粒子径が６ｎｍ〜２０ｎｍである無機微粉末をトナー母体粒子１００重量部に対し０．５〜２．５重量部と、３０ｎｍ〜２００ｎｍである無機微粉末をトナー母体粒子１００重量部に対し１．０〜３．５重量部とを少なくとも外添処理する構成が好ましい。この構成により機能分離したシリカの使用で、現像でのハンドリング性、転写時の逆転写、中抜け、飛散りに対しよりマージンが取れる。またキャリアへのスペントを防止できる。
【０１５１】
さらには、平均粒子径が６ｎｍ〜２０ｎｍの無機微粉末の強熱減量が１．５〜２５ｗｔ％、平均粒子径が３０ｎｍ〜２００ｎｍの強熱減量が０．５〜２３ｗｔ％であることが好ましい。
【０１５２】
シリカの強熱減量を特定することにより、転写時の逆転写、中抜け、飛散りに対しよりマージンが取れる。また前記したキャリアやワックスと組合わせた使用により、耐スペント性をより向上でき、現像器内でのハンドリング性を向上させトナー濃度の均一性を上げることが出きる。また現像メモリー発生を抑制できる。
【０１５３】
平均粒子径が６ｎｍ〜２０ｎｍの強熱減量が１．５ｗｔ％よりも少ないと、逆転写、中抜けに対する転写マージンが狭くなる。２５ｗｔ％よりも多くなると、表面処理がムラになり、帯電のバラツキが生じる。好ましくは強熱減量が１．５〜２０ｗｔ％、より好ましくは５〜１９ｗｔ％である。
【０１５４】
平均粒子径が３０ｎｍ〜２００ｎｍの強熱減量が０．５ｗｔ％よりも少ないと、逆転写、中抜けに対する転写マージンが狭くなる。２３ｗｔ％よりも多くなると、表面処理がムラになり、帯電のバラツキが生じる。好ましくは強熱減量が１．５〜１８ｗｔ％、より好ましくは５〜１６ｗｔ％である。
【０１５５】
さらには、平均粒子径６ｎｍ〜２００ｎｍ、強熱減量が０．５〜２５ｗｔ％である正帯電性無機微粉末をさらにトナー母体粒子１００重量部に対し０．５〜１．５重量部とを少なくとも外添処理する構成も好ましい。
【０１５６】
正帯電性無機微粉末を添加する効果は、トナーが長期連続使用の際に過帯電になることを抑え、より現像剤寿命を延ばすことが可能トナーる。さらには過帯電による転写時の飛散りを抑える効果も得られる。またキャリアへのスペントを防止できる。０．５重量部よりも少ないとその効果が得にくい。１．５重量部よりも多くなると、現像でのかぶりが増大する。強熱減量は好ましくは１．５〜２０ｗｔ％、より好ましくは５〜１９ｗｔ％である。
【０１５７】
乾燥減量（％）は、予め乾燥、放冷、精秤した容器に試料約１ｇを取り、精秤する。熱風乾燥器（１０５℃±１℃）で２時間乾燥する。デシケータ中で３０分間放冷後その重量を精秤し次式より算出する。
乾燥減量（％）＝乾燥による減量（ｇ）／試料量（ｇ）×１００
強熱減量は、予め乾燥、放冷、精秤した磁性ルツボに試料約１ｇを取り、精秤する。５００℃に設定した電気炉中で２時間強熱する。デシケータ中で１時間放冷後その重量を精秤し次式より算出する。
【０１５８】
強熱減量（％）＝強熱による減量（ｇ）／試料量（ｇ）×１００
また処理された無機微粉末の水分吸着量が１ｗｔ％以下であることが好ましい。好ましくは０．５ｗｔ％以下、より好ましくは０．１ｗｔ％以下、さらに好ましくは０．０５ｗｔ％以下である。１ｗｔ％より多いと、帯電性の低下、耐久時の感光体へのフィルミングを生じる。水分吸着量の測定は、水吸着装置については、連続蒸気吸着装置（ＢＥＬＳＯＲＰ１８：日本ベル株式会社）にて測定した。
【０１５９】
疎水化度の測定は、２５０ｍｌのビーカー中に装入した蒸留水５０ｍｌに試験すべき生成物０．２ｇを秤取する。先端に、液体中に浸威しているビュレットからメタノールを無機微粉末の総量がぬれるまで滴下する。その際不断に電磁攪拌機でゆっくりと攪拌する。完全に濡らすために必須なメタノール量ａ（ｍｌ）から次式により疎水化度が算出される。
疎水化度＝（ａ／（５０＋ａ））×１００（％）
またトナー母体の体積平均粒子径の２〜６倍の体積平均粒子径を有する粗大粒子をトナー母体に対し、１．０〜６．０重量部有することが好ましい。これによりトナーを小粒径化して画質を向上させる際に生じるトナーの流動性を維持し、かつ感光体、中間転写体上でのトナーのクリーニング性を向上できる。
【０１６０】
小粒径化したトナーの流動性を向上させるために、シリカ等の無機微粉末を多く添加する構成を取るが、この構成だとトナー粒子間に多量のシリカ等の微粉末が介在し、定着時のトナー同士の融着を妨げ、定着強度を悪化させたり、高温オフセット性を悪化させる。
【０１６１】
しかし上記した粗大粒子を添加することによりトナー粒子間に存在するため、定着時のトナー同士の融着を妨げることが少なく、また流動性を保持するとともに定着性への影響は少ない。また長期使用時にトナーとキャリアとの中間的な大きさに位置しトナーに加わる衝撃を緩和でき、キャリアとの混合性を良化させ、帯電安定化に寄与できる効果が得られる。
【０１６２】
好ましくはトナー母体の体積平均粒子径の２．５〜５倍の体積平均粒子径を有する粗大粒子をトナー母体に対し、２．０〜５．０重量部有することが好ましい。さらに好ましくはトナー母体の体積平均粒子径の２．５〜４倍の体積平均粒子径を有する粗大粒子をトナー母体に対し、３．０〜５．０重量部有することが好ましい。
【０１６３】
さらには、その粗大粒子中に前記した脂肪酸エステル、脂肪酸アミド、脂肪酸金属塩等の滑性剤を添加することにより衝撃の緩和や流動性の維持、トナーのクリーニング性に対してより効果が得られる。添加量としては１〜２０重量部で少ないと効果がえられ得ず、多過ぎるとトナーの帯電低下を生じさせる。
粗大粒子は、アクリル樹脂、シリコン樹脂、ポリエステル樹脂、スチレン樹脂、エポキシ樹脂、メラミン樹脂等が好適に使用でき、添加されるトナー色に着色されていることも好ましい。これらの樹脂を溶融して、滑性剤や着色剤を添加し、冷却後に所定の粒径に粉砕する方法や、粒子を懸濁または乳化重合法により形成する方法がある。粒子の体積基準の変動係数は流動性付与、トナーのクリーニング性の効果を発現させるためには体積基準で４０％以下が好ましい。より好ましくは３５％以下である。さらに好ましくは３０％以下である。粒径の測定は後術する方法で行われる。
（７）トナーの粉体物性
本実施形態では、結着樹脂、着色剤及びワックスを含む少なくとも結着樹脂、着色剤及びワックスを含むトナー母体粒子の体積平均粒径が３〜８μｍ、好ましくは３．５〜７．５μｍ、より好ましくは４〜６．５μｍであり、個数分布における２．５２〜４μｍの粒径を有するトナー母体粒子の含有量が５〜５５個数％含有し、体積分布における６．３５〜１０．１μｍの粒径を有するトナー母体粒子が５〜６０体積％で含有する粒度分布とする構成である。
【０１６４】
より好ましくは個数分布における２．５２〜４μｍの粒径を有するトナー母体粒子の含有量が１０〜４５個数％含有し、体積分布における６．３５〜１０．１μｍの粒径を有するトナー母体粒子が１２〜５０体積％で含有する粒度分布とする構成である。
【０１６５】
さらに好ましくは個数分布における２．５２〜４μｍの粒径を有するトナー母体粒子の含有量が１５〜４０個数％含有し、体積分布における６．３５〜１０．１μｍの粒径を有するトナー母体粒子が１２〜４５体積％で含有する粒度分布とする構成である。
【０１６６】
高解像度画質、さらにはタンデム転写における逆転写の防止、中抜けを防止し、オイルレス定着との両立を図ることを可能とできる。
【０１６７】
体積平均粒径が８μｍより大きいと画質と転写の両立が図れない。体積平均粒径が３μｍより小さいと現像でのトナー粒子のハンドリグ性が困難トナーる。個数分布における２．５２〜４μｍの粒径を有するトナー母体粒子の含有量が５個数％よりも少なくなると、画質と転写の両立が図れない。５５個数％よりも多く含有すると現像でのトナー母体粒子のハンドリグ性が困難トナーる。６．３５〜１０．１μｍの粒径を有するトナー母体粒子が５５体積％よりも多く含有すると、画質と転写の両立が図れない。５体積％よりも少ないとトナー生産性の低下とコストアップになる。
【０１６８】
また、体積平均粒子径から換算した真球相当の比表面積値Ｓｔ（Ｓｔ＝６／（真比重×体積平均粒子径））との比表面積比ＳＳｔ（ＳＳｔ＝（Ｓｔ／粉砕されたトナー母体粒子の比表面積測定値）が０．４〜０．９、好ましくは０．５〜０．８５、より好ましくは０．５５〜０．８である。０．９よりも大きいと球形化が進み、帯電性の低下を招き、転写時の飛び散り等の弊害を招く。０．４よりも小さいと形状が不定形になり過ぎるか、または過粉砕された微粉量が多い原因である。
【０１６９】
トナー母体粒子の体積粒径分布の変動係数が１５〜３２％、個数粒径分布の変動係数が１５〜３５％であることが好ましい。より好ましくは、体積粒径分布の変動係数が１５〜３０％、個数粒径分布の変動係数が１５〜３０％、さらに好ましくは、体積粒径分布の変動係数が１５〜２５％、個数粒径分布の変動係数が１５〜２５％である。
【０１７０】
変動係数とはトナーの粒径における標準偏差を平均粒径で割ったものである。コールターカウンタ（コールター社）を使用して測定した粒子径をもとにしたものである。標準偏差は、ｎ個の粒子系の測定を行なった時の、各測定値の平均値からの差の２乗を（ｎ−１）で割った値の平方根であらわされる。
【０１７１】
つまり変動係数とは粒度分布の広がり具合をあわらしたもので、体積粒径分布の変動係数が１５％未満、又は個数粒径分布の変動係数が１５％未満トナーると、生産的に困難であり、コストアップの要因トナーる。体積粒径分布の変動係数が３２％より大、または個数粒径分布の変動係数が３５％を超えると、粒度分布がブロードトナーるとトナーの凝集性が強くなり、感光体へのフィルミング、転写不良、クリーナーレスプロセスでの残留トナーの回収が困難トナーる。
【０１７２】
トナー中の微粉はトナーの流動性、画質、貯蔵安定性、感光体や現像ローラ、転写体ヘのフィルミング、経時特性、転写性、特にタンデム方式での多層転写性に影響する。さらにはオイルレス定着での非オフセット性、光沢性、透光性に影響する。オイルレス定着実現のためにワックス等の離型剤を配合したトナーにおいて、タンデム転写性との両立において微粉量が影響する。
【０１７３】
微粉量が過大、すなわち２．５２〜４μｍの粒径を有するトナー母体粒子の含有量が５５個数％以上とすると、分散しきれないワックスがトナー表面の露出が多くなり、感光体、現像ローラ、転写体へのフィルミングが発生する。さらには微粉は熱ローラとの付着性も大きいためオフセットしやすい傾向にある。またタンデム方式において、トナーの凝集が強くなりやすく、多層転写時に２色目の転写不良を生じ易くなる。逆に微粉量が少なくなると、画質の低下を招き、適当な範囲が必要トナーる。
【０１７４】
粒度分布測定は、コールターカウンタＴＡ−ＩＩ型（コールターカウンタ社）を用い、個数分布、体積分布を出力するインターフェイス（日科機製）及びパーソナルコンピュータを接続して測定する。電解液は濃度１％トナーるよう界面活性剤（ラウリル硫酸ナトリウム）を加えたもの５０ｍｌ程度に被測定トナーを２ｍｇ程度加え、試料を懸濁した電解液は超音波分散器で約３分間分散処理を行い、コールターカウンタＴＡ−ＩＩ型にてアパーチャー７０μｍのアパーチャーを用いた。７０μｍのアパーチャー系では、粒度分布測定範囲は１．２６μｍ〜５０．８μｍであるが、２．０μｍ未満の領域は外来ノイズ等の影響で測定精度や測定の再現性が低いため実用的ではない。よって測定領域を２．０μｍ〜５０．８μｍとした。
【０１７５】
また、静嵩密度と動嵩密度から算出されるのが圧縮度で、トナー流動性の指標の一つである。トナーの流動性はトナーの粒度分布、トナー粒子形状、外添剤、ワックスの種類や量に影響される。トナーの粒度分布が狭く微粉が少ない場合、トナーの表面に凹凸が少なく形状が球形に近い場合、外添剤の添加量が多い場合、外添剤の粒径が小さい場合は、圧縮度が小さくなりトナーの流動性は高くなる。圧縮度は５〜４０％が好ましい。より好ましくは、１０〜３０％である。オイルレス定着と、タンデム方式多層転写との両立を図ることが可能トナーる。５％より小さいと、定着性が低下し、特に透光性が悪化しやすい。現像ロ−ラからトナー飛散が多くなりやすい。４０％よりも大きい転写性が低下し、タンデム方式での中抜け、転写不良を生じる
（８）キャリア
本実施形態の樹脂被覆キャリアは、キャリア芯材に、アミノシランカップリング剤を含有したフッ素変性シリコーン系樹脂からなる被覆樹脂層を有するキャリアが好適に使用される。
【０１７６】
キャリア芯材には、鉄粉系キャリア芯材、フェライト系キャリア芯材、マグネタイト系キャリア芯材、また磁性体を樹脂中に分散した樹脂分散型キャリア芯材等がある。
【０１７７】
ここでフェライト系キャリア芯材の例としては、一般的に下記式で表される。
【０１７８】
（ＭＯ）_Ｘ（Ｆｅ_２Ｏ_３）_Ｙ
式中、Ｍは、Ｃｕ，Ｚｎ，Ｆｅ，Ｍｇ，Ｍｎ，Ｃａ，Ｌｉ，Ｔｉ，Ｎｉ，Ｓｎ，Ｓｒ，Ａｌ，Ｂａ，Ｃｏ，Ｍｏ等から選ばれる少なくとも１種を含有する。またＸ，Ｙは重量モル比を示し、かつ条件Ｘ＋Ｙ＝１００を満たす。
【０１７９】
フェライト系キャリア芯材は、Ｆｅ_２Ｏ_３を主原料に、Ｍは、Ｃｕ，Ｚｎ，Ｆｅ，Ｍｇ，Ｍｎ，Ｃａ，Ｌｉ，Ｔｉ，Ｎｉ，Ｓｎ，Ｓｒ，Ａｌ，Ｂａ，Ｃｏ，Ｍｏ等から選ばれる少なくとも１種の酸化物を混合して原料に用いる。
【０１８０】
フェライト系キャリア芯材の製造方法の例としては、まず上記各酸化物等の原料を適量配合し、湿式ボールミルで１０時間粉砕、混合し、乾燥させた後、９５０℃で４時間保持する。これを湿式ボ−ルミルで２４時間粉砕し、さらに結着剤としてポリビニルアルコール、消泡剤、分散剤等を加え、原料粒子径が５μｍ以下のスラリ−とする。このスラリーを造粒乾燥し、造粒物を得て、酸素濃度をコントロールしながら１３００℃で６時間保持した後、粉砕し、さらに所望の粒度分布に分級して得る。
【０１８１】
本発明の樹脂被覆層に用いる樹脂としては、フッ素変性シリコーン系樹脂が必須である。そのフッ素変性シリコーン系樹脂としては、パーフロロアルキル基含有の有機ケイ素化合物を必須とし、下記（化６）及び／または（化７）を加水分解させて得られる硬化性架橋型フッ素変性シリコーン樹脂が好ましい。
【０１８２】
【化６】

【０１８３】
【化７】

【０１８４】
（式中、Ｒ_１、Ｒ_２、Ｒ_３は水素原子、ハロゲン原子、ヒドロキシ基、メトキシ基、炭素数１〜４のアルキル基、フェニル基を示す。）
パーフロロアルキル基含有の有機ケイ素化合物の例としては、ＣＦ_３ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３、Ｃ_４Ｆ_９ＣＨ_２ＣＨ_２Ｓｉ（ＣＨ_３）（ＯＣＨ_３）_２、Ｃ_８Ｆ_１７ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３、Ｃ_８Ｆ_１７ＣＨ_２ＣＨ_２Ｓｉ（ＯＣ_２Ｈ_５）_３、（ＣＦ_３）_２ＣＦ（ＣＦ_２）_８ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３等が挙げられるが、特にトリフロロプロピル基を有するものが好ましい。
【０１８５】
また、本実施形態においては、アミノシランカップリング剤を被覆樹脂層に含有させる。このアミノシランカップリング剤としては公知のものでよく、例えばγ−（２−アミノエチル）アミノプロピルトリメトキシシラン、γ−（２−アミノエチル）アミノプロピルメチルジメトキシシラン、オクタデシルメチル〔３−（トリメトキシシリル）プロピル〕アンモニウムクロライド（上からＳＨ６０２０、ＳＺ６０２３、ＡＹ４３−０２１：共に東レダウコーニングシリコーン社製）、ＫＢＭ６０２、ＫＢＭ６０３、ＫＢＥ９０３、ＫＢＭ５７３（信越シリコーン社製）等が挙げられるが、特には、１級アミンのものが好ましい。メチル基、エチル基、フェニル基等で置換された２級または３級のアミンでは極性が弱く、トナーとの帯電立ち上がり特性に対して効果が少ない。また、アミノ基の部分が、アミノメチル基、アミノエチル基、アミノフェニル基になると、シランカップリング剤の最先端は、１級アミンであるが、シランから伸びる直鎖の有機基中のアミノ基は、トナーとの帯電立ち上がり特性に寄与せず、逆に高湿時に水分の影響を受けるため、最先端のアミノ基により初期のトナーとの帯電付与能力は有するものの、耐刷時に帯電付与能力が下がり、最終的には寿命が短いものトナーる。
【０１８６】
そこで、これらのアミノシランカップリング剤とフッ素変成シリコーンを組み合わせて併用することにより、トナーに対して正極性の帯電性を有するフッ素変性シリコ−ン樹脂層に、シャ−プな帯電量分布を確保したまま、負帯電性を付与でき、かつ補給されたトナーに対し、早い帯電立ち上がり性を有し、トナー消費量を低減させることができる。さらに、アミノシランカップリング剤が架橋剤の如き効果を発現し、ベース樹脂であるフッ素変性シリコーン樹脂層の架橋度を向上させ、被膜樹脂硬度をさらに向上させ、長期使用での摩耗・剥離等が低減でき、耐スペント性を向上させ、帯電付与能力の低下を抑えられ、帯電の安定化が図られ、耐久性が向上する。さらに後述する特定の低融点のワックスを一定量以上添加したトナーと組合わせて使用することにより、現像器内でのハンドリング性が向上し、画像上において現像の奥側と手前側での濃度の均一性が向上する。またベタ画像採取後に履歴が残るいわゆる現像メモリーも低減できる。
【０１８７】
アミノシランカップリング剤の使用割合としては、樹脂に対して、５〜４０重量％、好ましくは１０〜３０重量％である。５重量％未満であるとアミノシランカップリング剤の効果がなく、４０重量％を越えると樹脂被覆層の架橋度が高くなり過ぎ、チャ−ジアップ現象を引き起こし易くなり、現像性不足等の画像欠陥の発生原因トナーることがある。
【０１８８】
また、帯電安定化のため，チャージアップを防止するため、樹脂被覆層には導電性微粒子を含有することも可能である。導電性微粒子としては、オイルファーネスカーボンやアセチレンブラックのカーボンブラック、酸化チタン、酸化亜鉛などの半導電性酸化物、酸化チタン、酸化亜鉛、硫酸バリウム、ホウ酸アルミニウム、チタン酸カリウム等の粉末表面を酸化スズやカーボンブラック、金属で被覆したもの等が挙げられ、その固有抵抗が１０^１０Ω・ｃｍ以下のものが好ましい。導電性微粒子を用いる場合の含有量は１〜１５重量％が好ましい。導電性微粒子は、樹脂被覆層に対し、ある程度の含有量であれば、フィラ−効果により樹脂被覆層の硬度の向上をもたらすが、１５重量％を越えると、逆に樹脂被覆層の形成を阻害し、密着性・硬度の低下の原因トナーる。さらには、フルカラ−現像剤における導電性微粒子の過剰の含有量は、紙面上に転写・定着されたトナーの色汚れの原因トナーる。
【０１８９】
本実施形態のキャリアの平均粒径は２０〜７０μｍが好ましい。キャリアの平均粒径が２０μｍ未満では、キャリア粒子の分布において微粒子の存在率が高くなり、それらのキャリア粒子はキャリア１粒子当たりの磁化が低くなるため、キャリアが感光体に現像されやすくなる。また、キャリアの平均粒子が７０μｍを超えると、キャリア粒子の比表面積が小さくなり、トナー保持力が弱くなるため、トナー飛散が発生する。また、ベタ部分の多いフルカラーでは、特にベタ部の再現が悪く好ましくない。
【０１９０】
キャリア芯材上に被覆層を形成する方法には、特に制限はなく、公知の被覆方法、例えば、キャリア芯材である粉末を、被膜層形成用溶液中に浸漬する浸漬法、被膜層形成用溶液をキャリア芯材の表面に噴霧するスプレー法、キャリア芯材を流動エアーにより浮遊させた状態で被膜層形成用溶液を噴霧する流動床法、ニーダーコーター中でキャリア芯材と被膜層形成用溶液を混合し、溶剤を除去するニーダーコーター法等の湿式被覆方法の他、粉末状の樹脂とキャリア芯材とを高速混合し、その摩擦熱を利用することで樹脂粉末をキャリア芯材表面に融着被覆する乾式被覆方法等が挙げられ、いずれも適用することができるが、湿式被覆方法が特に好ましく用いられる。
【０１９１】
被膜層形成用塗布液に使用する溶剤は、前記コート樹脂を溶解するものであれば特に限定されるものではなく、用いられるコート樹脂に適合するように選択することができる。一般的には、例えば、トルエン、キシレン等の芳香族炭化水素類、アセトン、メチルエチルケトン等のケトン類、テトラヒドロフラン、ジオキサンなどのエーテル類が使用できる。
【０１９２】
樹脂被覆量はキャリア芯材に対し、０．２〜６．０重量％が好ましく、より好ましくは０．５〜５．０重量％、さらに好ましくは０．６〜４．０重量％、０．７〜３重量％である。樹脂の被覆量が０．２重量％未満になると、キャリア表面に均一な被覆を形成することができずキャリア芯材の特性の影響を大きく受けてしまい、本発明のフッ素変性シリコ−ン樹脂とアミノシランカップリング剤の効果を充分に発揮できない。６．０重量％を超えると被覆層が厚くなり過ぎ、キャリア粒子同士の造粒が発生し、均一なキャリア粒子が得られない傾向にある。
【０１９３】
樹脂を被覆した後は、硬化処理の条件としては、１２０〜２８０℃、０．５〜２．５時間が適当である。処理温度が低いと被膜樹脂自体の硬度が低下する。処理温度が高すぎると帯電低下が生じる。
（９）粉砕
本実施形態に係るトナーは、小粒径化してもキャリアへのスペントを防止でき、オイルレス定着を実現することができる。
【０１９４】
その粉砕の一手法として例示すると、小粒径でかつ粒度分布をシャープにするため、トナー組成物を溶融混練した後、表面に凹凸を有し高速に回転する円筒状の回転体と、回転体の外側に０．５ｍｍ〜４０ｍｍの間隙を存して嵌装され、回転体と中心軸を共有する表面に凹凸を有する円筒状の固定体と、被トナー粉砕物を流入させる供給口と、粉砕処理されたトナー粉砕物を排出する排出口とを具備する粉砕機により、所定の粒度分布に粉砕される。このとき、被トナー粉砕物を供給口から流入させる前に、被トナー粉砕物の凝集を緩和する手段を付加させ、前記供給口から流入させて所定の粒度分布へ粉砕させる構成とする。
【０１９５】
被トナー粉砕物の凝集を緩和する手段としては、被トナー粉砕物を供給口から流入させる前に、被トナー粉砕物に蒸発性の媒体、例えば、水蒸気、エタノール、ｉｓｏ−プロピルアルコール、ｎ−ブチルアルコール、ｓｅｃ−ブチルアルコール、ｉｓｏ−ブチルアルコール等で粉体の電荷を除去できることが目的である。被トナー粉砕物に霧状に噴霧供給して混合又は付着させ、粉砕供給口から流入させる方法である。
【０１９６】
また、被トナー粉砕物を供給口から流入させる前に、前記被トナー粉砕物に振動手段を付加させて、供給する方法で、振動手段としては超音波振動、バイブレーション振動等がある。被トナー粉砕物が配管内を通過して粉砕部供給口から流入させる前に配管部に振動装置を具備させ、被トナー粉砕物を分散させながら供給口から流入させる。
【０１９７】
また、被トナー粉砕物を定量供給機から流入させる前に、前記被トナー粉砕物と無機微粉末とあらかじめ混合しておき、その混合物を前記定量供給機から流入させて粉砕する方法がある。無機微粉末としては前記した材料が適当である。
【０１９８】
また、トナーを粉砕処理する際、被トナー粉砕物を定量供給機から流入させる前に、無機微粉末を無機微粉末供給機から供給して混合させ、粉砕入口から流入させて所定の粒度分布へ粉砕する構成も取れる。また同時に投入させることも可能である。
【０１９９】
これにより被トナー粉砕物が均一に分散した状態で回転体を有する粉砕部に突入し、回転体の生ずる渦流により被トナー粉砕物が均一に粉砕される。これにより小粒径化粉砕と、粗粉をシャープにカットされた状態での粉砕が可能となる。
【０２００】
このとき供給して混合させる無機微粉末が、平均粒径８〜４０ｎｍ、強熱減量が０．５〜２５ｗｔ％であるシリカ又は酸化チタン微粉末が好ましい。さらには脂肪酸エステル、脂肪酸アミド、脂肪酸金属塩のいずれか１種または２種以上を表面処理したシリカ又は酸化チタン微粉末が好ましい。さらには、無機微粉末が、シリコーンオイルを表面処理したシリカ又は酸化チタン微粉末が好ましい材料である。また被トナー粉砕物の電荷を緩和する目的でトナー母体粒子の帯電極性と逆帯電極性を有する無機微粉末も有効な手段である。
【０２０１】
平均粒径が８ｎｍより小さいと、定量切出しが不安定トナーる。平均粒径が４０ｎｍより大きいと均一粉砕性が良くならない。強熱減量が０．５ｗｔ％より小さいと、微粉末が飛散してしまう。強熱減量が２５ｗｔ％より大きいと微粉末の凝集が強くなり、被トナー粉砕物の均一供給性が悪くなる。
【０２０２】
この無機微粉末はトナー母体に固着されるこトナーく静電気的な付着状態でトナー表面に付着する。無機微粉末の供給量としては被トナー粉砕物の供給量の０．１〜５ｗｔ％程度が好ましい。
【０２０３】
回転体の凸部と、固定体の凸部との間隙を０．５〜４０ｍｍ、好ましくは０．５〜１０ｍｍ、より好ましくは０．５〜６ｍｍにすることにより粉砕効率と球形化作用をより高めることができる。０．５ｍｍより小さいと粒子と回転体、固定体との接触が著しく増大するので、摩擦熱の発生が著しくなり、上記の先端部でトナーの融着が生じる。４０ｍｍより大きいと高速気流の激しい流動を発生させることができず、充分な粉砕性が得られない。
【０２０４】
この方式で行うと粉砕と同時に外添処理を施すことが可能であるため、製造工程が短縮できるメリットが大きい。またトナーは粒子の角が取られ球形化されるため、流動性は向上する。
【０２０５】
トナーの流動性が低いとベタ画像部にムラが発生したり、摩擦帯電性が低下し、逆極性トナーが増加し、感光体の非画像部にトナーが強く付着し除去できず、地カブリトナーって画像を劣化させるし、また転写効率が低下する。外添剤シリカを増量してトナーの流動性を上げると、摩擦帯電が均一化し、地カブリの減少と、画像濃度の増加、ベタ黒画像部のムラが解消される傾向にある。しかし感光体へのシリカやトナーのフィルミングや、シリカ凝集物のベタ黒画像部への白点付着等の課題が発生する。
【０２０６】
そのため、少量のシリカの添加量で高流動性が得られ、浮遊シリカの発生が抑えられ、ベタ黒画像部へのシリカの白点や、中間転写体や感光体へのシリカ、トナーフィルミングの発生が抑えられる。また低流動性のトナーで見られるベタ黒画像部のムラの発生が抑えられ、均一な転写性が得られ、さらに逆極性トナーの発生を低く抑えられるため、転写効率が向上する要因トナーる。
【０２０７】
さらに転写時において、特に高温高湿時、文字やライン等のトナーが集中しているところで、所定の押圧力で転写しても、トナーの高流動性のため、トナー同士の凝集が起きにくく、中抜けのない鮮明な画像が得られる。
【０２０８】
図３に示した本実施形態のトナーの粉砕装置の１実施例について説明する。
混練物を粗粉砕によりメッシュ径約１〜５ｍｍパスした被トナー粉砕物５０３は定量供給機５０８から投入され、冷却器５０９によって供給される冷却エアー５１１により、粉砕供給部に送られ、粉砕処理部５００で粉砕される。原料５０３は粉砕入口５０４から投入され、高速に回転し表面に凹凸部５０６を有する回転体５０１と、この回転体５０１と狭ギャップの間隙で位置している表面に凹凸部５０７を有する固定体５０２との空間に運ばれ、高速に回転する回転体と固定体の間に発生する高速気流の流動に伴って、原料粒子相互が強力な衝突により粉砕されながら球形化される。球形化された粒子５１０は排出口５０５から出て、粗粉分級機５１３に送られ、粗い粒子は再度エアー５１１により、粉砕入口５０４に送られる。製品はサイクロン５１５に送られ、補集容器５２０に回収される。５１２は温度計、５１４はバグフィルター、５１６は風量計、５１７はブロアである。
【０２０９】
５１９はバイブレータ振動装置、５１８は無機微粉末供給機である。粗粉分級によリ分離され再度粉砕部に供給されるとき、無機微粉末供給をその後ろから供給することが好ましい。これにより無機微粉末が粉砕物への衝突の際に均一に混合される。無機微粉末の代わりに蒸発性の溶剤の供給の可能である。
【０２１０】
図４に図３のＩ−Ｉ断面図を上から見たものである。凹凸部は全周に渡り付加されている。図にはその一部を記載し、後は省略している。図５は図４のＢの箇所を拡大したものである。ｓ１は固定体５０２の表面凹凸部５０７の凸部の幅、ｓ２は固定体５０２の表面凹凸部５０７の凸部間の距離、ｓ３は固定体５０２の表面凹凸部５０７の凸部の高さ、ｒ１は回転体５０１の表面凹凸部５０６の凸部の幅、ｒ２は回転体５０１の表面凹凸部５０６の凸部間の距離、ｒ３は固定体５０１の表面凹凸部５０６の凸部の高さを示す。回転体が高速に回転し、シリカ等の無機微粉末の供給を受けながら効率よくトナーを小粒径化しかつ球形化して粉砕するためには、固定体５０２の表面凹凸部５０７の密度を回転体５０１の表面凹凸部５０６の密度よりも高くする構成とすることにより実現できる。凸部は周長１ｃｍ当り１個以上とする構成が好ましい。好ましくは２．５個以上である。さらには０．２≦ｓ１／ｒ１≦０．７、０．２≦ｓ２／ｒ２≦０．７の関係を有することが好ましい。特に無機微粉末を供給しながら粉砕処理する際、被粉砕物が均一に分散された状態で投入されるため、固定体の壁面との衝突を安定化させるためには密度を高する必要がある。０．２よりも小さくなると、表面加工の際のコストアップトナーる。０．７よりも大きくなると、渦流の流れが不均一トナーり小粒径への粉砕が困難トナーる。
（１０）重合方法
小粒径トナーの作成方法としては、乳化重合法、懸濁重合法なども好適に使用できる。
【０２１１】
乳化重合法では、イオン性界面活性剤を含有する樹脂微粒子分散液を調製し、着色剤粒子分散液及びワックスの離型剤粒子分散液と混合し、前記イオン性界面活性剤とは反対の極性を有するイオン性界面活性剤により凝集を生じさせることによりトナー径の凝集粒子を形成させ、その後樹脂微粒子のガラス転移点以上の温度に加熱して前記凝集粒子を融合して、洗浄、乾燥する手段によりトナーを作成することができる。
【０２１２】
この時使用する界面活性剤を例示すると、硫酸エステル塩系、スルホン酸塩系、リン酸エステル系、せっけん系等のアニオン性界面活性剤、及びアミン塩型、４級アンモニウム塩型等のカチオン性界面活性剤を使用することができる。また、ポリエチレングリコール系、アルキルフェノールエチレンオキサイド付加物系、多価アルコール系等の非イオン性界面活性剤を併用することも効果的である。これらの分散手段としては、回転剪断型ホモジナイザーやメディアを有するボールミル、サンドミル、ダイノミルなどの一般的なものを使用できる。
【０２１３】
粒子生成後は、任意の洗浄工程、固液分離工程、乾燥工程を経て所望のトナーを得ることができるが、洗浄工程は、帯電性を発現・維持するため、十分にイオン交換水による置換洗浄を施すことが好ましい。また、固液分離工程は、特に制限はないが、生産性の点から吸引濾過、加圧濾過等が好ましく用いられる。さらに乾燥工程も特に制限はないが、生産性の点から凍結乾燥、フラッシュジェット乾燥、流動乾燥、振動型流動乾燥等が好ましく用いられる。
【０２１４】
また懸濁重合法では、重合性単量体、ワックス、着色剤等の各種添加剤を均一に溶解または分散させて加熱しホモジナイザー、超音波分散機等によって均一に溶解又は分散せしめ単量体組成物としたのち、単量体系を、分散安定剤を含有する単量体系と同温の水相中に通常の攪拌機又はホモミキサー・ホモジナイザー等により分散せしめる。
【０２１５】
好ましくは、単量体液滴が所定のトナー粒子のサイズの粒径を有するように攪拌速度・時間を調整し、その後は分散安定剤の作用により、粒子状態が維持され、かつ粒子の沈降が防止される程度の攪拌を行えば良い。重合温度は４０℃以上、一般には５０〜８０℃の温度に設定させる。
【０２１６】
このとき定着助剤の高分散化と、定着助剤を包含したトナー粒子を小さく均一な粒度分布とするためにも、回転攪拌速度は３０ｍ／ｓｅｃ以上が好ましい。
【０２１７】
反応終了後、生成したトナー粒子を洗浄、ろ過により回収し、乾燥する。懸濁重合においては通常単量体系１００重量部に対して水３００〜３０００重量部を分散媒として使用するのが好ましい。
【０２１８】
用いられる分散媒は、いずれも適当な安定化剤、有機化合物として、ポリビニルアルコール、ゼラチン、メチルセルコロース、メチルヒドロキシプロピルセルロース、エチルセルロース、カルボキシメチルセルロースのナトリウム塩、ポリアクリル酸及びその塩、デンプン、無機化合物としては、りん酸三カルシウム、リン酸マグネシウム、リン酸アルミニウム、リン酸亜鉛、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、硫酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、メタケイ酸カルシウム、ベントナーイト、シリカ、アルミナ等を水相に分散させて使用できる。
【０２１９】
分散安定剤の中で、無機化合物を用いる場合、より細かい粒子を得るため、水系媒体中で該無機化合物を生成させても良い。例えば、りん酸カルシウムの場合高速攪拌下において、リン酸ナトリウム水溶液と塩化カルシウム水溶液を混合すると良い。
【０２２０】
またこれらの安定化剤の微細な分散のために、０．００１〜０．１重量部の界面活性剤を使用しても良い。これは上記分散安定剤の所期の作用を促進するためのものであり、その具体例として、ドデシルベンゼン硫酸ナトリウム、テトラデシル硫酸ナトリウム、ペンタデジル硫酸ナトリウム、オクチル硫酸ナトリウム、オレイン酸ナトリウム、ラウリル酸ナトリウム、ステアリン酸カリウム、オレイン酸カルシウム等が挙げられる。
【０２２１】
重合開始剤としては、２，２’−アゾビスー（２，４−ジメチルバレロニトリル）、２，２’−アゾビスイソブチロニトリル、１，１’−アゾビス（シクロヘキサンー１−カルボニトリル）、２，２’−アゾビスー４−メトキシー２，４−ジメチルバレロニトリル、アゾビスイソブチロニトリル等のアゾ系又はジアゾ系重合開始剤が使用できる。
（１１）二成分現像
感光体と現像ローラ間には直流バイアスと共に交流バイアスを印加する。そのときの周波数が１〜１０ｋＨｚ、交流バイアスが１．０〜２．５ｋＶ（ｐ−ｐ）であり、かつ感光体と現像ローラ間の周速度比が１：１．２〜１：２であることが好ましい。
【０２２２】
より好ましくは周波数が３．５〜８ｋＨｚ、交流バイアスが１．２〜２．０ｋＶ（ｐ−ｐ）であり、かつ感光体と現像ローラ間の周速度比が１：１．５〜１：１．８である。
【０２２３】
更に好ましくは周波数が５．５〜７ｋＨｚ、交流バイアスが１．５〜２．０ｋＶ（ｐ−ｐ）であり、かつ感光体と現像ローラ間の周速度比が１：１．６〜１：１．８である。
【０２２４】
この現像プロセス構成と本実施形態のトナー又は二成分現像剤の使用により、ドットを忠実に再現でき、現像γ特性をねかせる特性とできる。高画質画像とオイルレス定着性を両立できる。また高抵抗キャリアでも低湿下でのチャージアップを防止でき、連続使用においても高画像濃度を得ることができる。これは高帯電性を発現できるトナー、キャリア構成と交流バイアスとの併用により、キャリアとの付着力を低減でき画像濃度を維持できると共にカブリを低減でき、ドットをも忠実に再現できるものと思われる。
【０２２５】
周波数が１ｋＨｚより小さいと、ドット再現性が悪化し、中間調再現性が悪化する。周波数が１０ｋＨｚを超えると、現像領域での追随ができず、効果が現れない。この周波数の領域では高抵抗キャリアを使用した二成分現像において、現像ローラと感光体間よりもキャリアとトナー間での往復作用に働き、トナーをキャリアから微少に遊離させる効果があり、これによりドット再現性、中間調再現性が良好に行われ、かつ高画像濃度を出すことが可能になる。
【０２２６】
交流バイアスが１．０ｋＶ（ｐ−ｐ）未満であると、チャージアップの抑制の効果が得られず、交流バイアスが２．５ｋＶ（ｐ−ｐ）を超えるとカブリが増大する。感光体と現像ローラ間の周速度比が１：１．２より小さいと（現像ローラが遅くなる）画像濃度が得にくい。感光体と現像ローラ間の周速度比が１：２を超えると（現像ローラ速度が上がる）とトナー飛散が多くなる。
（１２）タンデムカラープロセス
また、高速にカラー画像を形成するために、本実施形態では、感光体と帯電手段とトナー担持体を含むトナー像形成ステーションを複数個有し、像担持体上に形成した静電潜像を顕像化したトナー像を、前記像担持体に無端状の転写体を当接させて前記転写体に転写させる一次転写プロセスが順次連続して実行して、前記転写体に多層の転写トナー画像を形成し、その後前記転写体に形成した多層のトナー像を、一括して紙やＯＨＰ等の転写媒体に一括転写させる二次転写プロセスが実行されるよう構成された転写プロセスにおいて、第１の一次転写位置から第２の一次転写位置までの距離をｄ１（ｍｍ）、感光体の周速度をｖ（ｍｍ／ｓ）とした場合、ｄ１／ｖ≦０．６５トナーる転写位置構成を取る構成で、マシンの小型化と印字速度の両立を図るものである。毎分１６枚（Ａ４）以上処理でき、かつマシンがＳＯＨＯ用途として使用できる大きさの小型化を実現するためには、複数のトナー像形成ステーション間を短く、かつプロセス速度を高める構成が必須である。その小型化と印字速度の両立のためには上記値が０．６５以下とする構成がミニマムと考えられる。
【０２２７】
しかし、この構成をとるとき、例えば１色目のイエロートナーが一次転写された後、次の２色目のマゼンタトナーが一次転写されるまでの時間が極めて短く、転写体の帯電緩和又は転写されたトナーの電荷緩和が殆ど生じず、イエロートナーの上にマゼンタトナーを転写する際に、マゼンタトナーがイエロートナーの電荷作用により反発され、転写効率の低下、転写時の文字の中抜けという問題が生じる。さらに第３色目のシアントナーの一次転写の時、前のイエロー、マゼンタトナーの上に転写される際にシアントナーの飛び散り、転写不良、転写中抜けが顕著に発生する。さらに繰り返し使用しているうちに特定粒径のトナーが選択的に現像され、トナー粒子個々の流動性が大きく異なると摩擦帯電する機会が異なるため、帯電量のバラツキが生じ、より転写性の劣化を招いてしまう。
【０２２８】
そこで、本実施形態のトナー又は二成分現像剤を使用することにより、帯電分布が安定化しトナーの過帯電を抑えると共に、流動性変動を抑えることができる。そのため定着特性を犠牲にするこトナーく、転写効率の低下、転写時の文字の中抜け、逆転写を防止することができる。
（１３）クリーナレスプロセス
また、本実施形態では、転写プロセス後に感光体上に残留したトナーをクリーニングにより回収するクリーニングプロセス工程を有さずに、次の帯電、露光、現像プロセスを行うクリーナーレスプロセスを基本構成とする電子写真装置に好適に使用される。
【０２２９】
本実施形態のトナー又は二成分現像剤の使用により、トナーの凝集を抑え、過帯電を防止し、帯電性の安定化が得られ、高転写効率を得ることが可能トナーる。また樹脂中での均一分散性の向上、良好な帯電性、材料の有する離型性により、非画像部に残留したトナーの現像での回収が良好に行える。そのため、非画像部の前の画像パターンが残る現像メモリーも発生もない。
（１４）オイルレスカラー定着
本実施形態では、トナーを定着する手段にオイルを使用しないオイルレス定着構成の定着プロセスを具備する電子写真装置に好適に使用される。その加熱手段としては電磁誘導加熱が温度立上り省エネの観点から好ましい構成である。磁場発生手段と、電磁誘導により発生する発熱層及び離型層を少なくとも有する回転加熱部材と、該回転加熱部材と一定のニップを形成している回転加圧部材とを少なくとも有する加熱加圧手段を使用して、回転加熱部材と回転加圧部材間にトナーが転写された複写紙等の転写媒体を通過させ、定着させる構成である。
【０２３０】
また加熱部材と定着部材を分離した定着ベルトを使用した構成も好ましく使用される。
【０２３１】
そのベルトとしては耐熱性と変形自在性とを有するニッケル電鋳ベルトやポリイミドベルトの耐熱ベルトが好適に用いられる。離形性を向上するために表面層としてシリコーンゴム、フッ素ゴム、フッ素樹脂を用いる構成である。
【０２３２】
これらの定着においてはこれまでは離型オイルを塗布してオフセットを防止してきた。オイルを使用せずに離型性を有するトナーにより、離型オイルを塗布する必要はなくなった。しかし離型オイルを塗布しないと帯電しやすく、未定着のトナー像が加熱部材又は定着部材と近接すると帯電の影響により、トナー飛びが生じる場合がある。特に低温低湿下において発生しやすい。
【０２３３】
そこで、本実施形態のトナーの使用により、オイルを使用せずともオフセットの発生を防止でき、カラー高透光性を得ることができる。またトナーの過帯電性を抑制でき加熱部材又は定着部材との帯電作用によるトナーの飛びを抑えられる。
【０２３４】
【実施例】
次に、実施例により本発明を更に詳細に説明する。ただし本発明はこれに限定されるものではない。なお、下記の実施例において、単に％と記載しているのはｗｔ％を意味する。
【０２３５】
（キャリア製造例１）
１５モル％のトリフロロプロピル基を含有する架橋型フッ素変性シリコーン樹脂を固形分換算で１２０ｇ、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン６ｇを３００ｃｃのトルエン溶剤に溶解させた。これを平均粒径５０μｍ、印加磁場が３０００エルステットの時の飽和磁化が６５ｅｍｕ／ｇであるフェライト粒子１０ｋｇに対し、液浸乾燥式被覆装置を用いてコーティング処理し、その後２３０℃で１．５時間焼き付けを行い、キャリアＡ１を得た。
【０２３６】
（キャリア製造例２）
被覆樹脂を１５モル％のＣ_８Ｆ_１７ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３を含有する架橋型フッ素変性シリコーン樹脂に変更した以外は、製造例１と同様の工程でコア材を製造し、コーティングを行い、キャリアＡ２を得た。
【０２３７】
（キャリア製造例３）
導電性カーボン（ケッチェンブラックインタ−ナショナル社製 ＥＣ）を樹脂固形分に対し５モル％をパールミルにて分散した以外は、製造例１と同様の工程でコア材を製造し、コーティングを行い、キャリアＡ３を得た。
【０２３８】
（キャリア製造例４）
アミノシランカップリング剤の添加量を３０ｇに変更した以外は、製造例３と同様の工程でコア材を製造し、コーティングを行い、キャリアＡ４を得た。
【０２３９】
（キャリア製造例５、比較例）
アミノシランカップリング剤の添加量を５０ｇに変更した以外は、製造例３と同様の工程でコア材を製造し、コーティングを行い、キャリアｂ１を得た。
【０２４０】
（キャリア製造例６、比較例）
被覆樹脂をストレートシリコーン（東レ・ダウコーニング社製 ＳＲ−２４１１）に変更した以外は、製造例１と同様の工程でコア材を製造し、コーティングを行い、キャリアｂ２を得た。
【０２４１】
（キャリア製造例７、比較例）
被覆樹脂をパーフルオロオクチルエチルアクリレート／メタクリレート共重合体に変更した以外は、製造例３と同様の工程でコア材を製造し、コーティングを行い、キャリアｂ３を得た。
【０２４２】
（キャリア製造例８、比較例）
被覆樹脂をアクリル変性シリコーン樹脂（信越化学社製 ＫＲ−９７０６）に変更した以外は、キャリア製造例３と同様の工程でコア材を製造し、コーティングを行い、キャリアｂ４を得た。
【０２４３】
（表１）に実施例で使用する結着樹脂の特性を示す。樹脂はビスフェノールＡプロピルオキシド付加物、テレフタル酸、トリメリット酸、コハク酸、フマル酸を主成分としたポリエステル樹脂を使用し、配合比、重合条件により熱特性を変えた樹脂を使用した。この２価のアルコールと２価のカルボン酸、３価のカルボン酸の構成が定着性、分散性、キャリアのスペント性、粉砕性を両立させるために好適な構成である。
【０２４４】
【表１】

【０２４５】
Ｍｎｆは結着樹脂の数平均分子量、Ｍｗｆは結着樹脂の重量平均分子量、Ｍｚｆは結着樹脂のＺ平均分子量、Ｗｍｆは重量平均分子量Ｍｗｆと数平均分子量Ｍｎｆとの比Ｍｗｆ／Ｍｎｆ、Ｗｚｆは結着樹脂のＺ平均分子量Ｍｚｆと数平均分子量Ｍｎｆの比Ｍｚｆ／Ｍｎｆ、Ｔｇ（℃）はガラス点移転、Ｔｍ（℃）は軟化点、Ｔｆｂ（℃）は流出開始温度、ＡＶは樹脂酸価を示す。
【０２４６】
（表２）（表３）（表４）に本実施例で使用するワックス及びその物性値を示す。Ｍｎｒはワックスの数平均分子量、Ｍｗｒはワックスの重量平均分子量、ＭｚｒはワックスのＺ平均分子量を示す。Ｔｗ（℃）はＤＳＣ法による融点、Ｃｔ（％）は融点＋１０℃での容積増加率（％）、Ｃｋ（ｗｔ％）は２２０℃の加熱減量を示す。
【０２４７】
【表２】

【０２４８】
【表３】

【０２４９】
【表４】

【０２５０】
（表５）に本実施例で使用する顔料を示す。
【０２５１】
【表５】

【０２５２】
（表６）に本実施例で使用する電荷制御剤及びその物性値を示す。
【０２５３】
サリチル酸誘導体の金属塩として、炭素数１〜１０のアルキル基としては例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基等が挙げられる。金属Ｙとしては亜鉛、ニッケル、コバルト、銅、クロムが挙げられ、亜鉛、クロムが好ましい。ベンジル酸誘導体の金属塩としては、Ｒ^１〜Ｒ^４がベンゼン環、アルカリ金属Ｘとしてはリチウム、ナトリウム、カリウム等が挙げられ、カリウムが好ましい。
【０２５４】
【表６】

【０２５５】
（表７）に本実施例で使用する外添剤を示す。その帯電量はノンコートのフェライトキャリアとの摩擦帯電のブローオフ法により測定したものである。２５℃４５ＲＨ％の環境下で、１００ｍｌのポリエチレン容器にキャリア５０ｇとシリカ等０．１ｇを混合し、縦回転にて１００ｍｉｎ^−１の速度で５分、３０分間攪拌した後、０．３ｇ採取し、窒素ガス１．９６×１０^４（Ｐａ）で１分間ブローした。
【０２５６】
正帯電性では５分間攪拌後の５分値が＋１００〜＋８００μＣ／ｇで、３０分間攪拌後の３０分の値が＋５０〜＋４００μＣ／ｇであることが好ましい。３０分値での帯電量が５分値での帯電量の４０％以上を維持しているシリカが好ましい。低下率が大きいと長期連続使用中での帯電量の変化が大きく、一定の画像を維持できなくなる。
【０２５７】
負帯電性では５分値が−１００〜−８００μＣ／ｇで、３０分の値が−５０〜−６００μＣ／ｇであることが好ましい。高い帯電量のシリカでは少量の添加量で機能を発揮できる。
【０２５８】
【表７】

【０２５９】
（表８）に本実施例で使用する粗大粒子を示す。形状は真球状でなく、不定形またはやや不定形のものが好ましい。不定形の方が帯電立上り性や、キャリアとの攪拌混合性が良好なためである
【０２６０】
【表８】

【０２６１】
（表９）に本実施例での粉砕条件を示す。
【０２６２】
本実施例では、ｓ１は１ｍｍ、ｓ２は４ｍｍ、ｓ３は３ｍｍ、ｒ１は４ｍｍ、ｒ２は７ｍｍ、ｒ３は３ｍｍ、回転体の周長は５６．５ｃｍとした。シリカ付着量は粉砕後にトナーに付着残留したシリカ量である。約４０％程度がトナーに残留せず、バグフィルタに持って行かれている。
【０２６３】
【表９】

【０２６４】
（表１０）（表１１）に本実施例に本実施例で使用したトナー材料組成、物性値を示す。
【０２６５】
【表１０】

【０２６６】
【表１１】

【０２６７】
図中、Ｓｓは粉砕されたトナーの比表面積値、Ｓｔは、Ｓｔ＝６／（トナーの真比重＊体積平均粒子径）、で表される値、ＳＳｔは、ＳｔをＳｓ（粉砕されたトナーの比表面積値）で割った値である。
【０２６８】
顔料の添加量は結着樹脂１００重量部に対して５重量部添加した。表中には示していないが表５に示した顔料を使用し、各色略同一の材料組成を使用した。電荷制御剤、ワックスの配合量比は結着樹脂１００重量部に対する配合量（重量部）比を括弧内に示す。外添剤はトナー母体１００重量部に対する配合量（重量部）を示している。
【０２６９】
外添処理はＦＭ２０Ｂにおいて、攪拌羽根Ｚ０Ｓ０型、回転数２０００ｍｉｎ^−１、処理時間５ｍｉｎ、投入量１ｋｇで行った。
【０２７０】
図１は本実施例で使用したフルカラー画像形成用の画像形成装置の構成を示す断面図である。図１において、カラー電子写真プリンタの外装筐は省略している。
転写ベルトユニット１７は、転写ベルト１２、弾性体よりなる第１色（イエロー）転写ローラ１０Ｙ、第２色（マゼンタ）転写ローラ１０Ｍ、第３色（シアン）転写ローラ１０Ｃ、第４色（ブラック）転写ローラ１０Ｋ、アルミローラよりなる駆動ローラ１１、弾性体よりなる第２転写ローラ１４、第２転写従動ローラ１３、転写ベルト１２上に残ったトナー像をクリーニングするベルトクリーナブレード１６、クリーナブレードに対向する位置にローラ１５を設けている。
【０２７１】
このとき、第１色（Ｙ）転写位置から第２色（Ｍ）転写位置までの距離は３５ｍｍ（第２色（Ｍ）転写位置から第３色（Ｃ）転写位置、第３色（Ｃ）転写位置から第４色（Ｋ）転写位置も同様距離）、感光体の周速度は１２５ｍｍ／ｓである。
【０２７２】
転写ベルト１２は、絶縁性ポリカーボネート樹脂中に導電性のフィラーを混練して押出機にてフィルム化して用いる。本実施例では、絶縁性樹脂としてポリカーボネート樹脂（たとえば三菱ガス化学製，ユーピロンＺ３００）９５重量部に、導電性カーボン（たとえばケッチェンブラック）５重量部を加えてフィルム化したものを用いた。また、表面にフッ素樹脂をコートし、厚みは約１００μｍ、体積抵抗は１０^７〜１０^１２Ω・ｃｍ、表面抵抗は１０^７〜１０^１２Ω／□である。ドット再現性を向上させためもある。転写ベルト１２の長期使用による弛みや，電荷の蓄積を有効に防止できるようにするためであり、また、表面をフッ素樹脂でコートしているのは、長期使用による転写ベルト表面へのトナーフィルミングを有効に防止できるようにするためである。体積抵抗が１０^７Ω・ｃｍよりも小さいと、再転写が生じ易く、１０^１２Ω・ｃｍよりも大きいと転写効率が悪化する。第１転写ローラは外径１０ｍｍのカーボン導電性の発泡ウレタンローラで、抵抗値は１０^２〜１０^６Ωである。第１転写動作時には、第１転写ローラ１０は、転写ベルト１２を介して感光体１に１．０〜９．８（Ｎ）の押圧力で圧接され、感光体上のトナーがベルト上に転写される。抵抗値が１０^２Ωよりも小さいと、再転写が生じ易い。１０^６Ωよりもおおきと転写不良が生じ易くなる。１．０（Ｎ）よりも小さいと転写不良を生じ、９．８（Ｎ）よりも大きいと転写文字抜けが生じる。
【０２７３】
第２転写ローラ１４は外径１５ｍｍのカーボン導電性の発泡ウレタンローラで、抵抗値は１０^２〜１０^６Ωである。第２転写ローラ１４は、転写ベルト１２及び紙、ＯＨＰ等の転写媒体１９とを介して転写ローラ１３に圧接される。この転写ローラ１３は転写ベルト１２に従動回転可能に構成している。第２次転写での第２転写ローラ１４と対向転写ローラ１３とは５．０〜２１．８（Ｎ）の押圧力で圧接され、紙等の記録材上１９に転写ベルトからトナーが転写される。抵抗値が１０^２Ωよりも小さいと、再転写が生じ易い。１０^６Ωよりも大きいと転写不良が生じ易くなる。５．０（Ｎ）よりも小さいと転写不良トナーり、２１．８（Ｎ）よりも大きいと負荷が大きくなり、ジッタが出やすくなる。
【０２７４】
イエロー（Ｙ）、マゼンタ（Ｍ）、シアン（Ｃ）、黒（Ｂ）の各色用の４組の像形成ユニット１８Ｙ、１８Ｍ、１８Ｃ、１８Ｋが、図のように直列状に配置されている。
【０２７５】
各像形成ユニット１８Ｙ、１８Ｍ、１８Ｃ、１８Ｋ、中に入れた現像剤を除きそれぞれ同じ構成部材よりなるので、説明を簡略化するためＹ用の像形成ユニット１８Ｙについて説明し、他色用のユニットの説明については省略する。
【０２７６】
像形成ユニットは以下のように構成されている。１は感光体、３は画素レーザ信号光、４は内部に１２００ガウスの磁力を有する磁石を有するアルミよりなる外径１２ｍｍの現像ロ−ラで、感光体とギャップ０．３ｍｍで対向し、矢印の方向に回転する。６は攪拌ローラで現像器内のトナーとキャリアを攪拌し、現像ローラへ供給する。キャリアとトナーの配合比を透磁率センサーにより読み取り（図示せず）、トナーホッパー（図示せず）から適時供給される構成である。５は金属製の磁性ブレードで現像ローラ上に現像剤の磁気フ゛ラシ層を規制する。現像剤量は１５０ｇ投入している。ギャップは０．４ｍｍとした。電源は、省略しているが、現像ローラ４には−５００Ｖの直流と、１．５ｋＶ（ｐ−ｐ）、周波数６ｋＨｚの交流電圧が印可される。感光体と現像ローラ間の周速度比は１：１．６とした。またトナーとキャリアの混合比は９３：７とし、現像器中の現像剤量は１５０ｇで行った。
【０２７７】
２はエピクロルヒドリンゴムよりなる外径１２ｍｍの帯電ローラで直流バイアス−１．２ｋＶが印加される。感光体１表面を−６００Ｖに帯電する。８はクリーナ、９は廃トナーボックス、７は現像剤である。
【０２７８】
紙搬送は転写ユニット１７の下方から搬送され、転写ベルト１２と第２転写ローラ１４との圧接されたニップ部に紙給送ローラ（図示せず）により紙１９が送られてくるように、紙搬送路が形成されている。
【０２７９】
転写ベルト１２上のトナーは第２転写ローラ１４に印加された＋１０００Ｖにより紙１９に転写され、定着ローラ２０１、加圧ローラ２０２、定着ベルト２０３、加熱媒体ローラ２０４、インダクションヒータ部２０５から構成される定着部に搬送され、ここで定着される。
【０２８０】
図２にその定着プロセス図を示す。定着ローラ２０１とヒートローラ２０４との間にベルト２０３がかけられている。定着ローラ２０１と加圧ローラ２０２との間に所定の加重がかけられており、ベルト２０３と加圧ローラ２０２との間でニップが形成される。ヒートローラ２０４の外部周面にはフェライトコア２０６、とコイル２０７よりなるインダクションヒータ部２０５が設けられ、外面には温度センサー２０８が配置されている。
【０２８１】
ベルトは３０μｍのＮｉを基体としてその上にシリコーンゴムを１５０μｍ、さらにその上にＰＦＡチューブ３０μｍの重ねあわせた構成である。
【０２８２】
加圧ローラ２０２は加圧バネ２０９により定着ローラ２０１に押しつけられている。トナー２１０を有する記録材１９は、案内板２１１に沿って動く。
【０２８３】
定着部材としての定着ローラ２０１は、長さが２５０ｍｍ、外径が１４ｍｍ、厚さ１ｍｍのアルミニウム製中空ローラ芯金２１３の表面に、ＪＩＳ規格によるゴム硬度（ＪＩＳ−Ａ）が２０度のシリコーンゴムからなる厚さ３ｍｍの弾性層２１４を設けている。この上にシリコーンゴム層２１５が３ｍｍの厚みで形成され外径が約２０ｍｍトナーっている。図示しない駆動モータから駆動力を受けて１２５ｍｍ／ｓで回転する。
【０２８４】
ヒートローラ２０４は肉厚１ｍｍ、外径２０ｍｍの中空パイプからなっている。定着ベルト表面温度はサーミスタを用いて表面温度１７０度に制御した。
【０２８５】
加圧部材としての加圧ローラ２０２は、長さが２５０ｍｍ、外径２０ｍｍである。これは外径１６ｍｍ、厚さ１ｍｍのアルミニウムからなる中空ローラ芯金２１６の表面にＪＩＳ規格によるゴム硬度（ＪＩＳ−Ａ）が５５度のシリコーンゴムからなる厚さ２ｍｍの弾性層２１７を設けている。この加圧ローラ２０２は、回転可能に設置されており、片側１４７Ｎのバネ加重のバネ２０９によって定着ローラ２０１との間で幅５．０ｍｍのニップ幅を形成している。
【０２８６】
以下、動作について説明する。フルカラーモードではＹ，Ｍ，Ｃ，Ｋのすべての第一転写ローラ１０が押し上げられ、転写ベルト１２を介して像形成ユニットの感光体１を押圧している。この時第一転写ローラには＋８００Ｖの直流バイアスが印可される。画像信号がレーザ光３から送られ、帯電ローラ２により表面が帯電された感光体１に入射し、静電潜像が形成される。感光体１と接触し回転する現像ローラ４上のトナーが感光体１に形成された静電潜像を顕像化する。
【０２８７】
このとき像形成ユニット１８Ｙの像形成の速度（感光体の周速に等しい１２５ｍｍ／ｓ）と転写ベルト１２の移動速度は感光体速度が転写ベルト速度よりも０．５〜１．５％遅くなるように設定されている。
【０２８８】
像形成工程により、Ｙの信号光３Ｙが像形成ユニット１８Ｙに入力され、Ｙトナーによる像形成が行われる。像形成と同時に第１転写ローラ１０Ｙの作用で、Ｙトナー像が感光体１Ｙから転写ベルト１２に転写される。このとき第１転写ローラ１０Ｙには＋８００Ｖの直流電圧を印加した。
【０２８９】
第１色（Ｙ）第一転写と第２色（Ｍ）第一転写間のタイムラグを持たせて、Ｍの信号光３Ｍが像形成ユニット１８Ｍに入力され、Ｍトナーによる像形成が行われ、像形成と同時に第１転写ローラ１０Ｍの作用で、Ｍトナー像が感光体１Ｍから転写ベルト１２に転写される。このとき第一色（Ｙ）トナーが形成されている上にＭトナーが転写される。同様にＣ（シアン）、Ｋ（ブラック）トナーによる像形成が行われ、像形成と同時に第１転写ローラ１０Ｃ、１０Ｂの作用で、ＹＭＣＫトナー像が転写ベルト１２上に形成される。いわゆるタンデム方式と呼ばれる方式である。
【０２９０】
転写ベルト１２上には４色のトナー像が位置的に合致して重ね合わされカラー像が形成された。最後のＢトナー像の転写後、４色のトナー像はタイミングを合わせて給紙カセット（図示せず）から送られる紙１９に、第２転写ローラ１４の作用で一括転写される。このとき転写ローラ１３は接地し、第２転写ローラ１４には＋１ｋＶの直流電圧を印加した。紙に転写されたトナー像は定着ローラ対２０１・２０２により定着された。紙はその後排出ローラ対（図示せず）を経て装置外に排出された。中間転写ベルト１２上に残った転写残りのトナーは、クリーニングブレード１６の作用で清掃され次の像形成に備えた。
【０２９１】
（表１２）に図１の電子写真装置により、画像出しを行った結果を示す。トナーが３色重なったフルカラー画像における文字部での転写不良の状態、及び定着での定着ベルトへの紙の巻付き性を評価した。帯電量はフェライトキャリアとの摩擦帯電のブローオフ法により測定したものである。２５℃４５％ＲＨの環境下で、耐久性評価のサンプルを０．３ｇ採取し、窒素ガス１．９６×１０^４（Ｐａ）で１分間ブローした。
【０２９２】
【表１２】

【０２９３】
現像剤ＤＭ１１〜ＤＭ１８を用いて画像出しを行ったところ、横線の乱れやトナーの飛び散り、文字の中抜けなどがなくベタ黒画像が均一で、１６本／ｍｍの画線をも再現した極めて高解像度高画質の画像が得られ、画像濃度１．３以上の高濃度の画像が得られた。
【０２９４】
ベタ画像を連続１０枚印字した後に白画像を取ったところ、非画像部への地かぶりは発生しなかった。
【０２９５】
その後にベタ画像を取った時に、トナーのキャリアへの供給不良混合性不良が見られず、現像メモリーの発生は見られなかった。
【０２９６】
Ａ４用紙１０万枚の長期耐久テストにおいても、流動性、画像濃度とも変化が少なく安定した特性を示した。キャリアへのトナー成分のスペントもほとんど生じていない。キャリア抵抗の変化、帯電量の低下も少なく、カブリは発生はない。高温高湿下、低温低湿下での帯電量の変動はほとんど生じていない。
【０２９７】
また転写においても中抜けは実用上問題ないレベルであり、逆転写の発生もごくわずかであった。転写効率は９５％程度を示した。また３色の重なったフルカラー画像においても、転写不良、逆転写は発生しなかった。
【０２９８】
また、感光体、転写ベルトへのトナーのフィルミングも実用上問題ないレベルであった。感光体上、転写ベルトのクリーニング不良も未発生であった。
【０２９９】
また３色の重なったフルカラー画像においても、定着時のトナーの乱れやトナー飛びもほとんど生じていない。定着時において、定着ベルトへの紙の巻付きは発生しなかった。
【０３００】
しかしｃｍ１〜ｃｍ１６の現像剤はプロセス速度１００ｍｍ／ｓ、感光体間の距離が７０ｍｍでは転写時の文字の飛び散り、転写文字中抜け、逆転写性は許容できるレベルであったが、プロセス速度が１２０ｍｍ／ｓに上げた時や、感光体間の距離を６０ｍｍとしたときには転写時の文字の飛び散り、転写文字中抜け、逆転写が発生し、実用上問題とされるレベルであった。
【０３０１】
またｃｍ５〜ｃｍ１６の現像剤ではさらに感光体上、中間転写ベルト上でのクリーニング不良が発生した。そして感光体のフィルミング、カブリも多く発生した。
【０３０２】
また、キャリアへのスペントが多く、キャリア抵抗の変化が大きく、帯電量の低下、カブリの増大する傾向が見られた。高温高湿下での帯電量の低下によるカブリの増大、低温低湿下での帯電量の増大による画像濃度の低下が見られた。転写効率は６０〜７０％程度まで低下した。現像時の全面ベタ画像を取ったときに後半部にかすれが生じた。連続使用時に現像ブレードにワックスが融着し、縦筋の異常画像が発生した。３色重ねの画像出力時には定着ベルトへの紙の巻付きが発生した。定着時にトナー飛びが発生した。
【０３０３】
次に（表１３）にＯＨＰ用紙に付着量１．２ｇ／ｃｍ^２以上のベタ画像をプロセス速度１００ｍｍ／ｓ、オイルを塗布しないベルトを用いた定着装置にて非オフセット性試験を行った。ＴＭ１〜ＴＭ１２のトナーは定着ニップ部でＯＨＰのジャムは発生しなかった。普通紙の全面ベタグリーン画像では、オフセットは１２２０００枚目までは全く発生しなかった。シリコン又はフッ素系の定着ベルトでオイルを塗布せずともベルトの表面劣化現象はみられない。
【０３０４】
透過率と、高温でのオフセット性を評価した。プロセス速度は１００ｍｍ／ｓ、定着温度１８０℃で透過率は分光光度計Ｕ−３２００（日立製作所）で、７００ｎｍの光の透過率を測定した。定着性、耐オフセット性、保存安定性の結果を示す。
【０３０５】
【表１３】

【０３０６】
ＯＨＰ透光性が８０％以上を示しており、また非オフセット温度幅も４０〜６０℃とオイルを使用しない定着ローラにおいて良好な定着性を示した。また６０℃、５時間の保存安定性においても凝集はほとんど見られなかった。しかしｔｍ１〜ｔｍ１２のトナーは貯蔵安定性テストで固まりが生じ、また非オフセット温度域も狭い結果トナーった。
【０３０７】
以上の実施例のように、ＤＳＣ法による吸熱ピーク温度が６０〜１２０℃であるワックスを含み、トナー母体粒子の平均粒子径を規定して、トナー母体粒子の体積平均粒子径の２〜６倍の体積平均粒子径を有する粗大粒子を配合するトナー構成とし、さらにはアミノシランカップリング剤を含有するフッ素変性シリコーン樹脂を被覆樹脂とするキャリアと組合わせた二成分現像剤により、オイルを塗布せずとも、高いＯＨＰ透光性を維持しながらオフセット性を防止するオイルレス定着を実現でき、キャリアへのトナー成分のスペントもなく長寿命化を図ることができる。さらには転写時の中抜けや飛び散りを防止し、高転写効率を得ることが可能トナーる。
【０３０８】
【発明の効果】
以上説明したとおり、本発明によれば、定着ローラにオイルを使用しないオイルレス定着トナーにおいて、トナー中にワックス等の離型剤を使用して高透光性、高光沢性を発現するオイルレス定着を提供できる。また、ワックス等の離型剤を含有したトナーとの組合わせた使用においてもスペント化による劣化も生じない高い耐久性のある長寿命のトナーと、二成分現像剤を提供できる。また、ベタ画像を連続して取るようなトナーが多く消費される場合、トナーが急速に補給される際にカブリや現像メモリ−が発生しにくく、帯電立上がり性が良好なトナーと、二成分現像剤を提供できる。特に小型の現像器においてその傾向がより強く現れるため、攪拌時の均一帯電性が要求される。また、感光体や、転写体上でのトナーのクリーニング性を向上し、フィルミングの発生を防止できる。またトナーを小粒径化して画質向上させるとともにトナーの流動性の低下を抑制して、トナー供給やキャリアとの良好な混合性、帯電立上がり性を有するトナーと、二成分現像剤を提供できる。また複数の感光体及び現像部を有する像形成ステーションを並べて配置し、転写体に順次各色のトナーを連続して転写プロセスを実行するタンデムカラープロセスにおいて、転写時の中抜けや逆転写、飛び散りを防止し、高転写効率が得られる画像形成装置を提供できる。
【図面の簡単な説明】
【図１】本発明の実施例で使用した画像形成装置の構成を示す断面図
【図２】本発明の実施例で使用した定着ユニットの構成を示す断面図
【図３】本発明の実施例で使用したトナー粉砕処理の構成図
【図４】本発明の実施例で使用したトナー粉砕処理の断面図
【図５】本発明の実施例で使用したトナー粉砕処理の断面図
【符号の説明】
１ 感光体
２ 帯電ローラ
３ レーザ信号光
４ 現像ローラ
５ ブレード
１０ 第１転写ローラ
１２ 転写ベルト
１４ 第２転写ローラ
１３ 駆動テンションローラ
１７ 転写ベルトユニット
１８Ｂ，１８Ｃ，１８Ｍ，１８Ｙ 像形成ユニット
１８ 像形成ユニット群
２０１ 定着ローラ
２０２ 加圧ローラ
２０３ 定着ベルト
２０５ インダクションヒータ部
２０６ フェライトコア
２０７ コイル
５０８ 定量供給機
５００ 粉砕処理部
５０１ 回転体
５０２ 固定体
５０３ 原料
５０６ 凹凸部
５０９ 冷却器
５１１ エアー
５１２ 温度計
５１４ バグフィルター
５１５ サイクロン
５１６ 風量計
５１７ ブロア
５１８ 無機微粉末供給装置
５１９ バイブレータ振動装置[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a toner, a two-component developer, and an image forming apparatus used in a copying machine, a laser printer, a plain paper FAX, a color PPC, a color laser printer, a color FAX, and a composite machine thereof.
[0002]
[Prior art]
2. Description of the Related Art In recent years, electrophotographic apparatuses are shifting from office use to personal use, and a technology for realizing miniaturization, high speed, high image quality, maintenance-free, and the like is required. Therefore, a cleaner-less process that collects waste toner during development without cleaning the residual toner remaining after transfer, a tandem color process that enables high-speed output of color images, and a fixing oil that does not use offset to prevent offset during fixing In addition, oil-less fixing, which achieves both a clear color image having high gloss and high translucency and non-offset properties, is required along with conditions such as good maintainability and low ozone exhaust. These functions must be compatible at the same time, and the improvement of toner properties as well as the process is an important factor.
[0003]
In a color printer, an image carrier (hereinafter, referred to as a photoconductor) is charged by corona discharge using a charging charger, and thereafter, a latent image of each color is irradiated as a light signal on the photoconductor to form an electrostatic latent image. The latent image is developed by developing with a color, for example, yellow toner. Thereafter, the transfer member charged to the opposite polarity to the charge of the yellow toner is brought into contact with the photoconductor, and the yellow toner image formed on the photoconductor is transferred. The photoreceptor is cleaned after removing the toner remaining at the time of transfer, and is then discharged, thereby completing the development and transfer of the first color toner. Thereafter, the same operation as that for the yellow toner is repeated for toners such as magenta and cyan to form a color image by superimposing toner images of each color on a transfer body. A 4-pass color process in which these superimposed toner images are transferred to paper charged to the opposite polarity to the toner has been put to practical use.
[0004]
In addition, a plurality of image forming stations having a charger, a photoconductor, a developing unit, etc. are arranged side by side, and an endless transfer body is brought into contact with the photoconductor to sequentially transfer toner of each color sequentially to the transfer body. A secondary transfer process is performed to form a multilayer transfer color toner image on the transfer body by executing the process, and then collectively transfer the multilayer toner image formed on the transfer body to a transfer medium such as paper or OHP. A tandem color process configured to be executed and a tandem color process for continuously transferring directly to paper or a transfer medium of an overhead projector (OHP) without using a transfer body have been proposed.
[0005]
In the fixing process, in a color image, it is necessary to melt and mix the color toner to enhance the light transmission. When the toner is defectively fused, light is scattered on the surface or inside of the toner image, so that the original color tone of the toner dye is deteriorated, and light does not enter the lower layer in the overlapped portion, so that color reproducibility is reduced. Therefore, it is a necessary condition that the toner has a perfect melting property and has a light transmitting property that does not hinder the color tone. The need for optical transparency on OHP paper is increasing as the opportunity for presentation in color increases.
[0006]
When a color image is obtained, a large amount of oil or the like must be applied to the fixing roller because toner adheres to the surface of the fixing roller to cause offset, which complicates the handling and the configuration of the device. Therefore, in order to reduce the size, maintenance-free, and cost of the device, it is required to realize oil-less fixing that does not use oil at the time of fixing, which will be described later. In order to make this possible, a configuration in which a release agent such as a wax is added to a binder resin having sharp melt characteristics is being put to practical use.
[0007]
However, the problem with such a toner configuration is that since the toner has a characteristic of strong cohesiveness, the toner image is disturbed at the time of transfer and the tendency of poor transfer occurs more remarkably, and it is difficult to achieve both transfer and fixing. In addition, when used as two-component development, the low melting point component of the toner adheres to the carrier surface due to heat generated by collision or friction between particles, or collision between particles and a developing device, mechanical collision such as friction, or friction. Spent is apt to occur, lowering the chargeability of the carrier, and hindering the extension of the life of the developer.
[0008]
In order to provide a long-life coat carrier, the following cited reference 1 discloses a copolymer of a nitrogen-containing fluorinated alkyl (meth) acrylate and a vinyl monomer, or a fluorinated alkyl (meth) acrylate and a nitrogen-containing vinyl A technique of coating the surface of a carrier core material with a resin such as a copolymer with a monomer has been proposed. These documents describe that a relatively long-life coated carrier can be obtained by coating a carrier core material surface with a copolymer of a nitrogen-containing monomer and a fluorinated monomer or a solvent-soluble fluoropolymer having an imide bond. Have been.
[0009]
However, since the resin bonding strength at the bonding interface with the carrier is weak and the strength of the resin is insufficient, sufficient impact resistance has not been obtained. Further, it is difficult to make the toner negatively charged due to the chargeability of fluorine, so that sufficient charge cannot be given to the toner, and there has been a problem that image fogging and density unevenness occur.
[0010]
Further, in the cited reference 2, the aminosilane coupling agent is used in combination with a toner having a limited component for the purpose of preventing a decrease in the charge amount of the toner in a high humidity atmosphere and improving the durability of the developer. Although a carrier coated with the contained silicone resin has been proposed, it has not been sufficient to prevent the toner from becoming spent.
[0011]
Patent Document 3 below proposes a carrier in which a fluorine-substituted alkyl group is introduced into a silicone resin of a coating layer for a positively charged toner. Further, in Patent Document 4 below, a coating carrier containing a conductive carbon and a crosslinked fluorine-modified silicone resin is proposed as a material having a high developing ability in a high-speed process and not deteriorating over a long period of time. Have been. Utilizing the excellent charging characteristics of the silicone resin and imparting characteristics such as slipperiness, peeling properties and water repellency by means of a fluorine-substituted alkyl group, abrasion, peeling, cracks, etc. are hardly generated, and spent can be prevented. However, wear, peeling, cracks, etc. are not satisfactory, and a toner having a positive charge can obtain an appropriate charge amount, but when a toner having a negative charge is used, the charge is When the amount was too low, a large amount of reversely chargeable toner (toner having positive chargeability) was generated, fog and toner scattering were deteriorated, and the toner was not usable.
[0012]
Also, various configurations of toner have been proposed. As is well known, a toner for electrostatic charge development used in an electrophotographic method generally includes a resin component as a binder resin, a coloring component comprising a pigment or a dye, a plasticizer, a charge controlling agent, and, if necessary, a releasing agent. It is composed of an additive component such as a molding agent. As the resin component, a natural or synthetic resin is used alone or in a suitable mixture.
[0013]
Then, the above additives are preliminarily mixed at an appropriate ratio, heated and kneaded by heat melting, finely pulverized by an airflow collision plate system, and classified into fine powder to complete a toner base. There is also a method in which a toner matrix is prepared by a chemical polymerization method. Thereafter, an external additive such as hydrophobic silica is externally added to the toner matrix to complete the toner. In the one-component development, a two-component developer is obtained by mixing the toner and a carrier composed of magnetic particles, although the toner is composed of only the toner.
[0014]
Patent Document 5 below discloses an external additive introducing means for introducing an external additive into a high-speed gas flow, and a collision plate provided in a flow path of the high-speed gas flow on which the pulverized raw material and the external additive are placed, and And crushing the crushed material against the impingement plate, and colliding the external additive with the crushed raw material in the vicinity of the crushed plate to mix the pulverized material and the additive component. ing. However, this configuration is intended for the purpose of homogeneous mixing with the added components. Particularly, in a crusher using a collision plate method, a toner containing a high concentration of wax is excessively exposed to the toner surface in a toner carrier. Spent, a factor that causes filming on the photoconductor.
[0015]
Further, in the following cited document 6, a coarse powder for toner is subjected to intermediate pulverization treatment, and a mixed powder of intermediate particles for toner having an average particle diameter of 10 to 50 μm and fine particles for modification having an average particle diameter of 1 μm or less is obtained. The frictional crushing treatment is performed by a mechanical crusher to obtain a toner in which the modifying particles are fixed to the toner particles. The modifying particles are fixed to the toner particles in a favorable manner, and high fluidity and excellent durability are obtained. There is disclosed an effect that a toner having a property can be manufactured with high efficiency. However, with this configuration, the toner cannot be efficiently reduced in particle size.
As release agents and waxes to be added, use of a defatty acid-type carnauba wax and / or montan-based ester wax and an oxidized rice wax having an acid value of 10 to 30 in the following Reference 7, and in Reference 8 below, Melting point: 85 to 100 ° C., a vinyl copolymer polymerized in the presence of a natural gas-based Fischer-Tropsch wax, in Patent Document 9 below, a polyhydric alcohol component and a dicarboxylic acid and a trivalent or higher polyvalent carboxylic acid compound. And the average dispersion particle diameter of the release agent is 0.1 to 3 μm, and the particle diameter of the external additive is 4 to 200 nm, and 1 to 5 parts by weight is disclosed. Patent Document 10 listed below discloses that perfluorooctyl methacrylate toner improves the fixability by a constitution containing a fluorine-modified polyolefin-based resin such as polypropylene modified with an organic fluorine compound. Patent Document 11 discloses that non-offset property at the time of fixing is improved by blending a softening point of 80 to 140 ° C., a low molecular weight polyolefin containing fluorine, and a molten mixture of low molecular weight olefin and polytetrafluoroethylene. Is disclosed, and the contents which are effective in improving the fixing property are described.
[0016]
Further, as a charge control agent for imparting chargeability to a toner, a toner using a metal salt of a benzylic acid derivative is disclosed in Patent Document 12 below. Patent Document 13 listed below discloses a toner using a metal salt of a salicylic acid derivative.
[0017]
However, for a resin composition in which a high molecular weight component and a low molecular weight component are blended or copolymerized, a low melting point release agent, for example, polyethylene, polypropylene wax, etc., has good releasability from a heat roller at the time of fixing. For the purpose of increasing the offset resistance. However, it is difficult for these release agents to improve the dispersibility in the binder resin, the toner of the opposite polarity is easily generated, and fogging occurs in the non-image area. There is a problem that the spent is easily generated on the carrier and the filming of the photoconductor is easily generated. In addition, the toner causing transfer failure is toner. Furthermore, in the transfer configuration in which the distance between the image forming stations is shorter in the tandem method described above, the repulsion is caused by the action of the charge of the toner, the image is disturbed by scattering of the toner image, the transfer efficiency is reduced, and the characters at the time of transfer are reduced. Hollows are likely to occur.
[0018]
Patent Document 14 below discloses a configuration in which the average particle diameter is 3 to 15 μm and the number of toner particles having a particle diameter of 5 to 20 times the average particle diameter is 0.003 to 2%. It is described that the property is improved. This is a configuration in which toner particles larger than the average particle diameter are added, and when used as a two-component developer, mixing with the carrier is not uniform, and fog is likely to occur when the toner is rapidly replenished. Further, in one-component development, there is a possibility that the toner remains in the developing device and changes with time.
[0019]
[Patent Document 1]
JP-A-61-80161
[0020]
[Patent Document 2]
Patent No. 2744790
[0021]
[Patent Document 3]
Patent No. 2801507
[0022]
[Patent Document 4]
JP-A-2002-23429
[0023]
[Patent Document 5]
JP-A-2-271364
[0024]
[Patent Document 6]
JP-A-6-89045
[0025]
[Patent Document 7]
JP-A-2-266372
[0026]
[Patent Document 8]
JP-A-9-281748
[0027]
[Patent Document 9]
JP-A-10-327196
[0028]
[Patent Document 10]
JP-A-5-333584
[0029]
[Patent Document 11]
JP-A-5-188632
[0030]
[Patent Document 12]
JP-A-7-84409
[0031]
[Patent Document 13]
JP-A-7-2171097
[0032]
[Patent Document 14]
JP-A-2002-258515
[0033]
[Problems to be solved by the invention]
The present invention solves the above-mentioned conventional problems by providing oilless fixing for preventing offset while maintaining high OHP translucency, and preventing high-density and scattering during transfer to obtain high transfer efficiency. It is an object of the present invention to provide a toner, a two-component developer, and an image forming apparatus that can be used.
[0034]
[Means for Solving the Problems]
In order to achieve the above object, the first toner of the present invention is a toner composed of toner base particles containing at least a binder resin, a colorant and a wax, and coarse particles, and is provided by differential scanning calorimetry ( A wax having an endothermic peak temperature of 60 to 120 ° C. according to DSC method) with respect to 100 parts by weight of the binder resin, the toner base particles have a volume average particle diameter of 3 to 8 μm, and a number distribution of 2 to 2 μm. 5 to 55% by number of toner base particles having a particle size of 0.52 to 4 μm, and 5 to 60% by volume of toner base particles having a particle size of 6.35 to 10.1 μm in a volume distribution. The particles have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and include 1 to 6 parts by weight based on 100 parts by weight of the toner base particles, and the average particle diameter is 6 nm to 200 nm. The inorganic fine powder which is m with respect to 100 parts by weight of the toner base particles, characterized in that it comprises 1.5 to 5.5 parts by weight.
[0035]
The second toner of the present invention is a toner composed of toner base particles containing at least a binder resin, a colorant and a wax, and coarse particles, and has an endothermic peak temperature determined by differential scanning calorimetry (DSC). Is 5 to 20 parts by weight with respect to 100 parts by weight of the binder resin, the volume average particle diameter of the toner base particles is 3 to 8 μm, and the particle size is 2.52 to 4 μm in the number distribution. 5 to 55% by number, and 5 to 60% by volume of toner base particles having a particle diameter of 6.35 to 10.1 μm in a volume distribution, wherein the coarse particles are the toner base particles. An inorganic fine powder having a volume average particle diameter of 2 to 6 times the volume average particle diameter of 1 to 6 parts by weight based on 100 parts by weight of the toner base particles and having an average particle diameter of 6 nm to 20 nm is prepared by toner. 0.5 to 2.5 parts by weight, based on 100 parts by weight of the base particles, and 1.0 to 3.5 parts by weight, based on 100 parts by weight of the toner base particles, of an inorganic fine powder having an average particle diameter of 30 nm to 200 nm. It is characterized by.
[0036]
The third toner of the present invention is a toner composed of a toner base containing at least a binder resin, a colorant and a wax, and coarse particles, and has an endothermic peak temperature by differential scanning calorimetry (DSC). A wax having a temperature of 60 to 120 ° C. is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the binder resin, and has a volume average particle diameter of 3 to 8 μm and a particle diameter of 2.52 to 4 μm in the number distribution. It contains 5 to 55% by number of the toner base, and 5 to 60% by volume of the toner base particles having a particle size of 6.35 to 10.1 μm in a volume distribution, and the coarse particles have a volume average of the toner base particles. A negative inorganic powder having a volume average particle diameter of 2 to 6 times the particle diameter, 1 to 6 parts by weight based on 100 parts by weight of the toner base particles, and an average particle diameter of 6 to 20 nm is used. 0.5 to 2.5 parts by weight, based on 100 parts by weight of the base particles, and 1.0 to 3.0 parts by weight of an inorganic fine powder having a negative polarity having an average particle diameter of 30 to 200 nm based on 100 parts by weight of the toner base particles. 5 parts by weight and 0.5 to 1.5 parts by weight of an inorganic fine powder having a positive polarity having an average particle diameter of 6 nm to 200 nm with respect to 100 parts by weight of the toner base particles.
[0037]
The fourth toner of the present invention is a toner composed of a toner base containing at least a binder resin, a colorant and a wax, and coarse particles, and has an endothermic peak temperature determined by differential scanning calorimetry (DSC). A wax having a temperature of 60 to 120 ° C. is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the binder resin, and has a volume average particle diameter of 3 to 8 μm and a particle diameter of 2.52 to 4 μm in the number distribution. 5 to 55% by volume of a toner base, 5 to 60% by volume of toner base particles having a particle size of 6.35 to 10.1 μm in a volume distribution, the coarse particles containing a lubricant, An inorganic fine powder having a volume average particle diameter of 2 to 6 times the volume average particle diameter of the base particles, and containing 1 to 6 parts by weight based on 100 parts by weight of the toner base, and having an average particle diameter of 6 nm to 200 nm. G Characterized in that it comprises 1.5 to 5.5 parts by weight per 100 parts by weight of over base particles.
[0038]
The fifth toner of the present invention is a toner composed of a toner base containing at least a binder resin, a colorant and a wax, and coarse particles, and has an endothermic peak temperature determined by differential scanning calorimetry (DSC). A wax having a temperature of 60 to 120 ° C. is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the binder resin, and has a volume average particle diameter of 3 to 8 μm and a particle diameter of 2.52 to 4 μm in the number distribution. 5 to 55% by volume of a toner base, 5 to 60% by volume of toner base particles having a particle size of 6.35 to 10.1 μm in a volume distribution, the coarse particles containing a lubricant, An inorganic fine powder having a volume average particle diameter of 2 to 6 times the volume average particle diameter of the base particles, 1 to 6 parts by weight based on 100 parts by weight of the toner base, and an average particle diameter of 6 nm to 20 nm. Toner mother 0.5 to 2.5 parts by weight based on 100 parts by weight of the particles and 1.0 to 3.5 parts by weight based on 100 parts by weight of the toner base particles of the inorganic fine powder having an average particle size of 30 nm to 200 nm. Features.
[0039]
The sixth toner of the present invention is a toner composed of a toner base containing at least a binder resin, a colorant and a wax, and coarse particles, and has an endothermic peak temperature by differential scanning calorimetry (DSC). A wax having a temperature of 60 to 120 ° C. is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the binder resin, and has a volume average particle diameter of 3 to 8 μm and a particle diameter of 2.52 to 4 μm in the number distribution. 5 to 55% by volume of a toner base, 5 to 60% by volume of toner base particles having a particle size of 6.35 to 10.1 μm in a volume distribution, the coarse particles containing a lubricant, An inorganic negative electrode having a volume average particle size of 2 to 6 times the volume average particle size of the base particles, containing 1 to 6 parts by weight based on 100 parts by weight of the toner base, and having an average particle size of 6 nm to 20 nm. Fine 0.5 to 2.5 parts by weight based on 100 parts by weight of the toner base particles, and an inorganic fine powder having an average particle diameter of 30 nm to 200 nm and having a negative polarity of 1.0 to 1.0 part by weight based on 100 parts by weight of the toner base particles. It is characterized by containing 3.5 parts by weight and 0.5 to 1.5 parts by weight of an inorganic fine powder having an average particle diameter of 6 nm to 200 nm and having positive polarity with respect to 100 parts by weight of the toner base particles.
[0040]
Next, the first two-component developer of the present invention is a two-component developer comprising at least a binder resin, a coloring agent and a wax, a toner base, and a toner composed of coarse particles and a carrier, A wax having an endothermic peak temperature of 60 to 120 ° C. by differential scanning calorimetry (DSC) is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the binder resin, and the toner base has a volume average particle diameter of 3 to 8 μm. Contains 5 to 55% by number of a toner base having a particle size of 2.52 to 4 μm in a number distribution, and contains 5 to 60% by volume of a toner base particle having a particle size of 6.35 to 10.1 μm in a volume distribution. The coarse particles have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and 1 to 6 parts by weight based on 100 parts by weight of the toner base, and the average particle diameter is 6 nm to 200 m, a toner containing 1.5 to 5.5 parts by weight of an inorganic fine powder with respect to 100 parts by weight of the toner base particles, and a surface of the core material at least coated with a fluorine-modified silicone resin containing an aminosilane coupling agent. And a carrier containing magnetic particles having a diameter of 30 to 60 μm.
[0041]
The second two-component developer of the present invention is a two-component developer composed of a toner base including at least a binder resin, a colorant and a wax, a toner composed of coarse particles, and a carrier, and has a differential scanning calorimetry. A wax having an endothermic peak temperature of 60 to 120 ° C. by an analytical method (DSC method) is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the binder resin, and the volume average particle diameter of the toner matrix is 3 to 8 μm, and the number distribution is Contains 5 to 55% by number of a toner matrix having a particle size of 2.52 to 4 μm, and 5 to 60% by volume of a toner matrix particle having a particle size of 6.35 to 10.1 μm in the volume distribution. The coarse particles have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and 1 to 6 parts by weight based on 100 parts by weight of the toner base, and the average particle diameter is 6 nm to 20 nm. 0.5 to 2.5 parts by weight of the inorganic fine powder based on 100 parts by weight of the toner base particles, and 1.0 to 3.0 parts by weight of the inorganic fine powder having an average particle diameter of 30 nm to 200 nm based on 100 parts by weight of the toner base particles. A toner comprising 5 parts by weight of a toner, and a carrier comprising magnetic particles having an average particle diameter of 30 to 60 μm, wherein the surface of the core material is at least coated with a fluorine-modified silicone resin containing an aminosilane coupling agent. I do.
[0042]
The third two-component developer of the present invention is a two-component developer consisting of a toner base containing at least a binder resin, a colorant and a wax, a toner composed of coarse particles and a carrier, and has a differential scanning calorimetry. A wax having an endothermic peak temperature of 60 to 120 ° C. by an analytical method (DSC method) is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the binder resin, and the volume average particle diameter of the toner matrix is 3 to 8 μm, and the number distribution is Contains 5 to 55% by number of a toner matrix having a particle size of 2.52 to 4 μm, and 5 to 60% by volume of a toner matrix particle having a particle size of 6.35 to 10.1 μm in the volume distribution. The coarse particles have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and 1 to 6 parts by weight based on 100 parts by weight of the toner base, and the average particle diameter is 6 nm to 20 nm. 0.5 to 2.5 parts by weight of the inorganic fine powder having negative polarity with respect to 100 parts by weight of the toner base particles, and 100 parts by weight of the inorganic fine powder having negative polarity having an average particle diameter of 30 nm to 200 nm. And a toner containing 0.5 to 1.5 parts by weight, based on 100 parts by weight of the toner base particles, of 1.0 to 3.5 parts by weight of an inorganic fine powder having an average particle diameter of 6 nm to 200 nm. And a carrier containing at least a magnetic particle having an average particle diameter of 30 to 60 μm, the surface of the core material being at least coated with a fluorine-modified silicone resin containing an aminosilane coupling agent.
[0043]
The fourth two-component developer of the present invention is a two-component developer composed of a toner base including at least a binder resin, a colorant and a wax, a toner composed of coarse particles and a carrier, and has a differential scanning calorimetry. A wax having an endothermic peak temperature of 60 to 120 ° C. by an analytical method (DSC method) is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the binder resin, and the volume average particle diameter of the toner matrix is 3 to 8 μm, and the number distribution is Contains 5 to 55% by number of a toner matrix having a particle size of 2.52 to 4 μm, and 5 to 60% by volume of a toner matrix particle having a particle size of 6.35 to 10.1 μm in the volume distribution. The coarse particles contain a lubricant, have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and contain 1 to 6 parts by weight with respect to 100 parts by weight of the toner base particles. Is 6 nm A toner containing 1.5 to 5.5 parts by weight of an inorganic fine powder having a thickness of 200 nm with respect to 100 parts by weight of the toner base particles, and a surface of the core material at least coated with a fluorine-modified silicone resin containing an aminosilane coupling agent, And a carrier containing magnetic particles having a diameter of 30 to 60 μm.
[0044]
The fifth two-component developer of the present invention is a two-component developer composed of a toner base containing at least a binder resin, a colorant and a wax, a toner composed of coarse particles, and a carrier, and has a differential scanning calorimetry. A wax having an endothermic peak temperature of 60 to 120 ° C. by an analytical method (DSC method) is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the binder resin, and the volume average particle diameter of the toner matrix is 3 to 8 μm, and the number distribution is Contains 5 to 55% by number of a toner matrix having a particle size of 2.52 to 4 μm, and 5 to 60% by volume of a toner matrix particle having a particle size of 6.35 to 10.1 μm in the volume distribution. The coarse particles contain a lubricant, have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and contain 1 to 6 parts by weight with respect to 100 parts by weight of the toner base particles. Is 6 nm The inorganic fine powder having a thickness of 20 nm is 0.5 to 2.5 parts by weight based on 100 parts by weight of the toner base particles, and the inorganic fine powder having an average particle diameter of 30 nm to 200 nm is 1.0 to 1.0 parts by weight based on 100 parts by weight of the toner base particles. And a carrier containing magnetic particles having an average particle diameter of 30 to 60 μm, wherein the surface of the core material is at least coated with a fluorine-modified silicone resin containing an aminosilane coupling agent. It is characterized by.
[0045]
The sixth two-component developer of the present invention is a two-component developer consisting of a toner base containing at least a binder resin, a colorant and a wax, and a toner and a carrier composed of coarse particles, and has a differential scanning calorimetry. A wax having an endothermic peak temperature of 60 to 120 ° C. by an analytical method (DSC method) is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the binder resin, and the volume average particle diameter of the toner matrix is 3 to 8 μm, and the number distribution is Contains 5 to 55% by number of a toner matrix having a particle size of 2.52 to 4 μm, and 5 to 60% by volume of a toner matrix particle having a particle size of 6.35 to 10.1 μm in the volume distribution. The coarse particles contain a lubricant, have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and contain 1 to 6 parts by weight with respect to 100 parts by weight of the toner base particles. Is 6 nm 0.5 to 2.5 parts by weight of an inorganic fine powder having a negative polarity of 20 nm with respect to 100 parts by weight of the toner base particles, and an inorganic fine powder of a negative polarity having an average particle diameter of 30 to 200 nm is used as the toner base particles. 1.0 to 3.5 parts by weight based on 100 parts by weight, and 0.5 to 1.5 parts by weight of an inorganic fine powder having a positive polarity having an average particle diameter of 6 nm to 200 nm based on 100 parts by weight of the toner base particles. And a carrier containing magnetic particles having an average particle diameter of 30 to 60 μm, the core material being at least coated with a fluorine-modified silicone resin containing an aminosilane coupling agent.
[0046]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention can achieve high digital image quality, high-definition color reproducibility color, high transparency and anti-offset properties without using oil for preventing offset in the fixing roller, and furthermore, two-component development. In this case, spent by the toner component of the carrier is prevented and the life is extended.
(1) Wax
As the wax to be added to the toner of the present embodiment, a wax having an iodine value of 25 or less and a saponification value of 30 to 300 is added by 5 to 20 parts by weight based on 100 parts by weight of the binder resin. The repulsion due to the toner charge action is mitigated at the time of multi-layer transfer of the toner, so that it is possible to suppress a decrease in transfer efficiency, a dropout of characters at the time of transfer, and a reverse transfer. Further, the use of the carrier in combination with the above-described carrier can suppress the occurrence of spent on the carrier, and can extend the life of the developer. Further, the handling property in the developing device is improved, and the uniformity of the image is improved on the back side and the front side of the development. Further, generation of development memory can be reduced.
[0047]
More preferably, the binder resin has an acid value of 1 to 40 mgKOH / g.
[0048]
Preferably, it is added in an amount of 7 to 20 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the binder resin. If the amount is less than 5 parts by weight, the effect of improving the fixing property cannot be obtained, and if it exceeds 20 parts by weight, there is a problem in storage stability.
[0049]
When the iodine value exceeds 25, repulsion due to the charge action of the toner during the multi-layer transfer of the toner in the primary transfer is difficult to be reduced. It has great environmental dependence and changes in the chargeability of the material during long-term continuous use, which hinders image stability. Also, development memory is likely to occur. If the saponification value is less than 30, the presence of unsaponifiable compounds and hydrocarbons increases, causing photoreceptor filming and deterioration of chargeability. Further, the dispersibility with the charge control agent causes poor toner, and causes a decrease in chargeability during filming or continuous use. If it exceeds 300, the dispersibility of the wax in the resin is deteriorated, and the repulsion due to the charge action of the toner is not easily reduced. Further, fog and toner scattering increase. When the resin acid value is less than 1 mgKOH / g, repulsion due to the charge action of the toner at the time of multi-layer transfer of the toner is difficult to be alleviated. If the resin acid value exceeds 40 mgKOH / g, the environmental resistance deteriorates and fog increases.
[0050]
Those having a melting point of 60 to 120 ° C by the DSC method are preferred. More preferably, the iodine value is 15 or less, the saponification value is 50 to 250, and the melting point according to the DSC method is 65 to 90 ° C. More preferably, the iodine value is 5 or less, the saponification value is 70 to 200, and the melting point according to the DSC method is 65 to 90. It is 85 ° C.
[0051]
Further, a material having a volume increase rate of 2 to 30% at a change of 10 ° C. at a temperature equal to or higher than the melting point is preferable. When it changes from a solid to a liquid and expands rapidly, when it is melted by the heat of fixing, the adhesion between the toners is further strengthened, the fixing properties are improved, and the releasability from the fixing roller is improved and the resistance is improved. The offset property is also improved. If it is less than 2, the effect is small, and if it exceeds 30, the dispersibility at the time of kneading decreases.
[0052]
The loss on heating of the wax at 220 ° C. is preferably 8% by weight or less. When the weight loss on heating exceeds 8% by weight, the glass transition point of the binder resin is lowered, and the storage stability of the toner is impaired. It adversely affects development characteristics and causes fogging and photoreceptor filming.
[0053]
The wax having an iodine value of 25 or less and a saponification value of 30 to 300 has a molecular weight characteristic in gel permeation chromatography (GPC), a number average molecular weight of 100 to 5,000, a weight average molecular weight of 200 to 10,000, and a weight average molecular weight. The ratio of the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.01 to 8, the ratio of the Z average molecular weight to the number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 10, and the molecular weight is 5 × 10.²~ 1 × 10⁴Preferably has at least one maximum molecular weight peak in the region. More preferably, the number average molecular weight is 500 to 4500, the weight average molecular weight is 600 to 9000, the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.01 to 7, and the Z average molecular weight and number average are The molecular weight ratio (Z-average molecular weight / number-average molecular weight) is 1.02 to 9, more preferably the number-average molecular weight is 700 to 4000, the weight-average molecular weight is 800 to 8000, and the ratio of the weight-average molecular weight to the number-average molecular weight (weight-average molecular weight). (Molecular weight / number average molecular weight) is 1.01 to 6, and the ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 8.
[0054]
If the number average molecular weight is less than 100 and the weight average molecular weight is less than 200, storage stability will deteriorate. Maximum molecular weight peak is 5 × 10²If it is located in a smaller range, the dispersibility of the charge control agent together with the wax deteriorates. Further, the handling property in the developing device is reduced, and the maintenance of the uniformity of the toner concentration is hindered. The storability of the toner deteriorates, and filming of the photoconductor occurs.
[0055]
The number average molecular weight is greater than 5000, the weight average molecular weight is greater than 10,000, the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) is greater than 8, and the ratio of Z average molecular weight to number average molecular weight (Z (Average molecular weight / number average molecular weight) is greater than 10, and the maximum molecular weight peak is 1 × 10⁴If it is located in a range larger than the region, the releasing effect is weakened, and the fixing properties such as fixing properties and anti-offset properties are reduced.
[0056]
As the wax, materials such as meadowfoam oil, jojoba oil, wood wax, beeswax, ozokerite, carnauba wax, canderia wax, ceresin wax, and rice wax are preferable, and derivatives thereof are also suitably used. One type or a combination of two or more types can also be used. In particular, carnauba wax having a melting point of 76 to 90 ° C by a DSC method, candelilla wax having a melting point of 66 to 80 ° C, hydrogenated jojoba oil having a temperature of 64 to 78 ° C, hydrogenated meadowfoam oil having a melting point of 64 to 78 ° C or 74. At least one kind or two or more kinds of waxes selected from the group consisting of rice wax having a temperature of up to 90 ° C are more preferable.
[0057]
The saponification value refers to the number of milligrams of potassium hydroxide KOH required to saponify 1 g of a sample. It is the sum of the acid value and the ester value. To determine the saponification value, saponify the sample in an alcoholic solution of about 0.5N potassium hydroxide and then titrate excess potassium hydroxide with 0.5N hydrochloric acid.
[0058]
The iodine value is a value obtained by converting the amount of halogen absorbed when a halogen is applied to a sample into iodine and expressing the amount in grams per 100 g of the sample. It is the number of grams of iodine absorbed in 100 g of fat, and the larger the value, the higher the degree of unsaturation of the fatty acid in the sample. An alcohol solution of iodine and mercury (II) chloride or a glacial acetic acid solution of iodine chloride is added to a chloroform or carbon tetrachloride solution of a sample, and after standing, iodine remaining without reacting is titrated with a standard solution of sodium thiosulfate to absorb iodine. Calculate the amount.
[0059]
For the measurement of the weight loss by heating, the weight of the sample cell is precisely weighed to 0.1 mg (W1 mg), 10 to 15 mg of the sample is put therein, and precisely weighed to 0.1 mg (W2 mg). The sample cell is set on a differential thermobalance, and measurement is started with the weighing sensitivity set to 5 mg. After the measurement, the weight loss at the time when the sample temperature reaches 220 ° C. is read from the chart to 0.1 mg (W3 mg). The apparatus is TGD-3000 manufactured by Vacuum Riko, a heating rate of 10 ° C./min, a maximum temperature of 220 ° C., a holding time of 1 min, and a heating loss (%) = W3 / (W2−W1) × 100. .
[0060]
As derivatives, for example, meadowfoam oil derivatives, meadowfoam oil fatty acids, metal salts of meadowfoam oil fatty acids, meadowfoam oil fatty acid esters, hydrogenated meadowfoam oil, meadowfoam oil amide, homomeadowfoam oil amide, meadowfoam oil Triester, maleic acid derivative of epoxidized Meadowfoam oil, isocyanate polymer of Meadowfoam oil fatty acid polyhydric alcohol ester, and halogenated modified Meadowfoam oil are effective for oilless fixing, longer life of developer, and improvement of transferability The preferred material obtained. These can be used alone or in combination of two or more.
[0061]
Jojoba oil derivatives include jojoba oil fatty acids, metal salts of jojoba oil fatty acids, jojoba oil fatty acid esters, hydrogenated jojoba oil, jojoba oil amide, homojojoba oil amide, jojoba oil triester, maleic acid derivatives of epoxidized jojoba oil, jojoba Isocyanate polymers of oil fatty acid polyhydric alcohol esters and halogenated modified jojoba oil are preferred materials that can achieve effects of oilless fixing, prolonging the life of the developer, and improving transferability. These can be used alone or in combination of two or more.
[0062]
In addition, materials such as hydroxystearic acid derivatives, glycerin fatty acid esters, glycol fatty acid esters, and polyhydric alcohol fatty acid esters such as sorbitan fatty acid esters are preferable, and one or a combination of two or more thereof can be used. By using the carrier in combination with the carrier described above, it is possible to extend the life of the developer together with the oilless fixing, to maintain uniformity in the developing device, and to suppress generation of a developing memory.
[0063]
As the derivatives of hydroxystearic acid, methyl 12-hydroxystearate, butyl 12-hydroxystearate, propylene glycol mono 12-hydroxystearate, glycerin mono 12-hydroxystearate, ethylene glycol mono 12-hydroxystearate and the like are preferable. Material. There is an effect of preventing paper wrapping and filming in oilless fixing.
[0064]
Preferred examples of the glycerin fatty acid ester include glycerin monostearate, glycerin tristearate, glycerin stearate, glycerin monopalmital, glycerin tripalmital, glycerin docosanoate, and the like. It has the effect of alleviating the cold offset property at low temperature in oilless fixing and the effect of preventing a decrease in transfer property.
[0065]
Preferred examples of the glycol fatty acid ester include propylene glycol fatty acid esters such as propylene glycol monopalmitate and propylene glycol monostearate, and ethylene glycol fatty acid esters such as ethylene glycol monostearate and ethylene glycol monopalmital. In addition to the oilless fixing property, it has the effect of improving the slip in development and preventing carrier spent.
[0066]
Suitable sorbitan fatty acid esters are sorbitan monopalmitate, sorbitan monostearate, sorbitan monotristearate, and sorbitan tripalmitate. Further, materials such as stearic acid ester of pentaerythritol and mixed esters of adipic acid and stearic acid or oleic acid are preferable, and one or more kinds of them can be used in combination. There is an effect of preventing paper wrapping and filming in oilless fixing.
[0067]
In the present embodiment, an aliphatic amide wax is added. Thereby, the translucency in a color image can be greatly improved. Particularly, a toner capable of promoting the smoothness of the surface of a fixed image to obtain a high-quality color image. Further, it is possible to prevent the wrapping of the copy sheet around the fixing roller at the time of fixing, to achieve both the translucency and the anti-offset property, and to prevent the dropout during the transfer. When used in combination with a carrier described later, generation of spent can be suppressed together with oilless fixing, the life of the developer can be extended, uniformity in the developing device can be maintained, and generation of a development memory can be suppressed.
[0068]
Examples of the aliphatic amide wax include palmitic acid amide, palmitoleic acid amide, stearic acid amide, oleic acid amide, arachidic acid amide, eicosenoic acid amide, behenic acid amide, erucic acid amide, and ligrinoselic acid amide. Saturated or monovalent unsaturated aliphatic amides having 16 to 24, preferably with a melting point of 60 to 120C. The temperature is more preferably from 70 to 100 ° C, and still more preferably from 75 to 95 ° C. The addition amount is preferably 5 to 20 parts by weight based on 100 parts by weight of the binder resin. If the melting point of the toner is lower than 60 ° C., the dispersibility of the toner in the resin decreases, and filming on the photoconductor is likely to occur. If the melting point exceeds 120 ° C., the smoothness of the surface of the fixed image decreases, and the light transmittance deteriorates. If the amount is more than 20 parts by weight, the storage stability will deteriorate. If the amount is less than 5 parts by weight, the function cannot be exhibited.
[0069]
Furthermore, methylene bis-stearic acid amide, ethylene bis-stearic acid amide, propylene bis-stearic acid amide, butylene bis-stearic acid amide, methylene bis-oleic acid amide, ethylene bis-oleic acid amide, propylene bis-oleic acid amide, butylene bis-oleic acid amide, Methylene bis lauric amide, ethylene bis lauric amide, propylene bis lauric amide, butylene bis lauric amide, methylene bis myristic amide, ethylene bis myristic amide, propylene bis myristic amide, butylene bis myristic amide, methylene bis Palmitic acid amide, ethylene bispalmitic acid amide, propylene bispalmitic acid amide, butylene bispalmitic acid amide, methylene bispalmitry Acid amide, ethylene bispalmitoleic amide, propylene bispalmitoleic amide, butylene bispalmitoleic amide, methylene bis arachidic amide, ethylene bis arachidic amide, propylene bis arachidic amide, butylene bis arachidic amide, methylene Biseicosenamide, ethylenebiseicosenamide, propylenebiseicosenamide, butylenebiseicosenamide, methylenebisbehenamide, ethylenebisbehenamide, propylenebisbehenamide Or alkylenes of saturated or 1-2-valent unsaturated fatty acids such as butylenebisbehenamide, methylenebiserucamide, ethylenebiserucamide, propylenebiserucamide, butylenebiserucamide, etc. Scan fatty acid amide wax are preferable.
[0070]
This makes it possible to improve the translucency of a color image and the resistance to offset to a roller. Further, generation of spent on the carrier can be suppressed, and the life of the developer can be extended.
[0071]
In the molecular weight distribution by GPC, the weight average molecular weight is 1000 to 6000, the Z average molecular weight is 1500 to 9000, and the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.1 to 3.8. , The ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.5 to 6.5, 1 × 10³~ 3 × 10⁴And a long-chain alkyl alcohol having 5 to 100 carbon atoms having an acid value of 5 to 80 mgKOH / g, a melting point of 60 to 120 ° C., and a penetration at 25 ° C. of 4 or less. Wax obtained by reaction of saturated polycarboxylic acid or its anhydride and unsaturated hydrocarbon wax, or reaction of long-chain alkylamine with unsaturated polycarboxylic acid or its anhydride and unsaturated hydrocarbon wax Or a wax obtained by the reaction of a long-chain fluoroalkyl alcohol with an unsaturated polycarboxylic acid or its anhydride and an unsaturated hydrocarbon wax is an image in which three layers of color toner are formed on thin paper. Is particularly effective in improving the separation of paper from the fixing roller and the belt. It is effective in improving the transparency of OHP without lowering the hot offset property. Further, the addition of the wax can exhibit fixing properties, particularly non-offset properties, high glossiness, and high translucency in oilless fixing, and do not lower the high-temperature storability. Further, even if a fluorine-based or silicon-based member is used for the fixing roller, offset of a halftone image can be prevented. By using the carrier in combination with the above-mentioned carrier, generation of spent can be suppressed together with oilless fixing, the life of the developer can be extended, uniformity in the developing device can be maintained, and generation of development memory can be suppressed. Further, the toner has a charge stability at the time of continuous use, and can achieve both a fixing property and a development stability.
[0072]
Furthermore, by improving the state of dispersion when adding this to the binder resin, it is possible to further improve the fixing properties such as releasability and translucency, and the developing properties such as charge stabilization. It is conceivable that the dispersibility of the other internal additives is reduced by the addition of a release agent. Can be planned.
[0073]
Here, if the carbon number of the long-chain alkyl of the wax is smaller than 5, the releasing effect is weakened, and the separability and the non-offset property at high temperatures are reduced. If the carbon number of the long-chain alkyl is larger than 100, the dispersibility in the binder resin is deteriorated. If the acid value is smaller than 5 mgKOH / g, the charge amount of the toner during long-term use is reduced. If the acid value is more than 80 mgKOH / g, the moisture resistance will decrease and the fog under high humidity will increase. If the melting point is lower than 60 ° C., the storability of the toner decreases. If the melting point is higher than 120 ° C., the releasing effect is weakened, and the non-offset temperature width is narrowed. If the penetration at 25 ° C. is greater than 4, the toughness is reduced, and photoreceptor filming occurs during long-term use.
[0074]
Weight average molecular weight is less than 1000, Z average molecular weight is less than 1500, weight average molecular weight / number average molecular weight is less than 1.1, Z average molecular weight / number average molecular weight is less than 1.5, maximum molecular weight peak Is 1 × 10³If it is located in a smaller range, the preservability of the toner is reduced, and filming occurs on the photoconductor and the intermediate transfer body. Further, the handling property in the developing device is reduced, and the uniformity of the toner density is reduced. Further, a development memory is easily generated.
[0075]
Weight average molecular weight greater than 6000, Z average molecular weight greater than 9000, weight average molecular weight / number average molecular weight greater than 3.8, Z average molecular weight / number average molecular weight greater than 6.5, 3 × 10 peaks⁴If it is located in a range larger than the region, the releasing effect is weakened and the fixing offset property is reduced.
[0076]
More preferably, the weight average molecular weight is 1,000 to 5,000, the Z average molecular weight is 1,700 to 8,000, the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.1 to 2.8, and the Z average molecular weight is The ratio of number average molecular weight (Z average molecular weight / number average molecular weight) is 1.5 to 4.5, 1 × 10³~ 1 × 10⁴Preferably has at least one maximum molecular weight peak in the region, more preferably has a weight average molecular weight of 1000 to 2500, a Z average molecular weight of 1900 to 3000, and a ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average). Molecular weight) is 1.2 to 1.8, and the ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.7 to 2.5, 1 × 10³~ 3 × 10³Has at least one molecular weight maximum peak in the region.
[0077]
As the alcohol, those having a long alkyl chain such as octanol, dodecanol, stearyl alcohol, nonacosanol, and pentadecanol can be used. As the amines, N-methylhexylamine, nonylamine, stearylamine, nonadecylamine and the like can be suitably used. As the fluoroalkyl alcohol, 1-methoxy- (perfluoro-2-methyl-1-propene), hexafluoroacetone, 3-perfluorooctyl-1,2-epoxypropane and the like can be preferably used. As the unsaturated polycarboxylic acid or anhydride thereof, one or more of maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and the like can be used. Of these, maleic acid and maleic anhydride are more preferred. As the unsaturated hydrocarbon wax, ethylene, propylene, α-olefin and the like can be suitably used.
[0078]
The unsaturated polycarboxylic acid or its anhydride is polymerized using an alcohol or an amine, and then this is added to a synthetic hydrocarbon wax in the presence of diculumi peroxide or tertiary butyl peroxyisopropyl monocarbonate. Can be obtained.
[0079]
The addition amount is preferably 5 to 20 parts by weight based on 100 parts by weight of the binder resin. If it is less than 5, the releasing effect is hardly obtained. If it is more than 20, not only the fluidity of the toner decreases, but even if it is added more, the effect is not improved due to saturation.
[0080]
Further, particles having a dispersion average particle diameter of 0.1 to 1.5 μm and a particle diameter distribution of less than 0.1 μm in the binder resin of the wax are 35% by number or less, and particles of 0.1 to 2.0 μm. It is preferable that the number of particles exceeding 65 number% and exceeding 2.0 μm is 5 number% or less. The particle size and the number thereof were determined from a cross-sectional photograph of the toner by TEM.
[0081]
When the dispersion average particle size is smaller than 0.1 μm and the particles having a dispersion average particle size of smaller than 0.1 μm are more than 35% by number, the releasing effect as a releasing agent is small and the fixing ability cannot be exhibited. When the average particle diameter of the dispersion is larger than 1.5 μm and the number of particles exceeding 2.0 μm is more than 5% by number, the dispersibility of the wax in the resin is deteriorated, and the repulsion due to the charge action of the toner is hardly alleviated. Further, fog and toner scattering increase.
[0082]
When the wax has a linear or elliptical structure in the resin, the long axis diameter is 0.5 to 3 μm on average, 35% by number or less of particles having a major axis diameter of less than 0.5 μm, and 65% or less of particles having a major axis diameter of 0.5 to 3.5 μm. It is preferable that the number of particles exceeding the number% and exceeding 3.5 μm is 5 number% or less. When the average diameter is smaller than 0.5 μm and the number of particles smaller than 0.5 μm is more than 35% by number, the releasing effect as a releasing agent is small and the fixing ability cannot be exhibited. When the number of particles having an average diameter of more than 3 μm and more than 3.5 μm is more than 5% by number, the dispersibility of the wax in the resin is deteriorated, and the repulsion due to the charge action of the toner is hardly alleviated. Further, fog and toner scattering increase. The handling property in the developing device is reduced, and the developing memory property is reduced.
(3) Binder resin
The binder resin of this embodiment has a molecular weight distribution of 2 × 10³~ 3 × 10⁴Has at least one molecular weight maximal peak in the region, and 3 × 10⁴Having a molecular weight component of 5% or more based on the entire binder resin, a weight average molecular weight of 10,000 to 300,000, a Z average molecular weight of 20,000 to 5,000,000, and a ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / Number average molecular weight) is 3 to 100, the ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 10 to 2000, and the melting temperature by a 1/2 method using a constant load extrusion type capillary rheometer flow tester. It is preferable to use a polyester resin having a (softening point) of 80 to 150 ° C, an outflow start temperature of 80 to 120 ° C, and a glass transition point of the resin in a range of 45 to 68 ° C.
[0083]
Preferably, the weight average molecular weight is 10,000 to 200,000, the Z average molecular weight is 20,000 to 3,000,000, the weight average molecular weight / number average molecular weight is 3 to 50, the Z average molecular weight / number average molecular weight is 20 to 1000, and the softening point is 90. １４０140 ° C., the outflow starting temperature is 85-115 ° C., and the glass transition point is preferably a polyester resin having a range of 52-68 ° C.
[0084]
More preferably, the weight average molecular weight is 10,000 to 150,000, the Z average molecular weight is 20,000 to 500,000, the weight average molecular weight / number average molecular weight is 3 to 15, the Z average molecular weight / number average molecular weight is 50 to 1000, and the softening point is It is preferable to use a polyester resin having a temperature of 105 to 135 ° C, an outflow start temperature of 90 to 120 ° C, and a glass transition temperature of 58 to 66 ° C.
[0085]
As a component existing in the high molecular weight region, preferably 1 × 10⁵It is preferable that the above-mentioned molecular weight components are contained in an amount of 3% or more based on the whole binder resin. Further, as a component existing in the high molecular weight region, 3 × 10⁵It is preferable that the above molecular weight components are contained in an amount of 0.5% or more based on the whole binder resin.
[0086]
Preferably, as a component existing in the high molecular weight region, 8 × 10⁴~ 1 × 10⁷Has a molecular weight component of 3% or more based on the whole binder resin, and 1 × 10⁷A configuration not containing the above components is preferable.
[0087]
More preferably, as a component existing in the high molecular weight region, 3 × 10⁵~ 9 × 10⁶Has a high molecular weight component of 1% or more based on the whole binder resin, and 9 × 10⁶The above components are not contained.
[0088]
More preferably, as a component existing in the high molecular weight region, 7 × 10⁵~ 6 × 10⁶Has a high molecular weight component of 1% or more based on the whole binder resin, and 6 × 10⁶The above components are not contained.
[0089]
If the amount of the high molecular weight component is too large or too large, the giant molecular weight component remains during kneading, which impairs light transmission. Also, the production efficiency of the resin itself decreases. Unnecessary scratches are made on the developing roller supply roller to cause vertical streaks in the image. Also, the dispersibility of the wax decreases.
[0090]
The binder resin has a weight average molecular weight of less than 10,000, a Z average molecular weight of less than 20,000, a weight average molecular weight / number average molecular weight of less than 3, a Z average molecular weight / number average molecular weight of less than 10, and a softening point of 80. When the temperature is lower than 80 ° C., the outflow starting temperature is lower than 80 ° C., and the glass transition point is lower than 45 ° C., the dispersibility at the time of kneading is reduced, and the fog is increased and the durability is deteriorated. Further, kneading stress during kneading is not sufficiently applied, and the molecular weight cannot be maintained at an appropriate value. The dispersibility of the wax and the charge control agent in the resin is deteriorated, and the repulsion due to the charge action of the toner is not easily reduced. Further, fog and toner scattering increase. In addition, the offset resistance and the high-temperature storage stability are deteriorated, and further, cleaning failure in the transfer member and filming on the photosensitive member occur.
[0091]
The binder resin has a weight average molecular weight of greater than 300,000, a Z average molecular weight of greater than 5,000,000, a weight average molecular weight / number average molecular weight of greater than 100, a Z average molecular weight / number average molecular weight of greater than 2000, and a softening point of 150. If the toner temperature is higher than 120 ° C, the outflow starting temperature is higher than 120 ° C, and the glass transition point is higher than 68 ° C, the load during the processing of the machine is excessive, and the productivity is extremely lowered. And the fixing strength are reduced.
[0092]
Further, the molecular weight distribution of the toner after the melt-kneading treatment by GPC is 2 × 10³~ 3 × 10⁴Has at least one maximum molecular weight peak in the region of 5 × 10⁴~ 1 × 10⁶The fixing property is improved by having at least one maximum molecular weight peak or shoulder in the region.
[0093]
The maximum molecular weight peak existing on the low molecular weight side of the toner is preferably 3 × 10³~ 2 × 10⁴At least one in the region, more preferably 4 × 10³~ 2 × 10⁴In at least one region.
[0094]
The position of the maximum molecular weight peak or shoulder present on the high molecular weight side of the toner is preferably 6 × 10⁴~ 7 × 10⁵At least one, more preferably 8 × 10⁴~ 5 × 10⁵Has at least one maximum molecular weight peak or shoulder in the region.
[0095]
The maximum molecular weight peak position of the molecular weight distribution of the toner existing on the low molecular weight side is 2 × 10³If less than 3 × 10 3⁴If the ratio exceeds the above range, the fixing property is deteriorated, and the light transmittance is reduced.
[0096]
Further, the position of the maximum molecular weight peak or shoulder of the molecular weight distribution of the toner existing on the high molecular weight side is 5 × 10⁴If it is less than 1, the offset resistance decreases and the storage stability deteriorates. Developability deteriorates and fog increases. 1 × 10⁶If it exceeds 300, the pulverizability decreases and the production efficiency decreases.
[0097]
Further, as a component existing in the high molecular weight region of the toner, 5 × 10⁵It is preferable that the content of the high molecular weight component is 10 wt% or less based on the whole binder resin. 5 × 10⁵The large amount or large state of the components existing in the high molecular weight region is a result of the fact that the kneading state is a defective toner without uniform kneading stress being applied to the toner constituent materials during kneading. This significantly impairs the translucency. In addition, fogging increases due to poor dispersion, transfer efficiency decreases, pulverizability of toner deteriorates, and manufacturing efficiency decreases.
[0098]
More preferably, 5 × 10⁵The content of the high molecular weight component is 5% or less based on the whole binder resin, and more preferably 1 × 10⁶The content of the above high molecular weight component is 1% or less with respect to the entire binder resin, or the content is not contained.
[0099]
The molecular weight distribution in the GPC chromatogram of the toner was 2 × 10³~ 3 × 10⁴The height of the molecular weight distribution of the maximum molecular weight peak existing in the region of⁴~ 1 × 10⁶Hb / Ha is 0.15 to 0.9, where Hb is the height of the maximum molecular weight peak or shoulder existing in the region.
[0100]
When Hb / Ha is less than 0.15, the offset resistance is deteriorated, the storage stability is also reduced, and the filming to the developing roller and the photoconductor is promoted, resulting in a toner. If it exceeds 0.9, the pulverizability deteriorates, the productivity decreases, and the cost increases. More preferably, Hb / Ha is 0.15 to 0.7, and still more preferably, Hb / Ha is 0.2 to 0.6.
[0101]
The molecular weight distribution of the toner by GPC is 2 × 10³~ 3 × 10⁴At least one molecular weight maximum peak in the region of 5 × 10⁴~ 1 × 10⁶Having at least one maximum molecular weight peak or shoulder in the region of⁴~ 1 × 10⁶Focusing on a molecular weight curve present in a region having a maximum molecular weight distribution or a molecular weight value larger than the molecular weight value corresponding to the shoulder existing in the region, and setting the maximum peak of the molecular weight distribution or the height of the shoulder as 100% as a reference, the maximum molecular weight peak thereof Alternatively, when the molecular weight corresponding to 90% of the height of the shoulder is M90 and the molecular weight corresponding to the maximum molecular weight peak or 10% of the height of the shoulder is M10, M10 / M90 is 0.1. By setting the ratio of (M10−M90) / M90 to 0.1 to 7, it is possible to secure high translucency and to prevent oil-less fixation without the need for a fixing oil. realizable. Further, generation of spent on the carrier can be suppressed, and the life of the developer can be extended.
[0102]
Defining the value of M10 / M90, and further, the value of (M10−M90) / M90 (the slope of the molecular weight distribution curve) can quantify the state of molecular cleavage of the ultrahigh molecular weight component. If it is within the stated range (indicating that the slope of the molecular weight distribution curve is steep), the ultra-high molecular weight component that inhibits light transmission is lost by cutting during kneading, resulting in high light transmission. Will have. Further, the high molecular weight component that forms peaks or shoulders appearing on the high molecular side contributes to the offset resistance, so that the occurrence of offset of the color toner can be prevented without using oil. Further, generation of spent on the carrier can be suppressed, and the life of the developer can be extended.
[0103]
Furthermore, when this ultra-high molecular weight component is molecularly cut, it is possible to uniformly disperse the wax and the charge control agent in the binder resin, and the charge amount is made uniform, and a sharp resolution is obtained. Even if used for a long period of time, the durability is not deteriorated. Further, the cleaning property of the transfer member is improved, the handling property in the developing device is improved, and the uniformity of the toner density is improved. Development memory can also be suppressed. It is a toner that can prevent image disturbance and dropout during transfer and can obtain highly efficient transferability.
[0104]
If the value of M10 / M90 is greater than 8, or (M10-M90) / M90 is greater than 7, the ultrahigh molecular weight component still remains, impairing light transmission. If the value of M10 / M90 is smaller than 0.5, or if (M10-M90) / M90 is smaller than 0.1, the mechanical load during kneading is excessive, and the toner productivity is reduced. The durability of the toner decreases. More preferably, the value of M10 / M90 is 0.5 to 6, and (M10-M90) / M90 is 0.1 to 4.5. More preferably, the value of M10 / M90 is 0.5 to 4.5, and (M10-M90) / M90 is 0.1 to 3.5.
[0105]
As a result, digital high image quality, high color reproducibility, color can be prevented from being spent on the carrier in two-component development, and high transparency and anti-offset are achieved without using offset prevention oil on the fixing roller. I can do it.
[0106]
Further, it is possible to realize a cleaner process, to prevent a dropout in a transfer step in a high-speed tandem transfer process, a short distance between transfers, and to realize high transferability.
[0107]
By kneading the above-mentioned binder resin with a high shearing force in the melt-kneading process, a toner capable of exhibiting unprecedented characteristics can be obtained. By fixing without using oil, it is possible to achieve both the high translucency and the offset resistance of the color toner. In other words, the binder resin to which the ultra-high molecular weight component has been imparted has a high shear force to lower the ultra-high molecular weight component to a low molecular weight, thereby exhibiting high translucency. Offset properties are also satisfactory. In addition, since it has an ultra-high molecular weight component, a high shearing force is applied during kneading, so that wax can be more uniformly dispersed. Toner has improved light transmittance, non-offset properties, high image quality, and high color reproducibility And good transferability can be obtained. Further, generation of spent on the carrier can be suppressed, and the life of the developer can be extended.
[0108]
After the melt-kneading process, the toner has a weight average molecular weight of 8,000 to 180,000, a Z average molecular weight of 18,000 to 450,000, a ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) of 3 to 80, and Z average. The ratio of the molecular weight to the number average molecular weight (Z average molecular weight / number average molecular weight) is 10 to 1000 toner.
[0109]
By kneading the toner in this proper range with a high shearing force, the toner can achieve both high translucency and offset resistance of the color toner by fixing without using oil.
[0110]
Preferably, the weight average molecular weight is 8,000 to 100,000, the Z average molecular weight is 18,000 to 300,000, the weight average molecular weight / number average molecular weight is 3 to 60, and the Z average molecular weight / number average molecular weight is 10 to 500.
[0111]
More preferably, the weight average molecular weight is 10,000 to 40,000, the Z average molecular weight is 20,000 to 80,000, the weight average molecular weight / number average molecular weight is 3 to 30, and the Z average molecular weight / number average molecular weight is 10 to 50. preferable.
[0112]
If the weight average molecular weight is less than 8000, the Z average molecular weight is less than 18,000, the weight average molecular weight / number average molecular weight is less than 3, and the Z average molecular weight / number average molecular weight is less than 10, kneading stress is not sufficiently applied. In addition, the molecular weight cannot be maintained at an appropriate value. The dispersibility of the wax is reduced, and the offset resistance and the high-temperature preservability are deteriorated. Further, poor cleaning at the intermediate transfer member and filming on the photoreceptor occur.
[0113]
When the weight average molecular weight is greater than 180,000, the Z average molecular weight is greater than 450,000, the weight average molecular weight / number average molecular weight is greater than 80, and when the Z average molecular weight / number average molecular weight exceeds 1000, conversely, the charge control agent, etc. The internal additives cause mutual agglomeration, leading to a decrease in dispersibility, resulting in an increase in fog, a decrease in image density, and the occurrence of poor transfer. Further, the fixing strength is reduced, and the light transmittance and glossiness are reduced.
[0114]
The binder resin has a THF-insoluble component of 5% by weight or less, and preferably has no THF-insoluble component. When the amount of the THF-insoluble component is more than 5% by weight, the toner which deteriorates the light transmittance of the color image and the image quality are deteriorated.
[0115]
As the binder resin suitably used in the present embodiment, a polyester resin obtained by polycondensation of an alcohol component and a carboxylic acid component such as a carboxylic acid, a carboxylic acid ester or a carboxylic acid anhydride is preferably used.
[0116]
Examples of the divalent carboxylic acid or lower alkyl ester include aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, hexahydrophthalic anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic acid. And aliphatic dibasic acids such as phthalic anhydride, phthalic acid, terephthalic acid and isophthalic acid, and their methyl esters and ethyl esters. Among these, aromatic dibasic acids such as succinic acid, phthalic acid, terephthalic acid, and isophthalic acid, and lower alkyl esters thereof are preferred. It is preferable to use a combination of succinic acid and terephthalic acid, or a combination of phthalic acid and terephthalic acid.
[0117]
The trivalent or higher carboxylic acid component includes 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, , 2,4-Naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexatricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) Examples thereof include methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empoll trimer acid, acid anhydrides thereof, and alkyl (C1 to C12) esters.
[0118]
Examples of the dihydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, Examples thereof include diols such as dipropylene glycol, bisphenol A ethylene oxide adduct, and bisphenol A propylene oxide adduct, triols such as glycerin, trimethylolpropane, and trimethylolethane, and mixtures thereof. Among them, bisphenol A represented by the following chemical formula (Chemical Formula 1), a derivative thereof, an alkylene oxide adduct thereof, neopentyl glycol, and totimethylolpropane are preferable.
[0119]
Embedded image

[0120]
Examples of the trihydric or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, , 2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like. Can be
[0121]
For the polymerization, known polycondensation, solution polycondensation and the like can be used. As a result, it is possible to obtain a good toner for the toner which impairs the PVC mat resistance and the color of the color material of the color toner.
[0122]
Generally, the ratio of the number of hydroxyl groups to the number of carboxyl groups (OH / COOH) is generally 0.8 to 1.4.
[0123]
The molecular weights of resins, waxes and toners are values measured by gel permeation chromatography (GPC) using several types of monodisperse polystyrene as standard samples.
[0124]
The apparatus was HPLC 8120 series manufactured by Tosoh Corporation, the column was TSKgel super HM-H H4000 / H3000 / H2000 (7.8 mm diameter, 150 mm × 3), eluent THF (tetrahydrofuran), flow rate 0.6 ml / min, sample concentration 0.1. %, Injection volume: 20 μL, detector RI, measurement temperature: 40 ° C., pre-measurement treatment: After dissolving the sample in THF, filter with a 0.45 μm filter and remove resin components such as silica to measure the resin component. The measurement condition is a condition in which the molecular weight distribution of the target sample is within the range in which the logarithm of the molecular weight and the count number in a calibration curve obtained from several types of monodisperse polystyrene standard samples are linear toners.
[0125]
The measurement of a wax obtained by reaction with a long-chain alkyl alcohol having 5 to 100 carbon atoms, an unsaturated polycarboxylic acid or an anhydride thereof, and an unsaturated hydrocarbon-based wax was performed by using a GPC-150C manufactured by WATERS, and using a column. Shodex HT-806M (8.0 mm ID-30 cm × 2), eluent o-dichlorobenzene, flow rate 1.0 mL / min, sample concentration 0.3%, injection volume 200 μL, detector RI The measurement temperature was 130 ° C., and the pre-measurement treatment was such that the sample was dissolved in a solvent and then filtered with a 0.5 μm sintered metal filter. The measurement condition is a condition in which the molecular weight distribution of the target sample is within the range in which the logarithm of the molecular weight and the count number in a calibration curve obtained from several types of monodisperse polystyrene standard samples are linear toners.
[0126]
The softening point of the binder resin was 1 cm using a constant load extrusion type capillary rheometer flow tester (CFT500) manufactured by Shimadzu Corporation.³While heating the sample at a heating rate of 6 ° C./min, about 9.8 × 10⁵N / m²  From the die having a diameter of 1 mm and a length of 1 mm, and the temperature at which the piston stroke starts to rise is determined as the outflow start temperature (Tfb ), The half of the difference between the minimum value of the curve and the outflow end point is determined, and the temperature at the point where the minimum value of the curve and the minimum value of the curve are added is determined as the melting temperature (softening point Tm) in the 1/2 method.
[0127]
The glass transition point of the resin was measured using a differential scanning calorimeter by raising the temperature to 100 ° C., allowing the resin to stand at that temperature for 3 minutes, and then cooling the sample to room temperature at a rate of 10 ° C./min. When the heat history was measured by raising the temperature at the rate of / min, the temperature at the intersection of the extension line of the baseline below the glass transition point and the tangent line showing the maximum slope from the rising portion of the peak to the peak of the peak was calculated. Say.
[0128]
For the melting point of the endothermic peak by DSC, a differential calorimeter DSC-50 manufactured by Shimadzu Corporation was used. The temperature was raised to 200 ° C. at 5 ° C./min, rapidly cooled to 10 ° C. for 5 minutes, left standing for 15 minutes, then raised at 5 ° C./min, and determined from the endothermic (melting) peak. The amount of the sample to be charged into the cell was 10 mg ± 2 mg.
[0129]
As the binder resin suitably used in the present embodiment, a homopolymer or a copolymer of various vinyl monomers can also be suitably used. For example, styrene, O-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pnbutylstyrene, p-tert-butylstyrene, pn-hexylstyrene And styrene and its derivatives such as pn-octylstyrene, pn-hexylstyrene and P-chlorostyrene, and styrene is particularly preferred.
[0130]
Examples of the acrylic monomer include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, hexyl methacrylate, and methacryl. 2-ethylhexyl acid, ethyl β-hydroxyacrylate, propyl γ-hydroxyacrylate, butyl α-hydroxyacrylate, ethyl β-hydroxymethacrylate, propyl γ-aminoacrylate, propyl γ-N, N-diethylaminoacrylate And ethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Styrene-acrylic copolymers suitable for the purpose of the present invention are styrene / butyl acrylate copolymers, especially those containing 75 to 85% by weight of styrene and 15 to 25% by weight of butyl acrylate. used.
(4) Charge control agent
In the present embodiment, a charge control agent is added for the purpose of controlling the charge of the toner and for strengthening the oilless fixing. As a preferable material, an acrylic sulfonic acid polymer such as a vinyl copolymer of a styrene monomer and an acrylic acid monomer having a sulfonic acid group as a polar group is preferable. In particular, a copolymer with acrylamido-2-methylpropanesulfonic acid can exhibit preferable characteristics. When used in combination with the carrier described above, the handling property in the developing device is improved, and the uniformity of the toner density is improved. Further, generation of development memory can be suppressed. As a preferable material, a metal salt of a salicylic acid derivative represented by the following chemical formula (Formula 2) is used.
[0131]
Embedded image

[0132]
As a preferable material, a metal salt of a benzylic acid derivative represented by the following chemical formula (Formula 3) is used.
[0133]
Embedded image

[0134]
With this configuration, it is possible to secure a wide non-offset temperature range in oilless fixing, and to prevent image disturbance due to a charging action during fixing. This is probably due to the effect of the charge polarity of the metal salt and the functional group having the acid value of the wax. Also, it is possible to prevent a decrease in the charge amount during continuous use.
[0135]
The addition amount is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the binder resin. It is more preferably 1 to 4 parts by weight, and still more preferably 3 to 4 parts by weight. If the amount is less than 0.5 parts by weight, the charging effect is lost. If the amount is more than 5 parts by weight, color turbidity in a color image becomes conspicuous.
(5) Pigment
Examples of the pigment used in the present embodiment include carbon black, iron black, graphite, nigrosine, metal complexes of azo dyes, C.I. I. Pigment Yellow 1,3,74,97,98 and the like. I. Acetoacetate arylamide disazo yellow pigments such as CI Pigment Yellow 12, 13, 14, 17; I. Solvent Yellow 19, 77, 79, C.I. I. Disperse Yellow 164 is blended, and C.I. I. Pigment Yellow 93, 180, 185 benzimidazolones are effective for photoreceptor filming.
[0136]
C. I. Red pigments such as CI Pigment Red 48, 49: 1, 53: 1, 57, 57: 1, 81, 122, 5; I. Red dyes such as Solvent Red 49, 52, 58, 8; I. One or more blue dyes of phthalocyanine and its derivatives such as Pigment Blue 15: 3 are blended. The addition amount is preferably 3 to 8 parts by weight based on 100 parts by weight of the binder resin.
(6) External additives
In the present embodiment, as an external additive, fine powders of metal oxides such as silica, alumina, titanium oxide, zirconia, magnesia, ferrite, and magnetite; titanates such as barium titanate, calcium titanate, and strontium titanate; Zirconates such as barium acid, calcium zirconate and strontium zirconate, or mixtures thereof are used. The external additive is subjected to a hydrophobic treatment as required.
[0137]
As the silicone oil-based material to be treated with silica, a material represented by the following chemical formula (Formula 4) is preferable.
[0138]
Embedded image

[0139]
For example, dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, cyclic dimethyl silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, carbinol modified silicone oil, methacryl modified silicone oil, mercapto modified silicone oil, polyether modified Silica treated with at least one of silicone oil, methylstyryl-modified silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, amino-modified silicone oil, and chlorophenyl-modified silicone oil is preferably used. For example, SH200, SH510, SF230, SH203, BY16-823, BY16-855B, etc., manufactured by Toray Dow Corning Silicone Co., Ltd. may be mentioned. For the treatment, a method of mixing inorganic fine powder and a material such as silicone oil with a mixer such as a Henschel mixer, a method of spraying a silicone oil-based material onto silica, or a method of dissolving or dispersing a silicone oil-based material in a solvent After that, there is a method of mixing with the fine silica powder and then removing the solvent to prepare. It is preferable that 1 to 20 parts by weight of a silicone oil-based material is blended with respect to 100 parts by weight of the inorganic fine powder.
[0140]
As the silane coupling agent, dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzylmethylchlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, There are vinyltriacetoxysilane, divinylchlorosilane, dimethylvinylchlorosilane and the like. The silane coupling agent treatment is a dry process in which a vaporized silane coupling agent is reacted with a cloud of fine powder by stirring or the like, or a wet process in which a silane coupling agent in which fine powder is dispersed in a solvent is dropped. Processed by the method.
[0141]
It is also preferable to treat the silicone oil-based material after the silane coupling treatment.
[0142]
The inorganic fine powder having positive electrode chargeability is treated with aminosilane, an amino-modified silicone oil represented by the following chemical formula (5), or an epoxy-modified silicone oil.
[0143]
Embedded image

[0144]
In order to enhance the hydrophobic treatment, it is also preferable to use a combination of treatment with hexamethyldisilazane, dimethyldichlorosilane, or another silicone oil. For example, it is preferable to treat with at least one of dimethyl silicone oil, methylphenyl silicone oil, and alkyl-modified silicone oil.
[0145]
It is also preferable to treat the surface of the inorganic fine powder with a fatty acid ester, a fatty acid amide, or a fatty acid metal salt. Silica or titanium oxide fine powder having one or two or more kinds of surface treated is more preferable.
[0146]
Examples of fatty acids and fatty acid metal salts include caprylic acid, capric acid, undecylic acid, lauric acid, mystyric acid, parimitic acid, stearic acid, behenic acid, montanic acid, lacceric acid, oleic acid, erucic acid, sorbic acid, linoleic acid, etc. Is mentioned. Among them, fatty acids having 15 to 20 carbon atoms are preferable.
[0147]
Examples of the metal constituting the fatty acid metal salt include aluminum, zinc, calcium, magnesium, lithium, sodium, lead and barium, and among them, aluminum, zinc and sodium are preferred. Particularly preferably, aluminum distearate (Al (OH) (C₁₇H₃₅COO)₂) Or aluminum monostearate (Al (OH)₂(C₁₇H₃₅COO)), etc., and aluminum difatty acids and aluminum monofatty acids are preferred. Having an OH group can prevent overcharging and suppress transfer failure. Further, it is considered that the processability with an inorganic fine powder such as silica during the treatment is improved.
[0148]
Further, the handling property of the small particle size toner can be improved, and both high image quality and improved transferability can be achieved in development and transfer. In development, the latent image can be reproduced more faithfully. Then, it is possible to transfer the toner particles which deteriorate the transfer rate of the toner particles at the time of transfer. Further, even in tandem transfer, re-transfer can be prevented, and the occurrence of voids can be suppressed. Furthermore, high image density can be obtained even if the development amount is reduced. Further, by using the carrier in combination with a carrier described later, the spent resistance can be further improved, the handling property in the developing device can be improved, and the uniformity of the toner density can be improved. Further, generation of development memory can be suppressed.
[0149]
It is preferable that the inorganic fine powder having an average particle diameter of 6 nm to 200 nm is externally added to 1.5 to 5.5 parts by weight based on 100 parts by weight of the toner base particles. If the average particle size is smaller than 6 nm, silica floating and filming on the photoreceptor are likely to occur. The occurrence of reverse transfer during transfer cannot be suppressed. If it is larger than 200 nm, the fluidity of the toner deteriorates. If the amount is less than 1.5 parts by weight, the fluidity of the toner deteriorates. The occurrence of reverse transfer during transfer cannot be suppressed. If the amount is more than 5.5 parts by weight, silica floating and filming on the photoreceptor are likely to occur. High temperature offset property is deteriorated.
[0150]
Further, 0.5 to 2.5 parts by weight of an inorganic fine powder having an average particle diameter of 6 nm to 20 nm to 100 parts by weight of the toner base particles, and 100 parts by weight of the inorganic fine powder having an average particle diameter of 30 nm to 200 nm are used. It is preferable that at least 1.0 to 3.5 parts by weight of the compound be externally added. With the use of the silica whose functions are separated according to this configuration, it is possible to obtain more margin for handling in development, reverse transfer at the time of transfer, dropout, and scattering. In addition, spent on a carrier can be prevented.
[0151]
Furthermore, it is preferable that the ignition loss of the inorganic fine powder having an average particle diameter of 6 nm to 20 nm is 1.5 to 25 wt%, and the ignition loss of the inorganic fine powder having an average particle diameter of 30 nm to 200 nm is 0.5 to 23 wt%.
[0152]
By specifying the loss on ignition of the silica, more margin can be secured for reverse transfer, dropout, and scattering during transfer. In addition, the use in combination with the above-described carrier or wax can further improve the spent resistance, improve the handling in the developing device, and increase the uniformity of the toner concentration. Further, generation of development memory can be suppressed.
[0153]
If the ignition loss at an average particle diameter of 6 nm to 20 nm is less than 1.5 wt%, the transfer margin for reverse transfer and hollowing will be narrow. If the content is more than 25 wt%, the surface treatment becomes uneven, and the charging varies. Preferably, the ignition loss is 1.5 to 20 wt%, more preferably 5 to 19 wt%.
[0154]
When the ignition loss at an average particle diameter of 30 nm to 200 nm is less than 0.5 wt%, the transfer margin for reverse transfer and hollowing is reduced. If the content is more than 23 wt%, the surface treatment becomes uneven, and uneven charging occurs. Preferably, the ignition loss is 1.5 to 18 wt%, more preferably 5 to 16 wt%.
[0155]
Further, at least 0.5 to 1.5 parts by weight of a positively chargeable inorganic fine powder having an average particle diameter of 6 nm to 200 nm and a loss on ignition of 0.5 to 25 wt% with respect to 100 parts by weight of the toner base particles. A configuration for externally adding is also preferable.
[0156]
The effect of adding the positively chargeable inorganic fine powder is that the toner can be prevented from being overcharged during long-term continuous use, and the life of the developer can be further extended. Further, an effect of suppressing scattering at the time of transfer due to overcharging can be obtained. In addition, spent on a carrier can be prevented. If the amount is less than 0.5 parts by weight, it is difficult to obtain the effect. If the amount is more than 1.5 parts by weight, fogging in development increases. The ignition loss is preferably 1.5 to 20 wt%, more preferably 5 to 19 wt%.
[0157]
The loss on drying (%) is determined by taking about 1 g of a sample in a container which has been dried, cooled and precisely weighed in advance, and precisely weighed. Dry for 2 hours in a hot air dryer (105 ° C ± 1 ° C). After cooling in a desiccator for 30 minutes, the weight is precisely weighed and calculated by the following equation.
Loss on drying (%) = Loss on drying (g) / Sample weight (g) x 100
For the ignition loss, about 1 g of a sample is placed in a magnetic crucible previously dried, cooled, and precisely weighed, and precisely weighed. Ignite for 2 hours in an electric furnace set at 500 ° C. After allowing to cool in a desiccator for one hour, the weight is precisely weighed and calculated by the following equation.
[0158]
Loss on ignition (%) = Loss on ignition (g) / Sample amount (g) x 100
Further, the treated inorganic fine powder preferably has a water adsorption amount of 1 wt% or less. It is preferably at most 0.5 wt%, more preferably at most 0.1 wt%, even more preferably at most 0.05 wt%. If the content is more than 1 wt%, the chargeability is reduced and filming on the photoconductor at the time of durability is caused. The water adsorption amount was measured with a continuous vapor adsorption device (BELSORP18: Bell Japan Co., Ltd.).
[0159]
For the determination of the degree of hydrophobicity, 0.2 g of the product to be tested is weighed in 50 ml of distilled water charged in a 250 ml beaker. At the tip, methanol is dropped from a burette immersed in the liquid until the total amount of the inorganic fine powder is wet. At this time, the mixture is constantly stirred slowly with a magnetic stirrer. The degree of hydrophobicity is calculated from the amount of methanol a (ml) essential for complete wetting by the following equation.
Degree of hydrophobicity = (a / (50 + a)) × 100 (%)
Further, it is preferable to have 1.0 to 6.0 parts by weight of coarse particles having a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base, based on the toner base. As a result, it is possible to maintain the fluidity of the toner, which is generated when the image quality is improved by reducing the particle size of the toner, and to improve the cleaning property of the toner on the photosensitive member and the intermediate transfer member.
[0160]
In order to improve the fluidity of the toner having a reduced particle diameter, a configuration is used in which a large amount of inorganic fine powder such as silica is added. At the time of fusing, the fixing strength is deteriorated, and the high-temperature offset property is deteriorated.
[0161]
However, since the presence of the coarse particles described above causes the toner particles to be present between the toner particles, it does not hinder the fusion of the toners at the time of fixing, maintains the fluidity, and has little effect on the fixing property. Further, it is located at an intermediate size between the toner and the carrier during long-term use, so that the impact applied to the toner can be reduced, and the effect of improving the mixing with the carrier and stabilizing the charge can be obtained.
[0162]
Preferably, coarse particles having a volume average particle diameter of 2.5 to 5 times the volume average particle diameter of the toner base are contained in the toner base in an amount of 2.0 to 5.0 parts by weight. More preferably, the toner has 3.0 to 5.0 parts by weight of coarse particles having a volume average particle diameter of 2.5 to 4 times the volume average particle diameter of the toner base.
[0163]
Further, by adding a lubricant such as the above-mentioned fatty acid ester, fatty acid amide, or fatty acid metal salt to the coarse particles, it is possible to obtain more effects on the relaxation of impact, the maintenance of fluidity, and the cleaning property of the toner. . If the amount is 1 to 20 parts by weight, the effect cannot be obtained if the amount is small, and if the amount is too large, the charge of the toner is reduced.
As the coarse particles, an acrylic resin, a silicone resin, a polyester resin, a styrene resin, an epoxy resin, a melamine resin, or the like can be suitably used, and it is also preferable that the coarse particles are colored in a toner color to be added. There is a method in which these resins are melted, a lubricating agent or a coloring agent is added, and the resin is cooled and pulverized to a predetermined particle size, or a method in which particles are formed by a suspension or emulsion polymerization method. The volume-based variation coefficient of the particles is preferably 40% or less on a volume basis in order to impart the fluidity and to exert the effect of cleaning the toner. It is more preferably at most 35%. More preferably, it is 30% or less. The measurement of the particle size is performed by a method described later.
(7) Powder physical properties of toner
In this embodiment, the volume average particle diameter of the toner base particles containing at least the binder resin, the colorant and the wax containing the binder resin, the colorant and the wax is 3 to 8 μm, preferably 3.5 to 7.5 μm, Preferably, the particle size is 4 to 6.5 μm, the content of the toner base particles having a particle size of 2.52 to 4 μm in the number distribution is 5 to 55% by number, and the particles of 6.35 to 10.1 μm in the volume distribution. It is configured to have a particle size distribution in which toner base particles having a diameter are contained at 5 to 60% by volume.
[0164]
More preferably, the content of the toner base particles having a particle size of 2.52 to 4 μm in the number distribution is 10 to 45% by number, and the toner base particles having the particle size of 6.35 to 10.1 μm in the volume distribution are more preferable. The particle size distribution is 12 to 50% by volume.
[0165]
More preferably, the content of the toner base particles having a particle size of 2.52 to 4 μm in the number distribution is 15 to 40% by number, and the toner base particles having the particle size of 6.35 to 10.1 μm in the volume distribution are preferable. The particle size distribution is 12 to 45% by volume.
[0166]
It is possible to achieve high-resolution image quality, prevent reverse transfer in tandem transfer, prevent omission, and achieve compatibility with oilless fixing.
[0167]
If the volume average particle size is larger than 8 μm, it is impossible to achieve both image quality and transfer. If the volume average particle diameter is smaller than 3 μm, the toner becomes difficult to handle easily during development. When the content of the toner base particles having a particle size of 2.52 to 4 μm in the number distribution is less than 5% by number, it is not possible to achieve both image quality and transfer. When the content is more than 55% by number, the toner has difficulty in hand rigging of the toner base particles during development. When the content of the toner base particles having a particle diameter of 6.35 to 10.1 μm is more than 55% by volume, it is impossible to achieve both image quality and transfer. If it is less than 5% by volume, the productivity of the toner decreases and the cost increases.
[0168]
Further, a specific surface area ratio SSt (SSt = (St / pulverized toner base particles) with a specific surface area value St (St = 6 / (true specific gravity × volume average particle diameter)) equivalent to a true sphere converted from the volume average particle diameter. Is 0.4 to 0.9, preferably 0.5 to 0.85, and more preferably 0.55 to 0.8. This leads to a decrease in chargeability and adverse effects such as scattering at the time of transfer, etc. If it is smaller than 0.4, the shape becomes too irregular, or the amount of over-pulverized fine powder is large.
[0169]
Preferably, the variation coefficient of the volume particle size distribution of the toner base particles is 15 to 32%, and the variation coefficient of the number particle size distribution is 15 to 35%. More preferably, the coefficient of variation of the volume particle size distribution is 15 to 30%, the coefficient of variation of the number particle size distribution is 15 to 30%, even more preferably, the coefficient of variation of the volume particle size distribution is 15 to 25%, The coefficient of variation of the distribution is 15 to 25%.
[0170]
The variation coefficient is obtained by dividing the standard deviation of the toner particle diameter by the average particle diameter. It is based on the particle diameter measured using a Coulter counter (Coulter). The standard deviation is represented by the square root of a value obtained by dividing the square of the difference from the average value of each measured value when measuring n particle systems by (n-1).
[0171]
In other words, the coefficient of variation is an expression of the degree of spread of the particle size distribution. If the coefficient of variation of the volume particle size distribution is less than 15% or the variation coefficient of the number particle size distribution is less than 15%, it is difficult to produce the toner. The cause of the cost increase is the toner. If the coefficient of variation of the volume particle size distribution is larger than 32% or the coefficient of variation of the number particle size distribution exceeds 35%, if the particle size distribution is broad toner, the cohesiveness of the toner becomes strong, and filming on the photoreceptor becomes difficult. Poor transfer, toner difficult to collect residual toner in cleaner-less process.
[0172]
Fine powder in the toner affects the fluidity, image quality, storage stability of the toner, filming on the photosensitive member, the developing roller, and the transfer member, aging characteristics, and transferability, particularly, multi-layer transferability in a tandem system. Furthermore, it affects non-offset properties, glossiness, and light transmission in oilless fixing. In a toner containing a release agent such as wax for realizing oil-less fixing, the amount of fine powder affects compatibility with tandem transferability.
[0173]
If the amount of the fine powder is excessive, that is, if the content of the toner base particles having a particle size of 2.52 to 4 μm is 55% by number or more, the wax that cannot be completely dispersed increases the exposure of the toner surface, and the photosensitive member, the developing roller, Filming on the transfer member occurs. Further, the fine powder tends to be easily offset due to high adhesion to the heat roller. Further, in the tandem method, the aggregation of the toner is likely to be strong, and the transfer failure of the second color is likely to occur during the multi-layer transfer. Conversely, when the amount of fine powder is reduced, the image quality is reduced, and an appropriate range of toner is required.
[0174]
The particle size distribution is measured using a Coulter Counter TA-II (Coulter Counter Co., Ltd.) and connected to an interface (manufactured by Nikkaki) for outputting the number distribution and volume distribution and a personal computer. The electrolyte solution is a 1% toner with a surfactant (sodium lauryl sulfate) added. About 50 ml of the toner to be measured is added about 2 mg, and the electrolyte solution in which the sample is suspended is subjected to dispersion treatment with an ultrasonic disperser for about 3 minutes. And an aperture of 70 μm was used with a Coulter Counter TA-II. In the case of a 70 μm aperture system, the particle size distribution measurement range is 1.26 μm to 50.8 μm. However, the area smaller than 2.0 μm is not practical because measurement accuracy and measurement reproducibility are low due to external noise and the like. Therefore, the measurement area was set to 2.0 μm to 50.8 μm.
[0175]
The degree of compression is calculated from the static bulk density and the dynamic bulk density, and is one of the indexes of toner fluidity. The fluidity of the toner is affected by the particle size distribution of the toner, the shape of the toner particles, the type and amount of external additives and wax. When the particle size distribution of the toner is narrow and the amount of fine powder is small, when the surface of the toner has little irregularity and the shape is nearly spherical, when the amount of the external additive added is large, and when the particle size of the external additive is small, the degree of compression is small. The fluidity of the toner becomes higher. The degree of compression is preferably from 5 to 40%. More preferably, it is 10 to 30%. A toner that can achieve both oilless fixing and tandem-type multi-layer transfer. If it is less than 5%, the fixing property is reduced, and particularly the light transmittance tends to be deteriorated. The toner scatters easily from the developing roller. Transferability of more than 40% is reduced, resulting in tandem dropout and poor transfer.
(8) Career
As the resin-coated carrier of the present embodiment, a carrier having a coating resin layer made of a fluorine-modified silicone resin containing an aminosilane coupling agent on a carrier core material is preferably used.
[0176]
Examples of the carrier core material include an iron powder-based carrier core material, a ferrite-based carrier core material, a magnetite-based carrier core material, and a resin-dispersed carrier core material in which a magnetic substance is dispersed in a resin.
[0177]
Here, an example of the ferrite carrier core material is generally represented by the following formula.
[0178]
(MO)_X(Fe₂O₃)_Y
In the formula, M contains at least one selected from Cu, Zn, Fe, Mg, Mn, Ca, Li, Ti, Ni, Sn, Sr, Al, Ba, Co, Mo, and the like. X and Y indicate the molar ratio by weight and satisfy the condition X + Y = 100.
[0179]
Ferrite carrier core material is Fe₂O₃Is mixed with at least one oxide selected from Cu, Zn, Fe, Mg, Mn, Ca, Li, Ti, Ni, Sn, Sr, Al, Ba, Co, Mo, etc. Used for raw materials.
[0180]
As an example of a method for producing a ferrite carrier core material, first, an appropriate amount of the above-mentioned oxides and the like are blended, pulverized and mixed by a wet ball mill for 10 hours, dried, and then held at 950 ° C. for 4 hours. This is pulverized by a wet ball mill for 24 hours, and further, polyvinyl alcohol, an antifoaming agent, a dispersing agent and the like are added as a binder to form a slurry having a raw material particle diameter of 5 μm or less. The slurry is granulated and dried to obtain a granulated product, which is maintained at 1300 ° C. for 6 hours while controlling the oxygen concentration, pulverized, and further classified into a desired particle size distribution.
[0181]
As the resin used for the resin coating layer of the present invention, a fluorine-modified silicone resin is essential. As the fluorine-modified silicone resin, a perfluoroalkyl group-containing organosilicon compound is essential, and a curable crosslinkable fluorine-modified silicone resin obtained by hydrolyzing the following (Chem. 6) and / or (Chem. 7) is used. preferable.
[0182]
Embedded image

[0183]
Embedded image

[0184]
(Where R₁, R₂, R₃Represents a hydrogen atom, a halogen atom, a hydroxy group, a methoxy group, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. )
Examples of perfluoroalkyl group-containing organosilicon compounds include CF₃CH₂CH₂Si (OCH₃)₃, C₄F₉CH₂CH₂Si (CH₃) (OCH₃)₂, C₈F₁₇CH₂CH₂Si (OCH₃)₃, C₈F₁₇CH₂CH₂Si (OC₂H₅)₃, (CF₃)₂CF (CF₂)₈CH₂CH₂Si (OCH₃)₃And the like, but those having a trifluoropropyl group are particularly preferred.
[0185]
In the present embodiment, an aminosilane coupling agent is contained in the coating resin layer. The aminosilane coupling agent may be a known one, for example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, octadecylmethyl [3- (trimethoxysilane) Silyl) propyl] ammonium chloride (SH6020, SZ6023, AY43-021: both manufactured by Toray Dow Corning Silicone Co., Ltd.), KBM602, KBM603, KBE903, KBM573 (manufactured by Shin-Etsu Silicone Co., Ltd.), etc. Amines are preferred. A secondary or tertiary amine substituted with a methyl group, an ethyl group, a phenyl group, or the like has a weak polarity, and has little effect on the charge rising characteristics with the toner. When the amino group becomes an aminomethyl group, an aminoethyl group, or an aminophenyl group, the leading edge of the silane coupling agent is a primary amine, but the amino group in a linear organic group extending from silane is used. Does not contribute to the charge rise characteristics of the toner, and is adversely affected by moisture at the time of high humidity. The toner eventually falls and has a short life.
[0186]
Therefore, by combining and using these aminosilane coupling agents and fluorine-modified silicone, a sharp charge amount distribution was secured in the fluorine-modified silicone resin layer having a positive chargeability for the toner. As it is, a negative chargeability can be imparted, and the replenished toner has a quick charge rising property and can reduce the toner consumption. In addition, the aminosilane coupling agent exhibits the effect of a crosslinking agent, improves the degree of crosslinking of the fluorine-modified silicone resin layer as the base resin, further improves the coating resin hardness, and reduces wear and peeling during long-term use Thus, the spent resistance is improved, the decrease in the charge applying ability is suppressed, the charging is stabilized, and the durability is improved. Further, by using in combination with a toner to which a specific low-melting wax described later is added in a certain amount or more, the handling property in the developing device is improved, and the density of the image on the rear side and the front side of the image on the image is improved. The uniformity is improved. Further, a so-called development memory in which a history remains after solid image collection can be reduced.
[0187]
The use ratio of the aminosilane coupling agent is 5 to 40% by weight, preferably 10 to 30% by weight, based on the resin. When the amount is less than 5% by weight, the effect of the aminosilane coupling agent is not obtained. When the amount exceeds 40% by weight, the degree of crosslinking of the resin coating layer becomes too high, and the charge-up phenomenon is easily caused. The cause may be toner.
[0188]
Further, in order to stabilize charging and prevent charge-up, the resin coating layer may contain conductive fine particles. Examples of the conductive fine particles include carbon black such as oil furnace carbon and acetylene black, semiconductive oxides such as titanium oxide and zinc oxide, powder surfaces such as titanium oxide, zinc oxide, barium sulfate, aluminum borate, and potassium titanate. Examples thereof include tin oxide, carbon black, and those coated with a metal.¹⁰Ω · cm or less is preferable. When the conductive fine particles are used, the content is preferably 1 to 15% by weight. If the content of the conductive fine particles is a certain level with respect to the resin coating layer, the filler effect improves the hardness of the resin coating layer, but if it exceeds 15% by weight, the formation of the resin coating layer is hindered. In addition, the toner causes a decrease in adhesion and hardness. Further, an excessive content of the conductive fine particles in the full color developer is a toner which causes color stain of the toner transferred and fixed on the paper surface.
[0189]
The average particle size of the carrier of the present embodiment is preferably from 20 to 70 μm. If the average particle diameter of the carrier is less than 20 μm, the abundance of the fine particles in the distribution of the carrier particles becomes high, and the magnetization per carrier particle of the carrier particles becomes low, so that the carrier is easily developed on the photoconductor. On the other hand, when the average particle size of the carrier exceeds 70 μm, the specific surface area of the carrier particles becomes small, and the toner holding power becomes weak, so that toner scattering occurs. Further, in a full color having many solid portions, the reproduction of the solid portion is particularly poor, which is not preferable.
[0190]
The method of forming the coating layer on the carrier core material is not particularly limited, and is a known coating method, for example, an immersion method in which a powder that is a carrier core material is immersed in a coating layer forming solution, Spray method for spraying the solution onto the surface of the carrier core material, fluid bed method for spraying the solution for forming the coating layer in a state where the carrier core material is suspended by flowing air, solution for forming the carrier core material and the coating layer in a kneader coater In addition to the wet coating method such as a kneader coater method to remove the solvent, the powdered resin and the carrier core material are mixed at high speed, and the frictional heat is used to melt the resin powder onto the carrier core material surface. Examples include a dry coating method for coating and coating, and any of them can be applied, but a wet coating method is particularly preferably used.
[0191]
The solvent used in the coating solution for forming the coating layer is not particularly limited as long as it dissolves the coating resin, and can be selected so as to be compatible with the coating resin used. Generally, for example, aromatic hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, and ethers such as tetrahydrofuran and dioxane can be used.
[0192]
The resin coating amount is preferably from 0.2 to 6.0% by weight, more preferably from 0.5 to 5.0% by weight, even more preferably from 0.6 to 4.0% by weight, based on the carrier core material. 7 to 3% by weight. If the coating amount of the resin is less than 0.2% by weight, a uniform coating cannot be formed on the surface of the carrier, and the characteristics of the carrier core material are greatly affected. The effect of the aminosilane coupling agent cannot be sufficiently exerted. If it exceeds 6.0% by weight, the coating layer becomes too thick, and granulation of carrier particles occurs, so that uniform carrier particles tend not to be obtained.
[0193]
After coating with the resin, the conditions for the curing treatment are suitably 120 to 280 ° C. and 0.5 to 2.5 hours. If the processing temperature is low, the hardness of the coating resin itself decreases. If the processing temperature is too high, a reduction in charge occurs.
(9) Crushing
The toner according to the exemplary embodiment can prevent spent on the carrier even if the particle diameter is reduced, and can realize oilless fixing.
[0194]
As an example of the pulverization method, in order to obtain a small particle size and a sharp particle size distribution, after melt-kneading the toner composition, a cylindrical rotating body having a surface with irregularities and rotating at a high speed, and a rotating body. A cylindrical fixed body fitted with a gap of 0.5 mm to 40 mm on the outside of the surface, and having irregularities on the surface sharing the central axis with the rotating body, a supply port through which the toner material to be ground is introduced, The pulverized product is pulverized to a predetermined particle size distribution by a pulverizer having a discharge port for discharging the processed pulverized toner. At this time, before flowing the pulverized material of the toner from the supply port, a means for alleviating the aggregation of the pulverized product of the toner is added, and the pulverized material of the toner is supplied from the supply port and pulverized to a predetermined particle size distribution.
[0195]
As means for alleviating the aggregation of the crushed toner material, an evaporating medium such as water vapor, ethanol, iso-propyl alcohol, and n-butyl may be added to the crushed toner material before flowing the pulverized toner material from the supply port. The purpose is to remove the charge of the powder with alcohol, sec-butyl alcohol, iso-butyl alcohol and the like. This is a method in which mist is supplied to the crushed toner by spraying and mixed or adhered to the crushed toner, and then the crushed material is supplied from a crushing supply port.
[0196]
In addition, a vibrating means may be added to the pulverized toner material before supplying the pulverized toner material from the supply port. The vibrating means includes ultrasonic vibration, vibration vibration, and the like. Before the pulverized product of the toner passes through the pipe and flows from the supply port of the pulverizing unit, a vibration device is provided in the pipe unit, and the pulverized product of the toner flows from the supply port while being dispersed.
[0197]
In addition, there is a method in which, before the pulverized material of the toner is allowed to flow from the quantitative supply device, the pulverized material of the toner and the inorganic fine powder are mixed in advance, and the mixture is pulverized by flowing the mixture from the quantitative supply device. The above-mentioned materials are suitable as the inorganic fine powder.
[0198]
Also, when the toner is pulverized, the inorganic fine powder is supplied from the inorganic fine powder supply machine and mixed before flowing the pulverized material of the toner from the fixed quantity supply machine, and the inorganic fine powder is caused to flow from the pulverization inlet to a predetermined particle size distribution. A configuration for crushing is also available. It is also possible to put them in at the same time.
[0199]
As a result, the material to be crushed enters the crushing section having the rotating body in a state where the crushed material of the toner is uniformly dispersed, and the crushed material of the toner is uniformly crushed by the vortex generated by the rotating body. Thereby, it is possible to carry out the pulverization to reduce the particle size and the pulverization in a state where the coarse powder is sharply cut.
[0200]
At this time, the inorganic fine powder supplied and mixed is preferably silica or titanium oxide fine powder having an average particle size of 8 to 40 nm and a loss on ignition of 0.5 to 25 wt%. Further, silica or titanium oxide fine powder obtained by surface-treating one or more of fatty acid esters, fatty acid amides, and fatty acid metal salts is preferable. Further, the inorganic fine powder is preferably a silica or titanium oxide fine powder obtained by surface-treating silicone oil. In order to alleviate the charge of the pulverized product of the toner, an inorganic fine powder having a polarity opposite to that of the toner base particles is also effective.
[0201]
When the average particle size is smaller than 8 nm, the toner is unstable in quantitative cutout. If the average particle size is larger than 40 nm, uniform pulverizability is not improved. If the ignition loss is less than 0.5 wt%, fine powder will be scattered. If the ignition loss is more than 25% by weight, the aggregation of the fine powder becomes strong, and the uniform supply of the pulverized product of the toner deteriorates.
[0202]
This inorganic fine powder adheres to the surface of the toner in a state of electrostatic adhesion, which is fixed to the toner base. The supply amount of the inorganic fine powder is preferably about 0.1 to 5% by weight of the supply amount of the pulverized product of the toner.
[0203]
By setting the gap between the convex portion of the rotating body and the convex portion of the fixed body to 0.5 to 40 mm, preferably 0.5 to 10 mm, and more preferably 0.5 to 6 mm, the pulverization efficiency and the spheroidizing effect are improved. Can be enhanced. When the diameter is smaller than 0.5 mm, the contact between the particles and the rotating body or the fixed body is remarkably increased, so that frictional heat is remarkably generated, and the toner is fused at the above-mentioned front end. If it is larger than 40 mm, a vigorous high-speed air flow cannot be generated, and sufficient pulverizability cannot be obtained.
[0204]
When this method is used, since the external addition process can be performed simultaneously with the pulverization, there is a great merit that the manufacturing process can be shortened. In addition, since the toner particles are rounded at the corners, the fluidity is improved.
[0205]
If the fluidity of the toner is low, unevenness occurs in the solid image area, the frictional charging property decreases, the amount of toner of the opposite polarity increases, and the toner adheres strongly to the non-image area of the photoconductor and cannot be removed. As a result, the image deteriorates, and the transfer efficiency decreases. When the flowability of the toner is increased by increasing the amount of the external additive silica, the triboelectric charging tends to be uniform, and the background fog is reduced, the image density is increased, and the unevenness of the solid black image portion tends to be eliminated. However, problems such as filming of silica or toner on the photoreceptor and adhesion of silica aggregates to white dots on a solid black image portion occur.
[0206]
Therefore, high fluidity can be obtained with a small amount of added silica, the generation of floating silica is suppressed, and white spots of silica on a solid black image area, silica on an intermediate transfer member and a photoconductor, and toner filming are suppressed. Generation is suppressed. In addition, the occurrence of unevenness in the solid black image area, which is observed with low-fluidity toner, is suppressed, uniform transferability is obtained, and the generation of reverse polarity toner is suppressed to a low level.
[0207]
Further, at the time of transfer, particularly at high temperature and high humidity, where toner such as characters and lines are concentrated, even when transferred with a predetermined pressing force, due to the high fluidity of the toner, aggregation of the toners hardly occurs, A clear image without any voids can be obtained.
[0208]
An example of the toner pulverizing device of the present embodiment shown in FIG. 3 will be described.
The kneaded material 503, to which the kneaded material has passed a mesh diameter of about 1 to 5 mm by coarse pulverization, is fed from the quantitative supply device 508 and sent to the pulverization supply unit by the cooling air 511 supplied by the cooler 509, and the pulverization processing unit. Milled at 500. The raw material 503 is supplied from the pulverizing inlet 504 and rotates at a high speed and has a rotating body 501 having an uneven portion 506 on the surface, and a fixed body 502 having an uneven portion 507 on the surface positioned at a gap between the rotating body 501 and the narrow gap. The raw material particles are conveyed into the space, and the high-speed airflow generated between the rotating body and the fixed body rotating at high speed causes the raw material particles to become spherical while being pulverized by strong collision. The spheroidized particles 510 exit from the outlet 505 and are sent to a coarse powder classifier 513, and the coarse particles are sent again to the grinding inlet 504 by air 511. The product is sent to the cyclone 515 and collected in the collection container 520. 512 is a thermometer, 514 is a bag filter, 516 is an air flow meter, and 517 is a blower.
[0209]
519 is a vibrator vibrator, and 518 is an inorganic fine powder feeder. When it is separated by coarse powder classification and supplied to the pulverizing section again, it is preferable to supply the inorganic fine powder from behind. Thereby, the inorganic fine powder is uniformly mixed at the time of collision with the pulverized material. It is possible to supply an evaporable solvent instead of the inorganic fine powder.
[0210]
FIG. 4 is a sectional view taken along line II of FIG. 3 as viewed from above. The concavo-convex portion is added over the entire circumference. The drawing shows a part thereof, and the rest is omitted. FIG. 5 is an enlarged view of a portion B in FIG. s1 is the width of the convex portion of the surface uneven portion 507 of the fixed body 502, s2 is the distance between the convex portions of the surface uneven portion 507 of the fixed body 502, s3 is the height of the convex portion of the surface uneven portion 507 of the fixed body 502, r1 is the width of the convex portion of the surface uneven portion 506 of the rotating body 501, r2 is the distance between the convex portions of the surface uneven portion 506 of the rotating body 501, and r3 is the height of the convex portion of the surface uneven portion 506 of the fixed body 501. Show. In order for the rotating body to rotate at a high speed and efficiently reduce the toner particle size and make the toner spherical while receiving the supply of the inorganic fine powder such as silica, and pulverize the toner, the density of the surface irregularities 507 of the fixed body 502 must be increased. This can be realized by adopting a configuration in which the density is higher than the density of the surface irregularities 506 of the surface 501. It is preferable that the number of the protrusions is one or more per 1 cm of the circumference. Preferably, the number is 2.5 or more. Furthermore, it is preferable to have a relationship of 0.2 ≦ s1 / r1 ≦ 0.7 and 0.2 ≦ s2 / r2 ≦ 0.7. In particular, when the crushing process is performed while supplying the inorganic fine powder, since the crushed material is charged in a uniformly dispersed state, it is necessary to increase the density in order to stabilize the collision with the wall surface of the fixed body. . When it is smaller than 0.2, the cost increases during surface processing. If it is larger than 0.7, the vortex flow becomes uneven and it is difficult to pulverize the toner into a small particle size.
(10) Polymerization method
Emulsion polymerization, suspension polymerization, and the like can also be suitably used as a method for producing a small particle size toner.
[0211]
In the emulsion polymerization method, a resin fine particle dispersion containing an ionic surfactant is prepared, mixed with a colorant particle dispersion and a wax release agent particle dispersion, and the polarity opposite to that of the ionic surfactant is used. Means for forming aggregated particles having a toner diameter by causing aggregation with an ionic surfactant having the following formula, followed by heating to a temperature equal to or higher than the glass transition point of the resin fine particles to fuse the aggregated particles, washing and drying. Can produce toner.
[0212]
Examples of the surfactant used at this time include anionic surfactants such as sulfate ester type, sulfonate type, phosphate ester type and soap type, and cationic type such as amine salt type and quaternary ammonium salt type. Surfactants can be used. It is also effective to use a nonionic surfactant such as polyethylene glycol, alkylphenol ethylene oxide adduct or polyhydric alcohol. As these dispersing means, general ones such as a rotary shearing homogenizer, a ball mill having a medium, a sand mill, and a dyno mill can be used.
[0213]
After the particles are formed, a desired toner can be obtained through an optional washing step, solid-liquid separation step, and drying step. However, the washing step is sufficiently replaced and washed with ion-exchanged water in order to develop and maintain the chargeability. Is preferably applied. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration and the like are preferably used from the viewpoint of productivity. Further, the drying step is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration type fluidized drying and the like are preferably used from the viewpoint of productivity.
[0214]
In the suspension polymerization method, various additives such as a polymerizable monomer, a wax, and a colorant are uniformly dissolved or dispersed, heated, and then uniformly dissolved or dispersed with a homogenizer, an ultrasonic disperser, or the like. After that, the monomer system is dispersed in an aqueous phase at the same temperature as that of the monomer system containing the dispersion stabilizer using a conventional stirrer or a homomixer / homogenizer.
[0215]
Preferably, the stirring speed and time are adjusted so that the monomer droplets have a particle size of a predetermined toner particle size. Thereafter, the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. What is necessary is just to perform stirring to the extent that it is performed. The polymerization temperature is set at a temperature of 40 ° C. or higher, generally 50 to 80 ° C.
[0216]
At this time, the rotational stirring speed is preferably 30 m / sec or more in order to increase the dispersion of the fixing aid and to obtain a small and uniform particle size distribution of the toner particles containing the fixing aid.
[0217]
After the completion of the reaction, the generated toner particles are collected by washing and filtration, and dried. In the suspension polymerization, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer system.
[0218]
The dispersion medium used is any suitable stabilizer, as an organic compound, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and salts thereof, starch, inorganic Compounds include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, calcium metasilicate, bentonite, silica, Alumina or the like can be used by dispersing it in an aqueous phase.
[0219]
When an inorganic compound is used in the dispersion stabilizer, the inorganic compound may be generated in an aqueous medium in order to obtain finer particles. For example, in the case of calcium phosphate, it is preferable to mix an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring.
[0220]
For fine dispersion of these stabilizers, 0.001 to 0.1 parts by weight of a surfactant may be used. This is to promote the intended action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, Potassium stearate, calcium oleate and the like can be mentioned.
[0221]
Examples of the polymerization initiator include 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), An azo or diazo polymerization initiator such as 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile can be used.
(11) Two-component development
An AC bias is applied between the photoconductor and the developing roller together with a DC bias. At this time, the frequency is 1 to 10 kHz, the AC bias is 1.0 to 2.5 kV (pp), and the peripheral speed ratio between the photosensitive member and the developing roller is 1: 1.2 to 1: 2. Is preferred.
[0222]
More preferably, the frequency is 3.5 to 8 kHz, the AC bias is 1.2 to 2.0 kV (pp), and the peripheral speed ratio between the photosensitive member and the developing roller is 1: 1.5 to 1: 1. .8.
[0223]
More preferably, the frequency is 5.5 to 7 kHz, the AC bias is 1.5 to 2.0 kV (pp), and the peripheral speed ratio between the photosensitive member and the developing roller is 1: 1.6 to 1: 1. .8.
[0224]
By using this development process configuration and the toner or the two-component developer of the present embodiment, the dots can be faithfully reproduced and the development γ characteristic can be made to be a characteristic. High-quality images and oil-less fixability can be compatible. In addition, even with a high-resistance carrier, charge-up under low humidity can be prevented, and a high image density can be obtained even in continuous use. This is thought to be due to the toner that can exhibit high chargeability, the combined use of the carrier configuration and the AC bias, the adhesion to the carrier can be reduced, the image density can be maintained, fog can be reduced, and dots can be faithfully reproduced. .
[0225]
When the frequency is lower than 1 kHz, dot reproducibility deteriorates, and halftone reproducibility deteriorates. If the frequency exceeds 10 kHz, it is impossible to follow in the development area, and no effect is obtained. In this frequency range, in the two-component development using a high-resistance carrier, the toner acts on the reciprocating action between the carrier and the toner rather than between the developing roller and the photoreceptor, and has an effect of slightly releasing the toner from the carrier. Good reproducibility and halftone reproducibility can be achieved, and high image density can be obtained.
[0226]
If the AC bias is less than 1.0 kV (pp), the effect of suppressing charge-up cannot be obtained, and if the AC bias exceeds 2.5 kV (pp), fog increases. If the peripheral speed ratio between the photosensitive member and the developing roller is smaller than 1: 1.2 (the developing roller is slowed down), it is difficult to obtain an image density. When the peripheral speed ratio between the photosensitive member and the developing roller exceeds 1: 2 (the developing roller speed increases), toner scattering increases.
(12) Tandem color process
Further, in order to form a color image at high speed, in the present embodiment, a plurality of toner image forming stations including a photoconductor, a charging unit, and a toner carrier are provided, and an electrostatic latent image formed on the image carrier is formed. A primary transfer process of transferring the visualized toner image to the transfer member by bringing an endless transfer member into contact with the image carrier is sequentially performed, and a multi-layer transfer toner image is formed on the transfer member. Is formed, and then a secondary transfer process is performed in which a multi-layer toner image formed on the transfer body is collectively transferred to a transfer medium such as paper or OHP. When the distance from the primary transfer position to the second primary transfer position is d1 (mm) and the peripheral speed of the photoconductor is v (mm / s), the transfer position configuration is d1 / v ≦ 0.65 toner. To reduce machine size and print speed. It is intended to improve the standing. In order to reduce the size of a machine capable of processing 16 sheets per minute (A4) or more and for use in a SOHO application, it is necessary to shorten the interval between a plurality of toner image forming stations and increase the process speed. is there. In order to achieve both miniaturization and printing speed, a configuration in which the above value is 0.65 or less is considered a minimum.
[0227]
However, when this configuration is used, for example, the time from the first transfer of the first color yellow toner to the first transfer of the next magenta toner of the second color is extremely short. When the magenta toner is transferred onto the yellow toner, the magenta toner is repelled by the charge action of the yellow toner, which causes a problem of a decrease in transfer efficiency and a dropout of characters during transfer. Further, at the time of primary transfer of the cyan toner of the third color, when the toner is transferred onto the previous yellow and magenta toners, scattering of the cyan toner, transfer failure, and omission during transfer occur remarkably. Further, the toner having a specific particle diameter is selectively developed during repeated use, and when the fluidity of each toner particle is significantly different, the chance of frictional charging is different, so that the charge amount varies, and the transferability is further deteriorated. Will be invited.
[0228]
Therefore, by using the toner or the two-component developer of the present embodiment, the charge distribution is stabilized, the toner is prevented from being overcharged, and the fluidity fluctuation can be suppressed. For this reason, it is possible to prevent the toner from sacrificing the fixing characteristics, to reduce the transfer efficiency, to prevent the dropout of characters during transfer, and to prevent reverse transfer.
(13) Cleanerless process
Further, in the present embodiment, an electronic device having a cleaner-less process for performing the next charging, exposure, and developing processes without a cleaning process for recovering the toner remaining on the photoreceptor after the transfer process by cleaning is used. It is suitably used for photographic devices.
[0229]
By using the toner or the two-component developer of this embodiment, aggregation of the toner can be suppressed, overcharging can be prevented, chargeability can be stabilized, and high transfer efficiency can be obtained. Further, due to the improvement in uniform dispersibility in the resin, the good charging property, and the releasability of the material, the toner remaining in the non-image area can be favorably collected by development. Therefore, there is no development memory in which the image pattern before the non-image portion remains.
(14) Oilless color fixing
In the present embodiment, the present invention is suitably used for an electrophotographic apparatus having a fixing process of an oilless fixing configuration in which oil is not used as a means for fixing toner. As the heating means, electromagnetic induction heating is a preferable configuration from the viewpoint of temperature rise and energy saving. A magnetic field generating means, a rotary heating member having at least a heating layer and a release layer generated by electromagnetic induction, and a heating and pressing means having at least a rotary pressing member forming a fixed nip with the rotary heating member. In use, a transfer medium such as copy paper on which toner has been transferred is passed between the rotary heating member and the rotary pressing member to fix the toner.
[0230]
Also, a configuration using a fixing belt in which a heating member and a fixing member are separated is preferably used.
[0231]
As the belt, a heat-resistant belt such as a nickel electroformed belt or a polyimide belt having heat resistance and flexibility is preferably used. In order to improve the releasability, the surface layer is made of silicone rubber, fluoro rubber, or fluoro resin.
[0232]
In these fixing methods, a releasing oil has been applied to prevent the offset. The use of a toner having releasability without using oil eliminates the need to apply a release oil. However, if the release oil is not applied, the toner is likely to be charged, and if the unfixed toner image comes close to the heating member or the fixing member, the toner may fly due to the influence of the charging. In particular, it easily occurs under low temperature and low humidity.
[0233]
Therefore, by using the toner of the present embodiment, it is possible to prevent the occurrence of offset without using oil, and to obtain high color translucency. Further, the overcharging property of the toner can be suppressed, and the flying of the toner due to the charging action with the heating member or the fixing member can be suppressed.
[0234]
【Example】
Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to this. In addition, in the following Examples, what is simply described as% means wt%.
[0235]
(Carrier manufacturing example 1)
120 g of a crosslinked fluorine-modified silicone resin containing 15 mol% of a trifluoropropyl group was converted into a solid content, and 6 g of γ- (2-aminoethyl) aminopropyltrimethoxysilane were dissolved in 300 cc of a toluene solvent. This is coated with 10 kg of ferrite particles having an average particle diameter of 50 μm and a saturation magnetization of 65 emu / g when the applied magnetic field is 3000 eersted using a liquid immersion drying type coating apparatus, and then at 230 ° C. for 1.5 hours. Baking was performed to obtain a carrier A1.
[0236]
(Carrier manufacturing example 2)
15% by mole of C₈F₁₇CH₂CH₂Si (OCH₃)₃A core material was produced and coated in the same steps as in Production Example 1, except that the carrier was changed to a crosslinked fluorine-modified silicone resin containing a carrier A2.
[0237]
(Carrier manufacturing example 3)
A core material was produced and coated in the same manner as in Production Example 1, except that 5 mol% of the conductive carbon (EC manufactured by Ketjen Black International) was dispersed in a pearl mill with respect to the resin solid content. Carrier A3 was obtained.
[0238]
(Carrier production example 4)
A core material was produced in the same process as in Production Example 3 except that the amount of the aminosilane coupling agent added was changed to 30 g, and coating was performed to obtain a carrier A4.
[0239]
(Carrier Production Example 5, Comparative Example)
A core material was produced and coated in the same process as in Production Example 3 except that the amount of the aminosilane coupling agent was changed to 50 g, and a carrier b1 was obtained.
[0240]
(Carrier Production Example 6, Comparative Example)
A core material was produced in the same process as in Production Example 1, except that the coating resin was changed to straight silicone (SR-2411 manufactured by Dow Corning Toray Co., Ltd.), and coating was performed to obtain a carrier b2.
[0241]
(Carrier Production Example 7, Comparative Example)
A core material was produced and coated in the same process as in Production Example 3, except that the coating resin was changed to a perfluorooctylethyl acrylate / methacrylate copolymer, and a carrier b3 was obtained.
[0242]
(Carrier Production Example 8, Comparative Example)
A core material was produced in the same process as in Carrier Production Example 3 except that the coating resin was changed to an acrylic-modified silicone resin (KR-9706 manufactured by Shin-Etsu Chemical Co., Ltd.), and coating was performed to obtain a carrier b4.
[0243]
Table 1 shows the characteristics of the binder resin used in the examples. As the resin, a polyester resin containing bisphenol A propyl oxide adduct, terephthalic acid, trimellitic acid, succinic acid, and fumaric acid as main components was used, and a resin whose thermal characteristics were changed according to the mixing ratio and polymerization conditions was used. The structure of the dihydric alcohol, the divalent carboxylic acid, and the trivalent carboxylic acid is a suitable structure for satisfying both the fixing property, the dispersibility, the spent property of the carrier, and the pulverizability.
[0244]
[Table 1]

[0245]
Mnf is the number average molecular weight of the binder resin, Mwf is the weight average molecular weight of the binder resin, Mzf is the Z average molecular weight of the binder resin, Wmf is the ratio Mwf / Mnf between the weight average molecular weight Mwf and the number average molecular weight Mnf, and Wzf is The ratio Mzf / Mnf between the Z-average molecular weight Mzf and the number-average molecular weight Mnf of the binder resin, Tg (° C) is the glass point transfer, Tm (° C) is the softening point, Tfb (° C) is the outflow start temperature, and AV is the resin acid value. Is shown.
[0246]
(Table 2), (Table 3) and (Table 4) show the waxes used in this example and the physical properties thereof. Mnr indicates the number average molecular weight of the wax, Mwr indicates the weight average molecular weight of the wax, and Mzr indicates the Z average molecular weight of the wax. Tw (° C.) indicates the melting point by the DSC method, Ct (%) indicates the volume increase rate (%) at the melting point + 10 ° C., and Ck (wt%) indicates the loss on heating at 220 ° C.
[0247]
[Table 2]

[0248]
[Table 3]

[0249]
[Table 4]

[0250]
Table 5 shows the pigments used in this example.
[0251]
[Table 5]

[0252]
Table 6 shows the charge control agents used in this example and their physical properties.
[0253]
As a metal salt of a salicylic acid derivative, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. And the like. Examples of the metal Y include zinc, nickel, cobalt, copper, and chromium, and zinc and chromium are preferable. Examples of metal salts of benzylic acid derivatives include R¹~ R⁴Is a benzene ring, and examples of the alkali metal X include lithium, sodium, and potassium, with potassium being preferred.
[0254]
[Table 6]

[0255]
(Table 7) shows the external additives used in this example. The charge amount is measured by a blow-off method of triboelectric charging with a non-coated ferrite carrier. Under an environment of 25 ° C. and 45 RH%, 50 g of a carrier and 0.1 g of silica or the like are mixed in a 100 ml polyethylene container, and the mixture is vertically rotated for 100 min.^-1After stirring for 5 minutes and 30 minutes at a speed of 0.3 g, 0.3 g was collected, and nitrogen gas 1.96 × 10⁴(Pa) for 1 minute.
[0256]
In the case of positive chargeability, it is preferable that the value for 5 minutes after stirring for 5 minutes is +100 to +800 μC / g, and the value for 30 minutes after stirring for 30 minutes is +50 to +400 μC / g. Silica having a charge amount at 30 minutes of 40% or more of a charge amount at 5 minutes is preferable. If the rate of decrease is large, the change in the charge amount during long-term continuous use is large, and a constant image cannot be maintained.
[0257]
In the case of negative chargeability, the value for 5 minutes is preferably -100 to -800 µC / g, and the value for 30 minutes is preferably -50 to -600 µC / g. Silica having a high charge amount can exhibit its function with a small amount of addition.
[0258]
[Table 7]

[0259]
(Table 8) shows coarse particles used in this example. It is preferable that the shape is not a true sphere, but an irregular or slightly irregular shape. This is because the irregular shape has better charge rising properties and better stirring and mixing with the carrier.
[0260]
[Table 8]

[0261]
Table 9 shows the pulverizing conditions in this example.
[0262]
In this embodiment, s1 was 1 mm, s2 was 4 mm, s3 was 3 mm, r1 was 4 mm, r2 was 7 mm, r3 was 3 mm, and the circumference of the rotating body was 56.5 cm. The silica adhesion amount is the amount of silica remaining on the toner after pulverization. About 40% does not remain in the toner and is taken to the bag filter.
[0263]
[Table 9]

[0264]
(Table 10) and (Table 11) show the toner material composition and physical properties used in this example.
[0265]
[Table 10]

[0266]
[Table 11]

[0267]
In the drawing, Ss is a specific surface area value of the pulverized toner, St is a value represented by St = 6 / (true specific gravity of toner * volume average particle diameter), and SSt is St to Ss (pulverized toner). (Specific surface area value).
[0268]
The pigment was added in an amount of 5 parts by weight based on 100 parts by weight of the binder resin. Although not shown in the table, the pigments shown in Table 5 were used, and substantially the same material composition was used for each color. The ratio of the charge control agent and the wax in the parentheses is the ratio of the charge (parts by weight) to 100 parts by weight of the binder resin. The amount of the external additive is shown as a blending amount (parts by weight) based on 100 parts by weight of the toner matrix.
[0269]
External addition processing was performed by using a stirring blade Z0S0 type and a rotation speed of 2,000 min in the FM20B.^-1The processing time was 5 min and the input amount was 1 kg.
[0270]
FIG. 1 is a sectional view showing a configuration of an image forming apparatus for forming a full-color image used in the present embodiment. In FIG. 1, an outer casing of the color electrophotographic printer is omitted.
The transfer belt unit 17 includes a transfer belt 12, a first color (yellow) transfer roller 10Y made of an elastic material, a second color (magenta) transfer roller 10M, a third color (cyan) transfer roller 10C, and a fourth color (black). A transfer roller 10K, a drive roller 11 made of an aluminum roller, a second transfer roller 14 made of an elastic body, a second transfer driven roller 13, a belt cleaner blade 16 for cleaning the toner image remaining on the transfer belt 12, and opposed to the cleaner blade. The roller 15 is provided at a position where the roller 15 is to be driven.
[0271]
At this time, the distance from the first color (Y) transfer position to the second color (M) transfer position is 35 mm (the second color (M) transfer position to the third color (C) transfer position, the third color (C) The transfer position of the fourth color (K) is also the same from the transfer position), and the peripheral speed of the photoconductor is 125 mm / s.
[0272]
The transfer belt 12 is used by kneading a conductive filler into an insulating polycarbonate resin and forming a film with an extruder. In the present embodiment, a film obtained by adding 5 parts by weight of conductive carbon (for example, Ketjen black) to 95 parts by weight of a polycarbonate resin (for example, Iupilon Z300 manufactured by Mitsubishi Gas Chemical) as an insulating resin was used. The surface is coated with a fluororesin, the thickness is about 100 μm, and the volume resistance is 10⁷-10¹²Ω · cm, surface resistance is 10⁷-10¹²Ω / □. Another purpose is to improve dot reproducibility. The reason for this is that the transfer belt 12 can be effectively prevented from being loosened or accumulated electric charge due to long-term use, and the surface is coated with a fluorine resin because toner filming on the transfer belt surface due to long-term use Is to be effectively prevented. Volume resistance is 10⁷If it is smaller than Ω · cm, retransfer is likely to occur and 10¹²If it is larger than Ω · cm, the transfer efficiency deteriorates. The first transfer roller is a carbon conductive urethane roller having an outer diameter of 10 mm and a resistance value of 10 mm.²-10⁶Ω. At the time of the first transfer operation, the first transfer roller 10 is pressed against the photosensitive member 1 via the transfer belt 12 with a pressing force of 1.0 to 9.8 (N), and the toner on the photosensitive member is transferred onto the belt. Is done. Resistance value is 10²If it is smaller than Ω, retransfer is likely to occur. 10⁶Large transfer defects are more likely to occur than Ω. If it is smaller than 1.0 (N), transfer failure occurs, and if it is larger than 9.8 (N), missing characters are caused.
[0273]
The second transfer roller 14 is a carbon conductive urethane roller having an outer diameter of 15 mm and a resistance value of 10 mm.²-10⁶Ω. The second transfer roller 14 is pressed against the transfer roller 13 via the transfer belt 12 and a transfer medium 19 such as paper and OHP. The transfer roller 13 is configured to be rotatable following the transfer belt 12. In the secondary transfer, the second transfer roller 14 and the opposing transfer roller 13 are pressed against each other with a pressing force of 5.0 to 21.8 (N), and the toner is transferred from the transfer belt onto a recording material 19 such as paper. You. Resistance value is 10²If it is smaller than Ω, retransfer is likely to occur. 10⁶If it is larger than Ω, transfer failure tends to occur. If it is smaller than 5.0 (N), the transfer failure toner is increased, and if it is larger than 21.8 (N), the load is increased, and jitter is likely to occur.
[0274]
Four sets of image forming units 18Y, 18M, 18C, and 18K for each color of yellow (Y), magenta (M), cyan (C), and black (B) are arranged in series as shown in the figure.
[0275]
Since each of the image forming units 18Y, 18M, 18C, and 18K is made of the same components except for the developer contained therein, the image forming unit 18Y for Y will be described to simplify the description, and the unit for other colors will be described. Is omitted.
[0276]
The image forming unit is configured as follows. Reference numeral 1 denotes a photosensitive member, 3 denotes a pixel laser signal light, and 4 denotes a developing roller having an outer diameter of 12 mm made of aluminum and having a magnet having a magnetic force of 1200 gauss. The developing roller faces the photosensitive member with a gap of 0.3 mm. Rotate in the direction of. A stirring roller 6 stirs the toner and the carrier in the developing device, and supplies the toner and the carrier to the developing roller. The configuration is such that the mixing ratio of the carrier and the toner is read by a magnetic permeability sensor (not shown) and supplied from a toner hopper (not shown) as appropriate. Reference numeral 5 denotes a metal magnetic blade which regulates a magnetic flash layer of the developer on the developing roller. The amount of the developer is 150 g. The gap was 0.4 mm. Although a power source is omitted, a DC of -500 V and an AC voltage of 1.5 kV (pp) and a frequency of 6 kHz are applied to the developing roller 4. The peripheral speed ratio between the photosensitive member and the developing roller was set to 1: 1.6. The mixing ratio of the toner and the carrier was 93: 7, and the amount of the developer in the developing device was 150 g.
[0277]
Reference numeral 2 denotes a charging roller made of epichlorohydrin rubber having an outer diameter of 12 mm, to which a DC bias of -1.2 kV is applied. The surface of the photoconductor 1 is charged to -600V. Reference numeral 8 denotes a cleaner, 9 denotes a waste toner box, and 7 denotes a developer.
[0278]
The paper is conveyed from below the transfer unit 17, and the paper 19 is fed by a paper feed roller (not shown) to a nip portion where the transfer belt 12 and the second transfer roller 14 are pressed. A transport path is formed.
[0279]
The toner on the transfer belt 12 is transferred to the paper 19 by + 1000V applied to the second transfer roller 14, and includes a fixing roller 201, a pressure roller 202, a fixing belt 203, a heating medium roller 204, and an induction heater unit 205. The sheet is conveyed to a fixing unit, where it is fixed.
[0280]
FIG. 2 shows the fixing process diagram. A belt 203 is hung between the fixing roller 201 and the heat roller 204. A predetermined load is applied between the fixing roller 201 and the pressure roller 202, and a nip is formed between the belt 203 and the pressure roller 202. An induction heater 205 including a ferrite core 206 and a coil 207 is provided on the outer peripheral surface of the heat roller 204, and a temperature sensor 208 is disposed on the outer surface.
[0281]
The belt has a structure in which 30 μm Ni is used as a base, silicone rubber is 150 μm thereon, and a PFA tube 30 μm is further superimposed thereon.
[0282]
The pressure roller 202 is pressed against the fixing roller 201 by a pressure spring 209. The recording material 19 having the toner 210 moves along the guide plate 211.
[0283]
The fixing roller 201 serving as a fixing member has a length of 250 mm, an outer diameter of 14 mm, a thickness of 1 mm, and a silicone rubber having a rubber hardness (JIS-A) of 20 degrees according to the JIS standard on the surface of a hollow metal core 213 made of aluminum. An elastic layer 214 having a thickness of 3 mm is formed. On this, a silicone rubber layer 215 is formed with a thickness of 3 mm, and the outer diameter is about 20 mm. It rotates at 125 mm / s by receiving a driving force from a driving motor (not shown).
[0284]
The heat roller 204 is formed of a hollow pipe having a thickness of 1 mm and an outer diameter of 20 mm. The surface temperature of the fixing belt was controlled at 170 ° C. using a thermistor.
[0285]
The pressing roller 202 as a pressing member has a length of 250 mm and an outer diameter of 20 mm. This is provided with a 2 mm thick elastic layer 217 made of silicone rubber having a rubber hardness (JIS-A) of 55 degrees according to JIS standards on the surface of a hollow roller core 216 made of aluminum having an outer diameter of 16 mm and a thickness of 1 mm. . The pressure roller 202 is rotatably installed, and forms a nip width of 5.0 mm between the pressure roller 202 and the fixing roller 201 by a spring-loaded spring 209 on one side 147N.
[0286]
Hereinafter, the operation will be described. In the full-color mode, all the first transfer rollers 10 of Y, M, C, and K are pushed up and press the photosensitive member 1 of the image forming unit via the transfer belt 12. At this time, a DC bias of +800 V is applied to the first transfer roller. An image signal is sent from the laser beam 3 and is incident on the photoreceptor 1 whose surface is charged by the charging roller 2 to form an electrostatic latent image. The toner on the developing roller 4 rotating in contact with the photoconductor 1 visualizes the electrostatic latent image formed on the photoconductor 1.
[0287]
At this time, the image forming speed of the image forming unit 18Y (125 mm / s equal to the peripheral speed of the photoconductor) and the moving speed of the transfer belt 12 are such that the photoconductor speed is 0.5 to 1.5% slower than the transfer belt speed. It is set as follows.
[0288]
In the image forming step, the Y signal light 3Y is input to the image forming unit 18Y, and an image is formed by the Y toner. At the same time as the image formation, the Y toner image is transferred from the photoreceptor 1Y to the transfer belt 12 by the operation of the first transfer roller 10Y. At this time, a DC voltage of +800 V was applied to the first transfer roller 10Y.
[0289]
With a time lag between the first transfer of the first color (Y) and the first transfer of the second color (M), the M signal light 3M is input to the image forming unit 18M, and an image is formed by the M toner. At the same time as the image formation, the M toner image is transferred from the photoconductor 1M to the transfer belt 12 by the operation of the first transfer roller 10M. At this time, the M toner is transferred onto the first color (Y) toner. Similarly, an image is formed by C (cyan) and K (black) toners, and a YMCK toner image is formed on the transfer belt 12 by the operation of the first transfer rollers 10C and 10B simultaneously with the image formation. This is a so-called tandem system.
[0290]
The four color toner images were superposed on the transfer belt 12 so as to match in position, and a color image was formed. After the transfer of the last B toner image, the four color toner images are collectively transferred to paper 19 sent from a paper feed cassette (not shown) at the same timing by the action of the second transfer roller 14. At this time, the transfer roller 13 was grounded, and a DC voltage of +1 kV was applied to the second transfer roller 14. The toner image transferred to the paper was fixed by the fixing roller pair 201 and 202. The paper was then discharged out of the apparatus via a discharge roller pair (not shown). The transfer residual toner remaining on the intermediate transfer belt 12 is cleaned by the action of the cleaning blade 16 to prepare for the next image formation.
[0291]
Table 12 shows the results of image output using the electrophotographic apparatus of FIG. In the full-color image in which three colors of toner overlap, the state of poor transfer at the character portion and the wrapping property of the paper around the fixing belt during fixing were evaluated. The charge amount is measured by a blow-off method of frictional charging with a ferrite carrier. Under an environment of 25 ° C. and 45% RH, 0.3 g of a sample for durability evaluation was collected, and nitrogen gas 1.96 × 10⁴(Pa) for 1 minute.
[0292]
[Table 12]

[0293]
When images were formed using the developers DM11 to DM18, the solid black image was uniform without horizontal line disturbance, toner scattering, and missing characters, and an extremely high image reproduction of 16 lines / mm was obtained. An image with high resolution and high image quality was obtained, and an image with high image density of 1.3 or more was obtained.
[0294]
When a white image was taken after continuous printing of 10 solid images, no background fogging occurred in the non-image area.
[0295]
Thereafter, when a solid image was taken, poor supply of toner to the carrier and poor mixing properties were not observed, and no generation of development memory was observed.
[0296]
Even in a long-term durability test of 100,000 A4 sheets, both fluidity and image density showed little change and stable characteristics. Spent of the toner component on the carrier hardly occurs. There is little change in carrier resistance and decrease in charge amount, and no fog occurs. There is almost no change in the charge amount under high temperature and high humidity and under low temperature and low humidity.
[0297]
Also, in the transfer, the hollowing was at a level that was not problematic in practical use, and the occurrence of reverse transfer was very small. The transfer efficiency was about 95%. In addition, no transfer failure or reverse transfer occurred in the three-color superposed full-color image.
[0298]
In addition, filming of the toner on the photosensitive member and the transfer belt was at a level at which there was no practical problem. No defective cleaning of the transfer belt on the photoreceptor occurred.
[0299]
Also, even in a full-color image in which three colors are overlapped, toner disturbance and toner jumping during fixing hardly occur. At the time of fixing, paper wrapping around the fixing belt did not occur.
[0300]
However, when the developer of cm1 to cm16 has a process speed of 100 mm / s and the distance between the photoconductors is 70 mm, characters scatter at the time of transfer, missing characters in the transferred character, and the reverse transfer property are at an acceptable level, but the process speed is 120 mm. / S, or when the distance between the photoconductors was set to 60 mm, characters scattered during transfer, missing characters in the transferred characters, and reverse transfer occurred, which were at a level that was considered a practical problem.
[0301]
Further, with the developer of cm5 to cm16, cleaning failure on the photoreceptor and the intermediate transfer belt further occurred. Filming and fogging of the photoreceptor also occurred frequently.
[0302]
In addition, a large amount of spent on the carrier, a large change in the carrier resistance, a decrease in the charge amount, and an increase in fog were observed. An increase in fog due to a decrease in charge amount under high temperature and high humidity, and a decrease in image density due to an increase in charge amount under low temperature and low humidity were observed. The transfer efficiency dropped to about 60-70%. When the entire solid image was taken at the time of development, blurring occurred in the latter half. During continuous use, the wax was fused to the developing blade, and an abnormal image of vertical streaks occurred. At the time of outputting the three-color superimposed image, the paper was wound around the fixing belt. Toner jump occurred during fixing.
[0303]
Next, Table 13 shows the amount of adhesion to OHP paper 1.2 g / cm.²The above solid image was subjected to a non-offset test with a fixing device using a belt not coated with oil at a process speed of 100 mm / s. For the toners of TM1 to TM12, no OHP jam occurred in the fixing nip portion. In a solid green image of plain paper, no offset occurred at all up to the 122,000th sheet. Even if a silicone or fluorine-based fixing belt is not coated with oil, no belt surface deterioration phenomenon is observed.
[0304]
The transmittance and the offset property at a high temperature were evaluated. The process speed was 100 mm / s, the fixing temperature was 180 ° C., and the transmittance was 700 nm with a spectrophotometer U-3200 (Hitachi, Ltd.). The results of fixability, offset resistance and storage stability are shown.
[0305]
[Table 13]

[0306]
The OHP light transmissivity was 80% or more, and the non-offset temperature range was 40 to 60 ° C., indicating a good fixing property in a fixing roller using no oil. Aggregation was hardly observed at 60 ° C. for 5 hours. However, the toners tm1 to tm12 were hardened in the storage stability test, and the non-offset temperature range was narrow.
[0307]
As in the above examples, the wax contains a wax having an endothermic peak temperature of 60 to 120 ° C. by the DSC method, and defines the average particle diameter of the toner base particles to be 2 to 6 times the volume average particle diameter of the toner base particles. With a toner composition in which coarse particles having a volume average particle diameter of are blended, and further, a two-component developer combined with a carrier having a coating resin of a fluorine-modified silicone resin containing an aminosilane coupling agent, without applying oil. In both cases, it is possible to realize oilless fixing in which offset properties are prevented while maintaining high OHP transmissivity, and it is possible to extend the life of the carrier without spent toner components on the carrier. Further, the toner is capable of preventing a dropout or scattering at the time of transfer and obtaining high transfer efficiency.
[0308]
【The invention's effect】
As described above, according to the present invention, in an oilless fixing toner that does not use oil for the fixing roller, an oilless toner that exhibits high translucency and high gloss by using a release agent such as wax in the toner. Can provide anchorage. In addition, it is possible to provide a two-component developer and a highly durable long-life toner which does not cause deterioration due to spent when used in combination with a toner containing a release agent such as wax. In addition, when a large amount of toner that continuously takes a solid image is consumed, fog and development memory are less likely to occur when the toner is rapidly replenished, and a toner having a good charge rising property and a two-component developing Agent can be provided. In particular, since the tendency is more pronounced in a small-sized developing device, uniform chargeability during stirring is required. Further, the cleaning property of the toner on the photosensitive member and the transfer member can be improved, and occurrence of filming can be prevented. Further, it is possible to provide a two-component developer and a toner having a good mixing property with a toner supply or a carrier and a charge rising property by suppressing a decrease in the fluidity of the toner by improving the image quality by reducing the particle size of the toner. Also, in a tandem color process in which an image forming station having a plurality of photoconductors and a developing unit are arranged side by side, and a transfer process is performed successively on each transfer toner in a tandem color process, dropout, reverse transfer, and scattering during transfer are prevented. Thus, it is possible to provide an image forming apparatus capable of preventing the occurrence of a high transfer efficiency.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view illustrating a configuration of an image forming apparatus used in an embodiment of the present invention.
FIG. 2 is a cross-sectional view illustrating a configuration of a fixing unit used in an embodiment of the present invention.
FIG. 3 is a configuration diagram of a toner crushing process used in an embodiment of the present invention.
FIG. 4 is a cross-sectional view of a toner crushing process used in an embodiment of the present invention.
FIG. 5 is a cross-sectional view of a toner crushing process used in an embodiment of the present invention.
[Explanation of symbols]
1 Photoconductor
2 Charging roller
3 Laser signal light
4 Developing roller
5 blade
10 First transfer roller
12 Transfer belt
14 Second transfer roller
13 Drive tension roller
17 Transfer belt unit
18B, 18C, 18M, 18Y image forming unit
18 Image forming unit group
201 fusing roller
202 pressure roller
203 fixing belt
205 Induction heater
206 Ferrite core
207 coil
508 metering feeder
500 crushing section
501 Rotating body
502 Fixed body
503 raw materials
506 Uneven part
509 Cooler
511 air
512 thermometer
514 Bag Filter
515 Cyclone
516 Anemometer
517 Blower
518 Inorganic fine powder supply device
519 Vibrator vibrator

Claims (35)

A toner comprising at least a binder resin, a toner base particle containing a colorant and a wax, and a coarse particle,
A wax having an endothermic peak temperature of 60 to 120 ° C. by differential scanning calorimetry (DSC method) based on 100 parts by weight of the binder resin,
The toner base particles have a volume average particle diameter of 3 to 8 μm, contain 5 to 55% by number of toner base particles having a particle size of 2.52 to 4 μm in the number distribution, and have a volume distribution of 6.35 to 10.1 μm in the volume distribution. Containing 5 to 60% by volume of toner base particles having a particle size,
The coarse particles have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and 1 to 6 parts by weight based on 100 parts by weight of the toner base particles,
A toner comprising 1.5 to 5.5 parts by weight of an inorganic fine powder having an average particle diameter of 6 nm to 200 nm based on 100 parts by weight of a toner base particle. A toner comprising at least a binder resin, a toner base particle containing a colorant and a wax, and a coarse particle,
A wax having an endothermic peak temperature of 60 to 120 ° C. by differential scanning calorimetry (DSC method) based on 100 parts by weight of the binder resin,
The toner base particles have a volume average particle diameter of 3 to 8 μm, contain 5 to 55% by number of toner base particles having a particle size of 2.52 to 4 μm in the number distribution, and have a volume distribution of 6.35 to 10.1 μm in the volume distribution. Containing 5 to 60% by volume of toner base particles having a particle size,
The coarse particles have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and 1 to 6 parts by weight based on 100 parts by weight of the toner base particles,
An inorganic fine powder having an average particle diameter of 6 nm to 20 nm is 0.5 to 2.5 parts by weight based on 100 parts by weight of the toner base particles, and an inorganic fine powder having an average particle diameter of 30 nm to 200 nm is 100 parts by weight of the toner base particles. Toner in an amount of 1.0 to 3.5 parts by weight per part by weight. At least a binder resin, a toner base including a colorant and a wax, and a toner composed of coarse particles,
A wax having an endothermic peak temperature of 60 to 120 ° C. by differential scanning calorimetry (DSC method) based on 100 parts by weight of the binder resin,
The toner base has a volume average particle diameter of 3 to 8 μm, contains 5 to 55% by number of toner bases having a particle size of 2.52 to 4 μm in the number distribution, and has a particle size of 6.35 to 10.1 μm in the volume distribution. Containing 5 to 60% by volume of toner base particles having
The coarse particles have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and 1 to 6 parts by weight based on 100 parts by weight of the toner base particles,
0.5 to 2.5 parts by weight of an inorganic fine powder having a negative polarity having an average particle size of 6 nm to 20 nm with respect to 100 parts by weight of the toner base particles, and an inorganic fine powder having an average particle size of 30 nm to 200 nm The fine powder was added in an amount of 1.0 to 3.5 parts by weight based on 100 parts by weight of the toner base particles, and the inorganic fine powder having an average particle diameter of 6 nm to 200 nm and having positive polarity was added in an amount of 0.5 to 100 parts by weight of the toner base particles. To 1.5 parts by weight. At least a binder resin, a toner base including a colorant and a wax, and a toner composed of coarse particles,
A wax having an endothermic peak temperature of 60 to 120 ° C. by differential scanning calorimetry (DSC method) based on 100 parts by weight of the binder resin,
The toner base has a volume average particle diameter of 3 to 8 μm, contains 5 to 55% by number of toner bases having a particle size of 2.52 to 4 μm in the number distribution, and has a particle size of 6.35 to 10.1 μm in the volume distribution. Containing 5 to 60% by volume of toner base particles having
The coarse particles include a lubricant, have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and include 1 to 6 parts by weight based on 100 parts by weight of the toner base.
A toner comprising 1.5 to 5.5 parts by weight of an inorganic fine powder having an average particle diameter of 6 nm to 200 nm based on 100 parts by weight of a toner base particle. At least a binder resin, a toner base including a colorant and a wax, and a toner composed of coarse particles,
A wax having an endothermic peak temperature of 60 to 120 ° C. by differential scanning calorimetry (DSC method) based on 100 parts by weight of the binder resin,
The toner base has a volume average particle diameter of 3 to 8 μm, contains 5 to 55% by number of toner bases having a particle size of 2.52 to 4 μm in the number distribution, and has a particle size of 6.35 to 10.1 μm in the volume distribution. Containing 5 to 60% by volume of toner base particles having
The coarse particles include a lubricant, have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and have 1 to 6 parts by weight based on 100 parts by weight of the toner base.
An inorganic fine powder having an average particle diameter of 6 nm to 20 nm is 0.5 to 2.5 parts by weight based on 100 parts by weight of the toner base particles, and an inorganic fine powder having an average particle diameter of 30 nm to 200 nm is 100 parts by weight of the toner base particles. Toner in an amount of 1.0 to 3.5 parts by weight per part by weight. At least a binder resin, a toner base including a colorant and a wax, and a toner composed of coarse particles,
A wax having an endothermic peak temperature of 60 to 120 ° C. by differential scanning calorimetry (DSC method) based on 100 parts by weight of the binder resin,
The toner base has a volume average particle diameter of 3 to 8 μm, contains 5 to 55% by number of toner bases having a particle size of 2.52 to 4 μm in the number distribution, and has a particle size of 6.35 to 10.1 μm in the volume distribution. Containing 5 to 60% by volume of toner base particles having
The coarse particles include a lubricant, have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and include 1 to 6 parts by weight based on 100 parts by weight of the toner base.
0.5 to 2.5 parts by weight of an inorganic fine powder having a negative polarity having an average particle size of 6 nm to 20 nm with respect to 100 parts by weight of the toner base particles, and an inorganic fine powder having an average particle size of 30 nm to 200 nm The fine powder was added in an amount of 1.0 to 3.5 parts by weight based on 100 parts by weight of the toner base particles, and the inorganic fine powder having an average particle diameter of 6 nm to 200 nm and having positive polarity was added in an amount of 0.5 to 100 parts by weight of the toner base particles. To 1.5 parts by weight. The toner according to any one of claims 1 to 6, wherein the inorganic fine powder includes silica or titanium oxide fine powder obtained by surface-treating silicone oil. The toner according to any one of claims 1 to 6, wherein the wax is an ester wax having an iodine value of 25 or less, a saponification value of 30 to 300, and a loss on heating at 220 ° C of 8% by weight or less. The wax has a number average molecular weight in gel permeation chromatography (GPC) of from 100 to 5,000, a weight average molecular weight of from 200 to 10,000, and a ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) of 1.01 to 1.01. 8, having at least one maximum molecular weight peak in the region of the ratio of Z-average molecular weight to number-average molecular weight (Z-average molecular weight / number-average molecular weight) of 1.02 to 10, and molecular weight of 5 × 10 ² to 1 × 10 ⁴ The toner according to claim 1, wherein the toner is an ester wax. The wax has an acid value of at least 5 to 80 mgKOH / g and a melting point of from 80 to 120 obtained by reacting the wax with a long-chain alkyl alcohol having at least 5 to 100 carbon atoms, an unsaturated polycarboxylic acid or an anhydride thereof, and an unsaturated hydrocarbon wax. The toner according to any one of claims 1 to 6, which is a wax having a penetration of 4 or less at 25C or 25C. The toner according to any one of claims 1 to 6, wherein the wax is an aliphatic amide type having 16 to 24 carbon atoms or an alkylenebisfatty acid amide type of a saturated or unsaturated divalent fatty acid. The toner according to any one of claims 1 to 6, wherein the wax is a polyhydric alcohol fatty acid ester selected from hydroxystearic acid derivatives, glycerin fatty acid esters, glycol fatty acid esters, and sorbitan fatty acid esters. The toner according to claim 1, wherein the coarse particles have a volume average particle diameter that is 2 to 5 times the volume average particle diameter of the toner base particles, and include 2 to 5 parts by weight based on 100 parts by weight of the toner base. Toner. The toner according to claim 1, wherein the coarse particles have a volume average particle diameter of 2.5 to 4 times the volume average particle diameter of the toner base particles, and include 3 to 5 parts by weight based on 100 parts by weight of the toner base. The toner according to 1. At least a binder resin, a toner base including a colorant and a wax, and a two-component developer including a toner and a carrier composed of coarse particles,
A wax having an endothermic peak temperature of 60 to 120 ° C. by differential scanning calorimetry (DSC) is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the binder resin, and the toner base has a volume average particle diameter of 3 to 8 μm. Contains 5 to 55% by number of a toner base having a particle size of 2.52 to 4 μm in a number distribution, and contains 5 to 60% by volume of a toner base particle having a particle size of 6.35 to 10.1 μm in a volume distribution. And
The coarse particles have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and include 1 to 6 parts by weight based on 100 parts by weight of the toner base.
A toner containing 1.5 to 5.5 parts by weight of an inorganic fine powder having an average particle diameter of 6 nm to 200 nm based on 100 parts by weight of the toner base particles;
A two-component developer comprising: a core material having at least a surface modified with a fluorine-modified silicone resin containing an aminosilane coupling agent; and a carrier containing magnetic particles having an average particle diameter of 30 to 60 μm. At least a binder resin, a toner base including a colorant and a wax, and a two-component developer including a toner and a carrier composed of coarse particles,
A wax having an endothermic peak temperature of 60 to 120 ° C. by differential scanning calorimetry (DSC method) based on 100 parts by weight of the binder resin,
The toner base has a volume average particle diameter of 3 to 8 μm, contains 5 to 55% by number of toner bases having a particle size of 2.52 to 4 μm in the number distribution, and has a particle size of 6.35 to 10.1 μm in the volume distribution. Containing 5 to 60% by volume of toner base particles having
The coarse particles have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and include 1 to 6 parts by weight based on 100 parts by weight of the toner base.
An inorganic fine powder having an average particle diameter of 6 nm to 20 nm is 0.5 to 2.5 parts by weight based on 100 parts by weight of the toner base particles, and an inorganic fine powder having an average particle diameter of 30 nm to 200 nm is 100 parts by weight of the toner base particles. And a toner containing 1.0 to 3.5 parts by weight per part.
A two-component developer comprising: a core material having at least a surface modified with a fluorine-modified silicone resin containing an aminosilane coupling agent; and a carrier containing magnetic particles having an average particle diameter of 30 to 60 μm. At least a binder resin, a toner base including a colorant and a wax, and a two-component developer including a toner and a carrier composed of coarse particles,
A wax having an endothermic peak temperature of 60 to 120 ° C. by differential scanning calorimetry (DSC method) based on 100 parts by weight of the binder resin,
The toner base has a volume average particle diameter of 3 to 8 μm, contains 5 to 55% by number of toner bases having a particle size of 2.52 to 4 μm in the number distribution, and has a particle size of 6.35 to 10.1 μm in the volume distribution. Containing 5 to 60% by volume of toner base particles having
The coarse particles have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and include 1 to 6 parts by weight based on 100 parts by weight of the toner base.
0.5 to 2.5 parts by weight of a negative inorganic powder having an average particle diameter of 6 nm to 20 nm based on 100 parts by weight of the toner base particles, and a negative inorganic powder having an average particle diameter of 30 nm to 200 nm. The fine powder is added in an amount of 1.0 to 3.5 parts by weight based on 100 parts by weight of the toner base particles, and the inorganic fine powder having an average particle diameter of 6 nm to 200 nm and having a positive polarity is added in an amount of 0.5 to 100 parts by weight of the toner base particles. A toner containing up to 1.5 parts by weight;
A two-component developer comprising: a core material having at least a surface modified with a fluorine-modified silicone resin containing an aminosilane coupling agent; and a carrier containing magnetic particles having an average particle diameter of 30 to 60 μm. At least a binder resin, a toner base including a colorant and a wax, and a two-component developer including a toner and a carrier composed of coarse particles,
A wax having an endothermic peak temperature of 60 to 120 ° C. by differential scanning calorimetry (DSC method) based on 100 parts by weight of the binder resin,
The toner base has a volume average particle diameter of 3 to 8 μm, contains 5 to 55% by number of toner bases having a particle size of 2.52 to 4 μm in the number distribution, and has a particle size of 6.35 to 10.1 μm in the volume distribution. Containing 5 to 60% by volume of toner base particles having
The coarse particles include a lubricant, have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and include 1 to 6 parts by weight based on 100 parts by weight of the toner base.
A toner containing 1.5 to 5.5 parts by weight of an inorganic fine powder having an average particle diameter of 6 nm to 200 nm based on 100 parts by weight of the toner base particles;
A two-component developer comprising: a core material having at least a surface modified with a fluorine-modified silicone resin containing an aminosilane coupling agent; and a carrier containing magnetic particles having an average particle diameter of 30 to 60 μm. At least a binder resin, a toner base including a colorant and a wax, and a two-component developer including a toner and a carrier composed of coarse particles,
A wax having an endothermic peak temperature of 60 to 120 ° C. by differential scanning calorimetry (DSC method) based on 100 parts by weight of the binder resin,
The toner base has a volume average particle diameter of 3 to 8 μm, contains 5 to 55% by number of toner bases having a particle size of 2.52 to 4 μm in the number distribution, and has a particle size of 6.35 to 10.1 μm in the volume distribution. Containing 5 to 60% by volume of toner base particles having
The coarse particles include a lubricant, have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and include 1 to 6 parts by weight based on 100 parts by weight of the toner base.
An inorganic fine powder having an average particle diameter of 6 nm to 20 nm is 0.5 to 2.5 parts by weight based on 100 parts by weight of the toner base particles, and an inorganic fine powder having an average particle diameter of 30 nm to 200 nm is 100 parts by weight of the toner base particles. And a toner containing 1.0 to 3.5 parts by weight per part.
A two-component developer comprising: a core material having at least a surface modified with a fluorine-modified silicone resin containing an aminosilane coupling agent; and a carrier containing magnetic particles having an average particle diameter of 30 to 60 μm. At least a binder resin, a toner base including a colorant and a wax, and a two-component developer including a toner and a carrier composed of coarse particles,
A wax having an endothermic peak temperature of 60 to 120 ° C. by differential scanning calorimetry (DSC method) based on 100 parts by weight of the binder resin,
The toner base has a volume average particle diameter of 3 to 8 μm, contains 5 to 55% by number of toner bases having a particle size of 2.52 to 4 μm in the number distribution, and has a particle size of 6.35 to 10.1 μm in the volume distribution. Containing 5 to 60% by volume of toner base particles having
The coarse particles include a lubricant, have a volume average particle diameter of 2 to 6 times the volume average particle diameter of the toner base particles, and include 1 to 6 parts by weight based on 100 parts by weight of the toner base.
0.5 to 2.5 parts by weight of a negative inorganic powder having an average particle diameter of 6 nm to 20 nm based on 100 parts by weight of the toner base particles, and a negative inorganic powder having an average particle diameter of 30 nm to 200 nm. The fine powder is added in an amount of 1.0 to 3.5 parts by weight based on 100 parts by weight of the toner base particles, and the inorganic fine powder having an average particle diameter of 6 nm to 200 nm and having a positive polarity is added in an amount of 0.5 to 100 parts by weight of the toner base particles. A toner containing up to 1.5 parts by weight;
A two-component developer comprising: a core material having at least a surface modified with a fluorine-modified silicone resin containing an aminosilane coupling agent; and a carrier containing magnetic particles having an average particle diameter of 30 to 60 μm. The two-component developer according to any one of claims 15 to 20, wherein the inorganic fine powder includes silica or titanium oxide fine powder obtained by surface-treating silicone oil. The two-component developer according to any one of claims 15 to 20, wherein the wax is an ester wax having an iodine value of 25 or less, a saponification value of 30 to 300, and a loss on heating at 220 ° C of 8% by weight or less. The wax has a number average molecular weight in gel permeation chromatography (GPC) of 100 to 5000, a weight average molecular weight of 200 to 10000, and a ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) of 1.01 to 1.01. 8, having at least one maximum molecular weight peak in the region of the ratio of Z-average molecular weight to number-average molecular weight (Z-average molecular weight / number-average molecular weight) of 1.02 to 10, and molecular weight of 5 × 10 ² to 1 × 10 ⁴ The two-component developer according to any one of claims 15 to 20, which is an ester wax. The wax has an acid value of at least 5 to 80 mgKOH / g and a melting point of from 80 to 120 obtained by reacting the wax with a long-chain alkyl alcohol having at least 5 to 100 carbon atoms, an unsaturated polycarboxylic acid or an anhydride thereof, and an unsaturated hydrocarbon wax. The two-component developer according to any one of claims 15 to 20, which is a wax having a penetration of 4 or less at 25C or 25C. The two-component developer according to any one of claims 15 to 20, wherein the wax is an aliphatic amide type having 16 to 24 carbon atoms or an alkylenebisfatty acid amide type of a saturated or monovalent unsaturated fatty acid. 21. The two-component developer according to claim 15, wherein the wax is a polyhydric alcohol fatty acid ester selected from hydroxystearic acid derivatives, glycerin fatty acid esters, glycol fatty acid esters, and sorbitan fatty acid esters. The two-component developer according to any one of claims 15 to 20, wherein the coating resin of the carrier contains 5 to 40 parts by weight of an aminosilane coupling agent based on 100 parts by weight of the coating resin. 21. The two-component developer according to claim 15, wherein the coating resin layer contains 1 to 15 parts by weight of a conductive fine powder based on 100 parts by weight of the coating resin. The two-component developer according to any one of claims 15 to 20, wherein the coating resin layer contains 5 to 40 parts by weight of an aminosilane coupling agent based on 100 parts by weight of the coating resin. The two-component developer according to any one of claims 15 to 20, wherein the coating resin is 0.1 to 5.0 parts by weight based on 100 parts by weight of the carrier core material. 21. The method according to claim 15, wherein the coarse particles have a volume average particle diameter of 2 to 5 times the volume average particle diameter of the toner base particles, and include 2 to 5 parts by weight based on 100 parts by weight of the toner base. Two-component developer. 21. The method according to claim 15, wherein the coarse particles have a volume average particle diameter of 2.5 to 4 times the volume average particle diameter of the toner base particles, and include 3 to 5 parts by weight based on 100 parts by weight of the toner base. 2. The two-component developer according to item 1. An AC bias having a frequency of 1 to 10 kHz and a bias of 1.0 to 2.5 kV (pp) is applied together with a DC bias between the photosensitive member and the developing roller, and a peripheral speed ratio between the photosensitive member and the developing roller. 33. An image forming apparatus, comprising: a developing unit having a ratio of 1: 1.2 to 1: 2, wherein the toner or the two-component developer according to claim 1 is used. An electrostatic latent image formed on the image carrier, comprising a plurality of toner image forming stations including at least an image carrier, a charging unit for forming an electrostatic latent image on the image carrier, and a toner carrier. The toner image obtained by visualizing the toner or the two-component developer according to any one of 1 to 32, and visualizing the electrostatic latent image, by contacting an endless transfer member to the image carrier. The primary transfer process of transferring to the transfer body is sequentially and continuously executed to form a multi-layer transfer toner image on the transfer body, and thereafter, the multi-layer toner image formed on the transfer body is collectively transferred to a transfer medium. A transfer system configured to perform a secondary transfer process, wherein the transfer process includes a distance from a first primary transfer position to a second primary transfer position, or a distance from a second primary transfer position. 3, the distance to the primary transfer position, In the case where d1 (mm) is the distance from the third primary transfer position to the fourth primary transfer position and v (mm / s) is the peripheral speed of the photoconductor, d1 / v ≦ 0.65 (sec) An image forming apparatus having a configuration satisfying a condition. An electrostatic latent image formed on the image carrier, comprising a plurality of toner image forming stations including at least an image carrier, a charging unit for forming an electrostatic latent image on the image carrier, and a toner carrier. A transfer process in which the toner image formed by visualizing the toner or the two-component developer according to any one of Items 1 to 32 and the electrostatic latent image is visualized is sequentially and continuously transferred to a transfer medium. And a transfer system, wherein the transfer process comprises a distance from a first transfer position to a second transfer position, or a distance from a second transfer position to a third transfer position, or a third transfer. When the distance from the position to the fourth transfer position is d1 (mm) and the peripheral speed of the photoconductor is v (mm / s), the configuration satisfies the condition of d1 / v ≦ 0.65 (sec). An image forming apparatus comprising:

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