JP3975788B2 - Toner manufacturing method and image forming apparatus - Google Patents

Description

【０１２８】
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。
【０１２９】
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となしに、良好なトナーを得ることができる。
【０１３０】
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。
【０１３１】
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。
【０１３２】
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となる範囲内に包含される条件である。
【０１３３】
また、結着樹脂の軟化点は、島津製作所のフローテスタ（ＣＦＴ５００）により、１ｃｍ³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９．８×１０⁵Ｎ／ｍ²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）となる。
【０１３４】
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１０Ｋ／ｍｉｎで室温まで冷却したサンプルを、昇温速度１０Ｋ／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言う。
【０１３５】
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。５Ｋ／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５Ｋ／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。
【０１３６】
本形態に好適に使用される結着樹脂は、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−ジメチルアスチレン、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。
【０１３７】
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。
【０１３８】
重合体の製造方法としては、バルク重合、塊状重合、溶液重合、懸濁重合、乳化重合などの公知の重合法を使用することができる。重合率３０〜９０重量％までバルク重合を行いついで溶剤と重合開始剤を添加して、溶液重合により反応を継続する方法等も好ましい。
【０１３９】
（実施の形態３：電荷制御剤）
本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。
【０１４０】
また、好ましい材料としては(化２)に示すサリチル酸誘導体の金属塩が用いられる。
【０１４１】
【化２】

【０１４２】
また、好ましい材料としては(化３)に示すベンジル酸誘導体の金属塩が用いられる。
【０１４３】
【化３】

【０１４４】
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。現像でのブレード融着を抑えられる。
【０１４５】
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重量部以上であるとカラー画像での色濁りが目立ってくる。
【０１４６】
（実施の形態４：外添剤）
また本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。
【０１４７】
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、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０．１〜１０重量部配合されるのが好ましい。
【０１４８】
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。
【０１４９】
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。
【０１５０】
正極帯電性を有する無機微粉末はアミノシランや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。さらに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。
【０１５１】
このとき無機微粉末は、窒素吸着によるＢＥＴ比表面積は５〜３００ｍ²／ｇが好ましい。より好ましい比表面積は１０〜２５０ｍ²／ｇ、さらに好ましくは２０〜１５０ｍ²／ｇの範囲にあるのが好ましい。比表面積が５ｍ²／ｇより小さいと、トナーの流動性が向上せず、保存安定性が低下する。比表面積が３００ｍ²／ｇより大きいと、凝集が悪化し、均一な外添処理が難しくなる。また感光体へのフィルミングを誘発しやすくなる。トナー母体粒子１００重量部に当たり０．１〜５重量部、好ましくは０．２〜３重量部配合される。０．１重量部より小さいとトナーの流動性が向上でず、５重量部より大きいと浮遊シリカが増加し、機内を汚染する。
【０１５２】
また、ＢＥＴ比表面積が５〜８０ｍ²／ｇのシリカ等の無機微粉末と、ＢＥＴ比表面積が１００〜３００ｍ²／ｇのシリカ等の無機微粉末とを混合して使用することも好ましい。流動性と、耐久性の機能を併せ持つ構成とすることができる。
【０１５３】
トナーを粉砕処理する際、被トナー粉砕物を供給口から流入させる前に、被トナー粉砕物に無機微粉末を供給して混合させ、供給口から流入させて所定の粒度分布へ粉砕する構成をとる。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。
【０１５４】
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０．５〜１０ｗｔ％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。
【０１５５】
平均粒径が８ｎｍより小さいと、定量切出しが不安定となる。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１０ｗｔ％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。
【０１５６】
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。
【０１５７】
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
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。
【０１５９】
疎水化度＝（ａ／（５０＋ａ））×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。
【０１６０】
（実施の形態５：顔料）
また、本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、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。
【０１６１】
（実施の形態６：トナーの粉体物性）
本形態の粉砕手段により結着樹脂、着色剤及びワックスを含むトナーの個数分布における５μｍ以下の含有量が６０個数％以上含有し、個数分布における３．１７μｍ以下の含有量が５〜３５個数％含有し、６．３５〜１０．１μｍの粒径を有するトナ−粒子が５５体積％以下で含有する粒度分布構成を処理能力を落とすことなく実現することが出来る。
【０１６２】
５μｍ以下の含有量が６０個数％以上であると画質改良が著しい。個数分布における３．１７μｍ以下の含有量が５〜３５個数％であると、微粉分級カットがほとんどいらず、収率向上につながる。６．３５〜１０．１μｍの粒径を有するトナ−粒子が５５体積％以下であると、現像でのトナー飛散が低減できる。
【０１６３】
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／粉砕されたトナーの比表面積値）が０．４〜０．９とできる。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。
【０１６４】
トナーの体積平均粒径は４〜６．５μｍとすることができる。トナーの体積粒径分布の変動係数が１５〜３５％、個数粒径分布の変動係数が２０〜４０％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２０〜３５％、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２０〜３０％である。
【０１６５】
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。
【０１６６】
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２０％未満となると、生産的に困難であり、コストアップの要因となる。体積粒径分布の変動係数が３５％より大、または個数粒径分布の変動係数が４０％より大きくなると、粒度分布がブロードとな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となる。
【０１６７】
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。
【０１６８】
微粉量が過大になると、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。微粉量が少なくなると、画質の低下を招く。
【０１６９】
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％となるよう界面活性剤（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。
【０１７０】
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となる。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。
【０１７１】
（実施の形態７：混練工法）
高せん断力さらには高圧縮せん断力による混練により、添加するワックスをより微細分散化できる。そのロールの温度設定及び温度勾配、回転数及び負荷電流の混練条件と結着樹脂の軟化点、ガラス転移点を最適な条件で処理させることにより高分散化処理を可能とできる。高せん断力とは狭い間隙で対向させたロールを高速で回転させることにより結着樹脂等のトナー材料に作用する混練力をいい、狭い間隙に挟まれた時に生じる力と、回転速度差を有する回転ロールから受けるせん断力をいう。従来の二軸押出し機では発揮できない混練力を有する。これにより結着樹脂の高分子量成分を低分子量化することが可能となる。
【０１７２】
具体的は、異方向に回転し、加熱または冷却が可能な対向する２本のロールを有し、一方のロール（ＲＬ１）のロール温度ともう一方のロール（ＲＬ２）のロール温度に温度差を設け、かつ前記ロール（ＲＬ１）と前記ロール（ＲＬ２）とを異なる周速で回転させて２本のロール間で混練処理することにより実現できる。さらには一方のロール（ＲＬ１）が前半部と後半部で温度差を有する構成とすることである。
【０１７３】
２本ロールの回転数比を１．１倍〜２．５倍の範囲内で行うことにより混練時に適切なせん断力が生じ、結着樹脂の分子切断、着色剤等の内部添加剤の分散性が向上し、定着性、現像性が向上する。加熱してトナーを溶融し巻き付ける側のロールの回転比を高くする構成である。１．１倍以下であると適切なせん断力が生じず、分散性が向上せず、透光性が悪化する。逆に２．５倍以上であると、生産性が急激に低下し、また分散性が向上せず、現像性の悪化を招く。
【０１７４】
またこのときの２本のロールにかかる負荷電流値の比を１．２５〜１０の範囲となるような条件で混練することで、適切なせん断力が加わりより内添剤の分散性が向上する。この範囲よりも小さいと分散性が向上せず、透光性が悪化する。また生産性も低下する。逆にこの範囲よりも大きいと、ローラにかかる負荷が大きくなりすぎ、超高分子量成分がより低分子量化しすぎるため、非オフセット性が低下し、オフセットが発生するようになる。
【０１７５】
図１にトナー溶融混練処理の概略斜視図を、図２に平面図、図３に正面図、図４に側面図を示す。６０１はトナー原料の定量供給機、６０２はロール（ＲＬ１）、６０３はロール（ＲＬ２）、６０４はロール（ＲＬ１）上に巻きついたトナーの溶融膜、６０２−１はロール（ＲＬ１）の前半部（原料の搬送方向の上流部）、６０２−２はロール（ＲＬ２）の後半部（原料の搬送方向の下流部）、６０５はロール（ＲＬ１）の前半部６０２−１を加熱するための熱媒体の流入口、６０６はロール（ＲＬ１）の前半部６０２−１を加熱した熱媒体の流出口、６０７はロール（ＲＬ１）の後半部６０２−２を加熱又は冷却するための媒体の流入口、６０８はロール（ＲＬ１）の後半部６０２−２を加熱又は冷却した媒体の流出口、６０９はロール（ＲＬ２）６０３を加熱又は冷却するための媒体の流入口、６１０はロール（ＲＬ２）６０３を加熱又は冷却した媒体の流出口、６１１はロール表面のスパイラル状の溝で深さは２〜１０ｍｍ程度、６１２はロール間で形成されるトナー溜りである。６１１の螺旋状の溝はトナーの混練時に材料が原料投入部の右端から排出部の左端にスムーズに搬送されるに好ましいものである。
【０１７６】
定量供給機から原料供給フィーダ６１３を伝わりながら開口部６１４からトナー原料が矢印６１５のようにロール（ＲＬ１）６０２−１側の端部付近に落下させる。供給フィーダの開口部の長さは６１６で表させる。この長さはロール半径の１／２〜４倍の長さが好ましい。短いと落下させる材料が溶融する前に２本のローラの隙間から下に落下する量が急増する。長すぎると原料フィーダでの搬送途中で原料が分離して均一な分散が得られない。
【０１７７】
また落下位置は図４の矢印にて図示するようにロール（ＲＬ１）６０２の２本のロールが最近接する点から２０°〜８０°の範囲の地点に落下させる。２０°よりも小さい角度であると２本のロールの隙間から落下する量が急増する。８０°以上であると落下させる際、トナー粉末の舞上りが多くなり周辺を汚染する。またカバー６１７は開口部長さ６１６よりも広い領域をカバーできるように設置する。図３ではカバーの図示は省略している。
【０１７８】
定量供給機６０１からトナー原料は供給フィーダ６１３を伝わりながら開口部６１４から落下する。落下したトナー原料はロール（ＲＬ１）６０２−１側の端部付近に投下される。そして６０２−１の熱とロール（ＲＬ２）６０３との圧縮せん断力により樹脂が溶融し、ロール（ＲＬ１）の前半部６０２−１に巻付くようになる。その状態がロール（ＲＬ１）の後半部６０２−２の端部にまで広がり、ロール（ＲＬ１）の前半部６０２−１よりも低い温度で加熱又は冷却されたロール（ＲＬ２）の後半部６０２−２からトナー魂として剥離される。なお、上記処理の間、ロール６０３は室温以下に冷却されている。ロール（ＲＬ１）６０２とロール（ＲＬ２）６０３のクリアランスは０．１〜０．９ｍｍである。本実施例では原料投入量は１０ｋｇ／ｈ、ロール（ＲＬ１）（ＲＬ２）の直径は１４０ｍｍ、長さは８００ｍｍで行った。
【０１７９】
（実施の形態８：粉砕）
本形態に係るトナーは、小粒径粉砕を可能し、粗粉側の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し、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。
【０１８０】
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。
【０１８１】
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。
【０１８２】
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無機微粉末を前記被トナー粉砕物に供給して混合させ、前記供給口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述した材料が適当である。この無機微粉末はトナー母体に固着されることなく静電気的な付着状態でトナー表面に付着する。投入量の約半分量程度以下がバグフィルターにもっていかれている。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。
【０１８３】
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。
【０１８４】
この方式で行うと粉砕と同時に球形化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。この方式により、トナーは粒子の角がきれいに取られ球形化されるため、流動性は飛躍的に向上する。
【０１８５】
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、地カブリとな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。
【０１８６】
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となる。
【０１８７】
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。
【０１８８】
図５に示した本形態のトナーの粉砕装置の１実施例について説明する。
【０１８９】
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、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。
【０１９０】
５１９はバイブレータ振動装置、５１８は無機微粉末供給装置である。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を媒体を供給できる。本実施例では、粉砕条件▲１▼回転体の周速：１３０ｍ／ｓ、回転体と固定体の間隙：１．５ｍｍ、被トナー粉砕物の供給量：５ｋｇ／ｈ、無機微粉末の供給量：０．０３ｋｇ／ｈ、冷却空気温度：０℃、排出部温度：４５℃、粉砕条件▲２▼回転体の周速：１２０ｍ／ｓ、回転体と固定体の間隙：１ｍｍ、被トナー粉砕物供給量：５ｋｇ／ｈ、無機微粉末の供給量：０．０２ｋｇ／ｈ、冷却空気温度：０℃、排出部温度：４０℃で行った。
【０１９１】
（実施の形態９：二成分現像、キャリア）
本形態の現像プロセスにおいては、マグネタイト、フェライト粒子に樹脂コートした抵抗が１×１０⁹〜１×１０¹⁴、粒径３０〜８０μｍのキャリアと混合して二成分現像として好適に使用される。
【０１９２】
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。
【０１９３】
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。
【０１９４】
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。
【０１９５】
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。
【０１９６】
この現像プロセス構成と本形態のトナーの使用により、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。
【０１９７】
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より大きくなると、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。
【０１９８】
交流バイアスが１．０ｋＶ（ｐ−ｐ）より小さくなると、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）より大きくな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より大きくなると（現像ローラ速度が上がる）とトナー飛散が多くなる。
【０１９９】
二成分現像として使用使用する時のキャリアとしては、フェライト粒子表面に樹脂被覆層を設けることにより作成される。フェライトはＦｅ₂Ｏ₃を主原料に、ＮｉＯ、ＣｕＯ、ＣｏＯ，ＭｇＯ、ＺｎＯ，ＭｎＣＯ₃、ＢａＣＯ₃、ＳｒＣＯ₃を混合して原料に用いる。フェライト粒子は、湿式法、乾式法で作成されるが、乾式法が好ましい。乾式法では、原料を混合後仮焼成し、水中にてボールミル等で微粉砕化し、さらに結着剤としてポリビニルアルコール、消泡剤、分散剤を加え造粒用スリラーとする。このスリラーを噴霧乾燥機で加熱乾燥しながら造粒し顆粒とし、本焼成する。本焼成は９００〜１４００℃で１０〜３０時間行い、その後解砕、分級してフェライト粒子を得る。
【０２００】
被覆層は、スプレー法、ディッピング法等公知の方法が用いられる。被覆量はキャリア粒子重量の０．１〜２ｗｔ％である。樹脂被覆層に用いる樹脂は、フッ素系樹脂またはシリコーン系樹脂が用いられる。樹脂被覆層に含有させるカーボンブラックは、種々の製法のカーボンブラックが用いられるが、オイルファーネスカーボンヤアセチレンブラックが好ましい。キャリアの平均粒径は３０〜７０μｍが好ましい。キャリアの平均粒径が３０μｍ未満では、キャリアが感光体に現像されやすくなり、キャリアの平均粒径が７０μｍより大きくなるとキャリアのトナー保持力が弱くなるため、トナー飛散が発生する。
【０２０１】
（実施の形態１０：一成分現像）
本形態の現像プロセスにおいては、弾性又は剛性の現像ローラ上にゴムやメタル等の弾性ブレード等を一定の圧力により接触させ、トナーの薄層を形成して感光体と接触又は非接触により現像する一成分現像法として好適に使用できる。一成分現像法としては、ウレタン樹脂からなるスポンジ系の供給ローラとシリコン樹脂又はウレタン樹脂からなる現像ローラを一定の食い込み量により接触させ、供給ローラから現像ローラにトナーを供給し、現像ローラ上に弾性体のゴムや金属ステンレスのドクターブレードを接触して、または金属性のローラを現像ローラとアゲインスト（同方向）に回転接触して、トナーの薄層を形成し、それを感光体と接触または非接触にて直流または交流印可してトナー像を形成する現像法が好適に使用される。
【０２０２】
このとき、交流バイアスの周波数が０．５〜１０ｋＨｚ、交流バイアスが０．３〜１．２ｋＶ（ｐ−ｐ）であり、感光体と現像ローラ間の周速度比が１：１．２〜１：１．８とすることにより、ドットを忠実に再現でき、良好な現像γ特性とでき、高画質画像を実現できる。そして低地カブリ、高画像濃度が得られる。周波数が０．５〜５ｋＨｚ、交流バイアスが０．３〜１．０ｋＶ（ｐ−ｐ）であり、かつ感光体と現像ローラ間の周速度比が１：１．２〜１：１．５がより好ましく、更に好ましくは周波数が０．５〜２ｋＨｚ、交流バイアスが０．５〜０．９ｋＶ（ｐ−ｐ）であり、かつ感光体と現像ローラ間の周速度比が１：１．２〜１：１．４である。
【０２０３】
このとき、周波数が０．５ｋＨｚ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より大きくなると、現像領域での追随ができず、効果が現れない。交流バイアスが０．３ｋＶ（ｐ−ｐ）より小さくなると、ベタ追随性維持効果が得られず、交流バイアスが１．２ｋＶ（ｐ−ｐ）より大きくな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１：１．８より大きくなると（現像ローラ速度が上がる）とトナー飛散が多くなる。
【０２０４】
供給ローラと現像ローラは同方向に回転させ、現像ローラと供給ローラの周速を１：１〜０．８：０．２の割合で現像ローラを早くする構成とする。また現像ローラは感光体表面に９．８〜９．８×１０²（Ｎ）の圧力で圧接して感光体上の静電潜像が現像される。また弾性ブレードは５〜５×１０²（Ｎ）の圧力で現像ローラ上に圧接してトナー層が形成される。
【０２０５】
さらに、トナー溜めから供給されるトナーの供給量を現像ローラ上へ搬送する際の現像ローラ上のトナー搬送量を一定量に制御するため、ウレタン樹脂等からなるスポンジ状の供給ローラを、現像ローラに対し一定の食い込み量０．１〜１ｍｍで、現像ローラと接触させる構成が取られる。
【０２０６】
トナー溜めから供給されるトナーの供給量を現像ローラ上へ搬送する際の現像ローラ上のトナー搬送量を一定量に制御するため、ウレタン樹脂等からなるスポンジ状の供給ローラを現像ローラと接触させて具備する構成が取られる。これはトナーの搬送量を一定量に規制するために有効な手段である。
【０２０７】
ただ従来のトナーでは、この現像構成においては、長期使用していると現像ローラ上での傷や、ブレードに異物の付着により画像上に縦筋が生じる画像不良が発生しやすい。特にカラー定着性を向上させるために、低軟化性の結着樹脂の使用や、低融点離型剤を添加したトナーではより顕著に発生する。
【０２０８】
また、長期連続使用中に現像ローラ上のトナーの搬送量が低下したり、べた黒画像を取った場合に画像後半部の濃度が部分的に低下するベタ追随性不良が発生しやすい。現像ローラ上のトナーの帯電量を吸引式により測定すると帯電量が大きく低下していることが分かった。さらに追求すると供給ローラ部のトナーの帯電量が大きく増加しており、つまり画像濃度の低下はトナーの帯電量が低下しているのではなくて、現像ローラに供給される前の供給ローラ部においてチャージアップしており供給ローラから現像ローラへの供給能力が低下したためである。よってトナーの飛散を防ぎながら画像濃度を確保できる構成が必要になる。ドクターブレードの圧接力を高めてトナーの帯電能力を上げる構成も有効であるが、トナーの融着を招きやすく現像ローラに傷を生じさせる。
【０２０９】
そこで、本形態のトナー構成とすることにより、定着特性を犠牲にすることなく、現像ローラ上の縦筋の発生、ベタ追随性不良、トナーの融着を防止することができることを見い出した。
【０２１０】
これは樹脂中での均一分散が可能となり、帯電分布が安定化し供給ローラでのトナーの過帯電を抑えると共に、流動性が安定化でき、ベタ画像の追随性も良好なものとなる。均一分散によりトナーの流動性が維持でき現像ローラ上でのトナーの搬送状態をスムーズなものとし、搬送状態を常に安定化できる効果がある。特に高湿下での搬送状態の安定化に効果が大きい。このとき現像ローラ上のトナーの吸引式ファラデーケージ法によるトナーの帯電量が｜５｜〜｜４５｜μＣ／ｇであることが好ましい。｜５｜μＣ／ｇ以下であるとトナー飛散が増大する。｜４５｜μＣ／ｇ以上となると画像濃度が出にくい。
【０２１１】
吸引式ファラデーケージ法によるトナーの帯電量測定は、現像ローラ上のトナーを回転させながら、吸引し、吸引されたトナーはフィルターに捕集し、その重量Ｗ（ｇ）を得る。また吸引時に帯電されたトナーが移動する際の電荷量をコンデンサに誘起される電圧Ｖ（Ｖ）を測定し、Ｑ(μＣ／ｇ)＝Ｃ（Ｆ）×Ｖ（Ｖ）／Ｗ（ｇ）から帯電量を算出する。
【０２１２】
（実施の形態１１：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となる転写位置構成を取る構成であるが、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。
【０２１３】
さらに最後のブラックトナーの第４色目の一次転写位置から二次転写位置までの距離をｄ２（ｍｍ）、感光体の周速度をｖ（ｍｍ／ｓ）とした場合、ｄ２／ｖ≦０．７５となる転写位置構成では、複写用紙に一括して二次転写される際、トナー相互の電荷による反発により画像乱れが生じる。
【０２１４】
そこで、本形態のトナー構成とすることにより、樹脂中でのワックス等の内添剤が均一分散化し、帯電分布が安定化し供給ローラでの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ため、定着特性を犠牲にすることなく、転写効率の低下、転写時の文字の中抜けを防止することができる。
【０２１５】
（実施の形態１２：クリーナレスプロセス）
また、本形態では、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。
【０２１６】
本形態のトナーの使用により、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となる。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。
【０２１７】
（実施の形態１３：オイルレスカラー定着）
本形態では、トナーを定着する手段にベルト式の定着媒体を使用する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。これらの定着ベルト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ベルト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。またトナーが高温オフセット防止のため一定以上の高分子量成分を付加し、ある程度の弾性要素を持たせたとき、トナーの細い縦線のパターンを描いた紙が曲率の大きいベルトからの隔離時に先端部がベルトに持っていかれる先端オフセットが生じる場合がある。また従来の剛性の定着ローラと比べて弾性体のベルト式では、オイルレスにより傷による寿命低下が問題となる。
【０２１８】
そこで、本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ベルトとの帯電作用によるトナーの飛びを抑えられる。またベルトからの隔離時に先端部がベルトに持っていかれるオフセットトナーの分子量分布と滑性の効果により防止することが可能となる。
【０２１９】
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。
【０２２０】
（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。
【０２２１】
【表１】

【０２２２】
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、ＡＶは樹脂酸価を示す。
【０２２３】
（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。
【０２２４】
【表２】

【０２２５】
【表３】

【０２２６】
【表４】

【０２２７】
（表５）に本実施例で使用する顔料を示す。
【０２２８】
【表５】

【０２２９】
（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。
【０２３０】
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、Ｒ¹〜Ｒ⁴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。
【０２３１】
【表６】

【０２３２】
（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℃４５％ＲＨ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１．９６×１０⁴（Ｐａ）で1分間ブローした。
【０２３３】
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。
【０２３４】
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。
【０２３５】
【表７】

【０２３６】
本実施例での混練条件を(表８)に示す。Ｔｒｊ１（℃）はロール（ＲＬ１）の前半部の加熱温度、Ｔｒｋ１（℃）はロール（ＲＬ１）の後半部の加熱温度、Ｔｒ２（℃）ロール（ＲＬ２）の加熱温度、Ｒｗ１はロール（ＲＬ１）の回転数、Ｒｗ２はロール（ＲＬ２）の回転数、ロール（ＲＬ１）の回転時の負荷電流値をＤｒ１、ロール（ＲＬ２）の負荷電流値をＤｒ２と示している。原料投入量は１５ｋｇ／ｈ、ロール（ＲＬ１）（ＲＬ２）の直径は１４０ｍｍ、長さは８００ｍｍで行った。
【０２３７】
【表８】

【０２３８】
（表９）（表１０）に本実施例での粉砕条件を示す。
【０２３９】
粉砕前に供給される無機微粉末とその供給量、バイブレータ振動付与、溶剤噴霧処理を施している。
【０２４０】
【表９】

【０２４１】
【表１０】

【０２４２】
（表１１）（表１２）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。
【０２４３】
【表１１】

【０２４４】
【表１２】

【０２４５】
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。
【０２４６】
混練のＰＣＭ３０は従来の二軸押出機で、混練温度１１０℃回転数２００ｍｉｎ^-1、供給量５ｋｇ／ｈで処理した。
【０２４７】
顔料、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。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。
【０２４８】
（表１３）（表１４）に本実施例で混練処理を施した後のトナーの分子量特性を示す。トナーはマゼンタトナーのＴＭ１からＴＭ７トナーで比較評価した。イエロー、シアン、ブラックトナーでも同様な結果になる。Ｍｎｖはトナーの数平均分子量、Ｍｗｖはトナーの重量平均分子量、Ｗｍｖはトナーの重量平均分子量Ｍｗｖと数平均分子量Ｍｎｖの比Ｍｗｖ／Ｍｎｖ、ＷｚｖはトナーのＺ平均分子量Ｍｚｖと数平均分子量Ｍｎｖの比Ｍｚｖ／Ｍｎｖを示す。
【０２４９】
ＭＬは分子量分布において低分子量側の分子量極大ピークを示す分子量値、ＭＨは高分子量側の分子量極大ピークを示す分子量値、ＳｍはＨｂ／Ｈａ、ＳＫ１はＭ１０／Ｍ９０、ＳＫ２は（Ｍ１０−Ｍ９０）／Ｍ９０を示す。
【０２５０】
【表１３】

【０２５１】
【表１４】

【０２５２】
また図６~２３に分子量分布特性を示す。
【０２５３】
図６、図７はそれぞれ結着樹脂ＰＥＳ−１、トナーＴＭ−１の分子量分布特性、 図８、図９はそれぞれ結着樹脂ＰＥＳ−２、トナーＴＭ−２の分子量分布特性、図１０、図１１はそれぞれ結着樹脂ＰＥＳ−３、トナーＴＭ−３の分子量分布特性、図１２、図１３はそれぞれ結着樹脂ＰＥＳ−４、トナーＴＭ−４の分子量分布特性、図１４、図１５はそれぞれ結着樹脂ＰＥＳ−５、トナーＴＭ−５の分子量分布特性、図１６、図１７はそれぞれ結着樹脂ＰＥＳ−６、トナーＴＭ−６の分子量分布特性、図１８、図１９はそれぞれ結着樹脂ｐｅｓ−７、トナーｔｍ−７の分子量分布特性を示す。を示す。
【０２５４】
結着樹脂ＰＥＳ−１では３×１０⁴以上の高分子量成分を結着樹脂分子量分布全体に対し面積比で５％以上存在している。また３×１０⁵〜９×１０⁶の高分子量成分を結着樹脂分子量分布全体に対し面積比で１％以上有している。同様にＰＥＳ−２、３、４、５、６も３×１０⁴以上の高分子量成分を結着樹脂分子量分布全体に対し面積比で５％以上存在している。また３×１０⁵〜９×１０⁶の高分子量成分を結着樹脂分子量分布全体に対し面積比で１％以上有している。
【０２５５】
混練によりトナーではそれが分子切断され、高分子成分側にピーク又はショルダーとなって現れていることが分かる。つまり透光性を阻害している成分が切断によりなくなり、高分子側に急峻な傾きとなってあらわれ、これが透光性を阻害せずに耐オフセット性を維持させている要因である。トナーＴＭ−１では３×１０⁵以上の高分子量成分量はトナー分子量分布全体に対し面積比で５％以下であり、１×１０⁶以上の高分子量成分はほとんど含有していない。同様にＴＭ−２、３、４、５、６も３×１０⁵以上の高分子量成分量はトナー分子量分布全体に対し面積比で５％以下であり、１×１０⁶以上の高分子量成分はほとんど含有していない。
【０２５６】
また図２０、図２１に分子量分布特性の一例を示す。図２０には高分子成分側に急峻な分子量ピークとなる特性のＭ１０、Ｍ９０を概略的に示している。分子量分布の極大ピークの高さを１００％としている。図２１はトナーＴＭ−４の分子量分布特性のＭ１０、Ｍ９０を概略的に示している。高分子成分側にはショルダー形状として現れており、このショルダー部の肩の頂点の高さを１００％の基準としている。これは結着樹脂ＰＥＳ３の高分子量成分が、混練により分子切断され、高分子成分側にショルダーとなって現れたためである。
【０２５７】
その高分子側の分布のピーク高さを１００％としたとき、極大ピーク又はショルダーに相当する分子量値よりも大きい領域にある分子量曲線、すなわちこの領域における分子量分布曲線の傾きが負となる部位、つまり分布曲線の右側の部位において、分子量分布の極大ピーク又はショルダーの高さを１００％とした場合に、分子量極大ピーク又はショルダーの高さの９０％に相当する分子量をＭ９０、分子量極大ピーク又はショルダーの高さの１０％に相当する分子量をＭ１０としている。ここで、Ｍ１０／Ｍ９０の値（分子量分布曲線の傾き）は、超高分子量成分の分子切断の状態を定量化できるものである。Ｍ１０／Ｍ９０の値が小さいということは分子量分布曲線の傾きが急峻であり、透光性を阻害している成分が切断によりなくなり、高透光性を有するわけである。さらには、この高分子側に現れるピ−クが耐オフセット性に寄与しているわけである。
【０２５８】
また図２２にワックスＷＡ−１の分子量分布特性を、図２３にワックスＷＡ−９の分子量分布特性示す。
【０２５９】
（実施例)
図２４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２４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。プリンタ内の転写ベルトユニット２の着脱操作や紙詰まり時などのプリンタ内部点検保守等は前面板を倒し開いてプリンタ内部を大きく解放することにより行われる。この転写ベルトユニット１７の着脱動作は、感光体の回転軸母線方向に対し平行方向になるように設計されている。
【０２６０】
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。
【０２６１】
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４２ｍｍ（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１００ｍｍ／ｓである。
【０２６２】
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１２０μｍ、体積抵抗は１０⁷〜１０¹²Ω・ｃｍ、表面抵抗は１０⁷〜１０¹²Ω／□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１０⁷Ω・ｃｍよりも小さいと、再転写が生じ易く、１０¹²Ω・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１４ｍｍのカーボン導電性の発泡ウレタンローラで、抵抗値は１０²〜１０⁶Ω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１０²Ωよりも小さいと、再転写が生じ易い。１０⁶Ω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。
【０２６３】
第２転写ローラ１４は外径２０ｍｍのカーボン導電性の発泡ウレタンローラで、抵抗値は１０²〜１０⁶Ω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１０²Ωよりも小さいと、再転写が生じ易い。１０⁶Ωよりもおおき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となり、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。
【０２６４】
図２４において、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。
【０２６５】
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。
【０２６６】
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ＪＩＳ−Ａ硬度６０°のシリコーンゴムよりなる外径１８ｍｍの現像ロ−ラで、感光体に２１Ｎの力で圧接され、矢印の方向に回転する。６は外径１４ｍｍの導電性ウレタンスポンジよりなる供給ローラで、トナーホッパ内のトナーを現像ローラに供給する。５は金属製のブレードで現像ローラ上にトナーの層を形成する。電源は、省略しているが、現像ローラ４には−２３０Ｖの直流と、５００Ｖ（ｐ−ｐ）、周波数１ｋＨｚの交流電圧が印可される。供給ローラ６には−３３０Ｖの直流バイアスが印可される。
【０２６７】
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−１ｋＶが印加される。感光体１表面を−４５０Ｖに帯電する。８はクリーナ、９は廃トナーボックス、７はトナーである。
【０２６８】
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。
【０２６９】
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＋１３００Ｖ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。
【０２７０】
図２６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。
【０２７１】
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。
【０２７２】
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２１１は、案内板２１２に沿って動く。
【０２７３】
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となっている。図示しない駆動モータから駆動力を受けて１００ｍｍ／ｓで回転する。
【０２７４】
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。定着ローラ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。
【０２７５】
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。
【０２７６】
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と接触し反対方向に回転する現像ローラ４上のトナー７が感光体１に形成された静電潜像を顕像化する。
【０２７７】
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１００ｍｍ／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。
【０２７８】
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。
【０２７９】
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。
【０２８０】
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＋１．３ｋＶ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。
【０２８１】
図２５にはベルトへの一次転写を行わずに紙搬送ベルト１７上に紙１９を搬送させ，ＯＰＣ上のトナーを直接転写させるタンデム方式を示す。
【０２８２】
(表１５)に図２５の電子写真装置により、画像出しを行った結果を示す。(表１６)ではトナーが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。
【０２８３】
【表１５】

【０２８４】
【表１６】

【０２８５】
図２５に示す画像形成装置により、前記のように製造したトナー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。また、非画像部の地かぶりも発生していなかった。更に、Ａ４用紙1万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。また現像時の全面ベタ画像を取ったときの均一性も良好であった。現像メモリーも発生していない。連続使用時においても、縦筋の異常画像は発生しなかった。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、転写効率は９８％程度を示した。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。転写ベルトのクリーニング不良も未発生であった。また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。またクリーニングブレード８を使用せずに転写時の残トナーをこのまま現像での回収を行うクリーナプロセスにおいても、回収がスムーズに行え、前画像の履歴が残ることがなかった。また３色の重なったフルカラー画像においても、転写不良は発生せず、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。図２４に示す画像形成装置によっても、同様な結果が得られた。
【０２８６】
しかしｔｍ７、ｔｙ７、ｔｃ７、ｔｂ７のトナーは感光体のフィルミングや転写不良や、転写時の文字の飛び散りが発生し、カブリも多く発生した。転写ベルトのフィルミングや、クリーニング不良も発生した。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。
【０２８７】
次に(表１７)にＯＨＰ用紙に付着量１．２ｇ／ｃｍ²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。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。
【０２８８】
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。
【０２８９】
【表１７】

【０２９０】
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４０〜６０Ｋ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。
【０２９１】
しかしｔｍ７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となった。
【０２９２】
【発明の効果】
以上のように、回転体による粉砕手段において、凝集を緩和する手段の付与により小粒径粉砕を可能し、粗粉側の分布をシャープにすることができる。さらにタンデム方式の転写プロセスにおける転写性、オイルレス定着を実現させるため、特定の結着樹脂、電荷制御剤、ワックスとを含むトナーにおていも、小粒径による高画質化と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となる。高湿下での長期使用においても、感光体、転写体のフィルミングを防止することができる。転写体のクリーニング性を向上することができる。クリーニングブレード等を使用しないクリーナーレスプロセスにおいても転写残トナーの回収がスムーズに行え、前画像の履歴が残らないようにすることができる。さらには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る。
【図面の簡単な説明】
【図１】本発明の実施例で使用したトナー溶融混練処理の概略斜視図
【図２】本発明の実施例で使用したトナー溶融混練処理の平面図
【図３】本発明の実施例で使用したトナー溶融混練処理の正面図
【図４】本発明の実施例で使用したトナー溶融混練処理の断面図
【図５】本発明の実施例で使用したトナー粉砕処理の構成図
【図６】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図７】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図８】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図９】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図１０】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図１１】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図１２】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図１３】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図１４】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図１５】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図１６】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図１７】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図１８】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図１９】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図２０】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図２１】本発明の実施例の結着樹脂及びトナーの分子量分布特性を示す図
【図２２】本発明の実施例のワックスの分子量分布特性を示す図
【図２３】本発明の実施例のワックスの分子量分布特性を示す図
【図２４】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２５】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２６】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
【符号の説明】
１ 感光体
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
６０２ ロール（ＲＬ１）
６０３ ロール（ＲＬ２）
６０４ ロール（ＲＬ１）上に巻きついたトナーの溶融膜
６０５ 熱媒体の流入口
６０６ 熱媒体の流出口[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a toner used for a copying machine, a laser printer, plain paper FAX, a color PPC, a color laser printer, and a color FAX.
[0002]
[Prior art]
In recent years, the electrophotographic apparatus is shifting from the purpose of office use to personal use, and there is a demand for technology that realizes miniaturization, high speed, high image quality, maintenance-free, and the like. Therefore, a cleaner-less process that collects waste toner during development without cleaning waste toner remaining after transfer, a tandem color process that enables high-speed output of color images, and no fixing oil to prevent offset during fixing In both cases, oilless fixing that achieves both a clear color image having high glossiness and high translucency and non-offset properties is required along with conditions such as good maintenance and low ozone exhaust. These functions need to be compatible at the same time, and not only the process but also the improvement in toner characteristics 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 then a latent image of each color is irradiated onto the photoconductor as an optical signal to form an electrostatic latent image. The latent image is developed by developing with color, for example, yellow toner. Thereafter, a transfer member charged with a polarity opposite to that of the yellow toner is brought into contact with the photosensitive member to transfer the yellow toner image formed on the photosensitive member. The photosensitive member is neutralized after cleaning the toner remaining at the time of transfer, and the development and transfer of the first color toner are completed. Thereafter, the same operation as that of the yellow toner is repeated for toners such as magenta and cyan, and a color image is formed by superimposing the toner images of the respective colors on the transfer body. A four-pass color process in which these superimposed toner images are transferred onto paper charged to a polarity opposite to that of the toner has been put into practical use.
[0004]
In addition, a primary transfer in which a plurality of image forming stations having a charger, a photosensitive member, a developing unit, etc. are arranged side by side, and an endless transfer member is brought into contact with the photosensitive member to successively transfer toner of each color sequentially to the transfer member. A secondary transfer process that executes a process to form a multilayer transfer color toner image on a transfer body, and then collectively transfers the multilayer toner image formed on the transfer body onto a transfer medium such as paper or OHP. There have been proposed a tandem color process configured to be executed and a tandem color process in which transfer is continuously performed directly on a paper or OHP transfer medium without using a transfer body.
[0005]
This method has a feature that a color image can be output at high speed. However, since the toner images of four colors are superimposed on the transfer body, the toner layer becomes thick, and a pressure difference between the toner layer is not present or is thin. For this reason, due to the toner aggregating effect, a “collapse” phenomenon that a part of the image is not transferred but becomes a hole is likely to occur. Further, when a material having a high toner release effect is used for the transfer member in order to surely clean the remaining toner, the voids appear remarkably and the quality of the image is remarkably lowered. Furthermore, edge development is performed on characters, lines, and the like, so that more toner is added, toners are agglomerated by pressurization, and voids become more prominent. In particular, it appears more conspicuously in a high humidity and high temperature environment.
[0006]
Further, in order to reduce the size and speed of the machine, it is required that the distance between the image forming stations (corresponding to the distance between the photoconductors) is shorter and the image is printed at a high speed. As a result, for example, after the yellow toner is first transferred, the time until the second transfer of the next magenta toner is very short, and the charge of the transfer body and the charge of the transferred toner are alleviated. First, when transferring the magenta toner onto the yellow toner, the magenta toner is repelled by the charge action of the yellow toner, causing image disturbance due to scattering of the toner image, lowering of transfer efficiency, and missing characters at the time of transfer. Arise.
[0007]
Further, in the configuration using the intermediate transfer member, the toner image is disturbed due to the repulsion due to the mutual charge of the toner when the last toner of the fourth color is primarily transferred and then secondarily transferred onto paper or the like.
[0008]
In addition, in order to improve the dot reproducibility in transfer, the configuration in which the resistance of the transfer body is set to a high resistance causes the toner image disturbance and the tendency of transfer failure to occur more remarkably.
[0009]
Further, it is desired to reduce the particle size of the toner in order to improve the resolution. However, simply reducing the particle size of the toner is insufficient to improve the image quality, leading to a decrease in productivity and an increase in production cost. In order to improve the image quality, the sharpness of the coarse powder side cut and the influence of the amount of fine powder side particles are strong. In terms of productivity, it is necessary to improve the method of pulverizing to reduce the particle size without reducing the production volume. In particular, in order to realize an oilless fixing color toner described later, a configuration in which wax is added is employed. The problem with this configuration is that the toner has a strong cohesiveness due to the wax, and the toner is not unraveled and is conveyed to the pulverization area without being loosened, making it difficult to pulverize small particles and to cut sharply on the coarse powder side. It becomes difficult. In addition, the air is strongly attached to the piping, which is also a factor that reduces productivity and grindability.
[0010]
Furthermore, in order to enable oilless fixing without using oil at the time of fixing, which will be described later, the toner composition in which a release agent such as wax is added to the sharp melt resin has strong charge retention properties and strong toner cohesive properties. Therefore, the tendency of toner image disturbance and transfer failure occurs more remarkably, making it difficult to achieve both transfer and fixing. In addition, in a toner to which a wax having a polar group is added in order to enhance dispersibility in a polyester resin, the cohesion becomes stronger and it is extremely difficult to achieve both oilless fixing and transferability.
[0011]
In the fixing process, in color images, it is necessary to melt and mix color toners to improve translucency. When toner melting failure occurs, light scattering occurs on the surface or inside of the toner image, and the original color tone of the toner dye is impaired. In addition, in the overlapping portion, light does not enter the lower layer and color reproducibility is deteriorated. Therefore, it is a necessary condition that the toner has a complete melting characteristic and a translucency that does not disturb the color tone. The need for light transparency on OHP paper is increasing with the increasing number of presentation opportunities in color.
[0012]
However, the resin composition having sharp melt melting characteristics due to the light transmissibility decreases the offset resistance and causes offset by adhering to the surface of the fixing roller, so a large amount of oil or the like must be applied to the fixing roller. , Handling and equipment configuration become complicated. Therefore, an oil-less color fixing configuration that does not require oil is required.
[0013]
Further, a fluorine-based material is used to improve the releasability and durability of the fixing roller and belt. However, it is easy to cause image disturbance in which an unfixed toner image electrostatically repels the fixing roller before entering the fixing portion. On the contrary, there is a case where the toner flies to the fixing roller before entering the fixing nip portion, thereby causing a halftone offset. In particular, the charging effect is likely to occur in a configuration in which the release oil is not applied. In addition, in a toner to which a release agent is added for the purpose of improving the offset property, the fixing roller is liable to be damaged due to a poorly dispersed state of the internal additive, which causes generation of vertical stripes in the image.
[0014]
As is well known, the toner for electrostatic charge development used in the electrophotographic method is generally a resin component which is a binder resin, a coloring component consisting of a pigment or a dye, a plasticizer, a charge control agent, and further if necessary. It is comprised by additional components, such as a mold release agent. As the resin component, natural or synthetic resins may be used alone or mixed in a timely manner.
[0015]
Then, the above additives are premixed at an appropriate ratio, heated and kneaded by heat melting, finely pulverized by an airflow type impact plate method, and finely classified to complete a toner base. Thereafter, an external additive such as hydrophobic silica is added to the toner base to complete the toner. In one-component development, the toner is composed only of toner, but a two-component developer can be obtained by mixing with toner and a carrier composed of magnetic particles.
[0016]
Japanese Patent Application Laid-Open No. 2-271364 includes an external additive feeding means for feeding an external additive into a high-speed gas flow, and a collision plate provided in a flow path of the high-speed gas flow carrying the pulverized raw material and the external additive. The structure in which the pulverized raw material collides with the collision plate and is pulverized, and the external additive collides with the pulverized raw material in the vicinity of the collision plate, so that the homogenous mixing of the pulverized body and the additive component can be easily performed. Is disclosed. However, this structure is intended for homogenous mixing with the added components, and the purpose of this application is to reduce the particle size, sharp cut of the coarse powder side, and further to the pulverized production of oilless fixing toner with added wax There is no suggestion regarding gender improvement. In particular, in a pulverizer using a collision plate method with toner added with a high concentration of wax, the wax is excessively exposed on the toner surface, which causes filming on the photoreceptor.
[0017]
Japanese Patent Application Laid-Open No. 6-89045 discloses a method in which coarse particles for toner are subjected to intermediate pulverization, and the resulting intermediate particles for toner having an average particle size of 10 to 50 μm and modifying fine particles having an average particle size of 1 μm or less are mixed. The body powder is frictionally pulverized by a mechanical pulverizer to obtain a toner in which the modifying fine particles are fixed to the toner particles, so that the modifying fine particles are well fixed to the toner particles, and high fluidity is achieved. An effect is disclosed in which a toner having excellent durability can be produced with high efficiency. However, there is no suggestion regarding the improvement in the pulverization productivity in the constitution of the oilless fixing toner to which the purpose of the present application is to reduce the particle size, the coarse-cutting sharpness, and the wax.
[0018]
In addition, a configuration that can improve image quality with toner that specifies the particle size distribution of the toner is disclosed, but as a means for realizing the particle size distribution configuration, for example, coarse powder and fine powder are simultaneously cut by an elbow jet classifier. Means are shown. However, there is no disclosure of the content of means for making a predetermined amount of coarse powder in the pulverization step, and there is a problem that the production yield is lowered by the coarse powder classification. In addition, a toner that realizes oil-less fixing has a configuration in which the resin has a high viscosity in order to prevent high temperature offset, and further pulverization efficiency is desired.
[0019]
As the release agent and wax to be added, JP-A-2-266372 discloses the use of de-free fatty acid type carnauba wax and / or montan ester wax, oxidized rice wax having an acid value of 10-30, and JP-A-9 No. -281748 discloses a vinyl copolymer polymerized in the presence of a natural gas Fischer-Tropsch wax at a melting point of 85 to 100 ° C., and JP-A-10-327196 discloses a polyhydric alcohol component, a dicarboxylic acid, and 3 It is disclosed that polycondensation with a polyvalent carboxylic acid compound having a value equal to or higher than that is performed, and an average dispersed particle size of a release agent is 0.1 to 3 μm, and a particle size of an external additive is 4 to 200 nm and 1 to 5 parts by weight are added. Has been. Japanese Patent Application Laid-Open No. 5-333584 discloses a content in which the fixability is improved by a constitution containing a fluorine-modified polyolefin resin such as polypropylene modified with an organic fluorine compound such as perfluorooctyl methacrylate. . In Japanese Patent Laid-Open No. 5-188632, softening point is 80-140 ° C., non-offset property at fixing is improved by blending a low molecular weight polyolefin containing fluorine, a molten mixture of low molecular weight olefin and polytetrafluoroethylene. The contents to be disclosed are disclosed, and the contents effective for improving the fixing property are described.
[0020]
In JP-A-59-148067, a softening point is specified by using an unsaturated ethylene polymer having a low molecular weight and a high molecular weight portion in the resin and defining a low molecular weight peak value and Mw / Mn. Toners containing such polyolefins are disclosed. As a result, fixing property and offset resistance are ensured. JP-A-56-158340 discloses a toner mainly composed of a resin comprising a specific low molecular weight polymer component and a high molecular weight polymer component. The purpose is to secure the fixing property by the low molecular weight component and to secure the offset resistance by the high molecular weight component. JP-A-58-223155 discloses a resin composed of an unsaturated ethylene polymer having a maximum value in a molecular weight region of 1000 to 10,000 and 200,000 to 1,000,000 and Mw / Mn of 10 to 40 and a specific softening. Toners containing polyolefins with dots are disclosed. It is used for the purpose of securing fixability with a low molecular weight component and ensuring offset resistance with a high molecular weight component and polyolefin.
[0021]
JP-A-63-56659 and JP-A-2000-98661 disclose toners relating to polyester resins, and disclose that good fixability can be obtained.
[0022]
Examples of the charge control agent for imparting chargeability to the toner include benzylic acid derivatives described in JP-A-2-221967, JP-A-7-84409, JP-A-5-72812, and JP-A-5-165257. Toners using metal salts are disclosed. JP-A-53-127726, JP-A-55-42752, JP-A-7-221797 and the like disclose toners using metal salts of salicylic acid derivatives.
[0023]
However, if the melt viscosity of the binder resin is lowered or a resin having a low molecular weight is used to increase the fixing strength, the grindability becomes easy. However, if two-component development is used during long-term use, the toner becomes a carrier. It becomes easy to generate so-called spent. The stress resistance of the developer decreases. Further, an offset in which toner adheres to the heat roller during fixing is likely to occur. Further, blocking occurs in which the toners are fused during long-term storage.
[0024]
For resin structures in which a high molecular weight component and a low molecular weight component are blended or copolymerized, a release agent having a low melting point, such as polyethylene or polypropylene wax, improves the releasability from the heat roller during fixing. It is added for the purpose of enhancing the offset resistance. However, it is difficult for these release agents to improve the dispersibility in the binder resin, reverse polarity toner due to poor dispersion is likely to occur, and fogging to non-image areas occurs. In addition, an image defect such as a brush scraped off at the rear end portion of the solid black image portion occurs, and the image quality is deteriorated. There is also a problem of filming contamination of the carrier, the photoconductor, and the developing sleeve.
[0025]
In addition, when using a toner with a structure that improves the glossiness and translucency of color images using a low-melting-point release agent and a low softening resin, vertical streaks occur on the developing roller during transfer and transfer. If the dispersibility is improved due to poor body cleaning, filming, or scraping failure of the transfer body cleaning roller, the effect of releasability will be reduced and the non-offset area will be narrowed, making it difficult to achieve both. .
[0026]
Further, in the contact type one-component development method in which an elastic blade that regulates the toner layer is used in contact with a developing roller such as silicon or urethane and a supply roller such as urethane that supplies toner to the developing roller is provided, the low melting point is low. In the toner added with a release agent, the rising property of charge is deteriorated, and the charge maintenance property is deteriorated during long-term continuous use. Further, the use of the toner added with the low melting point releasing agent described above gradually causes vertical stripes on the developing roller when thousands of sheets are used, which causes image defects such as white spots and black stripes. This is thought to be due to the occurrence of scratches on the developing roller due to poor dispersion of the release agent, fusion to the blade, and aggregation due to friction between the supply roller and the developing roller.
[0027]
Realizing a cleanerless process without a cleaning process is important because of the miniaturization of equipment and resource saving. After the toner that has visualized the electrostatic latent image formed on the photoconductor is transferred to a transfer body or paper by a transfer means, the toner remaining on the photoconductor is usually cleaned by means such as a blade or a fur brush. It is collected and becomes waste toner. At this time, the cleaner-less process performs the following charging, exposure, and development processes without having this cleaning process step. Some transfer residual toner remains on the photoconductor, and in the next development process, the residual toner in the non-image area is collected for development and returned to the image, and no image problems occur.
[0028]
In the case of a color image output, the toner of the previous color may be reversely transferred to the photoconductor in the transfer process of superimposing the color images, which may become an abnormal image as a memory. Therefore, it is important to take measures against the remaining toner and the reversely transferred toner.
[0029]
[Problems to be solved by the invention]
As described above, the toner must satisfy the above-mentioned problems comprehensively. In the oilless fixing toner that does not use oil for the fixing roller, the toner itself has the oil function used for the fixing member. Therefore, it is necessary to use a release agent such as wax in the toner to achieve oilless fixing, maintain transferability even in the tandem color process, and satisfy the cleanerless process. is there. Furthermore, in order to achieve high resolution, a method is required that can reduce the particle size of toner without reducing productivity and can sharply cut the coarse powder side to improve image quality.
[0030]
In view of the above problems, the present invention improves the image quality by reducing the particle size of toner without reducing productivity, and arranges an image forming station having a plurality of photosensitive members and developing units side by side, and sequentially transfers each color to the transfer medium. In the tandem color process that continuously executes the transfer process of toner, it prevents high-efficiency and avoids filming on the transfer body, prevents transfer from being scattered or scattered during transfer, and transfers and cleaning means An object of the present invention is to provide a toner, a toner manufacturing method, and an image forming apparatus that can prevent fusion to the toner.
[0031]
An object of the present invention is to provide a full-color electrophotographic toner and an image forming apparatus that exhibit high translucency and glossiness by oilless fixing in which oil is not applied to a fixing roller. In color toners using low-melting sharp melt resins, filming on developing rollers, doctor blades, transfer bodies, etc. can be avoided, and even for long-term use under high humidity, photoconductors, transfer bodies, etc. An object of the present invention is to provide a toner and an image forming apparatus capable of preventing filming.
[0032]
Even when used in the one-component development method, vertical streaks do not occur on the developing roller, and even when used continuously, the layer regulation blade and the developing roller do not cause thermal fusing or aggregation of toner, suppressing a decrease in charge amount, and resin. It is an object of the present invention to provide a toner and an image forming apparatus capable of improving the dispersibility of additives without deteriorating characteristics and maintaining stable developability.
[0033]
In addition, a toner and an image forming apparatus that can achieve a cleaner-less process with high transfer efficiency even in a cleaner-less process, no reduction in charge amount and fluidity, easy collection during development, no memory, and The purpose is to do.
[0034]
In toner added with a release agent such as low melting point wax, it can prevent contamination of the photoconductor, carrier, developing roller and transfer body due to bleeding such as exudation of wax, has a uniform charge distribution, and stable long-term image It is an object of the present invention to provide a toner and an image forming apparatus that can be realized.
[0035]
In addition, in the fixing process using a belt, and in the belt fixing using a roller having a large curvature with a low fixing pressure and a long fixing nip, the non-wrapping property of the paper to the belt is improved. An object of the present invention is to provide a toner and an image forming apparatus that can prevent chipping of an image portion that occurs when paper is separated, and that can achieve both development and transferability.
[0036]
[Means for Solving the Problems]
In view of the above problems, the configuration according to the present invention is such that after the toner pulverized material including at least the binder resin, the colorant, and the wax is discharged from the quantitative supply device,in frontBefore flowing the toner pulverized product into the supply port of the pulverizing means,Supplying inorganic fine powder to the pulverized toner to be mixed, and
Mixed with the inorganic fine powderFlowing the toner ground material from the supply port;
  The supply port through which the pulverized toner is introduced, a cylindrical rotating body having irregularities on the surface and rotating at a high speed, and a gap of 0.5 mm to 40 mm are fitted outside the rotating body. Pulverizing by a pulverizing means having at least a cylindrical fixed body that shares a central axis with the rotating body and has irregularities on the surface;
  And a step of discharging the pulverized toner pulverized product from a discharge port.
[0038]
  The configuration according to the present invention is as follows.After the toner pulverized material including at least the binder resin, the colorant, and the wax is discharged from the quantitative supply device, before the pulverized toner pulverized material flows into the supply port of the pulverizing means, the evaporable medium is added to the toner borne material. Supplying to the pulverized product, mixing or adhering, supplying the pulverized toner object from the supply port, supplying the pulverized toner object to be supplied, and rotating at a high speed with irregularities on the surface. A cylindrical rotating body, and a cylindrical fixed body that is fitted outside the rotating body with a gap of 0.5 mm to 40 mm, shares a central axis with the rotating body, and has irregularities on the surface; And a step of pulverizing the pulverized toner pulverized product from a discharge port.
[0039]
  The configuration according to the present invention is as follows. At least an image carrier, a charging unit that forms an electrostatic latent image on the image carrier, and a developing unit that visualizes the electrostatic latent image formed on the image carrier with toner that has been pulverized. A plurality of toner image forming stations, transfer means for sequentially transferring the visualized toner images to a transfer medium, or an endless transfer body in contact with the image carrier to transfer the transfer body And a secondary transfer unit that collectively transfers the multilayer toner images formed on the transfer body onto a transfer medium. An image forming apparatus comprising transfer means,
After the toner pulverized toner containing at least a binder resin, a colorant, and wax is discharged from the quantitative supply device, the toner is evacuated before the toner pulverized material flows into the supply port of the pulverizing means. Is supplied to the pulverized toner to be mixed or adhered, and is then introduced from the supply port, and has a cylindrical rotating body having irregularities on the surface and rotating at a high speed, and 0.5 mm to the outside of the rotating body. An image forming apparatus obtained by pulverizing by a pulverizing means having at least a cylindrical fixed body that is fitted with a gap of 40 mm, shares a central axis with the rotating body, and has an uneven surface. is there.
[0041]
  The configuration according to the present invention includes at least an image carrier, a charging unit that forms an electrostatic latent image on the image carrier, and a pulverization process on the electrostatic latent image formed on the image carrier. A plurality of toner image forming stations including a developing unit that visualizes with toner, a transfer unit that sequentially transfers the visualized toner images to a transfer medium, or an endless transfer to the image carrier. A primary transfer means for successively transferring the plurality of visualized toners to the transfer body in contact with each other, and a multi-layer toner image formed on the transfer body, collectively transferred to a transfer medium; An image forming apparatus including a secondary transfer unit configured to cause the toner to be discharged from the quantitative supply device by pulverizing the toner containing at least a binder resin, a colorant, and wax. After the toner powder Before the product is fed into the supply port of the pulverizing means, the inorganic fine powder is supplied to the pulverized toner to be mixed and then introduced into the supply port. And a cylindrical fixed body that is fitted on the outside of the rotating body with a gap of 0.5 mm to 40 mm, shares a central axis with the rotating body, and has irregularities on the surface. An image forming apparatus obtained by pulverizing with a pulverizing unit.
[0042]
DETAILED DESCRIPTION OF THE INVENTION
Digital image quality improvement, high-definition color reproducibility, colorization, high transparency and offset resistance can be achieved without using offset prevention oil for the fixing roller. This makes it possible to prevent the occurrence of vertical stripes due to blade fusion, and to achieve both stable transferability in a cleaner-less process and a tandem color process.
[0043]
(Embodiment 1: Wax)
As the wax added to the toner of the present embodiment, the toner having an iodine value of 25 or less and a saponification value of 30 to 300 is added by adding 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin. The repulsion due to the charge effect of the toner during multi-layer transfer can be alleviated, so that the transfer efficiency can be reduced, the character dropout during transfer and reverse transfer can be suppressed. More preferably, the binder resin has an acid value of 1 to 40 mgKOH / g.
[0044]
The addition amount is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin. If it is 0.1 parts by weight or less, the effect of improving the fixing property cannot be obtained, and if it is 20 parts by weight or more, there is a problem in storage stability.
[0045]
When the iodine value is larger than 25, the repulsion due to the charge effect of the toner is difficult to be mitigated during the toner multi-layer transfer in the primary transfer. The environmental dependency is large, and the change in the charging property of the material becomes large during long-term continuous use, which hinders the stability of the image. When the saponification value is less than 30, the presence of unsaponifiable matter and hydrocarbons increases, and photoconductor filming and chargeability are deteriorated. In addition, the dispersibility with the charge control agent becomes poor, leading to filming, fusion, and a decrease in chargeability during continuous use. If it exceeds 300, the dispersibility of the wax in the resin deteriorates, and the repulsion due to the charge action of the toner is difficult to be alleviated. In addition, fog and toner scattering increase. When the resin acid value is less than 1 mgKOH / g, the repulsion due to the charge effect of the toner is difficult to be mitigated during the toner multilayer transfer. When the resin acid value is larger than 40 mgKOH / g, the environmental resistance is deteriorated and the fog is increased. In particular, transferability is likely to deteriorate under low humidity, and at this time, transferability can be maintained by using it together with an external additive.
[0046]
The thing whose melting | fusing point by DSC method is 50-100 degreeC is preferable. More preferably, the iodine value is 15 or less, the saponification value is 50 to 250, the melting point by DSC method is 55 to 90 ° C., more preferably, the iodine value is 5 or less, the saponification value is 70 to 200, and the melting point by DSC method is 60 to 85 ° C.
[0047]
Furthermore, the material whose volume increase rate at the time of 10 degreeC change at the temperature more than melting | fusing point is 2 to 30% is preferable. When it changes from solid to liquid when it melts with heat during fixing, the adhesion between the toners is further strengthened, the fixing property is further improved, and the releasability from the fixing roller is also improved. Offset property is also improved. If it is smaller than 2, the effect is small, and if it is larger than 30, the dispersibility during kneading is lowered.
[0048]
Further, the heat loss at 220 ° C. of the wax is preferably 8% by weight or less. When the weight loss by heating is greater than 8% by weight, it remains in the binder resin during the heat-kneading, greatly reducing the glass transition point of the binder resin and impairing the storage stability of the toner. It adversely affects the development characteristics and causes fogging and filming of the photoreceptor intermediate transfer member.
[0049]
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 5000, a weight average molecular weight of 200 to 10,000, and a weight average molecular weight. The ratio of number average molecular weight (weight average molecular weight / number average molecular weight) is 1.01 to 8, the ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 10, molecular weight 5 × 10²~ 1x10^FourIt is preferable to have at least one molecular weight maximum peak in this region. More preferably, the number average molecular weight is 500-4500, the weight average molecular weight is 600-9000, the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) is 1.01-7, Z average molecular weight and number average. 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 / 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.
[0050]
When the number average molecular weight is less than 100 and the weight average molecular weight is less than 200, the storage stability is deteriorated. Molecular weight maximum peak is 5 × 10²If it is located in a smaller range, the dispersibility of the charge control agent is deteriorated together with the wax. The storage stability of the toner is deteriorated, filming of the photosensitive member and the transfer member, vertical stripes on the developing roller, and scraping failure on the cleaning roller may occur.
[0051]
The number average molecular weight is greater than 5000, the weight average molecular weight is greater than 10,000, the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is greater than 8, and the ratio of the Z average molecular weight to the number average molecular weight (Z (Average molecular weight / number average molecular weight) is greater than 10, and the molecular weight maximum peak is 1 × 10^FourIf it is located in a range larger than this area, the mold release action is weakened, and fixing functions such as fixing performance and offset resistance are deteriorated.
[0052]
As the wax, Meadowfoam oil derivatives, carnauba wax, jojoba oil derivatives, wood wax, beeswax, ozokerite, carnauba wax, canderia wax, montan wax, ceresin wax, rice wax and other natural waxes, Fischer Tropus wax, etc. These materials such as synthetic waxes are preferable, and can be used alone or in combination of two or more. In particular, carnauba wax having a melting point of 76-90 ° C., candelilla wax having 66-80 ° C., hydrogenated jojoba oil having 64-78 ° C., hydrogenated meadowfoam oil having 74-78 ° C. or 74 At least one or two or more waxes selected from the group consisting of rice waxes having a temperature of ˜90 ° C. are more preferable.
[0053]
Saponification value refers to the number of milligrams of potassium hydroxide KOH required to saponify 1 g of a sample. This is the sum of acid value and ester value. To determine the saponification value, a sample is saponified in an alcohol solution of about 0.5 N potassium hydroxide, and then excess potassium hydroxide is titrated with 0.5 N hydrochloric acid.
[0054]
The iodine value refers to the amount of halogen absorbed when halogen is allowed to act on a sample, and expressed in terms of g relative to 100 g of the sample. This is the number of grams of iodine absorbed by 100 g of fat, and the higher this value, the higher the degree of unsaturation of the fatty acid in the sample. Add iodine and mercury (II) chloride alcohol solution or iodine chloride glacial acetic acid solution to chloroform or carbon tetrachloride solution of sample and titrate the remaining iodine without reaction with sodium thiosulfate standard solution to absorb iodine Calculate the amount.
[0055]
For the measurement of the loss on heating, the weight of the sample cell is precisely weighed to 0.1 mg (W1 mg), and 10 to 15 mg of the sample is put in this, and then weighed to 0.1 mg (W2 mg). The sample cell is set on a differential thermobalance, and the measurement is started with a weighing sensitivity of 5 mg. Temperature control is performed by the following program. After the measurement, the weight loss when the sample temperature reaches 220 ° C. is read to 0.1 mg by the chart (W3 mg). Apparatus, TGD-3000 manufactured by Vacuum Riko Co., Ltd., heating rate 10 ° C./min, maximum temperature 220 ° C., holding time 1 min, loss on heating (%) = W 3 / (W 2 −W 1) × 100.
[0056]
Meadowfoam oil derivatives include Meadowfoam oil fatty acid, metal salt of Meadowfoam oil fatty acid, Meadowfoam oil fatty acid ester, hydrogenated Meadowfoam oil, Meadowfoam oil amide, Homo Meadowfoam oil amide, Meadowfoam oil triester, Epoxy Preferred materials are a maleic acid derivative of a halogenated meadowfoam oil, an isocyanate polymer of a meadowfoam oil fatty acid polyhydric alcohol ester, and a halogenated modified meadowfoam oil. These can be used alone or in combination of two or more.
[0057]
Meadowfoam oil fatty acids obtained by saponification and decomposition of meadowfoam oil are composed of fatty acids having 18 to 22 carbon atoms. As the metal salt, metal salts such as sodium, potassium, calcium, magnesium, barium, zinc, lead, manganese, iron, nickel, cobalt, and aluminum can be used.
[0058]
Meadow foam oil fatty acid esters include, for example, esters such as methyl, ethyl, butyl, glycerin, pentaerythritol, polypropylene glycol, and trimethylolpropane, and in particular, meadow foam oil fatty acid pentaerythritol monoester and meadowfoam oil fatty acid pentaerythritol triester. Ester, meadow foam oil fatty acid trimethylolpropane ester and the like are preferable.
[0059]
Furthermore, an esterification reaction product of meadow foam oil fatty acid and a polyhydric alcohol such as glycerin, pentaerythritol, trimethylolpropane, etc., such as tolylene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), etc. An isocyanate polymer of a meadow foam oil fatty acid polyhydric alcohol ester obtained by crosslinking with isocyanate can also be preferably used.
[0060]
Hydrogenated Meadowfoam oil is obtained by hydrogenating Meadowfoam oil to make unsaturated bonds saturated bonds.
[0061]
Meadowfoam oil amide is obtained by hydrolyzing meadowfoam oil and esterifying it into fatty acid methyl ester, and then reacting with a mixture of concentrated aqueous ammonia and ammonium chloride. Furthermore, it becomes possible to adjust melting | fusing point by hydrogenating this. It is also possible to hydrogenate before hydrolysis. A product having a melting point of 75 to 120 ° C. is obtained. Homomeadofoam oil amide is obtained through nitrile after hydrolyzing and reducing it to an alcohol.
[0062]
Jojoba oil derivatives include jojoba oil fatty acid, metal salt of jojoba oil fatty acid, jojoba oil fatty acid ester, hydrogenated jojoba oil, jojoba oil amide, homo jojoba oil amide, jojoba oil triester, maleic acid derivative of epoxidized jojoba oil, jojoba An isocyanate polymer of oil fatty acid polyhydric alcohol ester and halogenated modified jojoba oil are preferable materials. These can be used alone or in combination of two or more.
[0063]
Jojoba oil fatty acid obtained by saponifying and decomposing jojoba oil consists of fatty acids having 18 to 22 carbon atoms. As the metal salt, metal salts such as sodium, potassium, calcium, magnesium, barium, zinc, lead, manganese, iron, nickel, cobalt, and aluminum can be used.
[0064]
Examples of jojoba oil fatty acid esters include methyl, ethyl, butyl, glycerin, pentaerythritol, polypropylene glycol, trimethylolpropane and the like, and in particular, jojoba oil fatty acid pentaerythritol monoester, jojoba oil fatty acid pentaerythritol triester, jojoba Oil fatty acid trimethylolpropane ester and the like are preferable.
[0065]
Furthermore, esterification reaction products of jojoba oil fatty acid and polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane, tolylene diisocyanate (TDI), diphenylmethane-4,4′-disissocyanate (MDI), etc. An isocyanate polymer of jojoba oil fatty acid polyhydric alcohol ester obtained by crosslinking with the above isocyanate can also be preferably used.
[0066]
Hydrogenated jojoba oil is obtained by hydrogenating jojoba oil to make unsaturated bonds saturated bonds.
[0067]
Jojoba oil amide is obtained by hydrolyzing jojoba oil and then esterifying it into fatty acid methyl ester, and then reacting with a mixture of concentrated aqueous ammonia and ammonium chloride. Furthermore, it becomes possible to adjust melting | fusing point by hydrogenating this. It is also possible to hydrogenate before hydrolysis. A product having a melting point of 75 to 120 ° C. is obtained. Homo jojoba oil amide is obtained through hydrolysis of jojoba oil and then reducing it to alcohol, followed by nitrile.
[0068]
Materials such as hydroxystearic acid derivatives, polyhydric alcohol fatty acid esters such as glycerin fatty acid esters, glycol fatty acid esters, and sorbitan fatty acid esters are preferred, and they can be used alone or in combination of two or more.
[0069]
Derivatives of hydroxystearic acid include methyl 12-hydroxystearate, butyl 12-hydroxystearate, propylene glycol = mono 12-hydroxystearate, glycerin = mono 12-hydroxystearate, ethylene glycol = mono 12-hydroxystearate Etc. are suitable materials. It has the effect of preventing paper wrapping and the effect of preventing belt filming in oilless fixing.
[0070]
As the glycerin fatty acid ester, glycerin = monotristearate, glycerin = docosanoate and the like are suitable materials. It has the effect of reducing cold offset property at low temperatures and preventing transferability from being lowered in oilless fixing.
[0071]
As glycol fatty acid esters, propylene glycol fatty acid esters such as propylene glycol = monopalmitate, propylene glycol = monostearate, and ethylene glycol fatty acid esters such as ethylene glycol = monostearate are suitable materials. Along with oil-less fixability, it has the effect of preventing slipping by improving slippage during development.
[0072]
As sorbitan fatty acid ester, sorbitan = monopalmitate, sorbitan = monostearate, sorbitan = monotristearate are suitable materials. Furthermore, materials such as stearic acid ester of pentaerythritol and mixed esters of adipic acid and stearic acid or oleic acid are preferable, and one kind or a combination of two or more kinds can be used. It has the effect of preventing paper wrapping and the effect of preventing belt filming in oilless fixing.
[0073]
In this embodiment, an aliphatic amide wax is internally added to the polyester resin. Thereby, the translucency in a color image can be improved significantly. In particular, it is possible to promote the smoothness of the surface of the fixed image and obtain a high-quality color image. Furthermore, it is possible to prevent the copy paper from being wound around the fixing roller at the time of fixing, and it is possible to achieve both the light-transmitting property and the offset resistance and to prevent omission during transfer.
[0074]
Examples of the aliphatic amide wax include 16 to 16 carbon atoms such as 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 ligrinoseric acid amide. A saturated or monovalent unsaturated aliphatic amide having a melting point of 70 to 110 ° C. More preferably, it is 70-100 degreeC, More preferably, it is 75-95 degreeC. The addition amount is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the binder resin. When the melting point is lower than 70 ° C., the dispersibility in the resin is lowered, and filming on the photoconductor tends to occur. When the melting point is higher than 110 ° C., the smoothness of the surface of the fixed image is lowered and the translucency is deteriorated. On the other hand, if the amount added exceeds 10 parts by weight, the storage stability deteriorates. If the amount added is less than 0.5 parts by weight, the function cannot be exhibited.
[0075]
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 acid amide, ethylene bis lauric acid amide, propylene bis lauric acid amide, butylene bis lauric acid amide, methylene bis myristic acid amide, ethylene bis myristic acid amide, propylene bis myristic acid amide, butylene bis myristic acid amide, methylene bis Palmitic acid amide, ethylene bis palmitic acid amide, propylene bis palmitic acid amide, butylene bis palmitic acid amide, methylene bis palmitic tray Acid amide, ethylene bispalmitoleic acid amide, propylene bispalmitoleic acid amide, butylene bispalmitoleic acid amide, methylene bisarachidic acid amide, ethylene bisarachidic acid amide, propylene bisarachidic acid amide, butylene bisarachidic acid amide, methylene Biseicosenoic acid amide, ethylene biseicosenoic acid amide, propylene biseicosenoic acid amide, butylene biseicosenoic acid amide, methylene bisbehenic acid amide, ethylene bisbehenic acid amide, propylene bisbehenic acid amide , Alkylene of saturated or divalent unsaturated fatty acid such as butylene bisbehenic acid amide, methylene biserucic acid amide, ethylene biserucic acid amide, propylene biserucic acid amide, butylene biserucic acid amide Scan fatty acid amide wax are preferable.
[0076]
Thereby, it is possible to improve the translucency in the color image and to improve the resistance to offset to the roller. The addition amount is preferably 0.1 to 9 parts by weight with respect to 100 parts by weight of the binder resin. When the melting point is lower than 100 ° C., the effect of anti-offset decreases. When the melting point is higher than 145 ° C., the dispersibility in the resin deteriorates and fogging increases. If the addition amount is less than 0.1 parts by weight, the function cannot be exhibited, and if it is more than 9 parts by weight, fogging increases.
[0077]
Furthermore, the surface smoothness of the fixed image can be improved and the high translucency of the color image can be achieved by configuring the aliphatic amide system and the alkylene bis fatty acid amide system in a ratio of 3: 7 to 7: 3. And offset resistance can be made more excellent. The melting point at that time is required to be higher for the alkylene bis fatty acid amide than for the aliphatic amide. When the melting point of the alkylene bis-fatty acid amide is lowered, not only the offset resistance is lowered, but the resin itself is in a low softened state, and over-pulverization at the time of pulverization proceeds, resulting in an increase in fine powder and a decrease in productivity.
[0078]
In particular, aliphatic amides are low-melting-point materials, so when compatibility with the resin progresses, the resin itself is plasticized, resulting in reduced offset resistance and storage stability. Getting worse. Therefore, by using in combination with the alkylene bis fatty acid amide system, which is a higher melting point material than the aliphatic amide system, plasticization of the resin itself can be suppressed, and the effects of the high translucency and surface smoothness of the aliphatic amide system can be suppressed. Without losing, it is possible to prevent transfer from being lost during long-term use, and to maintain offset resistance and storage stability.
[0079]
In the molecular weight distribution in 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 the Z average molecular weight to the number average molecular weight (Z average molecular weight / number average molecular weight) is 1.5 to 6.5, 1 × 10^Three~ 3x10^FourAnd a long-chain alkyl alcohol having 5 to 100 carbon atoms having at least one maximum molecular weight peak in the region, an acid value of 5 to 80 mg KOH / g, a melting point of 80 to 120 ° C., and a penetration of 4 or less at 25 ° C. Wax obtained by reaction of saturated polycarboxylic acid or its anhydride and hydrocarbon wax, or wax obtained by reaction of long-chain alkylamine and unsaturated polycarboxylic acid or its anhydride and hydrocarbon wax Alternatively, a wax obtained by reacting a long-chain fluoroalkyl alcohol with an unsaturated polyvalent carboxylic acid or an anhydride thereof and a hydrocarbon wax can be used for fixing rollers and belts in an image in which three layers of color toner are formed on thin paper. This is particularly effective for improving the paper separation property. There is an effect in improving the transparency of OHP without reducing the high temperature offset property. Further, the addition of wax can exhibit fixing characteristics, in particular, non-offset property, high glossiness, and high translucency in oilless fixing, and does not deteriorate high temperature storage stability. Further, even if a fluorine-based or silicon-based member is used for the fixing roller, halftone offset can be prevented. Furthermore, charging stability during continuous use can be obtained, and both fixability and development charging stability can be achieved.
[0080]
Furthermore, by improving the dispersion state when this is added to the binder resin, it is possible to further improve the releasability, fixability such as translucency, and developability such as charge stabilization. Although it is conceivable that the dispersibility of other internal additives is lowered by the addition of a release agent, both the fixability and the developability are achieved without lowering the dispersibility of both by the configuration of the additive of this embodiment. be able to.
[0081]
Here, when the carbon number of the long-chain alkyl of the wax is smaller than 5, the releasing action is weakened, and the separation property and the high temperature non-offset property are deteriorated. When 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 less than 5 mgKOH / g, the charge amount during long-term use of the toner is reduced. When the acid value is greater than 80 mgKOH / g, the moisture resistance decreases, and the fogging under high humidity increases. When the melting point is lower than 80 ° C., the storage stability of the toner is lowered. When the melting point is higher than 120 ° C., the releasing action is weakened and the non-offset temperature range is narrowed. When the penetration at 25 ° C. is larger than 4, the toughness is lowered, and filming occurs on the photosensitive member and the intermediate transfer member during long-term use.
[0082]
Weight average molecular weight smaller than 1000, Z average molecular weight smaller than 1500, Weight average molecular weight / number average molecular weight smaller than 1.1, Z average molecular weight / number average molecular weight smaller than 1.5, molecular weight maximum peak Is 1 × 10^ThreeIf it is located in a smaller range, the storage stability of the toner is lowered, and filming of the photosensitive member and intermediate transfer member, vertical stripes on the developing roller, and scraping failure on the cleaning roller may occur.
[0083]
The weight average molecular weight is greater than 6000, the Z average molecular weight is greater than 9000, the weight average molecular weight / number average molecular weight is greater than 3.8, the Z average molecular weight / number average molecular weight is greater than 6.5, and the molecular weight maximum The peak is 3 × 10^FourIf it is located in a range larger than this area, the releasing action is weakened and the fixing offset property is lowered.
[0084]
More preferably, the weight average molecular weight is 1000 to 5000, the Z average molecular weight is 1700 to 8000, 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 Number-average molecular weight ratio (Z-average molecular weight / number-average molecular weight) is 1.5 to 4.5, 1 × 10^Three~ 1x10^FourIt is preferable to have at least one molecular weight maximum peak in the region, more preferably, the weight average molecular weight is 1000 to 2500, the Z average molecular weight is 1900 to 3000, and the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average). Molecular weight) is 1.2 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 × 10.^Three~ 3x10^ThreeIt has at least one molecular weight maximum peak in the region.
[0085]
As the alcohol, those having a long alkyl chain such as octanol, dodecanol, stearyl alcohol, nonacosanol, pentadecanol and the like can be used. Moreover, N-methylhexylamine, nonylamine, stearylamine, nonadecylamine, etc. can be used conveniently as amines. 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 polyvalent carboxylic 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 preferable. As the synthetic hydrocarbon wax, polyethylene, polypropylene, Fischer-Tropsch wax, α-olefin and the like can be suitably used.
[0086]
Unsaturated polyhydric carboxylic acid or its anhydride is polymerized with alcohol or amine, and this is then added to synthetic hydrocarbon wax in the presence of dicrummi peroxide or tertiary butyl peroxyisopropyl monocarbonate. Can be obtained.
[0087]
The addition amount is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin. If it is 1 or less, the mold release effect is hardly produced. When it is 20 or more, not only the fluidity of the toner is lowered, but even if it is added more, the effect is not improved because of saturation.
[0088]
Polyolefin waxes such as polyethylene and polypropylene, stearic acid, palmitic acid, lauric acid, aluminum stearate, barium stearate, zinc stearate, zinc palmitate, and other higher fatty acids or metal products thereof can be suitably used.
[0089]
The addition amount is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the binder resin. If it is less than 0.5, the effect of improving translucency cannot be obtained. If it exceeds 20, not only the fluidity of the toner will be lowered but also the addition will be saturated and the effect will not be improved.
[0090]
In addition, particles having a dispersion average particle size of 0.1 to 1.5 μm in the wax binder resin and a particle size distribution of less than 0.1 μm are 35% by number or less, and particles having a particle size of 0.1 to 2.0 μm. It is preferable that the number of particles of 65% by number or more and more than 2.0 μm is 5% by number or less. The particle size and the number thereof were determined from a cross-sectional photograph of the toner by TEM.
[0091]
When the dispersion average particle diameter is smaller than 0.1 μm and the number of particles smaller than 0.1 μm is larger than 35% by number, the releasing effect as a releasing agent is small and the fixing ability cannot be exhibited. When the dispersion average particle diameter 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 difficult to be alleviated. In addition, fog and toner scattering increase.
[0092]
(Embodiment 2: Binder resin)
As a binder resin of this embodiment, the molecular weight distribution in GPC is 2 × 10.^Three~ 3x10^Four3 × 10 as a component having at least one molecular weight maximum peak in the region and existing in the high molecular weight region^FourIt has 5% or more of the above molecular weight components with respect to the whole binder resin, the weight average molecular weight is 10,000 to 300,000, the Z average molecular weight is 20,000 to 500,000, and the ratio of the weight weight average molecular weight to the number average molecular weight (weight average The molecular weight / number average molecular weight) is 3 to 100, the ratio of the Z average molecular weight to the number average molecular weight (Z average molecular weight / number average molecular weight) is 10 to 2000, and the melting temperature by the 1/2 method using the Koka type flow tester (hereinafter softening) It is preferable that the component is a polyester resin having a point) of 80 to 150 ° C, an outflow start temperature of 80 to 120 ° C, and a glass transition point of the resin of 45 to 68 ° C.
[0093]
Preferably, the weight average molecular weight is 10,000 to 120,000, the Z average molecular weight is 20,000 to 300,000, the weight average molecular weight / number average molecular weight is 3 to 50, the Z average molecular weight / number average molecular weight is 10 to 1,000, and the softening point is 90. It is preferable to use as a component a polyester resin having a temperature of ~ 140 ° C, an outflow start temperature of 85 to 115 ° C, and a glass transition point of 52 to 65 ° C. More preferably, the weight average molecular weight is 10,000 to 40,000, the Z average molecular weight is 20,000 to 100,000, the weight average molecular weight / number average molecular weight is 3 to 20, the Z average molecular weight / number average molecular weight is 10 to 100, and the softening point is It is preferable to use as a component a polyester resin having a temperature of 105 to 135 ° C, an outflow start temperature of 90 to 120 ° C, and a glass transition point of 58 to 65 ° C.
[0094]
Moreover, as a component which exists in a high molecular weight area | region, Preferably it is 1x10.^FiveIt is preferable to have the above molecular weight components at 3% or more with respect to the entire binder resin. Furthermore, as a component existing in the high molecular weight region, 3 × 10^FiveIt is preferable to have 0.5% or more of the above molecular weight components with respect to the whole binder resin.
[0095]
Preferably 8 × 10 8 as a component present in the high molecular weight region^Four~ 1x10⁷Having a molecular weight component of 3% or more with respect to the entire binder resin, and 1 × 10⁷The structure which does not contain the above components is preferable.
[0096]
More preferably, as a component present in the high molecular weight region, 3 × 10^Five~ 9x10⁶Having a high molecular weight component of 1% or more with respect to the whole binder resin, and 9 × 10⁶The above components are not included.
[0097]
More preferably, as the component existing in the high molecular weight region, 7 × 10^Five~ 6 × 10⁶Having a high molecular weight component of 1% or more with respect to the whole binder resin, and 6 × 10⁶The above components are not included.
[0098]
If the amount of the high molecular weight component is too large or too large, the large molecular weight component remains at the time of kneading and hinders the translucency. In addition, the production efficiency of the resin itself decreases. Unnecessary scratches are made on the developing roller supply roller to cause vertical stripes in the image. Also, the dispersibility of the wax decreases.
[0099]
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 0 ° C., the outflow start temperature is lower than 80 ° C., and the glass transition point is lower than 45 ° C., the dispersibility at the time of kneading decreases, resulting in an increase in fog and a deterioration in durability. 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 hardly reduced. In addition, fog and toner scattering increase. In addition, offset resistance and storage stability at high temperatures are deteriorated, and further, poor cleaning on the transfer member and filming on the photosensitive member occur.
[0100]
The weight average molecular weight of the binder resin is greater than 300,000, the Z average molecular weight is greater than 500,000, the weight average molecular weight / number average molecular weight is greater than 100, the Z average molecular weight / number average molecular weight is greater than 2000, and the softening point is 150. If it is greater than ℃, the outflow start temperature is greater than 120 ℃, and the glass transition point is greater than 68 ℃, the load during processing of the machine becomes excessive, resulting in an extreme decrease in productivity and a decrease in translucency in color images. And lead to a decrease in fixing strength.
[0101]
Further, the molecular weight distribution in GPC of the toner after melt-kneading and pulverization classification is 2 × 10^Three~ 3x10^FourHaving at least one molecular weight maximum peak in the region of 5 × 10^Four~ 1x10⁶It is set as the structure which has at least 1 molecular weight maximum peak or shoulder in this area | region.
[0102]
The maximum molecular weight peak present on the low molecular weight side of the toner is preferably 3 × 10^Three~ 2x10^FourAt least one in the region, more preferably 4 × 10^Three~ 2x10^FourIt is the structure which has at least one in the area | region.
[0103]
The position of the maximum molecular weight peak or shoulder existing on the high molecular weight side of the toner is preferably 6 × 10.^Four~ 7 × 10^FiveAt least one in the region, more preferably 8 × 10^Four~ 5x10^FiveThis region has at least one molecular weight maximum peak or shoulder.
[0104]
The molecular weight maximum peak position of the molecular weight distribution of the toner present on the low molecular weight side is 2 × 10^ThreeWhen it becomes smaller, the durability deteriorates and 3 × 10^FourWhen it is larger, the fixing property is deteriorated, and the translucency is lowered.
[0105]
Further, the position of the molecular weight maximum peak or shoulder of the molecular weight distribution of the toner existing on the high molecular weight side is 5 × 10 5.^FourWhen it becomes smaller, the offset resistance is lowered, and the storage stability is deteriorated. Deterioration of developability and waste toner recyclability are also reduced. 1 × 10⁶When it is larger, the grindability is lowered and the production efficiency is lowered.
[0106]
Further, as a component present in the high molecular weight region of the toner, 5 × 10^FiveThe content of the high molecular weight component is preferably 10 wt% or less with respect to the entire binder resin. 5 × 10^FiveThe components present in the above high molecular weight region increase or the enormous state is a result of the kneading state becoming defective because a uniform kneading stress is not applied to the toner constituting material during kneading. Thereby, translucency is remarkably inhibited. Further, an increase in fog due to poor dispersion, generation of scratches on the developing roller and supply roller, deterioration of toner pulverization, and manufacturing efficiency are lowered.
[0107]
More preferably, 5 × 10^FiveThe content of the high molecular weight component is 5% or less with respect to the whole binder resin, more preferably 1 × 10.⁶The content of the above high molecular weight components is 1% or less with respect to the whole binder resin, or it does not contain.
[0108]
The molecular weight distribution in the GPC chromatogram of the toner is 2 × 10.^Three~ 3x10^FourThe height of the molecular weight distribution of the molecular weight maximum peak existing in the region of Ha is 5 × 10^Four~ 1x10⁶Hb / Ha is 0.15 to 0.9, where Hb is the maximum molecular weight peak or shoulder height existing in the region.
[0109]
When Hb / Ha is smaller than 0.15, the offset resistance is deteriorated, the storage stability is also lowered, and the filming on the developing sleeve and the photosensitive member is promoted. If it exceeds 0.9, the developing roller supply roller will be damaged, the grindability will deteriorate, the productivity will decrease, and the cost will increase. More preferably, Hb / Ha is 0.15 to 0.7, and still more preferably Hb / Ha is 0.2 to 0.6.
[0110]
Further, the molecular weight distribution in GPC of the toner is 2 × 10^Three~ 3x10^FourAt least one molecular weight maximum peak in the region of 5 × 10^Four~ 1x10⁶And having a molecular weight maximum of 5 × 10^Four~ 1x10⁶Pay attention to the molecular weight curve in the region larger than the molecular weight distribution corresponding to the maximum peak or shoulder of the molecular weight distribution existing in the region, and the molecular weight maximum peak with the maximum peak or shoulder height of the molecular weight distribution as the reference 100% Alternatively, when the molecular weight corresponding to 90% of the height of the shoulder is M90 and the molecular weight corresponding to the molecular weight maximum peak or the height of 10% of the shoulder is M10, M10 / M90 is 0.00. It is realizable by setting it as 5-8. Furthermore, when (M10−M90) / M90 is 0.1 to 7, high translucency can be secured, and oilless fixing capable of preventing offset can be realized without requiring fixing oil.
[0111]
Defining the value of M10 / M90, and further (M10-M90) / M90 (the slope of the molecular weight distribution curve) can quantify the state of molecular cleavage of the ultrahigh molecular weight component, and this value is If it is within the stated range (implying that the slope of the molecular weight distribution curve is steep), the ultra-high molecular weight component that impedes the light transmission is lost by cutting during kneading, resulting in high light transmission. To have. Furthermore, the high molecular weight component forming the peak or shoulder appearing on the polymer side contributes to offset resistance, and it is possible to prevent the occurrence of color toner offset without using oil.
[0112]
Furthermore, when this ultra-high molecular weight component is molecularly cut, the wax and charge control agent can be uniformly dispersed in the binder resin, the charge amount becomes uniform, and the resolution is clear. Even if it is used continuously for a long time, the durability is not deteriorated. Further, the cleaning property of the transfer body is improved, the vertical streak is not generated on the developing roller, the image is not disturbed during the transfer, and it is possible to prevent the image from being lost and to obtain a highly efficient transfer property.
[0113]
When the value of M10 / M90 is larger than 8 or (M10−M90) / M90 is larger than 7, the ultra-high molecular weight component still remains and inhibits translucency. When the value of M10 / M90 is smaller than 0.5 or (M10−M90) / M90 is smaller than 0.1, the mechanical load during kneading becomes excessive and productivity is lowered. The durability of the toner is reduced. 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.
[0114]
As a result, digital high image quality, high color reproducibility colorization, contact type one-component development, the development roller and supply roller can be used stably for a long time, and the fixing roller does not use oil for preventing offset. It is possible to achieve both of translucency and offset resistance, and furthermore, it is possible to realize a cleaner process, prevention of voids in a transfer process in a short distance between transfer and a short time tandem transfer process, and high transferability.
[0115]
By kneading the above-described binder resin with a high shearing force in the melt-kneading process, it is possible to develop characteristics that are not conventionally obtained. Fixing without using oil makes it possible to achieve both high translucency and offset resistance of color toners. In other words, the binder resin to which the ultra-high molecular weight component has been added has a high shearing force, the ultra-high molecular weight component is lowered to a high molecular weight, thereby exhibiting high translucency. The offset property is also satisfactory. In addition, since it has an ultra-high molecular weight component, a high shearing force is applied during kneading, so that the wax can be more uniformly dispersed, the translucency is improved, non-offset property, high image quality, high color reproducibility, Good transferability can be obtained.
[0116]
The weight average molecular weight of the toner after the melt-kneading treatment is 8000 to 180,000, the Z average molecular weight is 18,000 to 450,000, the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 3 to 80, Z average The ratio between the molecular weight and the number average molecular weight (Z average molecular weight / number average molecular weight) is 10 to 1000.
[0117]
By kneading the toner with a high shearing force within this suitable range, it is possible to achieve both high translucency and offset resistance of the color toner by fixing without using oil.
[0118]
Preferably, the weight average molecular weight is 8000 to 100,000, the Z average molecular weight is 18000 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.
[0119]
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.
[0120]
When the weight average molecular weight is less than 8000, the Z average molecular weight is less than 18000, 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, The molecular weight cannot be maintained at an appropriate value. The dispersibility of the wax is reduced, offset resistance and high-temperature storage stability are deteriorated, and further, poor cleaning on the intermediate transfer member and filming on the photosensitive member occur.
[0121]
If 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 the Z average molecular weight / number average molecular weight is greater than 1000, the pressure of the shearing force is too high On the contrary, internal additives such as charge control agents cause aggregation to each other, leading to a decrease in dispersibility, leading to an increase in fog during the cleaner process, a decrease in image density, and a transfer failure. In addition, the fixing strength is reduced, and the translucency and glossiness are reduced.
[0122]
The binder resin has a THF insoluble component of 5% by weight or less, and preferably has no THF insoluble component. If the THF-insoluble component is more than 5% by weight, the translucency of the color image is deteriorated and the image quality is deteriorated.
[0123]
As the binder resin suitably used in this 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 anhydride is preferably used.
[0124]
Examples of divalent carboxylic acids or lower alkyl esters include malonic acid, succinic acid, glutaric acid, adipic acid, hexahydrophthalic anhydride and other aliphatic dibasic acids, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid And aliphatic unsaturated dibasic acids such as phthalic anhydride, phthalic anhydride, terephthalic acid and isophthalic acid, and methyl and ethyl esters thereof. Of these, aromatic dibasic acids such as succinic acid, phthalic acid, terephthalic acid, and isophthalic acid, and lower alkyl esters thereof are preferred. The use of succinic acid and terephthalic acid or a combination of phthalic acid and terephthalic acid is preferred.
[0125]
Examples of the trivalent or higher carboxylic acid component include 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-methylenecarbopropane, tetra (methylenecarboxyl) Examples include methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, acid anhydrides thereof, and alkyl (carbon number 1 to 12) esters.
[0126]
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 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. Of these, bisphenol A represented by (Chemical Formula 1), derivatives thereof, alkylene oxide adducts thereof, neopentyl glycol, and totimethylolpropane are particularly preferable.
[0127]
[Chemical 1]

[0128]
Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1 , 2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. It is done.
[0129]
For the polymerization, known polycondensation, solution polycondensation or the like can be used. As a result, a good toner can be obtained without impairing the PVC mat resistance and the color of the color toner.
[0130]
The ratio of the polyvalent carboxylic acid and the polyhydric alcohol is generally 0.8 to 1.4 in terms of the ratio of the number of hydroxyl groups to the number of carboxyl groups (OH / COOH).
[0131]
The molecular weights of the resin, wax, and toner are values measured by gel permeation chromatography (GPC) using several types of monodisperse polystyrene as standard samples.
[0132]
The apparatus is HPLC 8120 series manufactured by Tosoh Corporation, the column is TSKgel superHM-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 amount 20 μL, detector RI, measurement temperature 40 ° C., pretreatment for measurement is to measure a resin component obtained by dissolving a sample in THF and filtering through a 0.45 μm filter to remove additives such as silica. The measurement conditions are conditions in which the molecular weight distribution of the target sample is included in a range in which the logarithm of the molecular weight and the count number are linear in a calibration curve obtained with several types of monodisperse polystyrene standard samples.
[0133]
The softening point of the binder resin is 1 cm by a flow tester (CFT500) manufactured by Shimadzu Corporation.^ThreeThe sample was heated at a rate of temperature increase of 6 ° C./min.^FiveN / m²The temperature at which the piston stroke starts to rise is the outflow start temperature (Tfb) from the relationship between the temperature rise characteristic in the relationship between the piston stroke and the temperature of the plunger. ), 1/2 of the difference between the lowest value of the curve and the end point of the outflow is obtained, and the temperature at the point of adding the lowest value of the curve is the melting temperature (softening point Tm) in the 1/2 method.
[0134]
The glass transition point of the resin was raised to 100 ° C. using a differential scanning calorimeter, left at that temperature for 3 minutes, and then cooled to room temperature at a cooling rate of 10 K / min. When the thermal history is measured by raising the temperature, the temperature at the intersection of the base line extension below the glass transition point and the tangent that indicates the maximum slope from the peak rising portion to the peak apex is said.
[0135]
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 K / min, rapidly cooled to 10 ° C. for 5 minutes, allowed to stand for 15 minutes, then heated at 5 K / min, and obtained from the endothermic (melting) peak. The amount of sample put into the cell was 10 mg ± 2 mg.
[0136]
As the binder resin preferably used in the present embodiment, homopolymers or copolymers of various vinyl monomers can also be suitably used. For example, styrene, O-methyl styrene, m-methyl styrene, p-methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn butyl styrene, p-tert-butyl styrene, pn-hexyl Styrene and its derivatives such as styrene, pn-octyl styrene, pn-hexyl styrene, P-chlorostyrene, and the like are exemplified, and styrene is particularly preferable.
[0137]
Examples of acrylic monomers include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, acrylate-2-ethylhexyl, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, hexyl methacrylate, methacrylic acid. Acid-2-ethylhexyl, β-hydroxyethyl acrylate, γ-hydroxyacrylate propyl α-hydroxyacrylate, β-hydroxyethyl methacrylate, γ-aminoacrylate, γ-N, N-diethylaminoacrylate , Ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and the like. Suitable styrene-acrylic copolymers for the purposes of the present invention are styrene / butyl acrylate copolymers, particularly those containing 75-85% by weight styrene and 15-25% by weight butyl acrylate. used.
[0138]
As a method for producing the polymer, known polymerization methods such as bulk polymerization, bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used. A method of carrying out bulk polymerization to a polymerization rate of 30 to 90% by weight and then adding a solvent and a polymerization initiator and continuing the reaction by solution polymerization is also preferred.
[0139]
(Embodiment 3: Charge control agent)
In this embodiment, a charge control agent is added in order to make the toner charge control purpose and oilless fixing stronger. A preferable material is an acrylic sulfonic acid polymer, and 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.
[0140]
Further, as a preferable material, a metal salt of a salicylic acid derivative shown in (Chemical Formula 2) is used.
[0141]
[Chemical 2]

[0142]
Further, as a preferable material, a metal salt of a benzylic acid derivative represented by (Chemical Formula 3) is used.
[0143]
[Chemical 3]

[0144]
With this configuration, a wide non-offset temperature range can be secured in oil-less fixing, and image disturbance due to charging during fixing can be prevented. This seems to be the effect of the functional group having the acid value of the wax and the charging polarity of the metal salt. In addition, it is possible to prevent a decrease in charge amount during continuous use. Blade fusion during development can be suppressed.
[0145]
The addition amount is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the binder resin. More preferably, it is 1-4 weight part, More preferably, it is 3-4 weight part. When the amount is less than 0.5 parts by weight, the charging effect is lost. When it is 5 parts by weight or more, color turbidity in a color image becomes conspicuous.
[0146]
(Embodiment 4: External additive)
Further, in this embodiment, as external additives, fine metal oxide powders such as silica, alumina, titanium oxide, zirconia, magnesia, ferrite and magnetite, titanates such as barium titanate, calcium titanate and strontium titanate, zirconic acid Zirconates such as barium, calcium zirconate, strontium zirconate, or mixtures thereof are used. The external additive is hydrophobized as necessary.
[0147]
Silicone oil-based materials treated with silica include 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, methacrylic acid. Treated with at least one of modified silicone oil, mercapto modified silicone oil, polyether modified silicone oil, methylstyryl modified silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, amino modified silicone oil, chlorophenyl modified silicone oil Silica is preferably used. For example, SH200, SH510, SF230, SH203, BY16-823, BY16-855B, etc. manufactured by Toray Dow Corning Silicone 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 solution in which a silicone oil-based material is dissolved or dispersed in a solvent Then, after mixing with silica fine powder, there is a method of removing the solvent to prepare. The silicone oil-based material is preferably blended in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the inorganic fine powder.
[0148]
As silane coupling agents, 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 treatment in which the vaporized silane coupling agent is reacted with a fine powder made into a cloud by stirring or the like, or a wet treatment in which a silane coupling agent in which the fine powder is dispersed in a solvent is dropped. Processed by law.
[0149]
It is also preferable to treat the silicone oil-based material after the silane coupling treatment.
[0150]
The inorganic fine powder having positive electrode chargeability is treated with aminosilane, amino-modified silicone oil, or epoxy-modified silicone oil. In order to further improve the hydrophobic treatment, a combination treatment with hexamethyldisilazane, dimethyldichlorosilane, or other silicone oil is also preferable. For example, it is preferable to treat with at least one of dimethyl silicone oil, methylphenyl silicone oil, and alkyl-modified silicone oil.
[0151]
At this time, the inorganic fine powder has a BET specific surface area of 5 to 300 m by nitrogen adsorption.²/ G is preferred. A more preferable specific surface area is 10 to 250 m.²/ G, more preferably 20 to 150 m²/ G is preferable. Specific surface area is 5m²When it is smaller than / g, the fluidity of the toner is not improved, and the storage stability is lowered. Specific surface area is 300m²When it is larger than / g, aggregation is deteriorated and uniform external addition treatment becomes difficult. In addition, filming on the photosensitive member is easily induced. The amount is 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight per 100 parts by weight of the toner base particles. If the amount is less than 0.1 parts by weight, the fluidity of the toner is not improved. If the amount is more than 5 parts by weight, the floating silica increases and the inside of the machine is contaminated.
[0152]
The BET specific surface area is 5 to 80m.²/ G of inorganic fine powder such as silica and BET specific surface area of 100 to 300 m²It is also preferable to use a mixture with inorganic fine powder such as silica / g. It can be set as the structure which has the function of fluidity | liquidity and durability.
[0153]
When the toner is pulverized, before the pulverized toner to be fed from the supply port, the inorganic fine powder is supplied to the pulverized toner to be mixed, and the pulverized toner is pulverized to a predetermined particle size distribution by flowing from the supply port. Take. As a result, the pulverized toner object enters the pulverizing portion having the rotating body in a uniformly dispersed state, and the pulverized toner object is uniformly pulverized by the vortex generated by the rotating body. As a result, pulverization with smaller particle size and pulverization in which the coarse powder is sharply cut are possible.
[0154]
The inorganic fine powder supplied and mixed at this time is preferably silica or titanium oxide fine powder having an average particle size of 8 to 40 nm and an ignition loss of 0.5 to 10 wt%. Furthermore, 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. Furthermore, the inorganic fine powder is preferably a silica or titanium oxide fine powder whose surface is treated with silicone oil. An inorganic fine powder having a charging polarity opposite to the charging polarity of the toner base particles is also an effective means for relaxing the charge of the pulverized toner.
[0155]
When the average particle size is smaller than 8 nm, the quantitative cutting becomes unstable. When the average particle size is larger than 40 nm, uniform grindability is not improved. If the ignition loss is less than 0.5 wt%, fine powder will be scattered. If the loss on ignition is larger than 10 wt%, the fine powder is strongly agglomerated and the uniform supply of the pulverized toner is deteriorated.
[0156]
For drying loss (%), about 1 g of a sample is placed in a container that has been dried, allowed to cool, and precisely weighed in advance, and weighed accurately. Dry in a hot air dryer (105 ° C ± 1 ° C) for 2 hours. After cooling in a desiccator for 30 minutes, the weight is precisely weighed and calculated from the following formula.
[0157]
Loss on drying (%) = Loss on drying (g) / Sample amount (g) × 100
For ignition loss, about 1 g of a sample is placed in a magnetic crucible that has been dried, allowed to cool, and precisely weighed in advance, and weighed accurately. Ignite for 2 hours in an electric furnace set to 500 ° C. After standing to cool in a desiccator for 1 hour, its weight is precisely weighed and calculated from the following formula.
[0158]
Loss on ignition (%) = Weight loss due to ignition (g) / Sample amount (g) x 100
For the determination of the degree of hydrophobicity, 0.2 g of the product to be tested is weighed into 50 ml of distilled water charged in a 250 ml beaker. At the tip, methanol is dropped from a burette invaded in the liquid until the total amount of the inorganic fine powder is wet. At that time, slowly stir slowly with an electromagnetic stirrer. From the amount of methanol a (ml) essential for complete wetting
The degree of hydrophobicity is calculated by the following formula.
[0159]
Hydrophobic degree = (a / (50 + a)) × 100 (%)
Moreover, it is preferable that the moisture adsorption amount of the processed inorganic fine powder is 1 wt% or less. Preferably it is 0.5 wt% or less, More preferably, it is 0.1 wt% or less, More preferably, it is 0.05 wt% or less. When the content is more than 1 wt%, chargeability is deteriorated and filming on the photoconductor during durability is caused. The water adsorption amount was measured with a continuous vapor adsorption device (BELSORP18: Nippon Bell Co., Ltd.) for the water adsorption device.
[0160]
(Embodiment 5: Pigment)
Examples of the pigment used in this embodiment include carbon black, iron black, graphite, nigrosine, azo dye metal complexes, C.I. I. Acetoacetic acid arylamide monoazo yellow pigments such as CI Pigment Yellow 1,3,74,97,98; I. Acetoacetic acid arylamide disazo yellow pigments such as C.I. Pigment Yellow 12, 13, 14, and 17; I. Solvent Yellow 19, 77, 79, C.I. I. Disperse Yellow 164, C.I. 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 two or more kinds of blue dyed pigments of phthalocyanine and derivatives thereof such as Pigment Blue 15: 3 are blended. The addition amount is preferably 3 to 8 parts by weight with respect to 100 parts by weight of the binder resin.
[0161]
(Sixth embodiment: toner powder physical properties)
By the pulverizing means of this embodiment, the content of 5 μm or less in the number distribution of the toner including the binder resin, the colorant, and the wax is 60% by number or more, and the content of 3.17 μm or less in the number distribution is 5 to 35% by number. It is possible to realize a particle size distribution structure containing toner particles having a particle size of 6.35 to 10.1 μm in an amount of 55% by volume or less without reducing the processing capacity.
[0162]
When the content of 5 μm or less is 60% by number or more, image quality improvement is remarkable. If the content of 3.17 μm or less in the number distribution is 5 to 35% by number, fine powder classification cut is hardly required, leading to an improvement in yield. When the toner particles having a particle size of 6.35 to 10.1 μm are 55% by volume or less, toner scattering during development can be reduced.
[0163]
Further, the specific surface area ratio Stt (SSt = (St / the ratio of the pulverized toner) to the specific surface area value St (St = 6 / (true specific gravity × volume average particle diameter)) equivalent to the true sphere converted from the volume average particle diameter. (Surface area value) can be 0.4 to 0.9, preferably 0.5 to 0.85, more preferably 0.55 to 0.8. This results in a decrease in properties and causes adverse effects such as scattering during transfer, etc. If it is less than 0.4, the shape becomes too irregular or the amount of finely pulverized powder is large.
[0164]
The volume average particle diameter of the toner can be 4 to 6.5 μm. It is preferable that the variation coefficient of the volume particle size distribution of the toner is 15 to 35% and the variation coefficient of the number particle size distribution is 20 to 40%. More preferably, the variation coefficient of the volume particle size distribution is 15 to 30%, the variation coefficient of the number particle size distribution is 20 to 35%, and more preferably, the variation coefficient of the volume particle size distribution is 15 to 25%, the number particle size. The coefficient of variation of the distribution is 20-30%.
[0165]
The coefficient of variation is the standard deviation of the toner particle size divided by the average particle size. This is based on the particle diameter measured using a Coulter counter (Coulter). The standard deviation is expressed as the square root of the value obtained by dividing the square of the difference from the average value of each measured value when (n-1) is measured when n particle systems are measured.
[0166]
In other words, the coefficient of variation refers to the degree of spread of the particle size distribution, and if the coefficient of variation of the volume particle size distribution is less than 15% or the coefficient of variation of the number particle size distribution is less than 20%, it is difficult to produce, This will increase costs. When the variation coefficient of the volume particle size distribution is larger than 35% or the variation coefficient of the number particle size distribution is larger than 40%, the toner is more cohesive when the particle size distribution becomes broader. It is difficult to collect residual toner in a defective and cleaner-less process.
[0167]
The fine powder in the toner affects toner fluidity, image quality, storage stability, filming on the photosensitive member, developing roller, and transfer member, aging characteristics, transferability, particularly multi-layer transfer in the tandem system. Furthermore, it affects the non-offset property, glossiness and translucency 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.
[0168]
When the amount of fine powder is excessive, wax that cannot be dispersed increases the exposure of the toner surface, and filming on the photosensitive member, developing roller, and transfer member occurs. Furthermore, fine powder tends to be offset because of its high adhesion to the heat roller. Further, in the tandem system, toner aggregation tends to be strong, and transfer failure of the second color is likely to occur during multilayer transfer. When the amount of fine powder is reduced, the image quality is degraded.
[0169]
The particle size distribution is measured by using a Coulter Counter TA-II type (Coulter Counter Co., Ltd.) and connecting an interface (manufactured by Nikkaki Co., Ltd.) for outputting the number distribution and volume distribution and a personal computer. The electrolyte solution is a surfactant (sodium lauryl sulfate) added to a concentration of 1%. About 2 mg of the toner to be measured is added to about 50 ml. The electrolyte solution in which the sample is suspended is dispersed for about 3 minutes with an ultrasonic disperser. And an aperture of 70 μm was used with a Coulter counter TA-II type. In the 70 μm aperture system, the particle size distribution measurement range is 1.26 μm to 50.8 μm, but the region less than 2.0 μm is not practical because the measurement accuracy and measurement reproducibility are low due to the influence of external noise and the like. Therefore, the measurement area was set to 2.0 μm to 50.8 μm.
[0170]
Further, the degree of compression is calculated from the static bulk density and the dynamic bulk density, which is one of the indicators of toner fluidity. The fluidity of the toner is affected by the particle size distribution of the toner, the toner particle shape, the external additive, and the type and amount of the wax. When the toner particle size distribution is narrow and the amount of fine powder is small, the toner surface is uneven and the shape is nearly spherical, the external additive is added in a large amount, or the external additive is small in particle size, the degree of compression is small. The fluidity of the toner becomes higher. The degree of compression is preferably 5 to 40%. More preferably, it is 10 to 30%. It is possible to achieve both oilless fixing and tandem multi-layer transfer. If it is less than 5%, the fixability is lowered, and the translucency is particularly likely to deteriorate. Toner scattering tends to increase from the developing roller. Transferability larger than 40% is lowered, and tandem system is lost and transfer failure occurs.
[0171]
(Embodiment 7: kneading method)
The added wax can be finely dispersed by kneading with a high shearing force or a high compression shearing force. A high dispersion treatment can be achieved by treating the kneading conditions of the roll temperature setting, temperature gradient, rotation speed and load current, the softening point of the binder resin, and the glass transition point under optimum conditions. High shearing force refers to the kneading force that acts on the toner material such as binder resin by rotating the rollers facing each other in a narrow gap at high speed, and has a rotational speed difference from the force generated when sandwiched between narrow gaps. Shearing force received from a rotating roll. It has a kneading force that cannot be exhibited by conventional twin screw extruders. As a result, the high molecular weight component of the binder resin can be lowered.
[0172]
Specifically, it has two opposing rolls that rotate in different directions and can be heated or cooled, and the temperature difference between the roll temperature of one roll (RL1) and the roll temperature of the other roll (RL2). The roll (RL1) and the roll (RL2) are rotated at different peripheral speeds and kneaded between the two rolls. Furthermore, one of the rolls (RL1) has a temperature difference between the first half and the second half.
[0173]
By carrying out the rotation ratio of the two rolls within a range of 1.1 times to 2.5 times, an appropriate shearing force is generated at the time of kneading, and the dispersibility of the internal additives such as the molecular cutting of the binder resin and the colorant. And the fixability and developability are improved. In this configuration, the rotation ratio of the roll on the side of heating and melting and winding the toner is increased. When it is 1.1 times or less, an appropriate shearing force is not generated, dispersibility is not improved, and translucency is deteriorated. On the other hand, if it is 2.5 times or more, productivity is drastically reduced, dispersibility is not improved, and developability is deteriorated.
[0174]
Further, by kneading under such conditions that the ratio of the load current values applied to the two rolls is in the range of 1.25 to 10, an appropriate shearing force is applied and the dispersibility of the internal additive is improved. . If it is smaller than this range, the dispersibility is not improved, and the translucency is deteriorated. Productivity also decreases. On the other hand, if it is larger than this range, the load applied to the roller becomes too large and the ultra-high molecular weight component becomes too low in molecular weight, so that the non-offset property is lowered and offset occurs.
[0175]
FIG. 1 is a schematic perspective view of the toner melt-kneading process, FIG. 2 is a plan view, FIG. 3 is a front view, and FIG. 4 is a side view. 601 is a toner raw material supply unit, 602 is a roll (RL1), 603 is a roll (RL2), 604 is a molten film of toner wound on the roll (RL1), and 602-1 is a front half of the roll (RL1). (Upstream part in the raw material conveyance direction), 602-2 is the latter half part of the roll (RL2) (downstream part in the raw material conveyance direction), and 605 is a heat medium for heating the first half part 602-1 of the roll (RL1). 606, a heat medium outlet for heating the first half 602-1 of the roll (RL1), 607, a medium inlet for heating or cooling the latter half 602-2 of the roll (RL1), 608 Is a medium outlet for heating or cooling the latter half portion 602-2 of the roll (RL1), 609 is a medium inlet for heating or cooling the roll (RL2) 603, and 610 is for heating the roll (RL2) 603 The outlet of the cooled medium, 611 depth spiral grooves of the roll surface is about 2 to 10 mm, is 612 a toner reservoir is formed between rolls. The spiral groove 611 is preferable for smoothly conveying the material from the right end of the raw material input portion to the left end of the discharge portion when the toner is kneaded.
[0176]
The toner raw material is dropped from the opening 614 to the vicinity of the end on the roll (RL1) 602-1 side as indicated by an arrow 615 while being transferred from the fixed amount feeder to the raw material supply feeder 613. The length of the opening of the supply feeder is represented by 616. This length is preferably 1/2 to 4 times the roll radius. If it is short, the amount of the material to be dropped will drop rapidly from the gap between the two rollers before the material to be melted. If the length is too long, the raw material is separated during conveyance with the raw material feeder, and uniform dispersion cannot be obtained.
[0177]
Further, the drop position is dropped to a point in the range of 20 ° to 80 ° from the point at which the two rolls (RL1) 602 are closest to each other as shown by the arrows in FIG. If the angle is smaller than 20 °, the amount of falling from the gap between the two rolls increases rapidly. When falling at 80 ° or more, the toner powder rises more and contaminates the surrounding area. The cover 617 is installed so as to cover an area wider than the opening length 616. In FIG. 3, the illustration of the cover is omitted.
[0178]
The toner raw material falls from the opening 614 while being transmitted through the supply feeder 613 from the fixed amount feeder 601. The dropped toner material is dropped near the end of the roll (RL1) 602-1 side. Then, the resin melts due to the heat of 602-1 and the compressive shear force between the roll (RL2) 603 and winds around the front half 602-1 of the roll (RL1). The state extends to the end of the second half 602-2 of the roll (RL1) and is heated or cooled at a lower temperature than the first half 602-1 of the roll (RL1). Is peeled off as a toner soul. During the above process, the roll 603 is cooled to room temperature or lower. The clearance between the roll (RL1) 602 and the roll (RL2) 603 is 0.1 to 0.9 mm. In this example, the raw material input was 10 kg / h, the rolls (RL1) and (RL2) had a diameter of 140 mm and a length of 800 mm.
[0179]
(Embodiment 8: Grinding)
The toner according to this embodiment can be pulverized with a small particle diameter, and in order to sharpen the distribution on the coarse powder side. And a cylindrical fixed body that is fitted on the outer side of the rotating body with a gap of 0.5 mm to 40 mm, shares the central axis with the rotating body, and has a concavo-convex surface, and a pulverized toner. The powder is pulverized to a predetermined particle size distribution by a pulverizer having a supply port and a discharge port for discharging the pulverized toner pulverized product. At this time, before the pulverized toner object flows from the supply port, a means for reducing the aggregation of the pulverized toner object is added, and the pulverized toner object flows from the supply port and is pulverized to a predetermined particle size distribution.
[0180]
As a means for alleviating the aggregation of the toner pulverized product, an evaporating medium such as water vapor, ethanol, iso-propyl alcohol, n-butyl, etc. The object is to remove the electric charge of the powder with alcohol, sec-butyl alcohol, iso-butyl alcohol or the like. This is a method of spraying and mixing or adhering the toner to be pulverized product in a mist state and allowing it to flow from the pulverization supply port.
[0181]
Further, before the pulverized toner object is fed from the supply port, a vibration means is added to the pulverized toner object to be supplied, and examples of the vibration means include ultrasonic vibration and vibration vibration. Before the pulverized toner object passes through the pipe and flows from the pulverization part supply port, the piping part is provided with a vibration device, and the pulverized toner substance flows from the supply port while being dispersed.
[0182]
In addition, there is a method in which an inorganic fine powder is supplied to the pulverized toner to be mixed with the pulverized toner before being pulverized from the supply port before being pulverized from the supply port. The above-mentioned materials are suitable as the inorganic fine powder. The inorganic fine powder adheres to the toner surface in an electrostatically attached state without being fixed to the toner base. Less than about half of the input is put in the bug filter. The supply amount of the inorganic fine powder is preferably about 0.1 to 5 wt% of the supply amount of the pulverized toner.
[0183]
By setting the gap between the convex part of the rotating body and the convex part of the fixed body to 0.5 to 40 mm, preferably 0.5 to 10 mm, more preferably 0.5 to 6 mm, the pulverization efficiency and the spheroidizing effect are further improved. Can be increased. If the diameter is smaller than 0.5 mm, contact between the particles, the rotating body, and the fixed body is remarkably increased, so that frictional heat is significantly generated, and toner fusion occurs at the tip portion. If it is larger than 40 mm, a high-speed air current cannot be vigorously generated, and sufficient pulverizability cannot be obtained.
[0184]
When this method is used, since the spheroidizing treatment can be performed simultaneously with the pulverization, there is a great merit that the manufacturing process can be shortened. According to this method, the toner has a finely rounded particle shape and is spheroidized, so that the fluidity is dramatically improved.
[0185]
If the fluidity of the toner is low, unevenness occurs in the solid image area, the frictional chargeability decreases, the reverse polarity toner increases, the toner strongly adheres to the non-image area of the photoconductor, and cannot be removed. As a result, the image is deteriorated and the transfer efficiency is lowered. Increasing the amount of the external additive silica to increase the fluidity of the toner tends to make the triboelectric charge uniform, reduce background fogging, increase the image density, and eliminate unevenness in the solid black image area. However, there are problems such as filming of silica and toner on the photoconductor and adhesion of white spots on solid black image portions of silica aggregates.
[0186]
Therefore, high fluidity is obtained with a small amount of silica added, the generation of floating silica is suppressed, the white point of silica on the solid black image area, the silica on the intermediate transfer member and the photosensitive member, and toner filming. Occurrence is suppressed. Further, the occurrence of unevenness in the solid black image portion seen with low-fluidity toner can be suppressed, uniform transferability can be obtained, and the occurrence of reverse polarity toner can be suppressed low, which is a factor for improving the transfer efficiency.
[0187]
Furthermore, at the time of transfer, particularly at high temperature and high humidity, where toner such as characters and lines is concentrated, even if transferred with a predetermined pressing force, the toner does not easily aggregate due to the high fluidity of the toner, A clear image without voids can be obtained.
[0188]
An embodiment of the toner pulverizing apparatus of this embodiment shown in FIG. 5 will be described.
[0189]
The to-be-ground toner 503 obtained by roughly pulverizing the kneaded material with a mesh diameter of about 1 to 5 mm is supplied from a constant supply unit 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 introduced from the inlet 504, and rotates at a high speed and has a rotator 501 having a concavo-convex portion 506 on the surface. With the flow of the high-speed airflow generated between the rotating body and the stationary body that are carried at high speed and are rotated at high speed, the raw material particles are spheroidized while being crushed by a powerful collision. The spherical particles 510 exit from the outlet 505 and are sent to the coarse powder classifier 513, and the coarse particles are sent again to the inlet 504 by the air 511. The product is sent to a cyclone 515 and collected in a collection container 520. 512 is a thermometer, 514 is a bag filter, 516 is an air flow meter, and 517 is a blower.
[0190]
519 is a vibrator vibration device, and 518 is an inorganic fine powder supply device. When separated by coarse powder classification and supplied again to the pulverizing section, it is preferable to supply the inorganic fine powder from behind. As a result, the inorganic fine powder is uniformly mixed when colliding with the pulverized product. An evaporable solvent can be supplied instead of the inorganic fine powder. In this example, grinding condition (1) peripheral speed of rotating body: 130 m / s, gap between rotating body and fixed body: 1.5 mm, supply amount of pulverized toner: 5 kg / h, supply amount of inorganic fine powder : 0.03 kg / h, cooling air temperature: 0 ° C., discharge part temperature: 45 ° C., grinding condition (2) peripheral speed of rotating body: 120 m / s, gap between rotating body and fixed body: 1 mm, ground toner Feed rate: 5 kg / h, feed rate of inorganic fine powder: 0.02 kg / h, cooling air temperature: 0 ° C., discharge part temperature: 40 ° C.
[0191]
(Embodiment 9: Two-component development, carrier)
In the development process of this embodiment, the resistance of the resin coated on the magnetite and ferrite particles is 1 × 10⁹~ 1x10¹⁴It is preferably used as a two-component development by mixing with a carrier having a particle size of 30 to 80 μm.
[0192]
An AC bias is applied between the photoconductor and the developing roller together with a DC bias.
[0193]
The frequency at that time is 1 to 10 kHz, the AC bias is 1.0 to 2.5 kV (pp), and the peripheral speed ratio between the photoconductor and the developing roller is 1: 1.2 to 1: 2. It is preferable.
[0194]
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 photoreceptor and the developing roller is 1: 1.5 to 1: 1. .8.
[0195]
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.
[0196]
With this development process configuration and the use of the toner of this embodiment, the dots can be faithfully reproduced and the development γ characteristics can be simulated. Both high-quality images and oilless fixability can be achieved. Further, even a high-resistance carrier can prevent charge-up under low humidity, and a high image density can be obtained even in continuous use. This is a toner that can exhibit high chargeability. By combining the carrier structure and AC bias, the adhesion to the carrier can be reduced, image density can be maintained, fog can be reduced, and dots can be reproduced faithfully. .
[0197]
If the frequency is smaller than 1 kHz, dot reproducibility is deteriorated and halftone reproducibility is deteriorated. When the frequency is higher than 10 kHz, the development region cannot be followed and the effect does not appear. In this frequency range, in the two-component development using a high resistance carrier, it works to reciprocate between the carrier and the toner rather than between the developing roller and the photoreceptor, and has the effect of slightly releasing the toner from the carrier. Good reproducibility and halftone reproducibility are achieved, and a high image density can be obtained.
[0198]
When the AC bias is smaller than 1.0 kV (pp), the effect of suppressing charge-up cannot be obtained, and when the AC bias is larger than 2.5 kV (pp), the fog increases. If the peripheral speed ratio between the photoconductor and the developing roller is smaller than 1: 1.2 (the developing roller becomes slow), it is difficult to obtain image density. When the peripheral speed ratio between the photosensitive member and the developing roller is larger than 1: 2 (the developing roller speed increases), the toner scattering increases.
[0199]
The carrier used for two-component development is prepared by providing a resin coating layer on the ferrite particle surface. Ferrite is Fe₂O_ThreeNiO, CuO, CoO, MgO, ZnO, MnCO_Three, BaCO_Three, SrCO_ThreeAre used as raw materials. The ferrite particles are prepared by a wet method or a dry method, but a dry method is preferable. In the dry method, the raw materials are mixed, temporarily fired, pulverized in a ball mill or the like in water, and polyvinyl alcohol, an antifoaming agent, and a dispersant are added as a binder to form a granulating thriller. The chiller is granulated while being heated and dried with a spray dryer, and is granulated, followed by firing. The main firing is performed at 900 to 1400 ° C. for 10 to 30 hours, and then pulverized and classified to obtain ferrite particles.
[0200]
A known method such as a spray method or a dipping method is used for the coating layer. The coating amount is 0.1 to 2 wt% of the carrier particle weight. As the resin used for the resin coating layer, a fluorine resin or a silicone resin is used. As carbon black to be contained in the resin coating layer, carbon black of various production methods is used, but oil furnace carbon acetylene black is preferable. The average particle size of the carrier is preferably 30 to 70 μm. When the average particle size of the carrier is less than 30 μm, the carrier is easily developed on the photoconductor, and when the average particle size of the carrier is larger than 70 μm, the toner holding power of the carrier is weakened, and thus toner scattering occurs.
[0201]
(Embodiment 10: one-component development)
In the development process of this embodiment, an elastic blade such as rubber or metal is brought into contact with an elastic or rigid developing roller with a constant pressure, and a thin layer of toner is formed and developed with contact or non-contact with the photoreceptor. It can be suitably used as a one-component development method. As a one-component development method, a sponge-based supply roller made of urethane resin and a development roller made of silicon resin or urethane resin are brought into contact with each other with a certain amount of biting, and toner is supplied from the supply roller to the development roller, and then on the development roller. A thin layer of toner is formed by contacting an elastic rubber or metal stainless steel doctor blade, or rotating a metallic roller against the developing roller against the developing roller (in the same direction), and contacting it with the photoreceptor. Alternatively, a developing method for forming a toner image by applying direct current or alternating current in a non-contact manner is preferably used.
[0202]
At this time, the frequency of the AC bias is 0.5 to 10 kHz, the AC bias is 0.3 to 1.2 kV (pp), and the peripheral speed ratio between the photoconductor and the developing roller is 1: 1.2 to 1. : 1.8 makes it possible to reproduce the dots faithfully, achieve good development γ characteristics, and realize a high-quality image. As a result, low fog and high image density can be obtained. The frequency is 0.5 to 5 kHz, the AC bias is 0.3 to 1.0 kV (pp), and the peripheral speed ratio between the photosensitive member and the developing roller is 1: 1.2 to 1: 1.5. More preferably, the frequency is 0.5 to 2 kHz, the AC bias is 0.5 to 0.9 kV (pp), and the peripheral speed ratio between the photoreceptor and the developing roller is 1: 1.2 to 1: 1.4.
[0203]
At this time, if the frequency is smaller than 0.5 kHz, dot reproducibility deteriorates and halftone reproducibility deteriorates. When the frequency is higher than 10 kHz, the development region cannot be followed and the effect does not appear. When the AC bias is smaller than 0.3 kV (pp), the solid followability maintaining effect cannot be obtained, and when the AC bias is larger than 1.2 kV (pp), the fog increases. If the peripheral speed ratio between the photoconductor and the developing roller is smaller than 1: 1.2 (the developing roller becomes slow), it is difficult to obtain image density. When the peripheral speed ratio between the photosensitive member and the developing roller is larger than 1: 1.8 (the developing roller speed is increased), toner scattering increases.
[0204]
The supply roller and the development roller are rotated in the same direction, and the peripheral speed of the development roller and the supply roller is increased by 1: 1 to 0.8: 0.2. The developing roller is 9.8 to 9.8 × 10 × 10 on the surface of the photoreceptor.²The electrostatic latent image on the photosensitive member is developed by pressing with the pressure of (N). The elastic blade is 5-5x10²A toner layer is formed by pressing on the developing roller with the pressure of (N).
[0205]
Further, a sponge-like supply roller made of urethane resin or the like is used as a developing roller in order to control the toner conveying amount on the developing roller when the amount of toner supplied from the toner reservoir is conveyed onto the developing roller. In contrast, a constant bite amount of 0.1 to 1 mm is used so as to contact the developing roller.
[0206]
A sponge-like supply roller made of urethane resin or the like is brought into contact with the developing roller in order to control the toner conveying amount on the developing roller when the amount of toner supplied from the toner reservoir is conveyed onto the developing roller to a constant amount. The structure which comprises is taken. This is an effective means for restricting the toner transport amount to a constant amount.
[0207]
However, with the conventional toner, in this developing configuration, when used for a long time, scratches on the developing roller and image defects in which vertical stripes are generated on the image due to adhesion of foreign matter to the blade are likely to occur. In particular, in order to improve the color fixing property, it occurs more remarkably in the use of a low softening binder resin or a toner to which a low melting point release agent is added.
[0208]
In addition, when the toner is transported on the developing roller during long-term continuous use, or when a solid black image is taken, a solid follow-up defect in which the density of the latter half of the image is partially reduced is likely to occur. When the charge amount of the toner on the developing roller was measured by a suction method, it was found that the charge amount was greatly reduced. Further pursuing, the charge amount of the toner in the supply roller portion is greatly increased. That is, the decrease in the image density is not the decrease in the charge amount of the toner, but in the supply roller portion before being supplied to the developing roller. This is because the charging capacity has been increased and the supply capability from the supply roller to the developing roller has been reduced. Therefore, it is necessary to have a configuration capable of ensuring image density while preventing toner scattering. Although it is also effective to increase the charging ability of the toner by increasing the pressure contact force of the doctor blade, the toner is likely to be fused, and the developing roller is damaged.
[0209]
Accordingly, it has been found that the toner configuration of the present embodiment can prevent the occurrence of vertical stripes on the developing roller, poor solid followability, and toner fusion without sacrificing the fixing characteristics.
[0210]
This enables uniform dispersion in the resin, stabilizes the charge distribution, suppresses overcharging of the toner on the supply roller, stabilizes the fluidity, and improves the followability of the solid image. Uniform dispersion can maintain the fluidity of the toner, and the toner can be smoothly transported on the developing roller, and the transport state can be constantly stabilized. In particular, the effect is great for stabilizing the conveyance state under high humidity. At this time, it is preferable that the charge amount of the toner on the developing roller by the suction type Faraday cage method is | 5 | to | 45 | μC / g. If it is | 5 | μC / g or less, toner scattering increases. If it is | 45 | μC / g or more, it is difficult to obtain an image density.
[0211]
In the toner charge amount measurement by the suction type Faraday cage method, the toner on the developing roller is sucked while rotating, and the sucked toner is collected on a filter to obtain its weight W (g). Further, the voltage V (V) induced in the capacitor is measured for the amount of charge when the charged toner moves during suction, and Q (μC / g) = C (F) × V (V) / W (g) The charge amount is calculated from
[0212]
(Embodiment 11: Tandem color process)
In addition, in order to form a color image at high speed, this embodiment has a plurality of toner image forming stations including a photosensitive member, a charging unit, and a toner carrier, and develops an electrostatic latent image formed on the image carrier. A primary transfer process in which an imaged toner image is transferred to the transfer body by bringing an endless transfer body into contact with the image carrier is sequentially performed, and a multilayer transfer toner image is formed on the transfer body. In the transfer process configured to execute a secondary transfer process in which a multi-layer toner image formed and then formed on the transfer body is collectively transferred to a transfer medium such as paper or OHP, the first primary When the distance from the transfer position to the second primary transfer position is d1 (mm) and the peripheral speed of the photoreceptor is v (mm / s), the transfer position configuration is d1 / v ≦ 0.65. For example, the first color yellow tona After the primary transfer, the time until the next magenta toner of the second color is primary transferred is extremely short, and there is little charge relaxation of the transfer body or charge relaxation of the transferred toner, and magenta on the yellow toner. When the toner is transferred, the magenta toner is repelled by the charge action of the yellow toner, causing problems such as a decrease in transfer efficiency and a lack of characters during transfer. Further, during the primary transfer of the cyan toner of the third color, the cyan toner scatters, transfer failure, and transfer loss occur remarkably when transferred onto the previous yellow and magenta toners. Furthermore, during repeated use, toner of a specific particle size is selectively developed, and if the fluidity of each toner particle differs greatly, the chance of frictional charging differs, resulting in variation in charge amount and further deterioration in transferability. Will be invited.
[0213]
Further, when the distance from the primary transfer position to the secondary transfer position of the fourth color of the last black toner is d2 (mm) and the peripheral speed of the photosensitive member is v (mm / s), d2 / v ≦ 0.75. In the transfer position configuration, the image is disturbed due to the repulsion caused by the mutual charge of the toner when the secondary transfer is collectively performed on the copy paper.
[0214]
Therefore, by adopting the toner configuration of this embodiment, the internal additive such as wax in the resin is uniformly dispersed, the charge distribution is stabilized, and the toner is not overcharged on the supply roller, and the fluidity fluctuation is suppressed. Therefore, it is possible to prevent a decrease in transfer efficiency and character dropout during transfer without sacrificing fixing characteristics.
[0215]
(Embodiment 12: Cleanerless process)
Further, in this embodiment, an electrophotography having a basic structure of a cleanerless process in which the following charging, exposure, and development processes are performed without having a cleaning process step of recovering toner remaining on the photoreceptor after the transfer process by cleaning. It is preferably used for an apparatus.
[0216]
By using the toner of this embodiment, toner aggregation can be suppressed, overcharging can be prevented, charging stability can be stabilized, and high transfer efficiency can be obtained. Further, the improvement in uniform dispersibility in the resin, good chargeability, and the releasability of the material make it possible to recover the toner remaining in the non-image area during development. For this reason, there is no development memory in which the image pattern in front of the non-image portion remains.
[0217]
(Embodiment 13: Oilless color fixing)
In this embodiment, it is suitably used for an electrophotographic apparatus having a fixing process in which a belt-type fixing medium is used as means for fixing toner. As the belt, a heat resistant belt such as a nickel electroformed belt or a polyimide belt having heat resistance and deformability is used. In order to improve releasability, silicone rubber, fluororubber, or fluororesin is used as the surface layer. Up to now, a release oil has been applied to these fixing belts to prevent offset. It is no longer necessary to apply release oil with toner having releasability without using oil. However, if the release oil is not applied, it is easy to be charged, and when an unfixed toner image comes close to the belt, toner jump may occur due to the influence of charging. It tends to occur especially at low temperatures and low humidity. Also, when the toner is added with a certain high molecular weight component to prevent high temperature offset and has a certain amount of elastic element, the paper with a thin vertical line pattern of the toner is separated from the belt with a large curvature at the leading edge. There may be a tip offset that is carried by the belt. Compared to the conventional rigid fixing roller, the elastic belt type has a problem in that the life is reduced due to scratches due to oillessness.
[0218]
Therefore, by using the toner of this embodiment, it is possible to prevent the occurrence of offset without using oil and to obtain high color translucency. Further, the toner can be prevented from being overcharged, and the toner can be prevented from flying due to the charging action with the belt. Further, it can be prevented by the molecular weight distribution and slipperiness effect of the offset toner that the tip part is brought to the belt when being separated from the belt.
[0219]
Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to this.
[0220]
Table 1 shows the characteristics of the binder resin used in the examples. As the resin, a polyester resin mainly composed of bisphenol A propyl oxide adduct, terephthalic acid, trimellitic acid, succinic acid and fumaric acid was used, and a resin whose thermal characteristics were changed depending on the blending ratio and polymerization conditions was used.
[0221]
[Table 1]

[0222]
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 of the weight average molecular weight Mwf to the number average molecular weight Mnf, Mwf / Mnf, and Wzf is The ratio Mzf / Mnf, AV of the Z-average molecular weight Mzf and the number-average molecular weight Mnf of the binder resin indicates the resin acid value.
[0223]
(Table 2) (Table 3) (Table 4) show the waxes used in this example and their physical properties. Mnr is the number average molecular weight of the wax, Mwr is the weight average molecular weight of the wax, and Mzr is the Z average molecular weight of the wax. Tw (° C.) represents the melting point by DSC method, Ct (%) represents the volume increase rate (%) at the melting point + 10 ° C., and Ck (wt%) represents the heating loss of 220 ° C.
[0224]
[Table 2]

[0225]
[Table 3]

[0226]
[Table 4]

[0227]
Table 5 shows the pigments used in this example.
[0228]
[Table 5]

[0229]
(Table 6) shows the charge control agents used in this Example and their physical property values.
[0230]
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. Etc. 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~ R^FourAs the benzene ring and alkali metal X, lithium, sodium, potassium and the like can be mentioned, and potassium is preferred.
[0231]
[Table 6]

[0232]
Table 7 shows the external additives used in this example. The amount of charge was measured by the blow-off method of frictional charging with an uncoated 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 100 minutes by longitudinal rotation.^-1After stirring for 30 minutes at a speed of 0.3g, 0.3g was collected and nitrogen gas 1.96x10^Four(Pa) was blown for 1 minute.
[0233]
For positive chargeability, the 5-minute value after stirring for 5 minutes is preferably +100 to +800 μC / g, and the 30-minute value after stirring for 30 minutes is preferably +50 to +400 μC / g. Silica having a charge amount at 30 minutes of 40% or more of the charge amount at 5 minutes is preferable. If the rate of decrease is large, the change in charge amount during long-term continuous use is large, and a constant image cannot be maintained.
[0234]
For negative chargeability, the 5-minute value is preferably −100 to −800 μC / g, and the 30-minute value is preferably −50 to −600 μC / g. Highly charged silica can function with a small amount of addition.
[0235]
[Table 7]

[0236]
The kneading conditions in this example are shown in (Table 8). Trj1 (° C.) is the heating temperature of the first half of the roll (RL1), Trk1 (° C.) is the heating temperature of the second half of the roll (RL1), Tr2 (° C.) is the heating temperature of the roll (RL2), and Rw1 is the roll (RL1) , Rw2 represents the rotation speed of the roll (RL2), the load current value during rotation of the roll (RL1) as Dr1, and the load current value of the roll (RL2) as Dr2. The raw material input amount was 15 kg / h, the rolls (RL1) and (RL2) had a diameter of 140 mm and a length of 800 mm.
[0237]
[Table 8]

[0238]
Table 9 and Table 10 show the grinding conditions in this example.
[0239]
Inorganic fine powder supplied before pulverization, its supply amount, vibrator vibration application, and solvent spraying are applied.
[0240]
[Table 9]

[0241]
[Table 10]

[0242]
Table 11 and Table 12 show the toner material composition and physical property values used in this example.
[0243]
[Table 11]

[0244]
[Table 12]

[0245]
In the figure, Ss is a specific surface area value of the pulverized toner, St is a value represented by St = 6 / (true specific gravity of the toner × volume average particle diameter), and SSt is St as Ss (the pulverized toner) Divided by the specific surface area).
[0246]
PCM30 for kneading is a conventional twin screw extruder, kneading temperature 110 ° C. rotation speed 200 min^-1, And processed at a supply rate of 5 kg / h.
[0247]
The ratio of the pigment, charge control agent, and wax is shown in parentheses in the ratio (part by weight) to 100 parts by weight of the binder resin. The external additive indicates a blending amount (parts by weight) with respect to 100 parts by weight of the toner base. External addition process is FM20B, stirring blade Z0S0 type, rotation speed 2000 min^-1The treatment time was 5 min and the input amount was 1 kg.
[0248]
Table 13 and Table 14 show the molecular weight characteristics of the toner after the kneading treatment in this example. The toner was a magenta toner TM1 to TM7 toner for comparative evaluation. Similar results are obtained with yellow, cyan, and black toners. Mnv is the number average molecular weight of the toner, Mwv is the weight average molecular weight of the toner, Wmv is the ratio of the weight average molecular weight Mwv of the toner to the number average molecular weight Mnv, Mwv / Mnv, and Wzv is the ratio of the Z average molecular weight Mzv of the toner to the number average molecular weight Mnv. Mzv / Mnv is shown.
[0249]
ML is a molecular weight value showing a molecular weight maximum peak on the low molecular weight side in the molecular weight distribution, MH is a molecular weight value showing a molecular weight maximum peak on the high molecular weight side, Sm is Hb / Ha, SK1 is M10 / M90, and SK2 is (M10-M90). / M90 is shown.
[0250]
[Table 13]

[0251]
[Table 14]

[0252]
6 to 23 show molecular weight distribution characteristics.
[0253]
FIGS. 6 and 7 are molecular weight distribution characteristics of the binder resin PES-1 and the toner TM-1, respectively. FIGS. 8 and 9 are molecular weight distribution characteristics of the binder resin PES-2 and the toner TM-2, respectively. 11 shows the molecular weight distribution characteristics of the binder resin PES-3 and the toner TM-3, FIGS. 12 and 13 show the molecular weight distribution characteristics of the binder resin PES-4 and the toner TM-4, respectively, and FIGS. The molecular weight distribution characteristics of the binder resin PES-5 and the toner TM-5, FIGS. 16 and 17 are the molecular weight distribution characteristics of the binder resin PES-6 and the toner TM-6, respectively, and FIGS. 18 and 19 are the binder resin pes- 7 shows the molecular weight distribution characteristics of Toner tm-7. Indicates.
[0254]
In the binder resin PES-1, 3 × 10^FourThe above high molecular weight components are present in an area ratio of 5% or more with respect to the entire binder resin molecular weight distribution. 3 × 10^Five~ 9x10⁶The high molecular weight component is 1% or more by area ratio with respect to the entire binder resin molecular weight distribution. Similarly, PES-2, 3, 4, 5, 6 are also 3 × 10^FourThe above high molecular weight components are present in an area ratio of 5% or more with respect to the entire binder resin molecular weight distribution. 3 × 10^Five~ 9x10⁶The high molecular weight component is 1% or more by area ratio with respect to the entire binder resin molecular weight distribution.
[0255]
It can be seen that the toner is molecularly cut by kneading and appears as a peak or shoulder on the polymer component side. That is, the component that inhibits the translucency disappears due to the cutting, and a steep inclination appears on the polymer side, which is a factor that maintains the offset resistance without inhibiting the translucency. For toner TM-1, 3 × 10^FiveThe amount of the above high molecular weight component is 5% or less in terms of area with respect to the entire toner molecular weight distribution, and is 1 × 10⁶The above high molecular weight components are hardly contained. Similarly, TM-2, 3, 4, 5, 6 are also 3 × 10.^FiveThe amount of the above high molecular weight component is 5% or less in terms of area with respect to the entire toner molecular weight distribution, and is 1 × 10⁶The above high molecular weight components are hardly contained.
[0256]
20 and 21 show examples of molecular weight distribution characteristics. FIG. 20 schematically shows M10 and M90 having characteristics that form a steep molecular weight peak on the polymer component side. The height of the maximum peak of the molecular weight distribution is 100%. FIG. 21 schematically shows M10 and M90 of the molecular weight distribution characteristic of the toner TM-4. It appears as a shoulder shape on the polymer component side, and the height of the apex of the shoulder of this shoulder portion is taken as a reference of 100%. This is because the high molecular weight component of the binder resin PES3 was molecularly cut by kneading and appeared as a shoulder on the high molecular component side.
[0257]
When the peak height of the distribution on the polymer side is 100%, a molecular weight curve in a region larger than the molecular weight value corresponding to the maximum peak or shoulder, that is, a region where the slope of the molecular weight distribution curve in this region is negative, In other words, in the region on the right side of the distribution curve, when the molecular weight distribution maximum peak or shoulder height is 100%, the molecular weight corresponding to 90% of the molecular weight maximum peak or shoulder height is M90, the molecular weight maximum peak or shoulder. The molecular weight corresponding to 10% of the height is M10. Here, the value of M10 / M90 (the slope of the molecular weight distribution curve) can quantify the state of molecular cleavage of the ultrahigh molecular weight component. When the value of M10 / M90 is small, the slope of the molecular weight distribution curve is steep, and the component that inhibits the translucency is eliminated by cutting and has high translucency. Furthermore, the peak appearing on the polymer side contributes to the offset resistance.
[0258]
FIG. 22 shows the molecular weight distribution characteristic of the wax WA-1, and FIG. 23 shows the molecular weight distribution characteristic of the wax WA-9.
[0259]
(Example)
FIG. 24 is a cross-sectional view showing a configuration of an image forming apparatus for forming a full color image used in this embodiment. In FIG. 24, the outer casing of the color electrophotographic printer is omitted. Printer internal inspection and maintenance such as when the transfer belt unit 2 in the printer is attached / detached or when a paper jam occurs, etc. is performed by tilting and opening the front plate to largely release the inside of the printer. The attaching / detaching operation of the transfer belt unit 17 is designed to be parallel to the rotation axis generating line direction of the photosensitive member.
[0260]
The transfer belt unit 17 includes a transfer belt 12, a first color (yellow) transfer roller 10Y made of an elastic body, a second color (magenta) transfer roller 10M, a third color (cyan) transfer roller 10C, and a fourth color (black). Transfer roller 10K, drive roller 11 made of aluminum roller, second transfer roller 14 made of elastic body, second transfer driven roller 13, belt cleaner blade 16 for cleaning the toner image remaining on the transfer belt 12, and opposed to the cleaner blade A roller 15 is provided at a position to be used.
[0261]
At this time, the distance from the first color (Y) transfer position to the second color (M) transfer position is 42 mm (the second color (M) transfer position to the third color (C) transfer position, the third color (C) The fourth color (K) transfer position is the same distance from the transfer position), and the peripheral speed of the photoconductor is 100 mm / s.
[0262]
The transfer belt 12 is used by kneading a conductive filler in an insulating polycarbonate resin and forming a film with an extruder. In the present example, a film obtained by adding 5 parts by weight of conductive carbon (for example, ketjen black) to 95 parts by weight of polycarbonate resin (for example, Iupilon Z300, manufactured by Mitsubishi Gas Chemical) as the insulating resin was used. Also, the surface is coated with a fluororesin, the thickness is about 120 μm, and the volume resistance is 10⁷-10¹²Ω · cm, surface resistance is 10⁷-10¹²Ω / □. This is also for improving dot reproducibility. This is for the purpose of effectively preventing loosening and charge accumulation due to long-term use of the transfer belt 12, and the reason that the surface is coated with fluororesin is that the toner filming on the surface of the transfer belt after long-term use. This is so that it can be effectively prevented. Volume resistance is 10⁷If it is smaller than Ω · cm, retransfer is likely to occur.¹²If it is larger than Ω · cm, the transfer efficiency deteriorates. The first transfer roller is a carbon conductive foamed urethane roller having an outer diameter of 14 mm, and the resistance value is 10²-10⁶Ω. During the first transfer operation, the first transfer roller 10 is pressed against the photoreceptor 1 with a pressing force of 1.0 to 9.8 (N) via the transfer belt 12, and the toner on the photoreceptor is transferred onto the belt. Is done. Resistance value is 10²If it is smaller than Ω, retransfer is likely to occur. 10⁶Larger transfer defects are more likely to occur than Ω. If it is less than 1.0 (N), transfer defects occur, and if it is greater than 9.8 (N), transfer character omission occurs.
[0263]
The second transfer roller 14 is a carbon conductive urethane foam roller having an outer diameter of 20 mm, and the resistance value is 10²-10⁶Ω. 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 or OHP. The transfer roller 13 is configured to be driven to rotate by the transfer belt 12. In the second transfer, the second transfer roller 14 and the counter 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 the recording material 19 such as paper. The Resistance value is 10²If it is smaller than Ω, retransfer is likely to occur. 10⁶Larger transfer defects are more likely to occur than Ω. If it is smaller than 5.0 (N), transfer failure occurs. If it is larger than 21.8 (N), the load increases and jitter tends to occur.
[0264]
In FIG. 24, 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. Has been.
[0265]
Each of the image forming units 18Y, 18M, 18C, and 18K is composed of the same constituent members except for the developer contained therein, so that the Y image forming unit 18Y will be described to simplify the description, and the units for other colors The description of is omitted.
[0266]
The image forming unit is configured as follows. 1 is a photoconductor, 3 is a pixel laser signal light, and 4 is a developing roller made of silicone rubber having a JIS-A hardness of 60 ° and having an outer diameter of 18 mm. To do. Reference numeral 6 denotes a supply roller made of conductive urethane sponge having an outer diameter of 14 mm, which supplies toner in the toner hopper to the developing roller. A metal blade 5 forms a toner layer on the developing roller. Although the power supply is omitted, a direct current of −230 V and an alternating voltage of 500 V (pp) and a frequency of 1 kHz are applied to the developing roller 4. A DC bias of −330 V is applied to the supply roller 6.
[0267]
A charging roller 2 having an outer diameter of 12 mm made of epichlorohydrin rubber is applied with a DC bias of −1 kV. The surface of the photoreceptor 1 is charged to -450V. 8 is a cleaner, 9 is a waste toner box, and 7 is toner.
[0268]
The paper is transported from below the transfer unit 17 so that the paper 19 is fed by a paper feed roller (not shown) to the nip portion where the transfer belt 12 and the second transfer roller 14 are pressed. A conveyance path is formed.
[0269]
The toner on the transfer belt 12 is transferred to the paper 19 by +1300 V 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. It is conveyed to the fixing unit and fixed there.
[0270]
FIG. 26 shows the fixing process. A belt 203 is placed 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 unit 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 provided on the outer surface.
[0271]
The belt has a structure in which 30 μm of Ni is used as a base, silicone rubber is 150 μm thereon, and further, PFA tube is 30 μm.
[0272]
The pressure roller 202 is pressed against the fixing roller 201 by a pressure spring 209. The recording material 211 having the toner 210 moves along the guide plate 212.
[0273]
A fixing roller 201 as a fixing member is a silicone rubber having a rubber hardness (JIS-A) of 20 degrees according to JIS standard on the surface of an aluminum hollow roller metal core 213 having a length of 250 mm, an outer diameter of 14 mm, and a thickness of 1 mm. An elastic layer 214 having a thickness of 3 mm is provided. A silicone rubber layer 215 is formed thereon with a thickness of 3 mm and has an outer diameter of about 20 mm. It receives a driving force from a driving motor (not shown) and rotates at 100 mm / s.
[0274]
The heat roller 204 is a hollow pipe having a thickness of 1 mm and an outer diameter of 20 mm. The surface temperature of the fixing roller was controlled to 170 ° using a thermistor.
[0275]
The pressure roller 202 as a pressure 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 metal 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 a nip width of 5.0 mm is formed between the pressure roller 202 and the fixing roller 201 by a spring-loaded spring 209 on one side 147N.
[0276]
The operation will be described below. In the full color mode, all of the first transfer rollers 10 of Y, M, C, and K are pushed up and press the photoreceptor 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 7 on the developing roller 4 in contact with the photoreceptor 1 and rotating in the opposite direction visualizes the electrostatic latent image formed on the photoreceptor 1.
[0277]
At this time, the image forming speed of the image forming unit 18Y (100 mm / s equal to the peripheral speed of the photoconductor) and the moving speed of the transfer belt 12 are 0.5 to 1.5% slower than the transfer belt speed. Is set to
[0278]
In the image forming process, the Y signal light 3Y is input to the image forming unit 18Y, and image formation with Y toner is performed. Simultaneously with the image formation, the first transfer roller 10Y causes the Y toner image to be transferred from the photoreceptor 1Y to the transfer belt 12. At this time, a DC voltage of +800 V was applied to the first transfer roller 10Y.
[0279]
With a time lag between the first color (Y) first transfer and the second color (M) first transfer, M signal light 3M is input to the image forming unit 18M, and image formation with M toner is performed. Simultaneously with the image formation, the M toner image is transferred from the photoreceptor 1M to the transfer belt 12 by the action of the first transfer roller 10M. At this time, the first color (Y) toner is formed and the M toner is transferred. Similarly, image formation with C (cyan) and K (black) toners is performed, and a YMCK toner image is formed on the transfer belt 12 by the action of the first transfer rollers 10C and 10B simultaneously with the image formation. This is a so-called tandem method.
[0280]
On the transfer belt 12, toner images of four colors are positioned and overlapped to form a color image. After the transfer of the last B toner image, the four color toner images are collectively transferred to the paper 19 fed from a paper feed cassette (not shown) at the same time by the action of the second transfer roller 14. At this time, the transfer roller 13 was grounded, and a DC voltage of +1.3 kV was applied to the second transfer roller 14. The toner image transferred to the paper was fixed by a pair of fixing rollers 201 and 202. The paper was then discharged out of the apparatus through a pair of discharge rollers (not shown). The residual transfer toner remaining on the intermediate transfer belt 12 was cleaned by the action of the cleaning blade 16 to prepare for the next image formation.
[0281]
FIG. 25 shows a tandem system in which the paper 19 is transported onto the paper transport belt 17 without primary transfer to the belt, and the toner on the OPC is directly transferred.
[0282]
Table 15 shows the results of image output using the electrophotographic apparatus shown in FIG. In Table 16, the state of transfer failure at the character portion in a full-color image in which three colors of toner are superimposed, and the paper wrapping property around the fixing belt during fixing were evaluated.
[0283]
[Table 15]

[0284]
[Table 16]

[0285]
When the image forming apparatus shown in FIG. 25 is used to produce an image using the toner manufactured as described above, there are no solid lines, no scattered toner, no missing characters, and so on. An image with an extremely high resolution and high image quality that reproduced an image line of / mm was obtained, and an image with a high density of 1.3 or more was obtained. In addition, the ground cover of the non-image area did not occur. Furthermore, even in the long-term durability test of 10,000 sheets of A4 paper, both the fluidity and the image density showed little change and stable characteristics. In addition, the uniformity when the entire solid image was taken at the time of development was also good. There is no development memory. Even during continuous use, no abnormal image of the vertical muscles occurred. Also, in the transfer, the void is at a level that causes no practical problem, and the transfer efficiency is about 98%. Further, the filming of the toner on the photosensitive member and the transfer belt was at a level where there was no practical problem. There was no defective cleaning of the transfer belt. Also, there is almost no toner disturbance or toner skipping during fixing. Further, even in the cleaner process in which the remaining toner at the time of transfer is recovered by development without using the cleaning blade 8, the recovery can be performed smoothly, and the history of the previous image does not remain. In addition, in the full-color image in which the three colors overlap, no transfer failure occurred, and no paper wrapping around the fixing belt occurred during fixing. Similar results were obtained with the image forming apparatus shown in FIG.
[0286]
However, toners of tm7, ty7, tc7, and tb7 caused filming and transfer failure of the photosensitive member, scattering of characters during transfer, and a lot of fogging. Filming of the transfer belt and poor cleaning occurred. When the entire solid image was taken at the time of development, the second half was blurred. During continuous use, the wax was fused to the developing blade, and an abnormal image of vertical stripes was generated. When the three-color image was output, the paper was wound around the fixing belt. Toner skip occurred during fixing.
[0287]
Next (Table 17), the amount of adhesion to OHP paper is 1.2 g / cm.²The above solid image was subjected to a non-offset property test with a fixing device using a belt at which the process speed was 100 mm / s and no oil was applied. No OHP jam occurred at the fixing nip. In the full-solid image of plain paper, the offset did not occur at all up to the 122,000th sheet. Even if the oil is not applied with a silicon or fluorine-based fixing belt, the surface deterioration of the belt is not observed.
[0288]
The transmittance and the offset property at high temperature were evaluated. The process speed was 100 mm / s, the fixing temperature was 180 ° C., and the transmittance was measured with a spectrophotometer U-3200 (Hitachi) to measure the transmittance of 700 nm light. The results of fixing property, offset resistance and storage stability are shown.
[0289]
[Table 17]

[0290]
The OHP translucency was 80% or more, and the non-offset temperature range was 40 to 60 K. The fixing roller using no oil showed good fixing properties. Also, almost no aggregation was observed in the storage stability at 60 ° C. for 5 hours.
[0291]
However, the toner of tm7 was hardened in the storage stability test, and the non-offset temperature range was narrow.
[0292]
【The invention's effect】
As described above, in the pulverizing means using the rotating body, by providing a means for relaxing aggregation, small particle size pulverization is possible, and the distribution on the coarse powder side can be sharpened. Furthermore, in order to realize transferability and oil-less fixing in the tandem transfer process, even with toners containing specific binder resins, charge control agents, and waxes, high image quality due to the small particle size and transfer during transfer. It is possible to prevent omission and scattering and to obtain high transfer efficiency. Filming of the photosensitive member and the transfer member can be prevented even during long-term use under high humidity. The cleaning property of the transfer body can be improved. Even in a cleaner-less process that does not use a cleaning blade or the like, the transfer residual toner can be collected smoothly, and the history of the previous image can be prevented from remaining. Furthermore, without applying oil, it is possible to realize oilless fixing that prevents offset while maintaining high OHP translucency.
[Brief description of the drawings]
FIG. 1 is a schematic perspective view of a toner melt-kneading process used in an embodiment of the present invention.
FIG. 2 is a plan view of a toner melt-kneading process used in an embodiment of the present invention.
FIG. 3 is a front view of a toner melt kneading process used in an embodiment of the present invention.
FIG. 4 is a cross-sectional view of a toner melt kneading process used in an embodiment of the present invention.
FIG. 5 is a configuration diagram of toner pulverization processing used in an embodiment of the present invention.
FIG. 6 is a graph showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 7 is a graph showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 8 is a graph showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 9 is a graph showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 10 is a graph showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 11 is a graph showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 12 is a graph showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 13 is a graph showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 14 is a view showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 15 is a graph showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 16 is a view showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 17 is a graph showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 18 is a graph showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 19 is a graph showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 20 is a view showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 21 is a graph showing molecular weight distribution characteristics of a binder resin and a toner according to an embodiment of the present invention.
FIG. 22 is a graph showing molecular weight distribution characteristics of the wax of the example of the present invention.
FIG. 23 is a graph showing molecular weight distribution characteristics of the wax of the example of the present invention.
FIG. 24 is a cross-sectional view showing a configuration of an image forming apparatus used in an example of the present invention.
FIG. 25 is a cross-sectional view showing a configuration of an image forming apparatus used in an embodiment of the present invention.
FIG. 26 is a cross-sectional view showing a configuration of a fixing unit used in an embodiment of the present invention.
[Explanation of symbols]
1 Photoconductor
3 Laser signal light
4 Development 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 units
201 Fixing roller
202 Pressure roller
203 fixing belt
205 induction heater
206 Ferrite core
207 coil
602 roll (RL1)
603 roll (RL2)
604 Molten film of toner wound on roll (RL1)
605 Heat medium inlet
606 Heat medium outlet

Claims (24)

At least a binder resin, a colorant and after the toner pulverized material is discharged from the dispensing device containing the wax, prior to flow into the pre-Symbol the toner ground material into the feed throat of the crushing means, the object toner inorganic fine powder Supplying and mixing the pulverized product;
Flowing the toner ground material mixed with the inorganic fine powder from the supply port;
The supply port through which the pulverized toner is introduced, a cylindrical rotating body having irregularities on the surface and rotating at a high speed, and a gap of 0.5 mm to 40 mm are fitted outside the rotating body. Pulverizing by a pulverizing means having at least a cylindrical fixed body that shares a central axis with the rotating body and has irregularities on the surface;
And a step of discharging the pulverized toner pulverized product from a discharge port. After the pulverized toner containing at least the binder resin, the colorant, and the wax is discharged from the quantitative supply device, before the pulverized toner to be fed into the supply port of the pulverizing means, the evaporable medium is added to the toner to be crushed. Supplying and mixing or adhering to the pulverized product;
A step of flowing a pre-Symbol the toner ground material from the supply port,
The supply port through which the pulverized toner is introduced, a cylindrical rotating body having irregularities on the surface and rotating at a high speed, and a gap of 0.5 mm to 40 mm are fitted outside the rotating body. Pulverizing by a pulverizing means having at least a cylindrical fixed body that shares a central axis with the rotating body and has irregularities on the surface;
And a step of discharging the pulverized toner pulverized product from a discharge port. In the number distribution of the toner produced by the pulverization treatment, the content of 5 μm or less is 60% by number or more, the content of 3.17 μm or less in the number distribution is 5 to 35% by number, 6.35 to 10.1 μm. And a specific surface area value St ( St = 6 / ( true specific gravity × volume average) equivalent to a true sphere converted from the volume average particle size. 3. The pulverization treatment is performed so that the specific surface area ratio SSt (SSt = (St / specific surface area value of pulverized toner)) with respect to the particle diameter )) is 0.4 to 0.9. the method for producing a toner. It said inorganic fine powder has an average particle size 8～40Nm, method for producing a toner according to claim 1 Symbol placement ignition loss comprises silica or titanium oxide fine powder is 0.5-10%. The inorganic fine powder, fatty esters, fatty amides, method for producing a toner according to claim 1 comprising any one or more of the surface-treated silica or titanium oxide fine powder of the fatty acid metal salt. The inorganic fine powder, method for producing a toner according to claim 1 comprising a silica or titanium oxide fine powder has been surface treated with silicone oil. The binder resin is a polyester resin having an acid value of 1 to 40 mgKOH / g, and the wax has a number average molecular weight of 100 to 5000 and a weight average molecular weight of 200 in a molecular weight distribution at least in gel permeation chromatography (GPC). -10,000, ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) is 1.01 to 8, ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02. 10, at least one molecular weight maximum peak in the region of molecular weight of ^{5 × 10 2 ~1 × 10 4} , an iodine value of 25 or less, according to claim 1 or 2, wherein a saponification value comprises an ester wax is 30 to 300 Toner production method. The binder resin is a polyester resin having an acid value of 1 to 40 mg KOH / g, and the wax is a long-chain alkyl alcohol having at least 5 to 100 carbon atoms, an unsaturated polycarboxylic acid or anhydride thereof, and a hydrocarbon wax. obtained by reaction with an acid value 5~80mgKOH / g, melting point 90 to 120 ° C., method for producing a toner according to claim 1 or 2, wherein including the wax penetration of 4 or less at 25 ° C.. The wax comprises one or more of hydroxystearic acid derivatives, glycerin fatty acid esters, glycol fatty acid esters, sorbitan fatty acid ester polyhydric alcohol fatty acid esters, meadowfoam oil derivatives, jojoba oil derivatives. Or a method for producing the toner according to 2 ; Among the waxes, an alkylene bis fatty acid amide system of saturated or monovalent unsaturated aliphatic amide having a melting point of 70 to 110 ° C. and having 16 to 24 carbon atoms, saturated or monovalent unsaturated fatty acid The toner production method according to claim 1, comprising one or more of the above. The molecular weight distribution in GPC of the toner has at least one molecular weight maximum peak in the region of molecular weight 2 × 10 ^{3 to} 3 × 10 ⁴ and at least one molecular weight maximum peak or shoulder in the region of molecular weight 5 × 10 ⁴ to 1 × 10 ^6. A molecular weight curve in a region larger than the molecular weight value corresponding to the maximum peak or shoulder of the molecular weight distribution existing in the region of molecular weight 5 × 10 ⁴ to 1 × 10 ⁶ , and the height of the maximum peak or shoulder in the molecular weight distribution When M1 is 1, the molecular weight corresponding to 90% of the molecular weight maximum peak or shoulder height is M90, and the molecular weight corresponding to 10% of the molecular weight maximum peak or shoulder height is M10, M10 / M90 is 3. The method for producing a toner according to claim 1, wherein the toner is 0.5-8 . The molecular weight distribution in GPC of the toner has at least one molecular weight maximum peak in the region of molecular weight 2 × 10 ^{3 to} 3 × 10 ⁴ and at least one molecular weight maximum peak or shoulder in the region of molecular weight 5 × 10 ⁴ to 1 × 10 ^6. The molecular weight distribution in a region larger than the molecular weight value corresponding to the maximum peak or shoulder of the molecular weight distribution existing in the region of molecular weight 5 × 10 ⁴ to 1 × 10 ⁶ , and the height of the maximum peak or shoulder of the molecular weight distribution Is M90, the molecular weight corresponding to 90% of the molecular weight maximum peak or shoulder height is M90, and the molecular weight corresponding to 10% of the molecular weight maximum peak or shoulder height is M10, (M10-M90 ) / M90 manufacturing method according to claim 1 or 2, wherein the toner is 0.1 to 7. At least an image carrier, a charging unit that forms an electrostatic latent image on the image carrier, and a developing unit that visualizes the electrostatic latent image formed on the image carrier with toner that has been crushed. A plurality of toner image forming stations, transfer means for sequentially transferring the visualized toner images to a transfer medium, or an endless transfer body in contact with the image carrier to transfer the transfer body A primary transfer unit that sequentially transfers the plurality of visualized toners sequentially, and a secondary transfer unit that collectively transfers the multilayer toner images formed on the transfer body onto a transfer medium. An image forming apparatus comprising transfer means,
  After the toner pulverized toner containing at least a binder resin, a colorant, and wax is discharged from the quantitative supply device, the toner is allowed to flow into the supply port of the pulverizing means and then the evaporable medium. Is supplied to the pulverized toner to be mixed or adhered, and then flows from the supply port.
  A cylindrical rotating body having irregularities on the surface and rotating at high speed, and a gap of 0.5 mm to 40 mm are fitted outside the rotating body, sharing the central axis with the rotating body, An image forming apparatus obtained by pulverizing by a pulverizing means having at least a cylindrical fixed body having irregularities. At least an image carrier, a charging unit that forms an electrostatic latent image on the image carrier, and a developing unit that visualizes the electrostatic latent image formed on the image carrier with toner that has been pulverized. A plurality of toner image forming stations, transfer means for sequentially transferring the visualized toner images to a transfer medium, or an endless transfer body in contact with the image carrier to transfer the transfer body And a secondary transfer unit that collectively transfers the multilayer toner images formed on the transfer body onto a transfer medium. An image forming apparatus comprising transfer means,
After the toner pulverized toner containing at least a binder resin, a colorant and wax is discharged from the quantitative supply device, before the toner pulverized material flows into the supply port of the pulverizing means, the inorganic fine powder is added. After being supplied to the pulverized toner to be mixed and then mixed, it flows from the supply port,
A cylindrical rotating body having irregularities on its surface and rotating at a high speed, and fitted on the outside of the rotating body with a gap of 0.5 mm to 40 mm, sharing the central axis with the rotating body, An image forming apparatus obtained by pulverizing by a pulverizing means having at least a cylindrical fixed body having irregularities. Toner having a particle size of 6.35 to 10.1 μm in which the content of 5 μm or less in the toner number distribution is 60% by number or more and the content of 3.17 μm or less in the number distribution is 5 to 35% by number. -The particle size distribution composition of particles contained at 55% by volume or less, and the specific surface area value St ( St = 6 / ( true specific gravity x volume average particle size )) equivalent to a true sphere converted from the volume average particle size . 15. The image forming apparatus according to claim 13, wherein the pulverization is performed so that the specific surface area ratio SSt (SSt = (St / specific surface area value of pulverized toner)) is 0.4 to 0.9 . The image forming apparatus according to claim 14, wherein the inorganic fine powder includes silica or titanium oxide fine powder having an average particle diameter of 8 to 40 nm and an ignition loss of 0.5 to 10 wt% . The inorganic fine powder, fatty acid esters, fatty acid amides, the image forming apparatus according to claim 1 4 Symbol mounting comprising any one or two or more surface-treated silica or titanium oxide fine powder of the fatty acid metal salt. The image forming apparatus according to claim 14 , wherein the inorganic fine powder includes silica or titanium oxide fine powder obtained by surface-treating silicone oil . The binder resin is a polyester resin having an acid value of 1 to 40 mgKOH / g, and the wax has a number average molecular weight of 100 to 5000 and a weight average molecular weight of 200 in a molecular weight distribution at least in gel permeation chromatography (GPC). -10,000, ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) is 1.01 to 8, ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02. 10, at least one molecular weight maximum peak in the region of molecular weight of ^{5 × 10 2 ~1 × 10 4} , an iodine value of 25 or less, according to claim 13 or 14, wherein a saponification value comprises an ester wax is 30 to 300 Image forming apparatus. The binder resin is a polyester resin having an acid value of 1 to 40 mg KOH / g, and the wax is a long-chain alkyl alcohol having at least 5 to 100 carbon atoms, an unsaturated polycarboxylic acid or anhydride thereof, and a hydrocarbon wax. The image forming apparatus according to claim 13 or 14 , comprising a wax obtained by the reaction with an acid value of 5 to 80 mg KOH / g, a melting point of 90 to 120 ° C, and a penetration at 25 ° C of 4 or less . The wax is a derivative of hydroxystearic acid, glycerol fatty acid esters, glycol fatty acid esters, claim 13 comprising a polyhydric alcohol fatty acid esters of sorbitan fatty acid esters, meadowfoam oil derivatives, one or more of jojoba oil derivative Or the image forming apparatus of 14 . The wax is a saturated or monovalent unsaturated aliphatic amide having a melting point of 70 to 110 ° C. and having 16 to 24 carbon atoms, or an alkylene bis fatty acid amide of a saturated or 1 to 2 unsaturated fatty acid. The image forming apparatus according to claim 13 , comprising one or more kinds . The molecular weight distribution in GPC of the toner has at least one molecular weight maximum peak in the region of molecular weight 2 × 10 ^{3 to} 3 × 10 ⁴ and at least one molecular weight maximum peak or shoulder in the region of molecular weight 5 × 10 ⁴ to 1 × 10 ^6. The molecular weight distribution in a region larger than the molecular weight value corresponding to the maximum peak or shoulder of the molecular weight distribution existing in the region of molecular weight 5 × 10 ⁴ to 1 × 10 ⁶ , and the height of the maximum peak or shoulder of the molecular weight distribution When M1 is 1, the molecular weight corresponding to 90% of the molecular weight maximum peak or shoulder height is M90, and the molecular weight corresponding to 10% of the molecular weight maximum peak or shoulder height is M10, M10 / M90 is The image forming apparatus according to claim 13 or 14, which is 0.5 to 8 . The molecular weight distribution in GPC of the toner has at least one molecular weight maximum peak in the region of molecular weight 2 × 10 ^{3 to} 3 × 10 ⁴ and at least one molecular weight maximum peak or shoulder in the region of molecular weight 5 × 10 ⁴ to 1 × 10 ^6. A molecular weight curve in a region larger than the molecular weight value corresponding to the maximum peak or shoulder of the molecular weight distribution existing in the region of molecular weight 5 × 10 ⁴ to 1 × 10 ⁶ , and the height of the maximum peak or shoulder in the molecular weight distribution Is M90, the molecular weight corresponding to 90% of the molecular weight maximum peak or shoulder height is M90, and the molecular weight corresponding to 10% of the molecular weight maximum peak or shoulder height is M10, (M10-M90 15. The image forming apparatus according to claim 13 , wherein / M90 is 0.1-7 .

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