JP4323884B2 - Toner and image forming method - Google Patents

Description

（式中、Ｒはエチレン基又はプロピレン基を示し、ｘ、ｙはそれぞれ１以上の整数であり、且つｘ＋ｙの平均値は２〜１０である。）
【００６０】
更に、結着樹脂としてポリエステルユニットとビニル系重合体ユニットを有しているハイブリッド樹脂を用いる場合、更に良好なワックス分散性と、低温定着性，耐オフセット性の向上が期待できる。本発明に用いられるハイブリッド樹脂とは、ビニル系重合体ユニットとポリエステルユニットが化学的に結合された樹脂を意味する。具体的には、ポリエステルユニットと（メタ）アクリル酸エステルの如きカルボン酸エステル基を有するモノマーを重合したビニル系重合体ユニットとがエステル交換反応によって形成されるものであり、好ましくはビニル系重合体を幹重合体、ポリエステルユニットを枝重合体としたグラフト共重合体（あるいはブロック共重合体）を形成するものである。
【００６１】
ここでポリエステルユニットとは少なくともポリオールとポリカルボン酸の縮重合物であるものを言う。また、ビニル系ユニットとは１種又は２種以上のビニル系モノマーが重合してなるものを言う。
【００６２】
ビニル系重合体を生成するためのビニル系モノマーとしては、次のようなものが挙げられる。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、α−メチルスチレン、ｐ−フェニルスチレン、ｐ−エチルスチレン、２，４−ジメチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−デシルスチレン、ｐ−ｎ−ドデシルスチレン、ｐ−メトキシスチレン、ｐ−クロルスチレン、３，４−ジクロルスチレン、ｍ−ニトロスチレン、ｏ−ニトロスチレン、ｐ−ニトロスチレンの如きスチレン誘導体；エチレン、プロピレン、ブチレン、イソブチレンの如き不飽和モノオレフィン類；ブタジエン、イソプレンの如き不飽和ポリエン類；塩化ビニル、塩化ビニリデン、臭化ビニル、フッ化ビニルの如きハロゲン化ビニル類；酢酸ビニル、プロピオン酸ビニル、ベンゾエ酸ビニルの如きビニルエステル類；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸ｎ−オクチル、メタクリル酸ドデシル、メタクリル酸２−エチルヘキシル、メタクリル酸ステアリル、メタクリル酸フェニル、メタクリル酸ジメチルアミノエチル、メタクリル酸ジエチルアミノエチルの如きα−メチレン脂肪族モノカルボン酸エステル類；アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸ｎ−オクチル、アクリル酸ドデシル、アクリル酸２−エチルヘキシル、アクリル酸ステアリル、アクリル酸２−クロルエチル、アクリル酸フェニルの如きアクリル酸エステル類；ビニルメチルエーテル、ビニルエチルエーテル、ビニルイソブチルエーテルの如きビニルエーテル類；ビニルメチルケトン、ビニルヘキシルケトン、メチルイソプロペニルケトンの如きビニルケトン類；Ｎ−ビニルピロール、Ｎ−ビニルカルバゾール、Ｎ−ビニルインドール、Ｎ−ビニルピロリドンの如きＮ−ビニル化合物；ビニルナフタリン類；アクリロニトリル、メタクリロニトリル、アクリルアミドの如きアクリル酸もしくはメタクリル酸誘導体等が挙げられる。
【００６３】
更に、マレイン酸、シトラコン酸、イタコン酸、アルケニルコハク酸、フマル酸、メサコン酸の如き不飽和二塩基酸；マレイン酸無水物、シトラコン酸無水物、イタコン酸無水物、アルケニルコハク酸無水物の如き不飽和二塩基酸無水物；マレイン酸メチルハーフエステル、マレイン酸エチルハーフエステル、マレイン酸ブチルハーフエステル、シトラコン酸メチルハーフエステル、シトラコン酸エチルハーフエステル、シトラコン酸ブチルハーフエステル、イタコン酸メチルハーフエステル、アルケニルコハク酸メチルハーフエステル、フマル酸メチルハーフエステル、メサコン酸メチルハーフエステルの如き不飽和二塩基酸のハーフエステル；ジメチルマレイン酸、ジメチルフマル酸の如き不飽和二塩基酸エステル；アクリル酸、メタクリル酸、クロトン酸、ケイヒ酸の如きα，β−不飽和酸；クロトン酸無水物、ケイヒ酸無水物の如きα，β−不飽和酸無水物、該α，β−不飽和酸と低級脂肪酸との無水物；アルケニルマロン酸、アルケニルグルタル酸、アルケニルアジピン酸、これらの酸無水物及びこれらのモノエステルの如きカルボキシル基を有するモノマーが挙げられる。
【００６４】
更に、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレートなどのアクリル酸又はメタクリル酸エステル類；４−（１−ヒドロキシ−１−メチルブチル）スチレン、４−（１−ヒドロキシ−１−メチルヘキシル）スチレンの如きヒドロキシ基を有するモノマーが挙げられる。
【００６５】
本発明のトナーにおいて、結着樹脂のビニル系重合体ユニットは、ビニル基を２個以上有する架橋剤で架橋された架橋構造を有していてもよいが、この場合に用いられる架橋剤は、芳香族ジビニル化合物として例えば、ジビニルベンゼン、ジビニルナフタレンが挙げられ；アルキル鎖で結ばれたジアクリレート化合物類として例えば、エチレングリコールジアクリレート、１，３−ブチレングリコールジアクリレート、１，４−ブタンジオールジアクリレート、１，５−ペンタンジオールジアクリレート、１，６ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられ；エーテル結合を含むアルキル鎖で結ばれたジアクリレート化合物類としては、例えば、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコール＃４００ジアクリレート、ポリエチレングリコール＃６００ジアクリレート、ジプロピレングリコールジアクリレート及び以上の化合物のアクリレートをメタアクリレートに代えたものが挙げられ；芳香族基及びエーテル結合を含む鎖で結ばれたジアクリレート化合物類として例えば、ポリオキシエチレン（２）−２，２−ビス（４−ヒドロキシフェニル）プロパンジアクリレート、ポリオキシエチレン（４）−２，２−ビス（４−ヒドロキシフェニル）プロパンジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられる。
【００６６】
多官能の架橋剤としては、ペンタエリスリトールトリアクリレート、トリメチロールエタントリアクリレート、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラアクリレート、オリゴエステルアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたもの；トリアリルシアヌレート、トリアリルトリメリテートが挙げられる。
【００６７】
本発明ではビニル系重合体成分及び／又はポリエステル樹脂成分中に、両樹脂成分と反応し得るモノマー成分を含むことが好ましい。ポリエステル樹脂成分を構成するモノマーのうちビニル系重合体と反応し得るものとしては、例えば、フタル酸、マレイン酸、シトラコン酸、イタコン酸の如き不飽和ジカルボン酸又はその無水物などが挙げられる。ビニル系重合体成分を構成するモノマーのうちポリエステル樹脂成分と反応し得るものとしては、カルボキシル基又はヒドロキシ基を有するものや、アクリル酸もしくはメタクリル酸エステル類が挙げられる。
【００６８】
ビニル系重合体とポリエステル樹脂の反応生成物を得る方法としては、先に挙げたビニル系重合体及びポリエステル樹脂のそれぞれと反応しうるモノマー成分を含むポリマーが存在しているところで、どちらか一方もしくは両方の樹脂の重合反応をさせることにより得る方法が好ましい。
【００６９】
本発明のビニル系重合体を製造する場合に用いられる重合開始剤としては、例えば、２，２'−アゾビスイソブチロニトリル、２，２'−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２'−アゾビス（−２，４−ジメチルバレロニトリル）、２，２'−アゾビス（−２メチルブチロニトリル）、ジメチル−２，２'−アゾビスイソブチレート、１，１'−アゾビス（１−シクロヘキサンカルボニトリル）、２−（カーバモイルアゾ）−イソブチロニトリル、２，２'−アゾビス（２，４，４−トリメチルペンタン）、２−フェニルアゾ−２，４−ジメチル−４−メトキシバレロニトリル、２，２'−アゾビス（２−メチル−プロパン）、メチルエチルケトンパーオキサイド、アセチルアセトンパーオキサイド、シクロヘキサノンパーオキサイドの如きケトンパーオキサイド類、２，２−ビス（ｔ−ブチルパーオキシ）ブタン、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、１，１，３，３−テトラメチルブチルハイドロパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルクミルパーオキサイド、ジ−クミルパーオキサイド、α，α'−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン、イソブチルパーオキサイド、オクタノイルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、３，５，５−トリメチルヘキサノイルパーオキサイド、ベンゾイルパーオキサイド、ｍ−トリオイルパーオキサイド、ジ−イソプロピルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ジ−ｎ−プロピルパーオキシジカーボネート、ジ−２−エトキシエチルパーオキシカーボネート、ジ−メトキシイソプロピルパーオキシジカーボネート、ジ（３−メチル−３−メトキシブチル）パーオキシカーボネート、アセチルシクロヘキシルスルホニルパーオキサイド、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシネオデカノエイト、ｔ−ブチルパーオキシ２−エチルヘキサノエイト、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシベンゾエイト、ｔ−ブチルパーオキシイソプロピルカーボネート、ジ−ｔ−ブチルパーオキシイソフタレート、ｔ−ブチルパーオキシアリルカーボネート、ｔ−アミルパーオキシ２−エチルヘキサノエート、ジ−ｔ−ブチルパーオキシヘキサハイドロテレフタレート，ジ−ｔ−ブチルパーオキシアゼレートが挙げられる。
【００７０】
本発明トナーに用いられるハイブリッド樹脂を調製できる製造方法としては、例えば、以下の（１）〜（６）に示す製造方法を挙げることができる。
【００７１】
（１）ビニル系重合体、ポリエステル樹脂及びハイブリッド樹脂をそれぞれ製造後にブレンドする方法であり、ブレンドは有機溶剤（例えば、キシレン）に溶解・膨潤した後に有機溶剤を留去して製造される。尚、ハイブリッド樹脂は、ビニル系重合体とポリエステル樹脂を別々に製造後、少量の有機溶剤に溶解・膨潤させ、エステル化触媒及びアルコールを添加し、加熱することによりエステル交換反応を行って合成されるエステル化合物を用いることができる。
【００７２】
（２）ビニル系重合体製造後に、これの存在下にポリエステルユニット及びハイブリッド樹脂を製造する方法である。ハイブリッド樹脂はビニル系重合体（必要に応じてビニル系モノマーも添加できる）とポリエステルモノマー（アルコール、カルボン酸）及び／又はポリエステルとの反応により製造される。この場合も適宜、有機溶剤を使用することができる。
【００７３】
（３）ポリエステル樹脂製造後に、これの存在下にビニル系重合体ユニット及びハイブリッド樹脂を製造する方法である。ハイブリッド樹脂はポリエステルユニット（必要に応じてポリエステルモノマーも添加できる）とビニル系モノマー及び／又はビニル系重合体ユニットとの反応により製造される。
【００７４】
（４）ビニル系重合体及びポリエステル製造後に、これらの重合体ユニット存在下にビニル系モノマー及び／又はポリエステルモノマー（アルコール、カルボン酸）を添加することによりハイブリッド樹脂が製造される。この場合も適宜、有機溶剤を使用することができる。
【００７５】
（５）ハイブリッド樹脂を製造後、ビニル系モノマー及び／又はポリエステルモノマー（アルコール、カルボン酸）を添加して付加重合及び／又は縮重合反応を行うことによりビニル系重合体ユニット及びポリエステルユニットが製造される。この場合、ハイブリッド樹脂は上記（２）〜（４）の製造方法により製造されるものを使用することもでき、必要に応じて公知の製造方法により製造されたものを使用することもできる。更に、適宜、有機溶剤を使用することができる。
【００７６】
（６）ビニル系モノマー及びポリエステルモノマー（アルコール、カルボン酸等）を混合して付加重合及び縮重合反応を連続して行うことによりビニル系重合体ユニット、ポリエステルユニット及びハイブリッド樹脂が製造される。更に、適宜、有機溶剤を使用することができる。
【００７７】
上記（１）〜（５）の製造方法において、ビニル系重合体ユニット及び／又はポリエステルユニットは複数の異なる分子量、架橋度を有する重合体ユニットを使用することができる。
【００７８】
なお、本発明のトナーに含有される結着樹脂は、上記ポリエステルとビニル系重合体との混合物、上記ハイブリッド樹脂とビニル系重合体との混合物、上記ポリエステル樹脂と上記ハイブリッド樹脂に加えてビニル系重合体の混合物を使用しても良い。
【００７９】
本発明のトナーに含有される着色剤として、黒色着色剤としては、カーボンブラック；磁性体；イエロー、マゼンタ、及びシアン着色剤を用いて黒色に調色したものが利用される。黒色着色剤として磁性体を用いる場合には、他の着色剤と異なり、樹脂１００質量部に対し５〜２００質量部を添加して用いられる。
【００８０】
磁性体としては、鉄、コバルト、ニッケル、銅、マグネシウム、マンガン、アルミニウム、ケイ素等の元素を含む金属酸化物等がある。中でも四三酸化鉄、γ−酸化鉄等、酸化鉄を主成分とするものが好ましい。また、トナーの帯電性のコントロールの観点から、ケイ素元素及びアルミニウム元素等、他の金属元素を含有していてもよい。前記磁性体は、窒素吸着法によるＢＥＴ比表面積が２〜３０ｍ²／ｇ、特に３〜２８ｍ²／ｇであることが好ましく、更にモース硬度が５〜７であることが好ましい。
【００８１】
磁性体の含有量は、トナーａを調製する場合、結着樹脂１００質量部に対し５〜２０質量部が好ましい。またトナーｂを調製する場合の磁性体の含有量は結着樹脂１００質量部に対し総量で３０〜２００質量部が好ましい。
【００８２】
マゼンタトナー用着色顔料としてはＣ．Ｉ．ピグメントレッド１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２１、２２、２３、３０、３１、３２、３７、３８、３９、４０、４１、４８、４９、５０、５１、５２、５３、５４、５５、５７、５８、６０、６３、６４、６８、８１、８３、８７、８８、８９、９０、１１２、１１４、１２２、１２３、１６３、２０２、２０６、２０７、２０９、２３８、Ｃ．Ｉ．ピグメントバイオレット１９；Ｃ．Ｉ．バットレッド１、２、１０、１３、１５、２３、２９、３５などが挙げられる。
【００８３】
着色剤には、上記顔料を単独で使用してもかまわないが、染料と顔料とを併用してその鮮明度を向上させた方がフルカラー画像の画質の点からより好ましい。
【００８４】
マゼンタトナー用染料としては、Ｃ．Ｉソルベントレッド１、３、８、２３、２４、２５、２７、３０、４９、８１、８２、８３、８４、１００、１０９、１２１；Ｃ．Ｉ．ディスパースレッド９；Ｃ．Ｉ．ソルベントバイオレット８、１３、１４、２１、２７；Ｃ．Ｉ．ディスパーバイオレット１の如き油溶染料、Ｃ．Ｉ．ベーシックレッド１、２、９、１２、１３、１４、１５、１７、１８、２２、２３、２４、２７、２９、３２、３４、３５、３６、３７、３８、３９、４０；Ｃ．Ｉ．ベーシックバイオレット１、３、７、１０、１４、１５、２１、２５、２６、２７、２８などの塩基性染料が挙げられる。
【００８５】
シアントナー用着色顔料としては、Ｃ．Ｉ．ピグメントブルー２、３、１５：３、１５：４、１６、１７；Ｃ．Ｉ．バットブルー６；Ｃ．Ｉ．アシッドブルー４５、及び下記式で示される構造を有するフタロシアニン骨格にフタルイミドメチル基を１〜５個置換した銅フタロシアニン顔料などが挙げられる。
【００８６】
【化２】

【００８７】
イエロー用着色顔料としては、Ｃ．Ｉ．ピグメントイエロー１、２、３、４、５、６、７、１０、１１、１２、１３、１４、１５、１６、１７、２３、６２、６５、７３、７４、８３、９３、９４、９５、９７、１０９、１１０、１１１、１２０、１２７、１２８、１２９、１４７、１５１、１５４、１５５、１６８、１７４、１７５、１７６、１８０、１８１、１８５；Ｃ．Ｉ．バットイエロー１、３、２０などが挙げられる。
【００８８】
イエロー用着色染料としては、Ｃ．Ｉ．ソルベントイエロー１６２等があり、顔料と染料を併用することも好ましい。
【００８９】
本発明における着色剤の含有量は、トナーａを調製する場合、結着樹脂１００質量部に対し０．１〜２．０質量部が好ましい。またトナーｂを調製する場合の着色剤の含有量は結着樹脂１００質量部に対し総量で２．５〜１５質量部が好ましい。
【００９０】
本発明のトナーは、更に荷電制御剤をトナー粒子内に添加されて有していても良い。本発明においてトナーに含有される荷電制御剤としては、公知のものが利用できるが、特に、無色でトナーの帯電スピードが速く且つ一定の帯電量を安定して維持できる芳香族カルボン酸の金属化合物が好ましい。
【００９１】
荷電制御剤のうちネガ系荷電制御剤としては、サリチル酸金属化合物、ナフトエ酸金属化合物、ダイカルボン酸金属化合物、スルホン酸又はカルボン酸を側鎖に持つ高分子型化合物、ホウ素化合物、尿素化合物、ケイ素化合物、カリックスアレーンが利用できる。ポジ系荷電制御剤としては、四級アンモニウム塩、該四級アンモニウム塩を側鎖に有する高分子型化合物、グアニジン化合物、イミダゾール化合物が利用できる。荷電制御剤は結着樹脂１００質量部に対し０．５〜１０質量部が好ましい。
【００９２】
本発明のトナーは、更に他の添加剤をトナー粒子に外添して有していてもよい。本発明においてトナー粒子に外添される添加剤としては、公知のものが利用できるが、特に、流動性向上剤が外添されていることが画質向上、高温環境下での保存性の点で好ましい。流動性向上剤としては、シリカ、酸化チタン、酸化アルミニウム等の無機微粉体が好ましい。該無機微粉体は、シラン化合物、シリコーンオイル又はそれらの混合物の如き疎水化剤で疎水化されていることが好ましい。
【００９３】
疎水化剤としては、シラン化合物、チタネートカップリング剤、アルミニウムカップリング剤、ジルコアルミネートカツプリング剤の如きカップリング剤が挙げられる。
【００９４】
具体的に例えばシラン化合物としては、下記一般式（２）で表されるものが好ましい。
【００９５】
【化３】
Ｒ_mＳｉＹ_n （２）
〔式中、Ｒはアルコキシ基を示し、ｍは１〜３の整数を示し、Ｙはアルキル基、ビニル基、フェニル基、メタアクリル基、アミノ基、エポキシ基、メルカプト基又はこれらの誘導体を示し、ｎは１〜３の整数を示す。〕
【００９６】
上記一般式（２）で表される化合物としては、例えば、ヘキサメチルジシラザン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−メタクリルオキシプロピルトリメトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、イソブチルトリメトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、トリメチルメトキシシラン、ヒドロキシプロピルトリメトキシシラン、フェニルトリメトキシシラン、ｎ−ヘキサデシルトリメトキシシラン、ｎ−オクタデシルトリメトキシシラン等を挙げることができる。
【００９７】
その処理量は、無機微粉体１００質量部に対して、好ましくは１〜６０質量部、より好ましくは３〜５０質量部である。
【００９８】
本発明で用いられるシラン化合物として特に好適なのは、下記一般式（３）で示されるアルキルアルコキシシランである。
【００９９】
【化４】
Ｃ_nＨ_2n+1−Ｓｉ−（ＯＣ_mＨ_2m+1）₃ （３）
〔式中、ｎは４〜１２の整数を示し、ｍは１〜３の整数を示す。〕
【０１００】
上記一般式（３）で表されるアルキルアルコキシシランにおいて、ｎが４より小さいと、処理は容易となるが疎水化度が低く、好ましくない。ｎが１２より大きいと、疎水性が十分になるが、酸化チタン微粒子同士の合一が多くなり、流動性付与能が低下しやすい。また、ｍが３より大きいと、アルキルアルコキシシランの反応性が低下して疎水化を良好に行いにくくなる。より好ましくはアルキルアルコキシシランはｎが４〜８であり、ｍが１〜２であるものである。
【０１０１】
アルキルアルコキシシランの処理量も、無機微粉体１００質量部に対して、好ましくは１〜６０質量部、より好ましくは３〜５０質量部である。
【０１０２】
疎水化処理は１種類の疎水化剤単独により行っても良いし、２種類以上を併用しても良い。例えば１種類の疎水化剤単独で疎水化処理を行っても良いし、２種類の疎水化剤で同時に、又は１種類の疎水化剤で疎水化処理を行った後、別の疎水化剤で更に疎水化処理を行っても良い。
【０１０３】
流動性向上剤は、トナー粒子１００質量部に対して０．０１〜５質量部添加することが好ましく、０．０５〜３質量部添加することがより好ましい。
【０１０４】
本発明のトナーは一成分現像方法にも、非磁性二成分現像方法にも好適に使用できるものである。
【０１０５】
本発明のトナーを二成分系現像剤に用いる場合は、トナーは磁性キャリアと混合して使用される。磁性キャリアとしては、例えば表面酸化又は未酸化の鉄、リチウム、カルシウム、マグネシウム、ニッケル、銅、亜鉛、コバルト、マンガン、クロム、希土類の如き金属粒子、それらの合金粒子、酸化物粒子及びフェライト等が使用できる。
【０１０６】
上記磁性キャリア粒子の表面を樹脂で被覆した被覆キャリアは、現像スリーブに交流バイアスを印加する現像法において特に好ましい。被覆方法としては、樹脂の如き被覆材を溶剤中に溶解又は懸濁させて調製した塗布液を磁性キャリアコア粒子表面に付着させる方法、磁性キャリアコア粒子と被覆材とを粉体で混合する方法等、従来公知の方法が適用できる。
【０１０７】
磁性キャリアコア粒子表面への被覆材料としては、シリコーン樹脂、ポリエステル樹脂、スチレン系樹脂、アクリル系樹脂、ポリアミド、ポリビニルブチラール、アミノアクリレート樹脂が挙げられる。これらは、単独或いは複数で用いる。上記被覆材料の処理量は、キャリアコア粒子に対し０．１〜３０質量％（好ましくは０．５〜２０質量％）が好ましい。これらキャリアの個数平均粒径は１０〜１００μｍ、好ましくは２０〜７０μｍを有することが好ましい。
【０１０８】
本発明のトナーと磁性キャリアとを混合して二成分系現像剤を調製する場合、その混合比率は現像剤中のトナー濃度として、２〜１５質量％、好ましくは４〜１３質量％にすると通常良好な結果が得られる。トナー濃度が２質量％未満では画像濃度が低下しやすく、１５質量％を超えるとカブリや機内飛散が発生しやすい。
【０１０９】
本発明においてトナー形状は優れた画像を形成するための重要な要素の１つである。トナーの円形度を上げることによって転写効率が向上するのは知られているが、本発明のトナーを用いて画像形成を行うと従来より多量のトナーが記録部材上に載せられるため、転写効率が悪いと画像のがさつき感が目立つようになることがある。また、トナーａとｂのように明度の異なるトナーを組み合わせて用いると、中間濃度域において、転写抜けが発生した場合、画像に濃度差によるムラが発生する危険性がある。本発明において好ましいトナー形状とは、円相当径３μｍ以上の粒子において、平均円形度が０．９４０〜０．９７０の範囲であり、好ましくは０．９４２〜０．９６５である。平均円形度が０．９４０未満であると転写性、特に転写効率に劣り、低濃度域において粒状感が顕著となり、がさつき感のある画像が得られることがある。逆に平均円形度が０．９７０より大きいと、形状が球形すぎるため、感光ドラムのクリーニング工程においてトナーがクリーニングブレードをすり抜けるなど、クリーニング不良に起因する画像弊害が出ることがある。更に、本発明のようにトナーを記録部材上に多量に載せて定着させる場合、定着装置通過時にトナーが記録部材上から転がり易くなるため、とくに濃トナーと淡トナーを組み合わせて用いるときには、がさつき感が目立ち易くなる傾向にある。
【０１１０】
次に、本発明のトナーを製造する手順について説明する。
【０１１１】
まず、トナー粒子を構成する少なくとも樹脂、着色剤などの材料（内添剤）を所定量秤量して配合し、混合する（これを「原料混合工程」という）。原料を混合する際に用いられる混合装置の一例としては、ダブルコン・ミキサー、Ｖ型ミキサー、ドラム型ミキサー、スーパーミキサー、ヘンシェルミキサー、ナウターミキサー等がある。
【０１１２】
次に、上記混合されたトナー原料を溶融混練して樹脂類を溶融し、その中に着色剤等を分散させることにより、着色樹脂組成物を得る（これを「溶融混練工程」という）。この溶融混練工程では、例えば、加圧ニーダー、バンバリィミキサー等のバッチ式練り機や、連続式の練り機を用いることができる。近年では、連続生産できる等の優位性から、１軸又は２軸押出機が主流となっており、例えば、神戸製鋼所社製ＫＴＫ型２軸押出機、東芝機械社製ＴＥＭ型２軸押出機、ケイ・シー・ケイ社製２軸押出機、ブス社製コ・ニーダー等が一般的に使用される。
【０１１３】
更に、上記溶融混練工程よって得られた着色樹脂組成物は、溶融混練後、２本ロール等で圧延され、水冷等で冷却する冷却工程を経て冷却される。
【０１１４】
次いで、得られた着色樹脂組成物の冷却物は、一般的には粉砕工程において所望の粒径にまで粉砕される。粉砕工程では、まず、クラッシャー、ハンマーミル、フェザーミル等で粗粉砕され、更に、川崎重工業社製のクリプトロンシステム、日清エンジニアリング社製のスーパーローター等で粉砕される。その後、必要に応じて慣性分級方式のエルボージェット（日鉄鉱業社製）、遠心力分級方式のターボプレックス（ホソカワミクロン社製）等の分級機等の篩分機を用いて分級し、重量平均粒子径が３〜１１μｍの分級品を得る。
【０１１５】
必要に応じて、表面改質工程で表面改質（即ち球形化処理）を行い、分級品としてもよい。このような表面改質を行う装置としては、例えば奈良機械製作所製のハイブリタイゼーションシステム、ホソカワミクロン社製のメカノフージョンシステム等が挙げられる。
【０１１６】
また、必要に応じて風力式篩のハイボルター（新東京機械社製）等の篩分機を用いても良い。更に、外添剤を外添処理する方法としては、分級されたトナーと公知の各種外添剤を所定量配合し、ヘンシェルミキサー、スーパーミキサー等の粉体にせん断力を与える高速撹拌機を外添機として用いて、撹拌・混合することによりトナーを得ることができる。
【０１１７】
図１に本発明で好ましく用いられる表面改質装置の一例の構成を示す模式的断面図であり、図２は図１の表面改質装置の模式的平面図である。
【０１１８】
図１示す表面改質装置では、ケーシング１５と、冷却水或いは不凍液を通水できるジャケット（図示しない）と、所定の粒径よりも大きい粒子と所定の粒径以下の微粒子とを分ける分級手段である分級ロータ１と、粒子に機械的な衝撃を与えて前記粒子の表面を処理する表面処理手段である分散ロータ６と、分散ロータ６の外周に対して所定の間隔を有して周設されるライナ４と、分級ロータ１で分けられた粒子のうちの所定の粒径より大きい粒子を分散ロータ６に案内する案内手段であるガイドリング９と、分級ロータ１で分けられた粒子のうちの所定の粒径以下の微粒子を装置の外に排出する排出手段である微粉回収用排出口２と、分散ロータ６で表面を処理された粒子を分級ロータ１に送る粒子循環手段である冷風導入口５と、被処理粒子をケーシング１５内に導入するための原料供給口３と、表面を処理された粒子をケーシング１５内から排出するための開閉自在な粉体排出口７及び排出弁８とを有する。
【０１１９】
分級ロータ１は円筒状のロータであり、ケーシング１５内の一端面側に設けられている。微粉回収用排出口２は、分級ロータ１の内側の粒子を排出するように、ケーシング１５の一端部に設けられている。原料供給口３は、ケーシング１５の周面の中央部に設けられている。冷風導入口５は、ケーシング１５の周面の他端面側に設けられている。粉体排出口７は、ケーシング１５の周面で原料供給口３に対向する位置に設けられている。排出弁８は、粉体排出口７を自在に開閉する弁である。
【０１２０】
冷風導入口５と、原料供給口３及び粉体排出口７との間には、分散ロータ６及びライナ４が設けられている。ライナ４は、ケーシング１５の内周面に沿って周設されている。分散ロータ６は、図２に示すように、円盤と、この円盤の周縁に、円盤の法線に沿って配置される複数の角型ディスク１０とを有する。分散ロータ６は、ケーシング１５の他端面側に設けられており、かつライナ４と角型ディスク１０との間に所定の間隔が形成される位置に設けられている。ケーシング１５の中央部にはガイドリング９が設けられている。ガイドリング９は、円筒体であり、分級ロータ１の外周面の一部に被さる位置から、かつ分級ロータ６の近傍まで延出するように設けられている。ガイドリング９は、ケーシング１５内に、ガイドリング９の外周面とケーシング１５の内周面とに挟まれた空間である第一の空間１１と、ガイドリング９の内側の空間である第二の空間１２とを形成する。
【０１２１】
なお、分散ロータ６は、角型ディスク１０の代わりに円柱状のピンを有していても良い。ライナ４は、本実施の形態では角型ディスク１０に対向する表面に多数の溝が設けられているものとするが、表面に溝を有さないものであっても良い。また、分級ロータ１の設置方向は、図１に示したように縦型でも構わないし、横型でも構わない。また、分級ロータ１の個数は、図１に示したように単体でも構わないし、複数でも構わない。
【０１２２】
以上のように構成してなる表面改質装置では、排出弁８を閉とした状態で原料供給口３から微粉砕品を一定量投入すると、投入された微粉砕品は、まずブロワー（図示しない）により吸引され、分級ロータ１で分級される。その際、分級された所定粒径以下の微粉は、分級ロータ１の周面を通過して分級ロータ１の内側に導かれ、装置外へ連続的に排出除去される。所定粒径以上の粗粉は、遠心力によりガイドリング９の内周（第二の空間１２）に沿いながら分散ロータ６により発生する循環流にのり、角型ディスク１０とライナ４との隙間（以下、「表面改質ゾーン」とも言う）へ導かれる。表面改質ゾーンに導かれた粉体は、分散ロータ６とライナ４との間で機械式衝撃力を受け、表面改質処理される。表面改質された表面改質粒子は、機内を通過する冷風にのって、ガイドリング９の外周（第一の空間１１）に沿いながら分級ロータ１に運ばれ、分級ロータ１により、更に微粉は機外へ排出され、粗粉は、循環流にのり、再度第二の空間１２に戻され、表面改質ゾーンで繰り返し表面改質作用を受ける。このように、図１の表面改質装置では、分級ロータ１による粒子の分級と、分散ロータ６による粒子の表面の処理とが繰り返される。一定時間経過後、排出弁８を開とし、排出口７より表面改質粒子を回収する。
【０１２３】
このような装置では、熱による離型剤のしみ出しはほとんど無く、前述した公知の機械的衝撃力を与えるシステムに比べ、新しい表面が出ることによるトナー粒子の表面への離型剤のしみ出しも生じ難く、トナー粒子の球形化と離型剤のしみ出しの調整を容易に行うことができ、非常に好ましい。
【０１２４】
本発明のトナーは、回転可能な定着ローラと、該定着ローラに押圧されて当接し、前記定着ローラの回転に伴ってニップ部を形成しながら回転する定着ベルトと、前記ニップ部を加熱する加熱手段とを有し、前記定着ローラ及び定着ベルトの回転によって前記記録部材を前記ニップ部で狭持搬送することにより、前記記録部材上にトナー像を定着する定着手段を備える画像形成方法に好適に用いられる。図３は本発明の画像形成方法において最も好ましい定着手段としての定着装置の概略構成図である。
【０１２５】
図３において、５０は定着ローラであり、Ｓｉゴムなどの弾性層を有する。特にＳｉゴムなどの弾性層が必ず必要というわけではないが、弾性層があったほうが性能上好ましい。５２は複数の支持ローラ５３〜５５に懸架され、定着ローラ５０に当接して定着ニップ部Ｎを形成するベルトであり、ポリイミド樹脂ベルト上に１ｍｍ程度のＳｉゴムなどの弾性部材を積層し、最外層にＰＴＦＥ、ＰＦＡ等の離型層を積層したものである。本例の定着装置において、定着ローラ５０は弾性層を有するφ５０ｍｍのヒートローラであり、厚さ５ｍｍのアルミ芯金の上に２ｍｍのシリコンゴムを積層し、最外層に、約５０μｍのＰＦＡチューブを積層したもので、矢印の時計方向に所定の周速度で回転駆動される。５１はこの定着ローラ５０の内空に挿入設置された、加熱手段としての８００Ｗのハロゲンランプである。定着ローラ５０はこのハロゲンランプ５１の通電発熱で内側より加熱され、表面温度が不図示の温度検知素子により検知され、その検知温度が不図示の温調回路に入力され、温度検知素子により検知される定着ローラ表面温度が所定の定着温度に維持されるようにハロゲンランプ５１に対する通電がｏｎ−ｏｆｆ制御されて温度制御される。
【０１２６】
また、定着ベルト５２はφ５０ｍｍのベルトで基材の１００μｍのポリイミドベルト上に１ｍｍのシリコンゴムを積層し、最外層に約５０μのＰＴＦＥ樹脂を積層したもので、第１〜第３の三本の支持ローラ５３〜５５に懸架され、定着ローラ５０と挟圧されて定着ニップ部Ｎを形成している。第１の支持ローラ５３は定着ベルト５２を挟んで定着ローラ５０に対して所定の押圧力で圧接している。このため、ベルト５２が定着ローラ５０に押圧されて当接する状態となっている。第２の支持ローラ５４は定着ニップ部Ｎよりも記録部材搬送方向上流側において定着ローラ５０から離れて位置している。
【０１２７】
第３の支持ローラ５５は第１と第２の支持ローラ５３、５４の間に位置してテンションローラとして機能している。定着ベルト５２は定着ローラ５０の回転に順方向に定着ローラ５０の回転周速度と同じ周速度で回転駆動される。この定着ローラ５２の駆動は、定着ローラ５０の回転に従動回転させることにより行っても良い。
【０１２８】
未定着画像を担持した記録部材Ｐは上記定着装置９の定着ローラ５０と定着ベルト５２の定着ニップ部Ｎに導入され、外定着ニップ部Ｎで挟持搬送されることで、未定着画像が記録部材面に定着ローラ５０の熱と定着ニップ部Ｎの加圧力で加熱定着される。
【０１２９】
このような構成の定着装置では、定着ニップ部の線圧を大きくすることが困難である。しかしながら、本発明のトナーは上述したように、（ペレット状に加圧成型した試料の状態で）温度１２０℃において４．０×１０³Ｐａの圧力を加えた際の変形量（Ｒ₂₀₀）が４５〜６５％であり、温度１２０℃において１．０×１０⁴Ｐａの圧力を加えた際の変形量（Ｒ₅₀₀）が６５〜８５％であるため、比較的小さな線圧でも記録部材上にトナーがしっかり固着し、トナーの飛び散りによるがさつき感が生じない。なお、上記変形量（Ｒ₂₀₀）が６５％、変形量（Ｒ₅₀₀）が８５％をそれぞれ超えると、定着時に記録部材上のトナーが潰れ過ぎて画像のがさつき感が発生する。
【０１３０】
更にこのような構成の定着装置では、ニップ幅を大きく取ることができるのが特徴である。複数の濃色トナーと淡色トナーとを同時に使用し、より多くのトナーを記録部材上に載せた場合、定着ニップ部の線圧を大きくして定着させようとすると、定着ニップ部通過時にトナーが飛び散り、良質な画像が得られない可能性がある。従って、このような広いニップ幅でトナーをしっかり加熱溶融させるのが非常に好ましい。なお、本発明においては定着ニップ幅が１０ｍｍ以上であるが、より好ましくは１５ｍｍ以上であると、定着性の面で非常に効果がある。
【０１３１】
図４は、本発明のトナーを用いた本発明の画像形成方法を好適に実現できる画像形成装置の一例を示す模式的断面図である。以下、本発明の淡色トナーａと濃色トナーｂとを同時に用いる画像形成方法及びそれを好適に実現できる画像形成装置の例を、図４を参照しながら具体的に説明する。図４において、Ａはプリンタ部、Ｂはこのプリンタ部Ａの上に搭載した画像読み取り部（イメージスキャナ）である。画像読み取り部Ｂにおいて、２０は固定の原稿台ガラスであり、この原稿台ガラス２０の上面に原稿Ｇを複写すべき面を下側にして載置し、その上に不図示の原稿板を被せてセットする。２１は原稿照射用ランプ２１ａ、短焦点レンズアレイ２１ｂ、ＣＣＤセンサー２１ｃ等を配置した画像読み取りユニットである。
【０１３２】
この画像読み取りユニット２１は、不図示のコピーボタンが押されることで、原稿台ガラス２０の下側においてこの原稿台ガラス２０の左辺側のホームポジションから右辺側にガラス下面に沿って往動駆動され、所定の往復終点に達すると復動駆動されて始めのホームポジションに戻される。
【０１３３】
画像読み取りユニット２１の往動駆動過程において、原稿台ガラス２０上の載置セット原稿Ｇの下向き画像面が原稿照射用ランプ２１ａにより左辺側から右辺側にかけて順次照明走査され、その照明走査光の原稿面反射光が短焦点レンズアレイ２１ｂによってＣＣＤセンサー２１ｃに結像入射する。
【０１３４】
ＣＣＤセンサー２１ｃは、不図示の受光部、転送部、出力部より構成されており、受光部において光信号が電荷信号に変えられて、転送部でクロックパルスに同期して順次出力部へ転送され、出力部において電荷信号を電圧信号に変換し、増幅、低インピーダンス化して出力する。このようにして得られたアナログ信号を周知の画像処理によりデジタル信号に変換してプリンタ部Ａに出力する。即ち、画像読み取り部Ｂにより原稿Ｇの画像情報が時系列電気デジタル画素信号（画像信号）として光電読み取りされる。
【０１３５】
なお、この画像形成装置にはパターンジェネレーター（不図示）がのせてあり、階調パターンが登録されていて、パルス幅変調器（不図示）に直接信号を渡すことができるようになっている。
【０１３６】
露光装置３は、画像読み取りユニット２１から入力される画像信号に基づいて感光体１表面をレーザ走査露光Ｌして、静電潜像を形成する。
【０１３７】
図５は、露光装置３の概略構成図である。この露光装置３により感光体１表面をレーザ走査露光Ｌする場合には、先ず画像読み取りユニット２１から入力された画像信号に基づき発光信号発生器２４により、固体レーザ素子２５を所定タイミングで明減（ＯＮ／ＯＦＦ）させる。そして、固体レーザ素子２５から放射された光信号であるレーザ光を、コリメーターレンズ系２６によりほぼ平行な光束に変換し、更に、矢印ｃ方向に高速回転する回転多面鏡２２により感光体１を矢印ｄ方向（長手方向）に走査することによって、ｆθレンズ群２３、反射ミラーにより感光体１表面にレーザスポットが結像される。このようなレーザ走査により感光体１表面には走査分の露光分布が形成され、更に、各走査毎に感光体１表面に対して垂直に所定量だけスクロールさせれば、感光体１表面に画像信号に応じた露光分布が得られる。
【０１３８】
即ち、感光体１の一様帯電面（今回は−７００Ｖに帯電）に画像信号に対応してＯＮ／ＯＦＦ発光される固体レーザ素子２５の光を高速で回転する回転多面鏡２２によって走査することにより、感光体１表面には走査露光パターンに対応した各色の静電潜像が順次形成されていく。
【０１３９】
現像装置４は、通常の４色回転型の現像装置４ａに高画質モード用の４色回転型の現像装置４ｂを備えている。現像装置４ａと４ｂの位置に関しては入れ替わっても何ら問題はない。図６に示すように、現像器４１ａ、４２ａ、４３ａ、４４ａ、にそれぞれ濃シアントナーを有する現像剤、濃マゼンタトナーを有する現像剤、濃イエロートナーを有する現像剤、及び、濃ブラックトナーを有する現像剤が導入される。また、現像器４１ｂ、４２ｂ、４３ｂ、４４ｂには、淡シアントナーを有する現像剤、淡マゼンタトナーを有する現像剤、淡イエロートナーを有する現像剤、及び、淡ブラックトナーを有する現像剤の中から少なくとも１種以上から選ばれる淡色トナーを有する現像剤が導入される。なお、現像装置４ｂに関しては４色すべての淡色トナーを導入する必要は無く、少なくとも１種以上の淡色トナーを有する現像剤を導入していれば、残りを空けても構わない。また、空いている所には他の色味を有する淡色トナー、緑色やオレンジ色、白色といった特色トナー、着色剤を含有しない無色トナー等を有する現像剤を導入してもよい。
【０１４０】
現像装置４ａ、４ｂは、磁気ブラシ現像方式によって、静電潜像担持体としての感光体１に形成された静電潜像を現像し、各色トナー像が感光体１に形成される。本発明に関わる現像剤は、現像の色順については問わない。これらの現像器として、図７に示すような２成分現像器は好ましい例の一つである。
【０１４１】
図７において、２成分現像器は矢印ｅ方向に回転駆動される現像スリーブ３０を備えており、現像スリーブ３０内にはマグネットローラ３１が固定配置されている。現像容器３２には、現像剤Ｔを現像スリーブ３０表面に薄層形成するための規制ブレード３３が設置されている。
【０１４２】
また、現像剤容器３２の内部は、隔壁３６によって現像室（第１室）Ｒｌと攪拌室（第２室）Ｒ２とに区画され、攪拌室Ｒ２の上方には、トナーホッパー３４が配置されている。
【０１４３】
現像室Ｒｌと攪拌室Ｒ２には、それぞれ搬送スクリュー３７、３８が設置されている。なお、トナーホッパー３４には補給口３５が設けられており、トナー補給時、トナーｔが該補給口３５を経て攪拌室Ｒ２内に落下補給される。
【０１４４】
一方、現像室Ｒｌ及び攪拌室Ｒ２内には、上記トナー粒子と磁性キャリア粒子が混合された現像剤Ｔが収容されている。
【０１４５】
また、現像室Ｒｌ内の現像剤Ｔは、搬送スクリュー３７の回転駆動によって現像スリーブ３０の長手方向に向けて搬送される。攪拌室Ｒ２内の現像剤Ｔは、搬送スクリュー３８の回転駆動によって現像スリーブ３０の長手方向に向けて搬送される。搬送スクリュー３８による現像剤搬送方向は、搬送スクリュー３７によるそれとは反対方向である。
【０１４６】
隔壁３６には、紙面と垂直方向である手前側と奥側に開口部（不図示）がそれぞれ設けられており、搬送スクリュー３７で搬送された現像剤Ｔがこの開口部の１つから搬送スクリュー３８に受け渡され、搬送スクリュー３８で搬送された現像剤Ｔが上記開口部の他の１つから搬送スクリュー３６に受け渡される。トナーは磁性粒子との摩擦で、潜像を現像するための極性に帯電する。
【０１４７】
アルミニウムや非磁性ステンレス銅等の非磁性材からなる現像スリーブ３０は、現像剤容器３２の感光体１に近接する部位に設けた開口部に設けられており、矢印ｅ方向（反時計方向）に回転してトナー及びキャリアの混合された現像剤Ｔを現像部Ｃに担持搬送する。現像スリーブ３０に担持された現像剤Ｔの磁気ブラシは現像部Ｃで矢印ａ方向（時計方向）に回転する感光体１に接触し、静電潜像はこの現像部Ｃで現像される。
【０１４８】
現像スリーブ３０には、電源（不図示）により交流電圧に直流電圧を重畳した振動バイアス電圧が印加される。潜像の暗部電位（非露光部電位）と明部電位（露光部電位）は、上記振動バイアス電位の最大値と最小値の間に位置している。これによって、現像部Ｃに、向きが交互に変化する交番電界が形成される。この交番電界中で、トナーとキャリアは激しく振動し、トナーが現像スリーブ３０及びキャリアへの静電的拘束を振り切って潜像に対応して感光体１表面の明部に付着する。
【０１４９】
振動バイアス電圧の最大値と最小値の差（ピーク間電圧）は１〜５ｋＶが好ましい。また、周波数は１〜１０ｋＨｚが好ましい。本実施形態では、振動バイアス電圧をピーク間電圧が２ｋＶの矩形波とし、周波数を２ｋＨｚとしている。なお、振動バイアス電圧の波形は、矩形波に限らず、サイン波、三角波等が使用できる。
【０１５０】
そして、上記直流電圧成分は、静電潜像の暗部電位と明部電位の間の値のものであるが絶対値で最小の明部電位よりも暗部電位の方により近い値であることが、暗部電位領域へのカブリトナーの付着を防止するうえで好ましい。本実施形態では、暗部電位−７００Ｖに対して、明部電位を−２００Ｖ、現像バイアスの直流成分を−５００Ｖとしている。また、現像スリーブ３０と感光体１の最小間隙（この最小間隙位置は現像部Ｃ内にある）は０．２〜１ｍｍであることが好適であるが、本実施形態では０．５ｍｍとしている。
【０１５１】
また、規制ブレード３３で規制されて現像部Ｃに搬送される現像剤Ｔの量は、マグネットローラ３１の現像磁極Ｓｌによる現像部Ｃでの磁界により形成される現像剤Ｔの磁気ブラシの現像スリーブ３０表面上での高さが、感光体１を取り去った状態で、現像スリーブ３０と感光体１間の最小間隙値の１．２〜３倍となるような量であることが好ましい。本実施形態では、現像剤Ｔの磁気ブラシの高さが７００μｍとなるように、現像部Ｃに搬送される現像剤Ｔの量を調整した。
【０１５２】
マグネットローラ３１の現像磁極Ｓｌは、現像部Ｃと対向する位置に配置されており、現像磁極Ｓｌが現像部Ｃに形成する現像磁界により現像剤Ｔの磁気ブラシが形成され、この磁気ブラシが感光体１に接触してドット分布静電潜像を現像する。その際、磁性キャリアの穂（ブラシ）に付着しているトナーも、この穂ではなくスリーブ表面に付着しているトナーも、静電潜像の露光部に転移してこれを現像する。
【０１５３】
現像磁極Ｓｌによる現像磁界の現像スリーブ３０表面上での強さ（現像スリーブ３０表面に垂直な方向の磁束密度）は、そのピーク値が５×１０^-2（Ｔ）〜２×１０^-1（Ｔ）であることが好適である。また、マグネットローラ３１には、上記現像磁極Ｓｌの他に、Ｎｌ、Ｎ２、Ｎ３、Ｓ２極を有している。
【０１５４】
ここで、感光体１表面の静電潜像を、現像装置４を用いて２成分磁気ブラシ法により顕像化する現像工程と現像剤Ｔの循環系について説明する。
【０１５５】
現像スリーブ３０の回転によりＮ２極で汲み上げられた現像剤ＴはＳ２極からＮｌ極と搬送され、その途中で規制ブレード３３で層厚が規制され、現像剤薄層を形成する。
【０１５６】
そして、現像磁極Ｓｌの磁界中で穂立ちした現像剤Ｔが感光体１上の静電潜像を現像する。その後、Ｎ３極、Ｎ２極間の反発磁界により現像スリーブ３０上の現像剤Ｔは現像室Ｒｌ内へ落下する。現像室Ｒｌ内に落下した現像剤Ｔは、搬送スクリュー３７により攪拌搬送される。
【０１５７】
本発明において、中間転写体及び転写手段としては、一般的な材料を用いることが可能である。転写体５（図４参照）は、表面に例えばポリエチレンテレフタレート樹脂フィルムからなる転写シート５ｃが張設されており、感光体１に対して当接、離間自在に設置されている。転写体５は矢印方向（時計方向）に回転駆動される。転写体５内には、転写帯電器５ａ、分離帯電器５ｂ等が設置されている。
【０１５８】
次に、上記した画像形成装置の画像形成動作について説明する。
感光体１は、中心支軸を中心に所定の周速度（プロセススピード）で矢印ａ方向（反時計方向）に回転駆動され、その回転過程において一次帯電器２により、本実施の形態では負極性の一様な帯電処理を受ける。
【０１５９】
そして、感光体１の一様帯電面に対して露光装置（レーザ走査装置）３から出力される、画像読み取り部Ｂからプリンタ部Ａ側に出力される画像信号に対応して変調されたレーザ光による走査露光Ｌによって、感光体１上に画像読み取り部Ｂにより光電読み取りされた原稿Ｇの画像情報に対応した各色の静電潜像が順次形成される。感光体１上に形成された静電潜像は現像装置４により、上述した２成分磁気ブラシ法によって、先ず現像器４１ａにより反転現像されて第１色目のトナー像として可視像化される。
【０１６０】
一方、感光体１上への上記トナー像の形成に同期して、給紙カセット１０内に収納された紙などの記録部材Ｐが給紙ローラ１１又は１２により１枚ずつ給送され、レジストローラ１３により所定のタイミングで転写体５に給紙され、吸着ローラ１４によって記録部材Ｐが転写体５上に静電吸着される。転写体５上に静電吸着された記録部材Ｐは、転写体５の矢印方向（時計方向）の回転によって感光体１と対向した位置に移動し、転写帯電器５ａによって記録部材Ｐの裏側に前記トナーと逆極性の電荷が付与されて、表面側に感光体１上のトナー像が転写される。
【０１６１】
この転写後、感光体１上に残留している転写残トナーはクリーニング装置６によって除去され、次のトナー像の形成に供される。
【０１６２】
以下、同様にして感光体１上の静電潜像が現像されて、感光体１上に形成された各色のトナー像が転写帯電器５ａにより転写体５上の記録部材Ｐに重ねて転写され、フルカラー画像が形成される。
【０１６３】
そして、記録部材Ｐを分離帯電器５ｂによって転写体５上から分離し、分離された記録部材Ｐは搬送ベルト８を通して定着装置９に搬送される。定着装置９に搬送された記録部材Ｐは、定着ローラ５０と弾性ベルト５２間で加熱、加圧されて表面にフルカラー画像が定着された後、排紙ローラ１５によりトレイ１６上に排紙される。
【０１６４】
また、感光体１表面は、クリーニング装置６によって転写残トナーが除去され、更に感光体１表面は、前露光ランプ７で除電され、次の画像形成に備える。
【０１６５】
以下、本発明における各物性の測定方法について説明する。
【０１６６】
（トナーの粘弾性特性（貯蔵弾性率Ｇ'₁₂₀及びＧ'₁₈₀）の測定）
トナーを直径２５ｍｍ、厚さ約２．５ｍｍの円板状の試料に加圧成型する。次に加圧成型された試料をパラレルプレートにセットし、５０〜２００℃の温度範囲内で徐々に昇温させ、温度分散測定を行う。昇温速度は２℃／ｍｉｎとし，角周波数（ω）は６．２８ｒａｄ／ｓｅｃに固定し、歪率は自動とする。横軸に温度，縦軸に貯蔵弾性率（Ｇ'）を取り、各温度（１２０℃及び１８０℃）における値を読み取る。測定にあたっては、ＡＲＥＳ（レオメトリックス社製）を用いる。
【０１６７】
（トナー変形量（Ｒ₂₀₀）、（Ｒ₅₀₀）の測定）
トナーは、５〜５．５ｇのトナーを錠剤成型器により８．０×１０⁶Ｐａの圧力で２分間加圧することで、直径２５ｍｍ、高さ１０〜１１ｍｍの円柱状試料に成型する。測定装置は、ＰＴＦＥコートしたＳＵＳ製の直径２５ｍｍパラレルプレートを装着したＡＲＥＳ（粘弾性測定装置、TA INSTRUMENTS社製）を使用する。
【０１６８】
変形量の測定方法は、ＰＴＦＥコートした直径２５ｍｍのパラレルプレートを使用する。トナーの成型試料をパラレルプレート上に設置し、治具温度を１２０℃に制御して、試料の温度が１２０℃に達したことを確認後、試料の高さ（ｇａｐ）を１０．０００ｍｍに調整する。Multiple Extension Mode Test の Rate Mode Test を選択し、Ｒａｔｅ＝−０．５ｍｍ／ｓでトナー成型試料を圧縮し、試料の高さ（ｇａｐ）と Normal Force の関係を測定する。
【０１６９】
Normal Force が荷重２００ｇ（圧力４．０×１０³Ｐａ）での試料の高さ（ｇａｐ）をＧ₂₀₀（ｍｍ）とすると、下記式からトナー変形量（Ｒ₂₀₀）が算出できる。
【０１７０】
【数６】

【０１７１】
同様にして、Normal Force が荷重５００ｇ（圧力１．０×１０⁴Ｐａ）での試料の高さＧ₅₀₀を用いることにより、トナー変形量（Ｒ₅₀₀）を測定することができる。
【０１７２】
（ＧＰＣによるトナー、結着樹脂の分子量の測定）
トナーの樹脂成分、結着樹脂のＧＰＣによる分子量分布は、下記の通り、トナーをＴＨＦ溶媒に溶解させて得られたＴＨＦ可溶成分を用いて、ＧＰＣにより測定する。
【０１７３】
すなわち、試料をＴＨＦ中に入れ、数時間放置した後十分に振とうしＴＨＦと良く混ぜ（試料の合一体がなくなるまで）、更に１２時間以上静置する。このときＴＨＦ中への放置時間が２４時間以上となるようにする。その後、サンプル処理フィルタ（ポアサイズ０．４５〜０．５μｍ、例えば、マイショリディスクＨ−２５−５ 東ソー社製、エキクロディスク２５ＣＲ ゲルマンサイエンスジャパン社製などが利用できる）を通過させたものを、ＧＰＣの試料とする。また試料濃度は、樹脂成分が０．５〜５ｍｇ／ｍｌとなるように調整する。上記の方法で調製された試料のＧＰＣの測定は、４０℃のヒートチャンバー中でカラムを安定化させ、この温度におけるカラムに溶媒としてテトラヒドロフラン（ＴＨＦ）を毎分１ｍｌの流速で流し、試料濃度として０．０５〜０．６質量％に調整した樹脂のＴＨＦ試料溶液を約５０〜２００μｌ注入して測定する。試料の分子量測定にあたっては、試料の有する分子量分布を数種の単分散ポリスチレン標準試料により作成された検量線の対数値とカウント数（リテンションタイム）との関係から算出する。検量線作成用の標準ポリスチレン試料としては、例えば東ソー社製或いはＰｒｅｓｓｕｒｅ Ｃｈｅｍｉｃａｌ Ｃｏ．製の分子量が６×１０²、２．１×１０³、４×１０³、１．７５×１０⁴、５．１×１０⁴、１．１×１０⁵、３．９×１０⁵、８．６×１０⁵、２×１０⁶、４．４８×１０⁶のものを用い、少なくとも１０点程度の標準ポリスチレン試料を用いるのが適当である。検出器にはＲＩ（屈折率）検出器を用いる。
【０１７４】
カラムとしては、１０³〜２×１０⁶の分子量領域を的確に測定するために、市販のポリスチレンジェルカラムを複数本組み合わせるのが良く、例えば昭和電工社製のｓｈｏｄｅｘ ＧＰＣ ＫＦ−８０１，８０２，８０３，８０４，８０５，８０６，８０７の組み合わせや、Ｗａｔｅｒｓ社製のμ−ｓｔｙｒａｇｅｌ ５００、１０³、１０⁴、１０⁵の組み合わせを挙げることができる。
【０１７５】
（ＧＰＣによるワックス分子量の測定）
装置 ：ＧＰＣ−１５０Ｃ（ウォーターズ社）
カラム：ＧＭＨ−ＨＴ３０ｃｍ、２連（東ソー社製）
温度 ：１３５℃
溶媒 ：ｏ−ジクロロベンゼン（０．１質量％アイオノール添加）
流速 ：１．０ｍｌ／ｍｉｎ
試料 ：０．１５質量％のワックスを０．４ｍｌ注入
以上の条件で測定し、ワックスの分子量算出にあたっては単分散ポリスチレン標準試料により作成した分子量校正曲線を使用する。更に、Ｍａｒｋ−Ｈｏｕｗｉｎｋ粘度式から導き出される換算式に基づいてポリエチレン換算することでワックスの分子量を算出する。
【０１７６】
（トナー及びワックスにおける最大吸熱ピークの極大温度の測定）
温度曲線：昇温Ｉ（３０℃〜２００℃、昇温速度１０℃／ｍｉｎ）
降温Ｉ（２００℃〜３０℃、降温速度１０℃／ｍｉｎ）
昇温II（３０℃〜２００℃、昇温速度１０℃／ｍｉｎ）
トナー及びワックスの最大吸熱ピークは、示差走査熱量計（ＤＳＣ測定装置）ＤＳＣ２９２０（ＴＡインスツルメンツジャパン社製）を用いてＡＳＴＭ Ｄ３４１８−８２に準じて測定する。
【０１７７】
測定試料は５〜２０ｍｇ、好ましくは１０ｍｇを精密に秤量する。それをアルミパン中に入れ、リファレンスとして空のアルミパンを用い、測定範囲３０〜２００℃の間で、昇温速度１０℃／ｍｉｎで常温常湿下で測定を行う。トナー及びワックスの最大吸熱ピークは、昇温IIの過程で、樹脂Ｔｇの吸熱ピーク以上の領域のベースラインからの高さが一番高いものを、若しくは樹脂Ｔｇの吸熱ピークが別の吸熱ピークと重なり判別し難い場合、その重なるピークの極大ピークから高さが一番高いものを本発明のトナーの最大吸熱ピークとする。
【０１７８】
（平均円形度の測定）
トナーの円相当径、円形度及びそれらの頻度分布とは、トナー粒子の形状を定量的に表現する簡便な方法として用いたものであり、本発明ではフロー式粒子像測定装置「ＦＰＩＡ−１０００型」（東亜医用電子社製）を用いて測定を行い、下記式を用いて算出する。
【０１７９】
【数７】
円相当径 ＝ （粒子投影面積／π）^1/2×２
【０１８０】
【数８】

【０１８１】
ここで、「粒子投影面積」とは二値化されたトナー粒子像の面積であり、「粒子投影像の周囲長」とは該トナー粒子像のエッジ点を結んで得られる輪郭線の長さと定義する。
【０１８２】
本発明における円形度はトナー粒子の凹凸の度合いを示す指標であり、トナー粒子が完全な球形の場合に１．０００を示し、表面形状が複雑になる程、円形度は小さな値となる。
【０１８３】
具体的な測定方法としては、容器中に予め不純固形物などを除去したイオン交換水１０ｍｌを用意し、その中に分散剤として界面活性剤、好ましくはアルキルベンゼンスルホン酸塩を加えた後、更に測定試料を０．０２ｇを加え、均一に分散させる。分散させる手段としては、超音波分散機「Ｔｅｔｏｒａ１５０型」（日科機バイオス社製）に振動子として５ｍｍφのチタン合金チップを装着したものを用い、５分間分散処理を用い、測定用の分散液とする。その際、該分散液の温度が４０℃以上とならない様に適宜冷却する。
【０１８４】
トナー粒子の形状測定には、前記フロー式粒子像測定装置を用い、測定時のトナー粒子濃度が３０００〜１万個／μｌとなる様に該分散液濃度を再調整し、トナー粒子を１０００個以上計測する。計測後、このデータを用いて、３μｍ以下のデータをカットして、トナー粒子の平均円形度を求める。
【０１８５】
（粉体状態における明度Ｌ^*の測定）
粉体状態のトナーにおけるＬ^*は、ＪＩＳ Ｚ−８７２２に準拠する分光式色差計「ＳＥ−２０００」（日本電色工業社製）を用い、光源はＣ光源２度視野で測定する。測定は付属の取り扱い説明書に沿って行うが、標準板の標準合わせには、オプションの粉体測定用セル内に２ｍｍ厚でφ３０ｍｍのガラスを介した状態で行うのが良い。より詳しくは、前記分光式色差計の粉体試料用試料台（アタッチメント）上に、試料粉体（トナー）を充填したセルを設置した状態で測定を行う。なお、セルを粉体試料用試料台に設置する以前に、セル内の内容積に対して８０％以上粉体試料を充填し、振動台上で１回／秒の振動を３０秒間加えた上で測定する。また、本発明において、球形化等の形状処理や外添剤を添加したトナーについて測定する場合には、該形状処理や外添剤混合がなされた状態のトナーを粉体試料として用いる。
【０１８６】
（キャリア粒径の測定方法）
光学顕微鏡によりランダムに３００個以上抽出し、ニレコ社（株）製の画像処理解析装置Ｌｕｚｅｘ３により水平方向フェレ径をもってキャリア粒径として測定するものとする。
【０１８７】
【実施例】
以下、本発明を製造例及び実施例により具体的に説明するが、これは本発明を何ら限定するものではない。
【０１８８】

四つ口フラスコ内でキシレン２００質量部を撹拌しながら四つ口フラスコ内を十分に窒素で置換し、１２０℃に昇温させた後、上記各成分を約４時間かけて四つ口フラスコ内に滴下した。更にキシレン還流下で重合を完了し、減圧下で溶媒を蒸留除去してビニル系重合体を得た。得られたビニル系重合体のＧＰＣによる分子量測定の結果を表１に示す。
【０１８９】
〈ハイブリッド樹脂の製造例〉
ビニル系共重合体の材料として、スチレン１０質量部、２−エチルヘキシルアクリレート５質量部、フマル酸２質量部、α−メチルスチレンの２量体５質量部にジクミルパーオキサイドを滴下ロートに入れた。また、ポリオキシプロピレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン２５質量部、ポリオキシエチレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン１５質量部、コハク酸９質量部、無水トリメリット酸５質量部、フマル酸２４質量部及び酸化ジブチル錫をガラス製４リットルの四つ口フラスコに入れ、温度計、撹拌棒、コンデンサー、及び窒素導入管を四つ口フラスコに取りつけ、この四つ口フラスコをマントルヒーター内に設置した。次に四つ口フラスコ内を窒素ガスで置換した後、撹拌しながら徐々に昇温し、１３０℃の温度で攪拌しつつ、先の滴下ロートより、ビニル系共重合体の単量体、架橋剤及び重合開始剤を約４時間かけて滴下した。次いで２００℃に昇温を行い、約４時間反応させてハイブリッド樹脂を得た。得られたハイブリッド樹脂のＧＰＣによる分子量測定の結果を表１に示す。
【０１９０】
〈ポリエステル樹脂１の製造例〉
ポリオキシプロピレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン２５質量部、ポリオキシエチレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン１５質量部、テレフタル酸２０質量部、無水トリメリット酸５質量部、フマル酸２５質量部及び酸化ジブチル錫をガラス製４リットルの四つ口フラスコに入れ、温度計、撹拌棒、コンデンサー、及び窒素導入管を四つ口フラスコに取りつけ、この四つ口フラスコをマントルヒーター内に設置した。窒素雰囲気下で、２１０℃で約５時間反応させ、ポリエステル樹脂１を得た。得られたポリエステル樹脂１のＧＰＣによる分子量測定の結果を表１に示す。
【０１９１】
〈ポリエステル樹脂２の製造例〉
ポリエステル樹脂１の製造例において、モノマー構成を表１に示すように変更し、更に窒素雰囲気下、２１０℃で４．５時間反応させた以外は、上記製造例と同様の方法によりポリエステル樹脂２を得た。得られたポリエステル樹脂１のＧＰＣによる分子量測定の結果を表１に示す。
【０１９２】
【表１】

【０１９３】
〈シアントナーａ１及びシアン現像剤ａ１の製造例〉
ハイブリッド樹脂、ワックスＡ（表２参照）及び表３に示す他のトナー材料を、表３に示す組成でヘンシェルミキサーにより十分予備混合を行った。得られた混合物を二軸式押出機で溶融混練し、溶融混練物を冷却し、冷却物をハンマーミルを用いて粒径約１〜２ｍｍ程度に粗粉砕した。次いで、粗粉砕物をエアージェット方式による微粉砕機で微粉砕した。
【０１９４】
更に、得られた微粉砕物を図１及び図２に示したような処理装置を用い、分級ロータの回転数を７３００ｒｐｍとして微粒子を除去しながら、分散ロータの回転数を９７／ｓ（回転周速を１３０ｍ／ｓｅｃ）として１回当たり６０秒間の表面処理を２０分間行った。なお、該表面処理において、原料供給口３より微粉砕物を投入し、６０秒間処理し、出弁８を開けて処理品として取り出す操作を一回と数えた。分散ロータ上部には角型のディスクを１０個設置し、ガイドリングと分散ロータ角型ディスクとの間隔を３０ｍｍとし、分散ロータとライナーとの間隔を５ｍｍとした。またブロワー風量を１４ｍ³／ｍｉｎとし、ジャケットに通す冷媒の温度及び冷風温度Ｔ１を−２０℃とした。この状態で２０分間運転した結果、分級ロータ後方の温度Ｔ２は２７℃で安定しており、重量平均粒径７．５μｍのシアントナーａ１樹脂粒子を得た。
【０１９５】
上記シアントナーａ１樹脂粒子１００質量部に対して、針状チタン（テイカ社製 ＭＴ−１００Ｔ）１．５質量部を前記シアントナーａ１樹脂粒子と混合してシアントナーａ１とした。得られたシアントナーａ１の物性を表４に示す。なお、実施例において各トナーの製造に用いられるワックスの種類及びその最大吸熱ピーク温度を、表２に示す。
【０１９６】
更にシアントナーａ１と、シリコーン樹脂で表面被覆した磁性マンガンマグネシウムフェライトキャリア粒子（個数平均粒径５０μｍ）とを、トナー濃度が６質量％になるように混合し、二成分系現像剤であるシアン現像剤ａ１を得た。
【０１９７】
〈シアントナーａ２〜ａ１５及びシアン現像剤ａ２〜ａ１５の製造例〉
トナー材料を表３に示すように変更し、また溶融混練の温度並びに表面処理時の分散ローターの回転数及び処理時間を適宜変更して、シアントナーａ２〜ａ１５を得た。得られた各トナーａ２〜ａ１５の物性を表４に示す。
【０１９８】
各シアントナーに、シアントナーａ１と同様にキャリアを混合して、シアン現像剤ａ２〜ａ１５を得た。
【０１９９】
〈シアントナーｂ１〜ｂ１５及びシアン現像剤ｂ１〜ｂ１５の製造例〉
シアントナーａ１〜ａ１５の製造例において、着色剤の使用量を表３に示すように変更した以外はそれぞれのトナーａの製造例と同様の方法を用いてシアントナーｂ１〜ｂ１５及びシアン現像剤ｂ１〜ｂ１５を得た。得られた各シアントナーｂ１〜ｂ１５の物性を表５に示す。
【０２００】
〈マゼンタトナーａ１及びマゼンタ現像剤ａ１の製造例〉
シアントナーａ１の製造例において、着色剤としてＣ．Ｉ．ピグメントレッド１２２を１部用いた以外は、上記製造例と同様の方法を用いてマゼンタトナーａ１及びマゼンタ現像剤ａ１を得た。得られたマゼンタトナーａ１の物性を表４に示す。
【０２０１】
〈マゼンタトナーａ２及びマゼンタ現像剤ａ２の製造例〉
シアントナーａ１１の製造例において、着色剤としてＣ．Ｉ．ピグメントレッド１２２を１部用いた以外は、上記製造例と同様の方法を用いてマゼンタトナーａ２及びマゼンタ現像剤ａ２を得た。得られたマゼンタトナーａ２の物性を表４に示す。
【０２０２】
〈マゼンタトナーｂ及びマゼンタ現像剤ｂの製造例〉
マゼンタトナーａ１の製造例において、着色剤の使用量を６部に変更した以外は、上記製造例と同様の方法を用いてマゼンタトナーｂ及びマゼンタ現像剤ｂを得た。得られたマゼンタトナーｂの物性を表５に示す。
【０２０３】
〈イエロートナーｂ及びイエロー現像剤ｂの製造例〉
シアントナーａ１の製造例において、着色剤としてＣ．Ｉ．ピグメントイエロー１８０を９部用いた以外は、上記製造例と同様の方法を用いてイエロートナーｂ及びイエロー現像剤ｂを得た。得られたイエロートナーｂの物性を表５に示す。
【０２０４】
〈ブラックトナーｂ及びブラック現像剤ｂの製造例〉
シアントナーａ１の製造例において、着色剤としてカーボンブラックを５部用いた以外は、上記製造例と同様の方法を用いてブラックトナーｂ及びブラック現像剤ｂを得た。得られたトナーｂの物性を表５に示す。
【０２０５】
【表２】

【０２０６】
【表３】

【０２０７】
【表４】

【０２０８】
【表５】

【０２０９】
〈実施例１〉
図４及び図６に示す画像形成装置及び現像装置を用いて、普通紙（カラーレーザーコピア用紙ＴＫＣＬＡ４；キヤノン製）を用い、プリンターモードでシアントナーａ１の画像を出力し、以下の各項目について評価を行った。上記画像形成装置及び現像装置については、発明の実施の形態において既に述べた通りである。
【０２１０】
（１）定着温度領域の測定
図４中の定着装置９を、定着温度を自由に設定できるようにし、図６の現像器４１ａにシアン現像剤ａ１をセットして定着試験を行った。このときの画像面積比率は２５％であり、単位面積当たりのトナー載り量は、１．５ｍｇ／ｃｍ²に設定した。定着開始温度とオフセット開始温度の測定は、プロセススピードを１５０ｍｍ／ｓ、定着器の設定温度を１４０〜２２０℃迄の温度範囲で５℃おきに温度調節して、各々の温度で定着画像を出力し、得られた定着画像を４．９ｋＰａ（５０ｇ／ｃｍ²）の圧力をかけたシルボン紙で摺擦し、摺擦前後の濃度低下率が１０％以下となる定着温度を定着開始温度とした。また定着開始温度から更に設定温度を上げて行き、目視で高温オフセットの発生した温度をオフセット開始温度とした。
【０２１１】
また、現像器４１ａにシアン現像剤ａ１、現像器４１ｂにシアン現像剤ｂ１をセットしてプリンターモードで１２階調のパッチ画像を形成した。単位面積当たりのトナー載り量は、トナーａとトナーｂのトータルで最大１．５ｍｇ／ｃｍ²になるように設定した。
【０２１２】
（２）転写効率の測定
転写効率測定用の画像として、初期と１０，０００枚耐久前後に画像面積比率５％のベタ画像を現像、転写し、感光体上の転写前のトナー量（単位面積あたり）と、記録部材上のトナー量（単位面積あたり）をそれぞれ測定し、下式により求めた。なお、耐久試験は上記画像面積比率２５％画像で行った。
【０２１３】
【数９】
転写率（％）
＝ （記録部材上のトナー量）／（感光体上の転写前のトナー量）×１００
【０２１４】
（３）光沢度（グロス）の測定
光沢度（グロス）の測定に関しては、ＶＧ−１０型光沢度計（日本電色製）を用い、定着温度領域の測定で用いた画像を１８５℃で定着させたものを試料として、測定を行った。測定としては、まず定電圧装置により電圧を６Ｖにセットした。次いで投光角度、受光角度をそれぞれ６０°に合わせた。０点調整及び標準板を用い、標準設定の後に試料台の上に前記試料画像を置き、更に白色紙を３枚上に重ね測定を行い、標示部に示される数値を％単位で読みとった。この時Ｓ，Ｓ／１０切替ＳＷはＳに合わせ、角度、感度切替ＳＷは４５−６０に合わせた。
【０２１５】
また、トナーａとトナーｂを用いて出力した１２階調の画像を測定し、光沢度の最大値と最小値の差を出して、以下の評価基準に従い評価した。
【０２１６】
ａ：グロス差が４未満
ｂ：グロス差が４以上７未満
ｃ：グロス差が７以上１０未満
ｄ：グロス差が１０以上
【０２１７】
（４）定着時における画像のがさつき性
細線画像（７本／１ｍｍ）を定着し、その解像度をルーペを用いて観察し、トナーの飛び散り、解像度が落ちた度合いについて確認して評価した。即ち、判別可能なライン数を下記の基準に従い評価した。この際、判別可能なライン数は、縦方向のライン及び横方向のラインそれぞれ１０カ所の平均値とした。なお、定着温度は各トナーの定着開始温度で測定した。
【０２１８】
Ａ：７本
Ｂ：５〜６本
Ｃ：３〜４本
Ｄ：２本以下
【０２１９】
本実施例のシアン現像剤ａ１は、優れた定着性、転写効率を示し、定着時における画像のがさつき感も無かった。現像剤ａ１のみを用いた評価結果を表６に、現像剤ａ１と現像剤ｂ１とを組み合わせて用いた評価結果を表７に示す。
【０２２０】
〈実施例２〉
シアン現像剤ａ１の代わりにシアン現像剤ａ２を、シアン現像剤ｂ１の代わりにシアン現像剤ｂ２をそれぞれ用いた以外は、実施例１と同様にして評価を行った。シアン現像剤ａ２を用いた場合、定着開始温度が若干高くなったが、何ら問題無かった。本実施例２においても優れた転写効率を示し、定着時における画像のがさつき感も無かった。また、現像剤ａ２と現像剤ｂ２の組み合わせにおいても同様に問題無かった。現像剤ａ２のみを用いた評価結果を表６に、現像剤ａ２と現像剤ｂ２とを組み合わせて用いた評価結果を表７に示す。
【０２２１】
〈実施例３〉
シアン現像剤ａ１の代わりにシアン現像剤ａ３を、シアン現像剤ｂ１の代わりにシアン現像剤ｂ３をそれぞれ用いた以外は、実施例１と同様にして評価を行った。シアン現像剤ａ３ではトナーがかなり球形化されていたためか、定着時における画像のがさつき感が若干悪くなったが何ら問題無かった。定着性、転写効率は非常に良かった。また、現像剤ａ３と現像剤ｂ３の組み合わせにおいても同様に問題無かった。現像剤ａ３のみを用いた評価結果を表６に、現像剤ａ３と現像剤ｂ３とを組み合わせて用いた評価結果を表７に示す。
【０２２２】
〈実施例４〉
シアン現像剤ａ１の代わりにシアン現像剤ａ４を、シアン現像剤ｂ１の代わりにシアン現像剤ｂ４をそれぞれ用いた以外は、実施例１と同様にして評価を行った。シアン現像剤ａ４ではトナーの球形化度が若干低いためか転写効率が低くなったが何ら問題無かった。シアン現像剤ａ４は優れた定着性を示し、定着時における画像のがさつき感も無かった。また、現像剤ａ４と現像剤ｂ４の組み合わせにおいても同様に問題無かった。現像剤ａ４のみを用いた評価結果を表６に、現像剤ａ４と現像剤ｂ４とを組み合わせて用いた評価結果を表７に示す。
【０２２３】
〈実施例５〉
シアン現像剤ａ１の代わりにシアン現像剤ａ５を、シアン現像剤ｂ１の代わりにシアン現像剤ｂ５をそれぞれ用いた以外は、実施例１と同様にして評価を行った。シアン現像剤ａ５ではＤＳＣの最大吸熱ピークの極大値が小さいため、転写効率が初期に比べ、若干下がったが何ら問題無かった。シアン現像剤ａ５は優れた定着性を示し、定着時における画像のがさつき感も無かった。また、現像剤ａ５と現像剤ｂ５の組み合わせにおいても同様に問題無かった。現像剤ａ５のみを用いた評価結果を表６に、現像剤ａ５と現像剤ｂ５とを組み合わせて用いた評価結果を表７に示す。
【０２２４】
〈実施例６〉
シアン現像剤ａ１の代わりにシアン現像剤ａ６を、シアン現像剤ｂ１の代わりにシアン現像剤ｂ６をそれぞれ用いた以外は、実施例１と同様にして評価を行った。シアン現像剤ａ６ではトナーのＤＳＣの最大吸熱ピークの極大値が大きいため、低温定着性が若干悪くなった。定着時における画像のがさつき感は無かった。転写効率は非常に良好であった。また、現像剤ａ６と現像剤ｂ６の組み合わせにおいても同様に問題無かった。現像剤ａ６のみを用いた評価結果を表６に、現像剤ａ６と現像剤ｂ６とを組み合わせて用いた評価結果を表７に示す。
【０２２５】
〈実施例７〉
シアン現像剤ａ１の代わりにシアン現像剤ａ７を、シアン現像剤ｂ１の代わりにシアン現像剤ｂ７をそれぞれ用いた以外は、実施例１と同様にして評価を行った。シアン現像剤ａ７ではトナー変形量Ｒ₂₀₀が比較的大きくなった。そのため、転写効率は初期に比べ、若干下がったが、使用可能レベルであった。また、Ｒ₅₀₀もやや大きくなり、定着時における画像のがさつき感も若干悪くなったが問題無かった。また、現像剤ａ７と現像剤ｂ７の組み合わせにおいても同様に使用可能レベルであった。現像剤ａ７のみを用いた評価結果を表６に、現像剤ａ７と現像剤ｂ７とを組み合わせて用いた評価結果を表７に示す。
【０２２６】
〈参考例１〉
シアン現像剤ａ１の代わりにシアン現像剤ａ８を、シアン現像剤ｂ１の代わりにシアン現像剤ｂ８をそれぞれ用いた以外は、実施例１と同様にして評価を行った。シアン現像剤ａ８ではトナーの変形量Ｒ_２００が比較的小さくなった。そのため、定着時にトナーの飛び散りが若干発生し、画像のがさつき性が若干悪くなったが、使用可能レベルであった。また、トナーの粘弾性特性が比較的大きいため、低温定着性が若干悪くなり、定着温度幅が若干狭くなった。また、光沢度が若干低くなったが問題無かった。転写効率は問題無かった。また、現像剤ａ８と現像剤ｂ８の組み合わせにおいては、画像の光沢度が若干不均一となったが使用可能レベルであった。現像剤ａ８のみを用いた評価結果を表６に、現像剤ａ８と現像剤ｂ８とを組み合わせて用いた評価結果を表７に示す。
【０２２７】
〈参考例２〉
シアン現像剤ａ１の代わりにシアン現像剤ａ９を、シアン現像剤ｂ１の代わりにシアン現像剤ｂ９をそれぞれ用いた以外は、実施例１と同様にして評価を行った。シアン現像剤ａ９ではトナーの変形量Ｒ_２００が比較的大きくなった。そのため、転写効率は初期に比べ若干下がったが、使用可能レベルであった。また、Ｒ_５００もやや大きくなり、定着時における画像のがさつき感も若干悪くなったが問題無かった。また、トナーの粘弾性特性が比較的小さいため、定着温度幅が狭くなり、巻きつきによるオフセットが発生し易くなった。また、現像剤ａ９と現像剤ｂ９の組み合わせにおいては、画像の光沢度が若干不均一となったが使用可能レベルであった。現像剤ａ９のみを用いた評価結果を表６に、現像剤ａ９と現像剤ｂ９とを組み合わせて用いた評価結果を表７に示す。
【０２２８】
〈実施例１０〉
シアントナーａ１及びｂ１を用いて一成分現像方法の評価を行った。装置はＬＢＰ−２０４０（キヤノン社製）の定着ユニットを取り外し、図３に示すような定着装置を外部につけて、連続して複写できるように改造を施したものを使用した。上記トナー及び装置を用いて実施例１と同様の評価を行った。定着可能温度及び定着時における画像のがさつき感は実施例１と同じであった。転写効率は耐久試験前が９１％で４０００枚の耐久試験後は９１％であり、非常に良好であった。トナーａ１とトナーｂ１の組み合わせでも転写効率は同じ結果で非常に良好であった。
【０２２９】
〈実施例１１〉
本実施例では、図４、図６に示す電子写真装置を用い、以下の（ａ）、（ｂ）に示す現像器と現像剤の組み合わせによって、記録部材である光沢紙（カラーレーザーコピア光沢厚紙 ＭＳ−７０１）上にオリジナルチャートを用いて画像を形成した。これにより、（ａ）及び（ｂ）の現像剤の組み合わせの有意差を調べた。
【０２３０】
（ａ）：現像器４１ａにシアン現像剤ａ１、現像器４２ａにマゼンタ現像剤ａ１、現像器４３ａ、４４ａは何も入れないで空けておいた。現像器４１ｂにシアン現像剤ｂ１、４２ｂにマゼンタ現像剤ｂ、現像器４３ｂにイエロー現像剤ｂ、現像器４４ｂブラック現像剤ｂをセットした。
【０２３１】
（ｂ）：現像器４１ａにシアン現像剤ａ１１、現像器４２ａにマゼンタ現像剤ａ２、現像器４３ａ、４４ａは何も入れないで空けておいた。現像器４１ｂにシアン現像剤ｂ１、４２ｂにマゼンタ現像剤ｂ、現像器４３ｂにイエロー現像剤ｂ、現像器４４ｂブラック現像剤ｂをセットした。
【０２３２】
その結果、（ａ）は低濃度部から高濃度部までの全域に渡り、濃度の変化が滑らかで、粒状性及びがさつきが抑制され、光沢にムラの無い写真のような画像を出力することができた。一方、（ｂ）は、定着温度幅が狭くなった。また、低濃度部から高濃度部までの濃度の変化が滑らかではあるが、低濃度部のがさつき感が目に付いた。また、光沢も均一ではなく、違和感のある画像になった。
【０２３３】
〈比較例１〉
シアン現像剤ａ１の代わりにシアン現像剤ａ１０を、シアン現像剤ｂ１の代わりにシアン現像剤ｂ１０をそれぞれ用いた以外は、実施例１と同様にして評価を行った。なお、光沢度の評価の際、本比較例では１８５℃で定着できなかったため、１７５℃で定着させたものを用いて評価した。シアン現像剤ａ１０ではトナー変形量Ｒ₂₀₀が大きいため、転写効率が下がる傾向にあった。また、Ｒ₅₀₀も大きくなり、定着時における画像のがさつき感も悪くなった。また、定着温度幅も狭くなった。また、現像剤ａ１０と現像剤ｂ１０の組み合わせにおいても評価結果は同様に悪くなった。現像剤ａ１０のみを用いた評価結果を表６に、現像剤ａ１０と現像剤ｂ１０とを組み合わせて用いた評価結果を表７に示す。
【０２３４】
〈比較例２〉
シアン現像剤ａ１の代わりにシアン現像剤ａ１１を、シアン現像剤ｂ１の代わりにシアン現像剤ｂ１１をそれぞれ用いた以外は、実施例１と同様にして評価を行った。なお、光沢度の評価の際、本比較例では１８５℃で定着できなかったため、１９５℃で定着させたものを用いて評価した。シアン現像剤１１ではトナーの変形量Ｒ₂₀₀が小さいため、定着時における画像のがさつき感も悪くなった。とくに現像剤ａ１１と現像剤ｂ１１を組み合わせて用いたものは画像の光沢性が不均一であった。更に低温定着性が悪くなり、定着温度幅も狭くなった。また、転写効率は初期から低い値となった。現像剤ａ１１のみを用いた評価結果を表６に、現像剤ａ１１と現像剤ｂ１１とを組み合わせて用いた評価結果を表７に示す。
【０２３５】
〈比較例３〉
シアン現像剤ａ１の代わりにシアン現像剤ａ１２を、シアン現像剤ｂ１の代わりにシアン現像剤ｂ１２をそれぞれ用いた以外は、実施例１と同様にして評価を行った。なお、光沢度の評価の際、本比較例では１８５℃で定着できなかったため、１９５℃で定着させたものを用いて評価した。シアン現像剤１２ではトナーの変形量Ｒ₂₀₀が小さいため、定着時における画像のがさつき感も悪くなった。現像剤ａ１２と現像剤ｂ１２とを組み合わせて用いたものは特にがさつき感が目立った。また、Ｒ₅₀₀も小さくなり、現像剤ａ１２と現像剤ｂ１２の組み合わせで用いたものは画像の光沢性が不均一であった。また、Ｌ^*（ａ）−Ｌ^*（ｂ）が４０より大きいため、低濃度部から高濃度部への濃度変化を滑らかに再現できなかった。更に低温定着性が悪くなり、定着温度幅も狭くなった。また、転写効率は初期から低い値となった。現像剤ａ１２のみを用いた評価結果を表６に、現像剤ａ１２と現像剤ｂ１２とを組み合わせて用いた評価結果を表７に示す。
【０２３６】
〈比較例４〉
シアン現像剤ａ１の代わりにシアン現像剤ａ１３を、シアン現像剤ｂ１の代わりにシアン現像剤ｂ１３をそれぞれ用いた以外は、実施例１と同様にして評価を行った。なお、光沢度の評価の際、本比較例では１８５℃で定着できなかったため、１６５℃で定着させたものを用いて評価した。シアン現像剤ａ１３ではトナー変形量Ｒ₂₀₀が大きいため、転写効率が下がる傾向にあった。また、Ｒ₅₀₀も大きくなり、定着時における画像のがさつき感も悪くなった。また、定着温度幅も狭くなった。更に、現像剤ａ１３と現像剤ｂ１３の組み合わせで用いると、Ｌ^*（ａ）−Ｌ^*（ｂ）が１０より小さいため、低濃度から高濃度までの色再現空間が広がりにくかった。現像剤ａ１３のみを用いた評価結果を表６に、現像剤ａ１３と現像剤ｂ１３とを組み合わせて用いた評価結果を表７に示す。
【０２３７】
〈比較例５〉
シアン現像剤ａ１の代わりにシアン現像剤ａ１４を、シアン現像剤ｂ１の代わりにシアン現像剤ｂ１４をそれぞれ用いた以外は、実施例１と同様にして評価を行った。なお、光沢度の評価の際、本比較例では１８５℃で定着できなかったため、１９５℃で定着させたものを用いて評価した。シアン現像剤ａ１４ではトナーの変形量Ｒ₂₀₀が小さいため、定着時における画像のがさつき感が非常に悪くなった。また、トナーの粘弾性特性が大きいため、低温定着性が悪くなり、定着温度幅が著しく狭くなった。更に、現像剤ａ１４と現像剤ｂ１４の組み合わせで用いても、光沢度の差はあまり大きくなかったが、画像の光沢性もほとんど無く、画質の品位は非常に悪かった。また、Ｌ^*（ａ）−Ｌ^*（ｂ）が４０より大きいため、低濃度部から高濃度部への濃度変化を滑らかに再現できなかった。現像剤ａ１４のみを用いた評価結果を表６に、現像剤ａ１４と現像剤ｂ１４とを組み合わせて用いた評価結果を表７に示す。
【０２３８】
〈比較例６〉
シアン現像剤ａ１の代わりにシアン現像剤ａ１５を、シアン現像剤ｂ１の代わりにシアン現像剤ｂ１５をそれぞれ用いた以外は、実施例１と同様にして評価を行った。シアン現像剤１５ではトナーの粘弾性特性が小さ過ぎて、すぐに巻きつきが発生し、定着点が無かった。そのため、定着時における画像のがさつき感や光沢度の測定は不可能であった。また、転写効率も下がる傾向にあった。現像剤ａ１５と現像剤ｂ１５の組み合わせでも評価結果は同様に悪くなった。現像剤ａ１５のみを用いた評価結果を表６に、現像剤ａ１５と現像剤ｂ１５とを組み合わせて用いた評価結果を表７に示す。
【０２３９】
【表６】

【０２４０】
【表７】

【０２４１】
【発明の効果】
本発明によれば、低濃度領域から高濃度領域まで、粒状感、ガサつきを低減できるトナー及び画像形成方法を提供することができる。また、記録部材上に多量のトナーを載せても幅広い定着温度幅を有し、連続複写後も優れた画像を保ち、耐オフセット性に優れたトナー及び画像形成方法を提供することができる。
【図面の簡単な説明】
【図１】本発明で好ましく用いられる表面改質装置の一例の模式的断面図
【図２】本発明で好ましく用いられる表面改質装置の一例の模式的平面図
【図３】本発明の画像形成方法に好ましく用いられる定着装置の一例を示す概略構成図
【図４】本発明の画像形成方法を好適に実現できる画像形成装置の一例を示す模式的断面図
【図５】図４の露光装置３の概略構成図
【図６】図６の現像装置の概略構成図
【図７】本発明で好ましく用いられる２成分現像器の一例を示す模式的断面図
【符号の説明】
１ 感光体
２ 一次帯電器
３ 露光装置
４、４ａ、４ｂ 現像装置
５ 転写体
６ クリーニング装置
７ 前露光ランプ
８ 搬送ベルト
９ 定着装置
１０ 給紙カセット
１１、１２ 給紙ローラ
１３ レジストローラ
１４ 吸着ローラ
１５ 排紙ローラ
２１ 原稿読みとりユニット
４１ａ、４１ｂ、４２ａ、４２ｂ、４３ａ、４３ｂ、４４ａ、４４ｂ 現像器
５０ 定着ローラ
５１ ハロゲンランプ
５２ ベルト
５３〜５５ 支持ローラ
Ａ プリンタ部
Ｂ 画像読み取り部
Ｐ 記録部材[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an image forming method such as electrophotography and electrostatic printing, and a toner used in the image forming method. In particular, the present invention relates to a toner and an image forming method that are preferably used in a fixing method in which a toner image is fixed on a recording member such as a print sheet by heating and pressing.
[0002]
[Prior art]
As electrophotographic color image forming apparatuses become widespread, their applications have been diversified and demands on image quality have become stricter. When copying images such as general photographs, catalogs, and maps, it is required to reproduce very finely and faithfully, even down to the finest parts. It is desired to extend the color reproduction range. In particular, with the recent advancement to the printing field, high-definition, high-definition, graininess, etc. that are equal to or higher than the printing quality are also required in the electrophotographic system.
[0003]
In a recent electrophotographic image forming apparatus using a digital image signal, a latent image is formed by gathering dots of a constant potential on the surface of a latent image carrier, a so-called photoconductor. The tone part and the line part are expressed by changing the dot density. However, with this method, it is difficult for toner particles to adhere faithfully to the dots, and the toner particles protrude from the dots, and the gradation of the toner image corresponding to the ratio of the black density and the white density of the digital latent image can be obtained. The problem of not occurring easily. Furthermore, when the resolution is improved by reducing the dot size in order to improve the image quality, the reproducibility of the latent image formed from minute dots becomes more difficult, and the resolution and particularly the gradation of the highlight area There is a tendency for images to be poor and lack sharpness. Further, irregular dot irregularities are perceived as graininess, which causes a reduction in the image quality of the highlight portion. Such an image has to be said to be inferior when compared with the recent ink jet technology which has been thinned to photographic quality.
[0004]
In order to improve these, a method has been proposed in which an image is formed using a dark color toner (dark toner) in the solid portion and a lighter toner (light toner) in the highlight portion.
[0005]
For example, an image forming method for forming an image by combining a plurality of toners each having a different density has been proposed (see, for example, Patent Documents 1 and 2). Further, an image forming apparatus has been proposed in which a light color toner having a maximum reflection density less than half of the maximum reflection density of dark toner is combined (for example, see Patent Document 3). The toner amount on the recording member is 0.5 mg / cm.²In this case, there has been proposed an image forming apparatus in which a dark toner having an image density of 1.0 or more and a light toner having a density of less than 1.0 are combined (for example, see Patent Document 4). Further, an image forming apparatus has been proposed in which toners having a recording density gradient ratio between dark toner and light toner are combined between 0.2 and 0.5 (see, for example, Patent Document 5). Although the image quality of the highlight portion is improved by these techniques, a large amount of toner must be placed on the recording member in the high density portion in order to produce a color tone with only light color toner. In addition, in a full-color image, when a light color toner is further overlapped in addition to cyan, magenta, yellow and black toner, the amount of toner placed on the recording member becomes enormous, and it is quite difficult to sufficiently fix this enormous amount of toner. Strict. In particular, when images were copied continuously at high speed, there were problems such as deterioration in image quality and occurrence of offset after multiple copies.
[0006]
Thus, until now, there has been a description of an image forming method using light color toner, but there has been mention of an image forming method that does not cause an offset or physical properties of a toner that exhibits excellent fixing properties even when a large amount of toner is placed thereon. There wasn't.
[0007]
[Patent Document 1]
Japanese Patent Laid-Open No. 11-84764
[Patent Document 2]
JP 2000-305339 A
[Patent Document 3]
JP 2000-347476 A
[Patent Document 4]
JP 2000-231279 A
[Patent Document 5]
JP 2001-290319 A
[0008]
[Problems to be solved by the invention]
An object of the present invention is to provide a full-color toner that can solve the above-described problems of the prior art.
[0009]
That is, an object of the present invention is to provide a toner and an image forming method that can reduce graininess and roughness from a low density region to a high density region.
[0010]
Further, the present invention provides a toner and an image forming method that have a wide fixing temperature range even when a large amount of toner is placed on a recording member, maintain an excellent image even after continuous copying, and have excellent offset resistance. Is an issue.
[0011]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a toner having a lightness and specific physical properties, so that it has a good image quality in a wide density region and a large amount on the recording member. The present inventors have found that an image forming method having excellent fixability can be provided even when the toner is transferred, and the present invention has been completed. That is, the present invention is as follows.
[0012]
(1) Contains at least a binder resin, a colorant, and a waxLight magentaToner,
  Lightness L in powder state^*Is 45-75,
  In the viscoelastic properties, the storage elastic modulus (G ′) at a temperature of 120 ° C.₁₂₀) Is 5 × 10²~ 1x10^Five[Pa] and storage elastic modulus (G ′) at a temperature of 180 ° C.₁₈₀) Is 10-5 × 10^Three[Pa]
  The toner was pressure-molded into pellets, and the height (gap) was adjusted to 10.000 mm.^ThreeDeformation amount when pressure of Pa is applied (R₂₀₀) Is 47-63% and the sample is 1.0 × 10 6 at a temperature of 120 ° C.^FourDeformation amount when pressure of Pa is applied (R₅₀₀) Is 65 to 85%, and the toner is a non-magnetic toner.Light magentatoner.
[0013]
(2)A light cyan toner containing at least a binder resin, a colorant, and a wax,
Lightness L in powder state ^* Is 45-75,
In viscoelastic properties, storage elastic modulus at a temperature of 120 ° C. (G ′ ₁₂₀ ) Is 5 × 10 ² ~ 1x10 ^Five [Pa] and storage elastic modulus at a temperature of 180 ° C. (G ′ ₁₈₀ ) Is 10-5 × 10 ^Three [Pa]
The toner was pressure-molded into pellets, and the height (gap) was adjusted to 10.000 mm. ^Three Deformation amount when pressure of Pa is applied (R ₂₀₀ ) Is 47-63% and the sample is 1.0 × 10 6 at a temperature of 120 ° C. ^Four Deformation amount when pressure of Pa is applied (R ₅₀₀ ) Is 65 to 85%, and the toner is a non-magnetic toner.
[0014]
(3)In the endothermic curve obtained by differential scanning calorimetry (DSC) measurement of the toner, one or a plurality of endothermic peaks exist in the temperature range of 30 to 200 ° C., and the maximum endothermic peak in the endothermic peak has a maximum value of 65. The toner according to (1) or (2), which is in a range of ˜105 ° C.
[0015]
(4)The toner according to any one of (1) to (3), wherein the wax contains at least an aliphatic hydrocarbon wax.
[0016]
(5)The toner according to any one of (1) to (4), wherein the toner has an average circularity A of 0.940 to 0.970 in particles having an equivalent circle diameter of 3 μm or more.
[0017]
(6) An image forming method in which a toner image made of toner formed on a recording member is heated and pressed and fixed by a fixing unit to form an image on the recording member,
The fixing unit includes a rotatable fixing roller, a fixing belt that is pressed against and contacts the fixing roller, and rotates while forming a nip portion as the fixing roller rotates, and a heating unit that heats the nip portion. And fixing the toner image on the recording member by nipping and conveying the recording member at the nip portion by the rotation of the fixing roller and the fixing belt,
The width of the nip portion in the rotation direction of the fixing roller is 10 mm or more;
The image forming method, wherein the toner is the light magenta toner described in (1).
[0018]
(7) An image forming method for forming an image on a recording member by heating and pressurizing and fixing a toner image made of toner formed on the recording member by a fixing unit,
The fixing unit includes a rotatable fixing roller, a fixing belt that is pressed against and contacts the fixing roller, and rotates while forming a nip portion as the fixing roller rotates, and a heating unit that heats the nip portion. And fixing the toner image on the recording member by nipping and conveying the recording member at the nip portion by the rotation of the fixing roller and the fixing belt,
The width of the nip portion in the rotation direction of the fixing roller is 10 mm or more;
The light-colored magenta toner (magenta toner a) according to claim 1 and at least a binder resin, a colorant, and a wax as the toner, and the lightness L of the magenta toner a in a powder state. ^* (A) Lower brightness L ^* (B), magenta toner b which is a non-magnetic toner,
Lightness L of the magenta toner a ^* (A) and lightness L of the magenta toner b ^* (B) satisfies the relationship of the following formula (1).
10 ≦ L ^* (A) -L ^* (B) ≦ 40
[0019]
(8)An image forming method for forming an image on a recording member by heating and pressing and fixing a toner image made of toner formed on the recording member by a fixing means,
  The fixing unit includes a rotatable fixing roller, a fixing belt that is pressed against and contacts the fixing roller, and rotates while forming a nip portion as the fixing roller rotates, and a heating unit that heats the nip portion. And fixing the toner image on the recording member by nipping and conveying the recording member at the nip portion by the rotation of the fixing roller and the fixing belt,
  The width of the nip portion in the rotation direction of the fixing roller is 10 mm or more;
The toner is the light cyan toner described in (2).An image forming method.
[0020]
(9)An image forming method for forming an image on a recording member by heating and pressing and fixing a toner image made of toner formed on the recording member by a fixing means,
  The fixing unit includes a rotatable fixing roller, a fixing belt that is pressed against and contacts the fixing roller, and rotates while forming a nip portion as the fixing roller rotates, and a heating unit that heats the nip portion. And fixing the toner image on the recording member by nipping and conveying the recording member at the nip portion by the rotation of the fixing roller and the fixing belt,
  The width of the nip portion in the rotation direction of the fixing roller is 10 mm or more;
As the toner, the light cyan toner (cyan toner a) described in (2);At least a binder resin, a colorant, and a wax,cyanLightness L of toner a^*(A) Lower brightness L^*Have (b)Cyan toner b which is a non-magnetic tonerAnd
Cyan toner aBrightness L^*(A) andCyan toner bBrightness L^*(B) satisfies the relationship of the following formula (1)DoAn image forming method.
[0021]
[Expression 4]
10 ≦ L^*(A) -L^*(B) ≦ 40
[0022]
DETAILED DESCRIPTION OF THE INVENTION
The toner of the present invention has a brightness L in a powder state.^*Is a storage elastic modulus (G ′) at a temperature of 120 ° C.₁₂₀) Is 5 × 10²~ 1x10^Five[Pa] and storage elastic modulus at a temperature of 180 ° C. (G ′₁₈₀) Is 10-5 × 10^Three[Pa] and 4.0 × 10 4 at a temperature of 120 ° C. on a sample obtained by press-molding the toner into pellets.^ThreeDeformation amount when pressure of Pa is applied (R₂₀₀) Is 45-65% and the sample is 1.0 × 10 6 at a temperature of 120 ° C.^FourDeformation amount when pressure of Pa is applied (R₅₀₀) Is 65 to 85%.
[0023]
In the present invention, the lightness L^*Indicates a value obtained as a toner in a powder state. Generally brightness L^*L^*a^*b^*In the system color system, the degree of brightness of a color that can be compared regardless of hue and saturation is shown in the range of 0 to 100. In the present invention, L in the powder toner^*Is measured using a spectroscopic color difference meter “SE-2000” (manufactured by Nippon Denshoku Industries Co., Ltd.).
[0024]
In the present invention, L^*Is a toner having a color strength of less than 45 and a higher brightness than normal toner. The reason why the image in the highlight portion is good when toner having high brightness is used is as follows. When an image in a highlight portion is formed with toner having low lightness (dark color), a low lightness portion with toner has a locally high density, and a clear contrast can be formed with a portion without toner. In this case, in the highlight portion, there are naturally many portions where no toner is attached, and an image having a shape in which high-density points with low brightness are dispersed is formed. This results in a very grainy and conspicuous image.
[0025]
Therefore, in the present invention, if the highlight portion is made of toner having a high brightness per particle to reduce the difference in brightness between paper and toner, and instead developed with a larger amount of toner than usual, the same density can be obtained. Since it is formed by a larger number of toners, that is, image points (color points) than the above development, as a result, a highlight portion having better graininess (less graininess) than the image is formed. .
[0026]
In the present invention, the lightness of the toner is defined not by the spectral sensitivity characteristic of the image after fixing, but by the spectral sensitivity characteristic in the powder state for the following reason. There are various types of fixing devices and recording members. Depending on the conditions and combinations thereof, the gloss and color gamut that appear even when the same toner is fixed vary greatly. Also, depending on the pressure of the fixing device, the way the toner is crushed differs, which affects the graininess (roughness). In that respect, when the direct colorimetry method according to the present invention is employed, the brightness of the toner itself can be accurately defined because it is not affected by the structure of the fixing device or the transferred material. That is, in the present invention, the type and amount of the colorant and wax added to the toner and the dispersion form are controlled, and the storage elastic modulus of the toner, the amount of deformation, and the brightness of the powdered toner are within the scope of the present invention. By adjusting, it is possible to obtain an image with less granularity (roughness) and a wide color reproduction range.
[0027]
The lightness L in the powder state of the toner a of the present invention.^*Is preferably 50 to 73, more preferably 55 to 70.
[0028]
Further, it is more advantageous to form an image by using different toners depending on the image density, such as using dark toner in the solid portion of the image to be formed and using the light color toner (toner a) of the present invention in the highlight portion. Is obtained. It is also a preferred form to use a combination of dark color toner and light color toner (toner a) as appropriate according to the density gradation of the image to be formed. The same effect can be obtained when used for any color toner such as yellow (Y), magenta (M), cyan (C), black (K) and the like.
[0029]
As described above, when a full-color image is formed by combining dark and light toners, it is necessary to place more toner on the recording member, so that it is difficult to obtain sufficient fixing performance. In addition, when images are continuously copied at a high speed, there is a concern that there are problems such as deterioration in image quality and occurrence of offset in images after a plurality of sheets. Therefore, the present inventors have found that in order to obtain a toner having a sufficient fixing temperature range and excellent offset resistance even in such a case, the physical properties of the toner may be limited as follows. It was.
[0030]
That is, the toner a of the present invention has a storage elastic modulus (G ′) at a temperature of 120 ° C. in viscoelastic characteristics.₁₂₀) Is 5 × 10²~ 1x10^Five[Pa] range, storage elastic modulus at a temperature of 180 ° C. (G ′₁₈₀) Is 10-5 × 10^Three[Pa]. G '₁₂₀Is 6 × 10²~ 9x10^Four[Pa] is preferred, 7 × 10²~ 8x10^Four[Pa] is preferable. G '₁₈₀20 ~ 4x10^Three[Pa] is preferable, and 30 to 3 × 10^Three[Pa] is preferable.
[0031]
G 'of toner a₁₂₀Is 5 × 10²If it is smaller than [Pa], when a large amount of toner has to be fixed as in the present invention, when the fixing temperature is high, the winding of the recording member around the fixing roller tends to become remarkable. G '₁₈₀Is less than 10 [Pa], an offset to the fixing roller occurs, and when a large amount of toner is placed on the recording member for fixing as in the present invention, the fixing region on the high temperature side becomes narrow.
[0032]
On the other hand, G '₁₂₀Is 1 × 10^FiveIf it is greater than [Pa], offset to the fixing roller is likely to occur when the fixing temperature is low, and if a large amount of toner is placed on the recording member and fixed as in the present invention, the toner below the recording member is fixed. Until the heat is not sufficiently transferred, the fixing area on the low temperature side becomes very narrow. G '₁₈₀Is 5 × 10^ThreeIf it is larger than [Pa], there is almost no glossiness of the image at the time of fixing, and the image quality deteriorates. In particular, with a light color toner as in the present invention, the image density does not increase no matter how much toner is loaded. In the toner of the present invention, the method for adjusting the storage elastic modulus is caused by the weight average molecular weight (Mw) of the binder resin and the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn). However, it is slightly different depending on the type of resin such as polyester and hybrid and the monomer composition. Specifically, by setting the above Mw to 60000 or more and Mw / Mn to 10-30, G ′₁₂₀And G '₁₈₀Can be easily adjusted to the above range.
[0033]
When the light color toner a of the present invention is used at the same time as the dark toner, it is desirable that the viscoelastic characteristics of the dark toner are also in the above range from the viewpoint of offset resistance and low temperature fixability.
[0034]
  Further, the toner a of the present invention is 4.0 × 10 4 at a temperature of 120 ° C. on a sample obtained by pressure-molding the toner into a pellet.³Deformation amount when pressure of Pa is applied (R₂₀₀) Is 45 to 65%. This deformation amount R₂₀₀Is preferably 47 to 63%, more preferably 48 to 62%. In addition, the toner a of the present invention is obtained by adding 1.0 × 10 6 to the pellet-like sample at a temperature of 120 ° C.⁴Deformation amount of pelletized material when pressure of Pa is applied (R₅₀₀) Is 65 to 85%. This deformation amount R _{5 00}Is preferably 67 to 82%, more preferably 68 to 81%.
[0035]
Deformation amount (R₂₀₀) Is less than 45%, the toner is not crushed when the recording member to which the toner is transferred passes through the fixing device, and the image is scattered around the image and a high-definition image cannot be obtained. In particular, such a problem is likely to appear remarkably when a large amount of toner is placed on a recording member to obtain an image density as in the present invention. The deformation amount (R₅₀₀) Is less than 65%, when the light color toner a of the present invention is used together with the dark color toner, the glossiness becomes non-uniform between where the light color toner a is used and where the dark toner is used much. The quality of
[0036]
Deformation amount (R₂₀₀) Exceeds 65%, the toner itself is soft, which hinders development and deteriorates the durability of the toner, thus lowering the transfer efficiency. Also, (R₅₀₀) Exceeds 85%, the toner is excessively crushed on the image, and when the toner is placed in a large amount, the image blurs and a feeling of roughness occurs. R of the toner of the present invention₂₀₀And R₅₀₀Is largely due to the conditions at the time of toner preparation. Specifically, in the case of pulverized toner, the above-described R₂₀₀And R₅₀₀Can be adjusted to the above range, but can also be adjusted by adding a molecular weight of the resin, a crosslinking agent, or the like.
[0037]
When the light color toner a of the present invention is used simultaneously with the dark color toner, it is desirable that the deformation amount of the dark color toner is also in the above range in order to obtain a high-definition image.
[0038]
Rather than using a light toner and a dark toner separately, it is possible to use a low-density area with no blurring by adjusting the amount of each toner used appropriately according to the density gradation of the image to be formed. Reproduction and smooth halftone reproduction up to high density are possible, but the following effects can be obtained by using the light color toner a and dark color toner of the present invention having the above viscoelastic characteristics and deformation amount. There is.
[0039]
When an image is output using a recording member such as glossy paper, a phenomenon occurs in which unevenness of gloss occurs in the image due to a difference in the amount of applied toner, and a portion with low brightness appears to float. Here, the toner a of the present invention exhibits excellent fixability with respect to a larger amount of applied toner. Therefore, the toner applied amount of the entire image is controlled to output a uniform glossy image such as a photograph. Is possible.
[0040]
Lightness L in powder state^*As described above, the toner “a” of the present invention having an A of 45 or more has a lower coloring power and higher brightness than a normal toner. Lightness L in the powder state of the toner a of the present invention.^*The value of L^*(A), the lightness L of the dark toner (hereinafter, this may be referred to as “toner b”) used together with the toner a.^*The value of L^*When expressed as (b), it is preferable to satisfy the relationship of the following formula (1).
[0041]
[Equation 5]
10 ≦ L^*(A) -L^*(B) ≦ 40
[0042]
When the light color toner (a) and the dark color toner (b) have lightness satisfying the above formula (1), the density change from the low density area to the high density area is smoothly reproduced, and the three-dimensional image in the full color image is obtained. This is preferable because the color reproduction space becomes wide. L^*(A) -L^*When the value of (b) is less than 10, the three-dimensional color reproduction space in the full color image may be lowered. On the other hand, L^*(A) -L^*When the value of (b) is larger than 40, there is a possibility that the reproduction of the halftone from the low density region to the high density region becomes difficult to be smooth.
[0043]
Next, a preferred toner configuration capable of maximizing the effects of the present invention will be described.
[0044]
The toners a and b of the present invention contain at least a binder resin, a colorant and a wax. The toner of the present invention has toner particles mainly composed of the binder resin, the colorant and the wax, and an external additive which is added to the toner particles as necessary.
[0045]
Furthermore, the present inventors have found that the thermal characteristics of the wax contained in the toner are an important factor for achieving both the above-described high image quality and necessary and sufficient fixing properties.
[0046]
In order to obtain a toner with good saturation of the output image and excellent feeling of roughness (graininess) in the low density range, it is necessary to contain wax in addition to the binder resin and the colorant. is there. In particular, the toner containing wax is preferably used when no oil is applied to the structure of the fixing device or when a fixing device of a small amount of oil coating system with a very small coating amount is used.
[0047]
  Toner differential measured due to wax usedscanningheatamountThe endothermic curve obtained by analysis (DSC) has one or more endothermic peaks in the temperature range of 30 to 200 ° C, and the maximum endothermic peak in the endothermic peak is in the range of 65 to 105 ° C. Preferably there is. The maximum value of the maximum endothermic peak in the endothermic peak of the toner in the above range is more preferably in the range of 70 to 100 ° C.
[0048]
When the maximum endothermic peak of the toner is less than 65 ° C, the wax tends to dissolve on the toner surface when left in a high temperature environment, and the anti-blocking performance is slightly deteriorated. There is. On the other hand, when the maximum value of the maximum endothermic peak is larger than 105 ° C., it becomes difficult for the wax to quickly migrate to the surface of the molten toner during low-temperature fixing, and high-temperature offset is likely to occur. In particular, in a system in which a large amount of toner is placed on a recording member as in the present invention, the fixing conditions become severe.
[0049]
The toner of the present invention contains one or more kinds of waxes, and preferably contains at least a hydrocarbon wax. By adding the hydrocarbon wax to the toner, the affinity between the colorant and the wax is improved, so that the colorant can be finely dispersed in the toner.
[0050]
The following are mentioned as an example of the wax used for this invention. Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight alkylene copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, or oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax, Or block copolymers thereof; waxes based on fatty acid esters such as behenate behenate and stearyl stearate, carnauba wax and montanate wax, and fatty acid esters such as deoxidized carnauba wax. What deoxidized one part or all part is mentioned. Further, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brandic acid, eleostearic acid, and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, and seryl alcohol , Saturated alcohols such as melyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis laurin Saturated fatty acid bisamides such as acid amides and hexamethylene bis stearic acid amides; ethylene bis oleic acid amides, hexamethylene bis oleic acid amides, N, N ′ dioleyl adipic amides, N, N ′ diols Unsaturated fatty acid amides such as rubebacic acid amide; Aromatic bisamides such as m-xylene bisstearic acid amide and N, N ′ distearyl isophthalic acid amide; Calcium stearate, calcium laurate, zinc stearate, magnesium stearate, etc. Aliphatic metal salts (generally referred to as metal soaps); waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides and many others Examples include partially esterified products of monohydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like.
[0051]
Examples of waxes that are particularly preferably used in the present invention include aliphatic hydrocarbon waxes. For example, low molecular weight polyalkylene wax obtained by radical polymerization of alkylene under high pressure or Ziegler catalyst or metallocene catalyst under low pressure; Fischer-Tropsch wax synthesized from coal or natural gas; thermal decomposition of high molecular weight alkylene polymer An alkylene polymer obtained by the above-mentioned method is preferably a hydrocarbon residue obtained by distilling hydrocarbons obtained from the synthesis gas containing carbon monoxide and hydrogen by the age method or by hydrogenating them. Furthermore, what carried out the fractionation of the hydrocarbon wax by the use of the press perspiration method, the solvent method, the vacuum distillation, or the fractional crystallization method is more preferably used. The hydrocarbon as a base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (mostly two or more multi-component systems) [for example, the Jintol method, the Hydrocol method (the fluidized catalyst bed Hydrocarbon compounds synthesized by use); hydrocarbons with up to several hundred carbon atoms obtained by the age method (using the identified catalyst bed) from which a large amount of wax-like hydrocarbons can be obtained; alkylene such as ethylene by Ziegler catalyst Polymerized hydrocarbons; paraffin waxes are preferred because they are linear hydrocarbons with little branching, small and long saturation. In particular, a wax synthesized by a method that does not rely on polymerization of alkylene is also preferred from its molecular weight distribution.
[0052]
In the molecular weight distribution of the wax, the main peak is preferably in the region of molecular weight 350 to 2,400, and more preferably in the region of 400 to 2,000. By giving such a molecular weight distribution, preferable thermal characteristics can be imparted to the toner.
[0053]
As the binder resin used in the present invention, various resins conventionally known as binder resins for electrophotography are used. Among them, (a) polyester resin, (b) polyester unit and vinyl copolymer unit are used. (C) a mixture of a hybrid resin and a vinyl copolymer, (d) a mixture of a hybrid resin and a polyester resin, (e) a mixture of a polyester resin and a vinyl copolymer, And (f) a resin selected from any of a mixture of a polyester resin, a hybrid resin, and a vinyl copolymer.
[0054]
When a polyester resin is used as the binder resin, a divalent or higher valent alcohol component and a divalent or higher valent acid component such as carboxylic acid, carboxylic acid anhydride, or carboxylic acid ester can be used as raw material monomers. Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.
[0055]
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. Can be mentioned.
[0056]
The divalent acid component includes aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides; And succinic acid substituted with 6 to 12 alkyl groups or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof;
[0057]
Examples of the trivalent or higher polyvalent carboxylic acid component for forming a polyester resin having a crosslinking site include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2 , 4-Naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof. In addition, it is preferable that the usage-amount of a trivalent or more polyvalent carboxylic acid component is 0.1-1.9 mol% on the basis of all the monomers.
[0058]
When the polyester resin is used as the binder resin of the toner of the present invention, among the above monomers, in particular, a bisphenol derivative represented by the following general formula (1) is used as a diol component, and a divalent or higher carboxylic acid or its acid Carboxylic acid components consisting of anhydrides or lower alkyl esters thereof (for example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) are used as acid components and these are condensed. A polymerized polyester resin is preferred because it has good charging characteristics as a color toner.
[0059]
[Chemical 1]

(In the formula, R represents an ethylene group or a propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)
[0060]
Further, when a hybrid resin having a polyester unit and a vinyl polymer unit is used as the binder resin, further improved wax dispersibility, low-temperature fixability, and offset resistance can be expected. The hybrid resin used in the present invention means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are formed by a transesterification reaction, preferably a vinyl polymer. Is used to form a graft copolymer (or block copolymer) having a backbone polymer and a polyester unit as a branch polymer.
[0061]
Here, the polyester unit means at least a polycondensation product of a polyol and a polycarboxylic acid. Moreover, a vinyl unit means the thing formed by superposing | polymerizing 1 type, or 2 or more types of vinyl monomers.
[0062]
  The following are mentioned as a vinyl-type monomer for producing | generating a vinyl-type polymer. Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyreneStyrene derivatives; Such as ethylene, propylene, butylene, isobutyleneUnsaturated monoolefinsUnsaturated vinylenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate , Ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, methacryl Α-methylene aliphatic monocarboxylic acid esters such as diethylaminoethyl acid; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-oacrylate Acrylic acid esters such as chill, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl Vinyl ketones such as ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; Vinyl naphthalenes; Acrylonitrile, methacrylonitrile And acrylic acid or methacrylic acid derivatives such as acrylamide.
[0063]
In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Unsaturated dibasic acid half esters such as alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; dimethyl maleic acid, unsaturated dibasic acid ester such as dimethyl fumaric acid; acrylic acid, Α, β-unsaturated acids such as phosphoric acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic anhydride and cinnamic anhydride, the α, β-unsaturated acids and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.
[0064]
Furthermore, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.
[0065]
In the toner of the present invention, the vinyl polymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. In this case, the crosslinking agent used is Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butanediol di Examples include acrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and the above compounds in which acrylate is replaced by methacrylate; linked by an alkyl chain containing an ether bond. As diacrylate compounds For example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate Examples of diacrylate compounds connected by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene ( 4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate.
[0066]
As polyfunctional cross-linking agents, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and acrylates of the above compounds are replaced by methacrylate; triallylcia Examples include nurate and triallyl trimellitate.
[0067]
In the present invention, it is preferable that a monomer component capable of reacting with both resin components is contained in the vinyl polymer component and / or the polyester resin component. Examples of the monomer constituting the polyester resin component that can react with the vinyl polymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl polymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
[0068]
As a method of obtaining a reaction product of a vinyl polymer and a polyester resin, either a polymer containing a monomer component capable of reacting with each of the vinyl polymer and the polyester resin listed above is present, or either A method obtained by polymerizing both resins is preferred.
[0069]
Examples of the polymerization initiator used for producing the vinyl polymer of the present invention include 2,2′-azobisisobutyronitrile and 2,2′-azobis (4-methoxy-2,4-dimethyl). Valeronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1 , 1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl -4-methoxyvaleronitrile, 2,2'-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone Ketone peroxides such as 2-oxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di- -T-butyl peroxide, t-butyl cumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, Lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl Pyrperoxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxide Oxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butylperoxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butylperoxyallyl carbonate, t-amylperoxy 2-ethylhexanoate, di-t-butylperoxyhexahydrote Phthalate, di -t- butyl peroxy azelate and the like.
[0070]
Examples of the production method capable of preparing the hybrid resin used in the toner of the present invention include the following production methods (1) to (6).
[0071]
(1) A method in which a vinyl polymer, a polyester resin, and a hybrid resin are blended after production. The blend is produced by dissolving and swelling in an organic solvent (for example, xylene) and then distilling off the organic solvent. The hybrid resin is synthesized by separately producing a vinyl polymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and heating to perform a transesterification reaction. An ester compound can be used.
[0072]
(2) A method for producing a polyester unit and a hybrid resin in the presence of a vinyl polymer after the production thereof. The hybrid resin is produced by a reaction between a vinyl polymer (a vinyl monomer can be added if necessary) and a polyester monomer (alcohol, carboxylic acid) and / or polyester. Also in this case, an organic solvent can be appropriately used.
[0073]
(3) A method for producing a vinyl polymer unit and a hybrid resin in the presence of a polyester resin after the production. The hybrid resin is produced by a reaction between a polyester unit (a polyester monomer can be added if necessary) and a vinyl monomer and / or a vinyl polymer unit.
[0074]
(4) After producing the vinyl polymer and polyester, a hybrid resin is produced by adding a vinyl monomer and / or polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. Also in this case, an organic solvent can be appropriately used.
[0075]
(5) After the hybrid resin is produced, a vinyl polymer unit and a polyester unit are produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) and performing an addition polymerization and / or a condensation polymerization reaction. The In this case, as the hybrid resin, those produced by the production methods (2) to (4) can be used, and those produced by a known production method can be used as necessary. Furthermore, an organic solvent can be appropriately used.
[0076]
(6) A vinyl polymer unit, a polyester unit, and a hybrid resin are produced by mixing a vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reaction. Furthermore, an organic solvent can be appropriately used.
[0077]
In the production methods of (1) to (5) above, a polymer unit having a plurality of different molecular weights and degrees of crosslinking can be used as the vinyl polymer unit and / or the polyester unit.
[0078]
The binder resin contained in the toner of the present invention includes a mixture of the polyester and a vinyl polymer, a mixture of the hybrid resin and a vinyl polymer, a vinyl resin in addition to the polyester resin and the hybrid resin. A mixture of polymers may be used.
[0079]
As the colorant contained in the toner of the present invention, as the black colorant, a carbon black; a magnetic material; a color adjusted to black using yellow, magenta, and cyan colorants is used. When a magnetic material is used as the black colorant, it is used by adding 5 to 200 parts by mass with respect to 100 parts by mass of the resin, unlike other colorants.
[0080]
Examples of the magnetic material include metal oxides containing elements such as iron, cobalt, nickel, copper, magnesium, manganese, aluminum, and silicon. Among these, those containing iron oxide as a main component, such as triiron tetroxide and γ-iron oxide, are preferable. Further, from the viewpoint of controlling the chargeability of the toner, other metal elements such as silicon element and aluminum element may be contained. The magnetic material has a BET specific surface area of 2 to 30 m by a nitrogen adsorption method.²/ G, especially 3 to 28m²/ G, and a Mohs hardness of 5 to 7 is preferred.
[0081]
When the toner a is prepared, the content of the magnetic material is preferably 5 to 20 parts by mass with respect to 100 parts by mass of the binder resin. Further, when the toner b is prepared, the content of the magnetic material is preferably 30 to 200 parts by mass in total with respect to 100 parts by mass of the binder resin.
[0082]
As a coloring pigment for magenta toner, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209, 238, C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.
[0083]
As the colorant, the above-mentioned pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.
[0084]
Examples of the magenta toner dye include C.I. I solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disper thread 9; I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28 may be mentioned.
[0085]
Examples of the color pigment for cyan toner include C.I. I. Pigment blue 2, 3, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, and a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by the following formula.
[0086]
[Chemical formula 2]

[0087]
Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat yellow 1, 3, 20, etc. are mentioned.
[0088]
Examples of the coloring dye for yellow include C.I. I. Solvent Yellow 162 and the like, and it is also preferable to use a pigment and a dye together.
[0089]
When the toner a is prepared, the content of the colorant in the present invention is preferably 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the binder resin. In addition, when the toner b is prepared, the content of the colorant is preferably 2.5 to 15 parts by mass with respect to 100 parts by mass of the binder resin.
[0090]
The toner of the present invention may further have a charge control agent added to the toner particles. As the charge control agent contained in the toner in the present invention, known ones can be used, and in particular, an aromatic carboxylic acid metal compound that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount. Is preferred.
[0091]
Among the charge control agents, the negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid in the side chain, boron compounds, urea compounds, silicon A compound, calixarene, can be used. As the positive charge control agent, a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, or an imidazole compound can be used. The charge control agent is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin.
[0092]
The toner of the present invention may further have other additives added to the toner particles. As the additive externally added to the toner particles in the present invention, known ones can be used. In particular, the addition of a fluidity improver is an improvement in image quality and storage stability in a high temperature environment. preferable. As the fluidity improver, inorganic fine powders such as silica, titanium oxide, and aluminum oxide are preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.
[0093]
Examples of the hydrophobizing agent include coupling agents such as silane compounds, titanate coupling agents, aluminum coupling agents, and zircoaluminate coupling agents.
[0094]
Specifically, for example, a silane compound represented by the following general formula (2) is preferable.
[0095]
[Chemical 3]
R_mSiY_n                            (2)
[In the formula, R represents an alkoxy group, m represents an integer of 1 to 3, Y represents an alkyl group, a vinyl group, a phenyl group, a methacryl group, an amino group, an epoxy group, a mercapto group, or a derivative thereof. , N represents an integer of 1 to 3. ]
[0096]
Examples of the compound represented by the general formula (2) include hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Examples include isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, and n-octadecyltrimethoxysilane.
[0097]
The processing amount is preferably 1 to 60 parts by mass, more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the inorganic fine powder.
[0098]
Particularly suitable as the silane compound used in the present invention is an alkylalkoxysilane represented by the following general formula (3).
[0099]
[Formula 4]
C_nH_{2n + 1}-Si- (OC_mH_{2m + 1})_Three                    (3)
[Wherein, n represents an integer of 4 to 12, and m represents an integer of 1 to 3. ]
[0100]
In the alkylalkoxysilane represented by the general formula (3), when n is smaller than 4, treatment is easy but the degree of hydrophobicity is low, which is not preferable. When n is larger than 12, hydrophobicity is sufficient, but coalescence of titanium oxide fine particles increases, and fluidity imparting ability tends to decrease. On the other hand, if m is larger than 3, the reactivity of the alkylalkoxysilane is lowered and it becomes difficult to perform hydrophobicity well. More preferably, the alkylalkoxysilane is one in which n is 4-8 and m is 1-2.
[0101]
The treatment amount of the alkylalkoxysilane is also preferably 1 to 60 parts by mass, more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the inorganic fine powder.
[0102]
The hydrophobizing treatment may be performed with one type of hydrophobizing agent alone, or two or more types may be used in combination. For example, one type of hydrophobizing agent may be used to perform the hydrophobizing treatment, or two hydrophobizing agents may be used at the same time, or after one hydrophobizing agent may be used to make another hydrophobizing agent. Further, a hydrophobizing treatment may be performed.
[0103]
The fluidity improver is preferably added in an amount of 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the toner particles.
[0104]
The toner of the present invention can be suitably used for both a one-component developing method and a non-magnetic two-component developing method.
[0105]
When the toner of the present invention is used for a two-component developer, the toner is used by mixing with a magnetic carrier. Examples of the magnetic carrier include surface oxidized or unoxidized iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, alloy particles thereof, oxide particles, ferrite and the like. Can be used.
[0106]
The coated carrier obtained by coating the surface of the magnetic carrier particles with a resin is particularly preferable in a developing method in which an AC bias is applied to the developing sleeve. Coating methods include a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the magnetic carrier core particles, and a method in which the magnetic carrier core particles and the coating material are mixed with powder. A conventionally known method can be applied.
[0107]
Examples of the coating material on the surface of the magnetic carrier core particle include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These are used alone or in plural. The treatment amount of the coating material is preferably 0.1 to 30% by mass (preferably 0.5 to 20% by mass) with respect to the carrier core particles. The number average particle size of these carriers is 10 to 100 μm, preferably 20 to 70 μm.
[0108]
When a two-component developer is prepared by mixing the toner of the present invention and a magnetic carrier, the mixing ratio is usually 2 to 15% by mass, preferably 4 to 13% by mass, as the toner concentration in the developer. Good results are obtained. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.
[0109]
In the present invention, the toner shape is one of the important factors for forming an excellent image. It is known that the transfer efficiency is improved by increasing the circularity of the toner. However, when an image is formed using the toner of the present invention, a larger amount of toner is placed on the recording member than before, so that the transfer efficiency is improved. If it is bad, the image may become noticeable. In addition, when toners having different brightness such as toners a and b are used in combination, there is a risk that unevenness due to the density difference occurs in the image when transfer omission occurs in the intermediate density range. In the present invention, a preferable toner shape has an average circularity in the range of 0.940 to 0.970, preferably 0.942 to 0.965 in particles having an equivalent circle diameter of 3 μm or more. If the average circularity is less than 0.940, the transferability, particularly the transfer efficiency, is inferior, the graininess becomes prominent in the low density region, and an image with a rough feeling may be obtained. On the other hand, if the average circularity is greater than 0.970, the shape is too spherical, which may cause image defects due to poor cleaning, such as toner slipping through the cleaning blade in the photosensitive drum cleaning process. Further, when fixing a large amount of toner on the recording member as in the present invention, the toner easily rolls off from the recording member when passing through the fixing device. The feeling tends to stand out.
[0110]
Next, a procedure for producing the toner of the present invention will be described.
[0111]
First, a predetermined amount of materials (internal additives) such as a resin and a colorant constituting the toner particles are weighed, mixed, and mixed (this is referred to as “raw material mixing step”). As an example of a mixing apparatus used when mixing raw materials, there are a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauter mixer, and the like.
[0112]
Next, the mixed toner raw materials are melted and kneaded to melt resins, and a colorant or the like is dispersed therein to obtain a colored resin composition (this is referred to as “melting and kneading step”). In this melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. In general, a twin-screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, or the like is used.
[0113]
Further, the colored resin composition obtained by the melt kneading step is melted and kneaded, rolled with two rolls or the like, and cooled through a cooling step of cooling with water cooling or the like.
[0114]
Next, the cooled product of the obtained colored resin composition is generally pulverized to a desired particle size in a pulverization step. In the pulverization step, first, coarse pulverization is performed with a crusher, a hammer mill, a feather mill or the like, and further, pulverization is performed with a kryptron system manufactured by Kawasaki Heavy Industries, Ltd., a super rotor manufactured by Nisshin Engineering Co., Ltd. or the like. After that, if necessary, classification is performed using a classifier such as an inertia class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.) or a centrifugal class turboturbo (manufactured by Hosokawa Micron Co.), and the weight average particle diameter Gives a classified product of 3 to 11 μm.
[0115]
If necessary, surface modification (that is, spheronization treatment) may be performed in the surface modification step to obtain a classified product. Examples of the apparatus for performing such surface modification include a hybridization system manufactured by Nara Machinery Co., Ltd., a mechano-fusion system manufactured by Hosokawa Micron Corporation, and the like.
[0116]
Further, if necessary, a sieving machine such as a wind-type sieve high voltor (manufactured by Shin Tokyo Machine Co., Ltd.) may be used. Furthermore, as a method of externally adding the external additive, a predetermined amount of classified toner and various known external additives are blended, and a high-speed stirrer that gives a shearing force to the powder such as a Henschel mixer or a super mixer is removed. The toner can be obtained by stirring and mixing as an accessory.
[0117]
FIG. 1 is a schematic cross-sectional view showing a configuration of an example of a surface modification apparatus preferably used in the present invention, and FIG. 2 is a schematic plan view of the surface modification apparatus of FIG.
[0118]
In the surface modification apparatus shown in FIG. 1, the casing 15, a jacket (not shown) through which cooling water or antifreeze liquid can be passed, and classification means for separating particles larger than a predetermined particle size and fine particles having a predetermined particle size or less. A certain classification rotor 1, a dispersion rotor 6 which is a surface treatment means for applying a mechanical shock to the particles to treat the surface of the particles, and a predetermined interval with respect to the outer periphery of the dispersion rotor 6. Liner 4, guide ring 9 that is a guide means for guiding particles larger than a predetermined particle size among particles divided by classification rotor 1 to dispersion rotor 6, and particles among particles divided by classification rotor 1 A fine powder collecting discharge port 2 that is a discharge unit that discharges fine particles having a predetermined particle diameter or less to the outside of the apparatus, and a cold air introduction port that is a particle circulation unit that sends particles whose surface is treated by the dispersion rotor 6 to the classification rotor 1 5 and processed Child has a raw material supply port 3 for introducing into the casing 15, and a closable powder discharge port 7 and the discharge valve 8 for discharging the treated surface particles from the casing 15 inside.
[0119]
The classification rotor 1 is a cylindrical rotor and is provided on one end face side in the casing 15. The fine powder collection outlet 2 is provided at one end of the casing 15 so as to discharge particles inside the classification rotor 1. The raw material supply port 3 is provided at the center of the peripheral surface of the casing 15. The cold air introduction port 5 is provided on the other end surface side of the peripheral surface of the casing 15. The powder discharge port 7 is provided at a position facing the raw material supply port 3 on the peripheral surface of the casing 15. The discharge valve 8 is a valve that freely opens and closes the powder discharge port 7.
[0120]
A dispersion rotor 6 and a liner 4 are provided between the cold air introduction port 5 and the raw material supply port 3 and the powder discharge port 7. The liner 4 is provided along the inner peripheral surface of the casing 15. As shown in FIG. 2, the dispersion rotor 6 includes a disk and a plurality of rectangular disks 10 arranged along the normal line of the disk at the periphery of the disk. The dispersion rotor 6 is provided on the other end surface side of the casing 15 and is provided at a position where a predetermined interval is formed between the liner 4 and the square disk 10. A guide ring 9 is provided at the center of the casing 15. The guide ring 9 is a cylindrical body and is provided so as to extend from a position covering a part of the outer peripheral surface of the classification rotor 1 to the vicinity of the classification rotor 6. The guide ring 9 includes a first space 11 that is a space between the outer peripheral surface of the guide ring 9 and the inner peripheral surface of the casing 15 in the casing 15, and a second space that is a space inside the guide ring 9. A space 12 is formed.
[0121]
The dispersion rotor 6 may have a cylindrical pin instead of the square disk 10. In the present embodiment, the liner 4 is provided with a large number of grooves on the surface facing the square disk 10, but may have no grooves on the surface. Moreover, the installation direction of the classification rotor 1 may be vertical as shown in FIG. 1 or horizontal. Further, the number of classification rotors 1 may be single or multiple as shown in FIG.
[0122]
In the surface reforming apparatus configured as described above, when a certain amount of finely pulverized product is introduced from the raw material supply port 3 with the discharge valve 8 closed, the charged finely pulverized product is first blower (not shown). ) And classified by the classification rotor 1. At that time, the classified fine powder having a predetermined particle size or less passes through the peripheral surface of the classification rotor 1, is guided to the inside of the classification rotor 1, and is continuously discharged and removed out of the apparatus. Coarse powder having a predetermined particle diameter or more is applied to a circulating flow generated by the dispersion rotor 6 along the inner periphery (second space 12) of the guide ring 9 due to centrifugal force, and the gap between the square disk 10 and the liner 4 ( Hereinafter, it is also referred to as “surface modification zone”. The powder guided to the surface modification zone is subjected to a surface modification treatment by receiving a mechanical impact force between the dispersion rotor 6 and the liner 4. The surface-modified particles whose surface has been modified are carried to the classification rotor 1 along the outer periphery (first space 11) of the guide ring 9 on the cold air passing through the machine. Is discharged to the outside of the machine, and the coarse powder is circulated into the second space 12 again and repeatedly subjected to the surface modification action in the surface modification zone. As described above, in the surface modification apparatus shown in FIG. 1, the classification of particles by the classification rotor 1 and the treatment of the surface of particles by the dispersion rotor 6 are repeated. After a certain period of time, the discharge valve 8 is opened and the surface modified particles are recovered from the discharge port 7.
[0123]
In such an apparatus, there is almost no exudation of the release agent due to heat, and the exudation of the release agent to the surface of the toner particles due to the emergence of a new surface as compared with the above-described system that gives a mechanical impact force. This is very preferable because it makes it easy to adjust the spheroidization of toner particles and the exudation of the release agent.
[0124]
The toner of the present invention includes a rotatable fixing roller, a fixing belt that is pressed against the fixing roller and rotates while forming the nip portion as the fixing roller rotates, and heating that heats the nip portion. And an image forming method including fixing means for fixing a toner image on the recording member by nipping and conveying the recording member at the nip portion by rotation of the fixing roller and the fixing belt. Used. FIG. 3 is a schematic configuration diagram of a fixing device as the most preferable fixing means in the image forming method of the present invention.
[0125]
In FIG. 3, reference numeral 50 denotes a fixing roller having an elastic layer such as Si rubber. In particular, an elastic layer such as Si rubber is not necessarily required, but the presence of an elastic layer is preferable in terms of performance. Reference numeral 52 denotes a belt that is suspended by a plurality of support rollers 53 to 55 and forms a fixing nip portion N in contact with the fixing roller 50. An elastic member such as Si rubber having a thickness of about 1 mm is laminated on the polyimide resin belt. A release layer such as PTFE or PFA is laminated on the outer layer. In the fixing device of this example, the fixing roller 50 is a φ50 mm heat roller having an elastic layer, a 2 mm silicon rubber is laminated on a 5 mm thick aluminum core, and a PFA tube of about 50 μm is formed on the outermost layer. These are stacked and rotated at a predetermined peripheral speed in the clockwise direction of the arrow. Reference numeral 51 denotes an 800 W halogen lamp inserted and installed in the interior of the fixing roller 50 as a heating means. The fixing roller 50 is heated from the inside by the heat generated by the halogen lamp 51, the surface temperature is detected by a temperature detection element (not shown), and the detected temperature is input to a temperature control circuit (not shown) and detected by the temperature detection element. The energization of the halogen lamp 51 is controlled on-off so that the surface temperature of the fixing roller is maintained at a predetermined fixing temperature.
[0126]
The fixing belt 52 is a φ50 mm belt in which 1 mm of silicon rubber is laminated on a substrate 100 μm polyimide belt, and about 50 μ of PTFE resin is laminated on the outermost layer. A fixing nip portion N is formed by being suspended from the support rollers 53 to 55 and being pressed by the fixing roller 50. The first support roller 53 is pressed against the fixing roller 50 with a predetermined pressing force with the fixing belt 52 interposed therebetween. Therefore, the belt 52 is pressed against the fixing roller 50 and is in contact therewith. The second support roller 54 is located away from the fixing roller 50 on the upstream side of the fixing nip portion N in the recording member conveyance direction.
[0127]
The third support roller 55 is located between the first and second support rollers 53 and 54 and functions as a tension roller. The fixing belt 52 is rotationally driven in the forward direction with respect to the rotation of the fixing roller 50 at the same peripheral speed as that of the fixing roller 50. The fixing roller 52 may be driven by rotating the fixing roller 50 following the rotation of the fixing roller 50.
[0128]
The recording member P carrying the unfixed image is introduced into the fixing nip N of the fixing roller 50 and the fixing belt 52 of the fixing device 9 and is nipped and conveyed by the outer fixing nip N, whereby the unfixed image is recorded on the recording member. The surface is heated and fixed by the heat of the fixing roller 50 and the pressure of the fixing nip N.
[0129]
In the fixing device having such a configuration, it is difficult to increase the linear pressure at the fixing nip portion. However, as described above, the toner of the present invention is 4.0 × 10 at a temperature of 120 ° C. (in the state of a pressure-molded sample in a pellet form).^ThreeDeformation amount when pressure of Pa is applied (R₂₀₀) Is 45 to 65%, and 1.0 × 10 6 at a temperature of 120 ° C.^FourDeformation amount when pressure of Pa is applied (R₅₀₀) Is 65 to 85%, the toner is firmly fixed on the recording member even at a relatively small linear pressure, and the feeling of roughness due to the scattering of the toner does not occur. The deformation amount (R₂₀₀) Is 65%, deformation (R₅₀₀) Exceeds 85%, the toner on the recording member is excessively crushed at the time of fixing, resulting in a feeling of image roughness.
[0130]
Further, the fixing device having such a configuration is characterized in that the nip width can be increased. When multiple dark toners and light toners are used at the same time and a larger amount of toner is placed on the recording member, if the linear pressure at the fixing nip is increased to fix the toner, There is a possibility that a high-quality image cannot be obtained due to scattering. Therefore, it is very preferable to heat and melt the toner firmly with such a wide nip width. In the present invention, the fixing nip width is 10 mm or more, but more preferably 15 mm or more is very effective in terms of fixing properties.
[0131]
FIG. 4 is a schematic cross-sectional view showing an example of an image forming apparatus that can suitably implement the image forming method of the present invention using the toner of the present invention. Hereinafter, an example of an image forming method using the light color toner a and the dark color toner b of the present invention at the same time and an example of an image forming apparatus that can suitably realize the method will be described in detail with reference to FIG. In FIG. 4, A is a printer unit, and B is an image reading unit (image scanner) mounted on the printer unit A. In the image reading section B, reference numeral 20 denotes a fixed platen glass. The platen glass 20 is placed on the upper surface of the platen glass 20 with the surface on which the original G is to be copied facing down. Set. An image reading unit 21 is provided with a document irradiation lamp 21a, a short focus lens array 21b, a CCD sensor 21c, and the like.
[0132]
When a copy button (not shown) is pressed, the image reading unit 21 is driven forward from the home position on the left side of the original table glass 20 to the right side along the lower surface of the glass on the lower side of the original table glass 20. When a predetermined reciprocating end point is reached, the actuator is driven backward and returned to the initial home position.
[0133]
In the forward drive process of the image reading unit 21, the downward image surface of the set original G on the platen glass 20 is sequentially illuminated and scanned from the left side to the right side by the original irradiation lamp 21a, and the original of the illumination scanning light is scanned. The surface reflected light is imaged and incident on the CCD sensor 21c by the short focus lens array 21b.
[0134]
The CCD sensor 21c includes a light receiving unit, a transfer unit, and an output unit (not shown). In the light receiving unit, an optical signal is changed to a charge signal and is sequentially transferred to the output unit in synchronization with a clock pulse. In the output section, the charge signal is converted into a voltage signal, amplified and reduced in impedance, and output. The analog signal thus obtained is converted into a digital signal by well-known image processing and output to the printer unit A. That is, the image information of the original G is photoelectrically read as a time-series electric digital pixel signal (image signal) by the image reading unit B.
[0135]
Note that this image forming apparatus is provided with a pattern generator (not shown), and a gradation pattern is registered so that a signal can be directly passed to a pulse width modulator (not shown).
[0136]
The exposure device 3 performs laser scanning exposure L on the surface of the photoreceptor 1 based on the image signal input from the image reading unit 21 to form an electrostatic latent image.
[0137]
FIG. 5 is a schematic block diagram of the exposure apparatus 3. When the exposure device 3 performs laser scanning exposure L on the surface of the photoreceptor 1, first, the solid-state laser element 25 is lightened or darkened at a predetermined timing by the light emission signal generator 24 based on the image signal input from the image reading unit 21 ( ON / OFF). The laser light, which is an optical signal emitted from the solid-state laser element 25, is converted into a substantially parallel light beam by the collimator lens system 26, and the photoreceptor 1 is further rotated by the rotating polygon mirror 22 that rotates at high speed in the direction of arrow c. By scanning in the direction of arrow d (longitudinal direction), a laser spot is imaged on the surface of the photoreceptor 1 by the fθ lens group 23 and the reflection mirror. By such laser scanning, an exposure distribution for the scan is formed on the surface of the photoconductor 1, and further, by scrolling a predetermined amount perpendicular to the surface of the photoconductor 1 for each scan, an image is formed on the surface of the photoconductor 1. An exposure distribution according to the signal is obtained.
[0138]
That is, the uniformly charged surface (charged to −700 V in this case) of the photosensitive member 1 is scanned by the rotating polygon mirror 22 that rotates at a high speed the light of the solid-state laser element 25 that emits ON / OFF light corresponding to the image signal. Thus, electrostatic latent images of respective colors corresponding to the scanning exposure pattern are sequentially formed on the surface of the photoreceptor 1.
[0139]
The developing device 4 includes a normal four-color rotating type developing device 4a and a four-color rotating type developing device 4b for high image quality mode. There is no problem even if the positions of the developing devices 4a and 4b are switched. As shown in FIG. 6, the developers 41a, 42a, 43a, and 44a each have a developer having dark cyan toner, a developer having dark magenta toner, a developer having dark yellow toner, and a dark black toner. Developer is introduced. The developing devices 41b, 42b, 43b, and 44b include a developer having a light cyan toner, a developer having a light magenta toner, a developer having a light yellow toner, and a developer having a light black toner. A developer having a light color toner selected from at least one kind is introduced. Note that it is not necessary to introduce all four colors of light toner with respect to the developing device 4b. If a developer having at least one kind of light color toner is introduced, the remaining may be left. Further, a developer having a light color toner having another color, a special color toner such as green, orange, or white, a colorless toner not containing a colorant, or the like may be introduced in the vacant space.
[0140]
The developing devices 4 a and 4 b develop the electrostatic latent image formed on the photosensitive member 1 as an electrostatic latent image carrier by a magnetic brush developing method, and each color toner image is formed on the photosensitive member 1. The developer relating to the present invention does not matter about the color order of development. As these developing devices, a two-component developing device as shown in FIG. 7 is one of preferred examples.
[0141]
In FIG. 7, the two-component developer includes a developing sleeve 30 that is rotationally driven in the direction of arrow e, and a magnet roller 31 is fixedly disposed in the developing sleeve 30. The developing container 32 is provided with a regulating blade 33 for forming a thin layer of the developer T on the surface of the developing sleeve 30.
[0142]
Further, the interior of the developer container 32 is divided into a developing chamber (first chamber) Rl and a stirring chamber (second chamber) R2 by a partition wall 36, and a toner hopper 34 is disposed above the stirring chamber R2. Yes.
[0143]
Conveying screws 37 and 38 are installed in the developing chamber Rl and the stirring chamber R2, respectively. The toner hopper 34 is provided with a replenishing port 35, and when toner is replenished, the toner t drops and is replenished into the stirring chamber R2 through the replenishing port 35.
[0144]
On the other hand, the developer T in which the toner particles and the magnetic carrier particles are mixed is accommodated in the developing chamber Rl and the stirring chamber R2.
[0145]
Further, the developer T in the developing chamber Rl is conveyed in the longitudinal direction of the developing sleeve 30 by the rotational driving of the conveying screw 37. The developer T in the stirring chamber R <b> 2 is transported in the longitudinal direction of the developing sleeve 30 by the rotational driving of the transport screw 38. The developer conveying direction by the conveying screw 38 is opposite to that by the conveying screw 37.
[0146]
The partition wall 36 is provided with openings (not shown) on the front side and the back side that are perpendicular to the paper surface, and the developer T transported by the transport screw 37 is fed from one of the openings to the transport screw. The developer T transferred to the transfer screw 38 and transferred by the transfer screw 38 is transferred to the transfer screw 36 from the other one of the openings. The toner is charged to a polarity for developing the latent image by friction with the magnetic particles.
[0147]
The developing sleeve 30 made of a non-magnetic material such as aluminum or non-magnetic stainless steel is provided in an opening provided in a portion of the developer container 32 that is close to the photoreceptor 1 and is in the direction of arrow e (counterclockwise). The developer T, which is rotated and mixed with toner and carrier, is carried and conveyed to the developing unit C. The magnetic brush of developer T carried on the developing sleeve 30 contacts the photosensitive member 1 rotating in the direction of arrow a (clockwise) at the developing portion C, and the electrostatic latent image is developed at the developing portion C.
[0148]
A vibration bias voltage obtained by superimposing a DC voltage on an AC voltage is applied to the developing sleeve 30 by a power source (not shown). The dark part potential (non-exposed part potential) and the bright part potential (exposed part potential) of the latent image are located between the maximum value and the minimum value of the vibration bias potential. As a result, an alternating electric field whose direction changes alternately is formed in the developing portion C. In this alternating electric field, the toner and the carrier vibrate violently, and the toner adheres to the bright portion of the surface of the photoreceptor 1 corresponding to the latent image by shaking off the electrostatic constraint on the developing sleeve 30 and the carrier.
[0149]
The difference (maximum peak voltage) between the maximum value and the minimum value of the vibration bias voltage is preferably 1 to 5 kV. The frequency is preferably 1 to 10 kHz. In this embodiment, the vibration bias voltage is a rectangular wave with a peak-to-peak voltage of 2 kV, and the frequency is 2 kHz. The waveform of the vibration bias voltage is not limited to a rectangular wave, and a sine wave, a triangular wave, or the like can be used.
[0150]
And, the DC voltage component is a value between the dark part potential and the light part potential of the electrostatic latent image, but the absolute value is closer to the dark part potential than the minimum light part potential. This is preferable in preventing fog toner from adhering to the dark potential region. In this embodiment, with respect to the dark portion potential of −700 V, the light portion potential is −200 V, and the DC component of the developing bias is −500 V. The minimum gap between the developing sleeve 30 and the photosensitive member 1 (the minimum gap position is in the developing portion C) is preferably 0.2 to 1 mm, but is 0.5 mm in this embodiment.
[0151]
The amount of the developer T that is regulated by the regulating blade 33 and conveyed to the developing unit C is the developing sleeve of the magnetic brush of the developer T formed by the magnetic field in the developing unit C by the developing magnetic pole S1 of the magnet roller 31. It is preferable that the height on the surface 30 be an amount that is 1.2 to 3 times the minimum gap value between the developing sleeve 30 and the photoconductor 1 with the photoconductor 1 removed. In this embodiment, the amount of the developer T conveyed to the developing unit C is adjusted so that the height of the magnetic brush of the developer T is 700 μm.
[0152]
The developing magnetic pole S1 of the magnet roller 31 is disposed at a position facing the developing portion C, and a magnetic brush of developer T is formed by a developing magnetic field formed by the developing magnetic pole S1 on the developing portion C, and this magnetic brush is photosensitive. The dot distribution electrostatic latent image is developed in contact with the body 1. At this time, the toner adhering to the ears (brushes) of the magnetic carrier and the toner adhering to the sleeve surface instead of the ears are transferred to the exposed portion of the electrostatic latent image and developed.
[0153]
The peak value of the strength of the developing magnetic field on the surface of the developing sleeve 30 by the developing magnetic pole S1 (the magnetic flux density in the direction perpendicular to the surface of the developing sleeve 30) is 5 × 10.^-2(T) ~ 2 × 10^-1(T) is preferred. Further, the magnet roller 31 has Nl, N2, N3, and S2 poles in addition to the developing magnetic pole Sl.
[0154]
Here, a developing process in which the electrostatic latent image on the surface of the photoreceptor 1 is visualized by the two-component magnetic brush method using the developing device 4 and a circulation system of the developer T will be described.
[0155]
The developer T pumped up at the N2 pole by the rotation of the developing sleeve 30 is transported from the S2 pole to the Nl pole, and the layer thickness is regulated by the regulating blade 33 in the middle thereof to form a developer thin layer.
[0156]
Then, the developer T spiked in the magnetic field of the developing magnetic pole S1 develops the electrostatic latent image on the photoreceptor 1. Thereafter, the developer T on the developing sleeve 30 falls into the developing chamber Rl due to the repulsive magnetic field between the N3 pole and the N2 pole. The developer T that has fallen into the developing chamber Rl is stirred and conveyed by the conveying screw 37.
[0157]
In the present invention, general materials can be used as the intermediate transfer member and the transfer means. The transfer body 5 (see FIG. 4) has a transfer sheet 5c made of, for example, a polyethylene terephthalate resin film stretched on its surface, and is placed in contact with and separated from the photoreceptor 1. The transfer body 5 is rotationally driven in the direction of the arrow (clockwise). In the transfer body 5, a transfer charger 5a, a separation charger 5b, and the like are installed.
[0158]
Next, an image forming operation of the above-described image forming apparatus will be described.
The photosensitive member 1 is driven to rotate in the direction of arrow a (counterclockwise) at a predetermined peripheral speed (process speed) around the central support shaft, and in the rotation process, the photosensitive member 1 is negatively charged in the present embodiment by the primary charger 2. The uniform charging process is applied.
[0159]
Then, a laser beam modulated in response to an image signal output from the image reading unit B to the printer unit A side, which is output from the exposure device (laser scanning device) 3 to the uniformly charged surface of the photoreceptor 1. As a result of the scanning exposure L, an electrostatic latent image of each color corresponding to the image information of the original G photoelectrically read by the image reading unit B is sequentially formed on the photoreceptor 1. The electrostatic latent image formed on the photoreceptor 1 is first reversely developed by the developing device 41a by the developing device 4 by the above-described two-component magnetic brush method to be visualized as a first color toner image.
[0160]
On the other hand, in synchronism with the formation of the toner image on the photosensitive member 1, a recording member P such as paper stored in the paper feed cassette 10 is fed one by one by the paper feed roller 11 or 12, and the registration roller 13 is fed to the transfer body 5 at a predetermined timing, and the recording member P is electrostatically attracted onto the transfer body 5 by the suction roller 14. The recording member P electrostatically attracted onto the transfer member 5 moves to a position facing the photosensitive member 1 by the rotation of the transfer member 5 in the direction of the arrow (clockwise), and is moved to the back side of the recording member P by the transfer charger 5a. A charge having a reverse polarity to that of the toner is applied, and the toner image on the photoreceptor 1 is transferred to the surface side.
[0161]
After this transfer, the untransferred toner remaining on the photoreceptor 1 is removed by the cleaning device 6 and used for forming the next toner image.
[0162]
Thereafter, the electrostatic latent image on the photosensitive member 1 is developed in the same manner, and the toner images of the respective colors formed on the photosensitive member 1 are transferred onto the recording member P on the transfer member 5 by the transfer charger 5a. A full color image is formed.
[0163]
Then, the recording member P is separated from the transfer member 5 by the separation charger 5 b, and the separated recording member P is conveyed to the fixing device 9 through the conveyance belt 8. The recording member P conveyed to the fixing device 9 is heated and pressed between the fixing roller 50 and the elastic belt 52 to fix the full color image on the surface, and is then discharged onto the tray 16 by the discharge roller 15. .
[0164]
Further, the transfer residual toner is removed from the surface of the photoconductor 1 by the cleaning device 6, and the surface of the photoconductor 1 is further neutralized by the pre-exposure lamp 7 to prepare for the next image formation.
[0165]
Hereafter, the measuring method of each physical property in this invention is demonstrated.
[0166]
(Viscoelastic properties of toner (storage modulus G ′₁₂₀And G '₁₈₀) Measurement)
The toner is pressure-molded into a disk-shaped sample having a diameter of 25 mm and a thickness of about 2.5 mm. Next, the pressure-molded sample is set on a parallel plate, and the temperature is gradually raised within a temperature range of 50 to 200 ° C. to measure temperature dispersion. The heating rate is 2 ° C./min, the angular frequency (ω) is fixed at 6.28 rad / sec, and the distortion is automatic. Taking the temperature on the horizontal axis and the storage elastic modulus (G ′) on the vertical axis, the value at each temperature (120 ° C. and 180 ° C.) is read. In the measurement, ARES (manufactured by Rheometrics) is used.
[0167]
(Toner deformation amount (R₂₀₀), (R₅₀₀) Measurement)
The toner is 8.0 × 10 5 to 5.5 g of toner using a tablet molding machine.⁶By pressurizing at a pressure of Pa for 2 minutes, a cylindrical sample having a diameter of 25 mm and a height of 10 to 11 mm is formed. As the measuring device, ARES (viscoelasticity measuring device, manufactured by TA INSTRUMENTS) equipped with a PTFE-coated SUS 25 mm diameter parallel plate is used.
[0168]
The deformation measurement method uses a PTFE-coated parallel plate with a diameter of 25 mm. Place the toner molding sample on the parallel plate and control the jig temperature to 120 ° C. After confirming that the sample temperature has reached 120 ° C, adjust the sample height (gap) to 10.000 mm. To do. Select Rate Mode Test of Multiple Extension Mode Test, compress the toner molding sample at Rate = −0.5 mm / s, and measure the relationship between the sample height (gap) and Normal Force.
[0169]
Normal Force is 200g load (pressure 4.0 × 10^ThreeThe height (gap) of the sample at Pa) is G₂₀₀(Mm), the toner deformation amount (R₂₀₀) Can be calculated.
[0170]
[Formula 6]

[0171]
Similarly, the normal force is 500 g load (pressure 1.0 × 10^FourSample height G in Pa)₅₀₀By using the toner deformation amount (R₅₀₀) Can be measured.
[0172]
(Measurement of molecular weight of toner and binder resin by GPC)
The molecular weight distribution by GPC of the resin component of the toner and the binder resin is measured by GPC using a THF soluble component obtained by dissolving the toner in a THF solvent as follows.
[0173]
That is, a sample is put in THF, allowed to stand for several hours, and then sufficiently shaken to mix well with THF (until the sample is no longer united), and then left to stand for 12 hours or more. At this time, the standing time in THF is set to be 24 hours or longer. Thereafter, a sample processing filter (pore size 0.45 to 0.5 μm, for example, Mysori Disc H-25-5 manufactured by Tosoh Corp., Excro Disc 25CR manufactured by Gelman Science Japan Ltd., etc.) can be used, A sample of GPC is used. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml. The GPC measurement of the sample prepared by the above method was performed by stabilizing the column in a heat chamber at 40 ° C., and flowing tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min as a solvent at this temperature. About 50 to 200 μl of a THF sample solution of resin adjusted to 0.05 to 0.6% by mass is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts (retention time). Examples of standard polystyrene samples for preparing a calibration curve include those manufactured by Tosoh Corporation or Pressure Chemical Co. Made molecular weight 6 × 10²2.1 × 10^Three4 × 10^Three1.75 × 10^Four5.1 × 10^Four1.1 × 10^Five3.9 × 10^Five8.6 × 10^Five2 × 10⁶4.48 × 10⁶It is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
[0174]
As column, 10^Three~ 2x10⁶In order to accurately measure the molecular weight region, it is preferable to combine a plurality of commercially available polystyrene gel columns. [Mu] -styragel 500, 10 manufactured by Waters^Three10^Four10^FiveCan be mentioned.
[0175]
(Measurement of wax molecular weight by GPC)
Apparatus: GPC-150C (Waters)
Column: GMH-HT 30 cm, 2 stations (manufactured by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% by mass ionol added)
Flow rate: 1.0 ml / min
Sample: 0.4 ml of 0.15 mass% wax was injected.
The molecular weight calibration curve prepared with the monodisperse polystyrene standard sample is used for the measurement of the molecular weight of the wax under the above conditions. Furthermore, the molecular weight of the wax is calculated by converting to polyethylene based on a conversion formula derived from the Mark-Houwink viscosity formula.
[0176]
(Measurement of maximum temperature of maximum endothermic peak in toner and wax)
Temperature curve: Temperature increase I (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (200 ° C-30 ° C, temperature drop rate 10 ° C / min)
Temperature increase II (30 ° C to 200 ° C, temperature increase rate 10 ° C / min)
The maximum endothermic peak of the toner and wax is measured according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring apparatus) DSC2920 (manufactured by TA Instruments Japan).
[0177]
The sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg. The sample is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rise rate of 10 ° C./min at room temperature and humidity in a measurement range of 30 to 200 ° C. The maximum endothermic peak of the toner and wax is the one having the highest height from the baseline in the region above the endothermic peak of the resin Tg in the process of temperature increase II, or the endothermic peak of the resin Tg is different from the endothermic peak. When it is difficult to discriminate the overlap, the maximum endothermic peak of the toner of the present invention is defined as the highest peak from the maximum peak of the overlapping peaks.
[0178]
(Measurement of average circularity)
The equivalent circle diameter, circularity and frequency distribution of the toner are used as a simple method for quantitatively expressing the shape of the toner particles. In the present invention, the flow type particle image measuring device “FPIA-1000 type” is used. ”(Manufactured by Toa Medical Electronics Co., Ltd.), and calculation is performed using the following formula.
[0179]
[Expression 7]
Equivalent circle diameter = (particle projected area / π)^1/2× 2
[0180]
[Equation 8]

[0181]
Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the toner particle image. Define.
[0182]
In the present invention, the circularity is an index indicating the degree of unevenness of the toner particles, and is 1.000 when the toner particles are completely spherical. The more complicated the surface shape, the smaller the circularity.
[0183]
As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, followed by further measurement. Add 0.02 g of sample and disperse uniformly. As a means for dispersion, an ultrasonic disperser “Tetora150 type” (manufactured by Nikka Ki Bios) equipped with a 5 mmφ titanium alloy chip as a vibrator is used, and a dispersion for measurement is performed using a dispersion process for 5 minutes. And In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more.
[0184]
To measure the shape of the toner particles, the flow type particle image measuring device is used, the concentration of the dispersion is readjusted so that the toner particle concentration at the time of measurement is 3000 to 10,000 / μl, and 1000 toner particles are obtained. Measure above. After the measurement, using this data, data of 3 μm or less is cut to determine the average circularity of the toner particles.
[0185]
(Lightness L in powder state^*Measurement)
L in powdered toner^*Uses a spectroscopic color difference meter “SE-2000” (manufactured by Nippon Denshoku Industries Co., Ltd.) conforming to JIS Z-8722, and the light source is measured with a C light source with a 2-degree field of view. The measurement is performed in accordance with the attached instruction manual. For standard adjustment of the standard plate, it is preferable to perform the measurement through a glass of 2 mm thickness and φ30 mm in an optional powder measurement cell. More specifically, the measurement is performed in a state where a cell filled with sample powder (toner) is placed on a sample table (attachment) for powder sample of the spectroscopic color difference meter. Before placing the cell on the sample table for powder sample, fill the powder sample with 80% or more with respect to the internal volume of the cell, and apply vibration once per second for 30 seconds on the vibration table. Measure with Further, in the present invention, when measuring the shape processing such as spheroidization or toner added with an external additive, the toner in a state where the shape processing or external additive is mixed is used as a powder sample.
[0186]
(Measurement method of carrier particle size)
300 or more are extracted at random with an optical microscope, and measured as a carrier particle diameter with a horizontal ferret diameter by an image processing analyzer Luzex3 manufactured by Nireco Corporation.
[0187]
【Example】
EXAMPLES Hereinafter, although a manufacture example and an Example demonstrate this invention concretely, this does not limit this invention at all.
[0188]

While stirring 200 parts by mass of xylene in a four-necked flask, the inside of the four-necked flask was sufficiently replaced with nitrogen, and the temperature was raised to 120 ° C. Then, the above components were placed in the four-necked flask over about 4 hours. It was dripped in. Furthermore, the polymerization was completed under reflux of xylene, and the solvent was distilled off under reduced pressure to obtain a vinyl polymer. Table 1 shows the results of molecular weight measurement of the obtained vinyl polymer by GPC.
[0189]
<Examples of hybrid resin production>
As a vinyl copolymer material, 10 parts by mass of styrene, 5 parts by mass of 2-ethylhexyl acrylate, 2 parts by mass of fumaric acid, and 5 parts by mass of a dimer of α-methylstyrene were placed in a dropping funnel. . In addition, 25 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 15 parts by mass of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane Parts, 9 parts by mass of succinic acid, 5 parts by mass of trimellitic anhydride, 24 parts by mass of fumaric acid, and dibutyltin oxide are put into a 4-liter four-necked flask made of glass, a thermometer, a stirring rod, a condenser, and a nitrogen introduction tube Was attached to a four-necked flask, and this four-necked flask was placed in a mantle heater. Next, after the inside of the four-necked flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and while stirring at a temperature of 130 ° C., the monomer of the vinyl copolymer and the cross-linking from the previous dropping funnel The agent and the polymerization initiator were added dropwise over about 4 hours. Next, the temperature was raised to 200 ° C. and reacted for about 4 hours to obtain a hybrid resin. The results of molecular weight measurement by GPC of the obtained hybrid resin are shown in Table 1.
[0190]
<Example of production of polyester resin 1>
25 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 15 parts by mass of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Put 20 parts by mass of terephthalic acid, 5 parts by mass of trimellitic anhydride, 25 parts by mass of fumaric acid and dibutyltin oxide into a 4-liter four-necked flask made of glass, and add four thermometers, stirring rods, condensers and nitrogen inlet tubes. The four-necked flask was installed in a mantle heater. Under a nitrogen atmosphere, reaction was carried out at 210 ° C. for about 5 hours to obtain polyester resin 1. The results of molecular weight measurement by GPC of the obtained polyester resin 1 are shown in Table 1.
[0191]
<Example of production of polyester resin 2>
In the production example of polyester resin 1, the monomer structure was changed as shown in Table 1, and the polyester resin 2 was prepared by the same method as in the above production example, except that the reaction was performed at 210 ° C. for 4.5 hours in a nitrogen atmosphere. Obtained. The results of molecular weight measurement by GPC of the obtained polyester resin 1 are shown in Table 1.
[0192]
[Table 1]

[0193]
<Production Example of Cyan Toner a1 and Cyan Developer a1>
The hybrid resin, wax A (see Table 2) and other toner materials shown in Table 3 were sufficiently premixed with a Henschel mixer with the composition shown in Table 3. The obtained mixture was melt-kneaded with a twin-screw extruder, the melt-kneaded product was cooled, and the cooled product was coarsely pulverized to a particle size of about 1 to 2 mm using a hammer mill. Subsequently, the coarsely pulverized product was finely pulverized by an air jet type fine pulverizer.
[0194]
Further, the obtained finely pulverized product was treated with a processing apparatus as shown in FIGS. 1 and 2, and the rotational speed of the dispersion rotor was set to 97 / s (rotational speed) while removing the fine particles by setting the rotational speed of the classification rotor to 7300 rpm. The surface treatment for 60 seconds was performed for 20 minutes at a speed of 130 m / sec. In this surface treatment, the finely pulverized product was charged from the raw material supply port 3, treated for 60 seconds, and the operation of opening the outlet valve 8 and taking it out as a treated product was counted as one time. Ten square disks were installed on the top of the dispersion rotor, the distance between the guide ring and the dispersion rotor square disk was 30 mm, and the distance between the dispersion rotor and the liner was 5 mm. Also, blower air volume is 14m^Three/ Min, and the temperature of the refrigerant passing through the jacket and the cold air temperature T1 were set to -20 ° C. As a result of operating for 20 minutes in this state, the temperature T2 behind the classification rotor was stable at 27 ° C., and cyan toner a1 resin particles having a weight average particle diameter of 7.5 μm were obtained.
[0195]
With respect to 100 parts by mass of the cyan toner a1 resin particles, 1.5 parts by mass of acicular titanium (MT-100T manufactured by Teica) was mixed with the cyan toner a1 resin particles to obtain cyan toner a1. Table 4 shows the physical properties of the obtained cyan toner a1. Table 2 shows the types of waxes used in the production of each toner and the maximum endothermic peak temperature in the examples.
[0196]
Further, cyan toner a1 and magnetic manganese magnesium ferrite carrier particles (number average particle size 50 μm) surface-coated with a silicone resin are mixed so that the toner concentration becomes 6% by mass, and cyan developing which is a two-component developer. Agent a1 was obtained.
[0197]
<Production Examples of Cyan Toners a2 to a15 and Cyan Developers a2 to a15>
The toner materials were changed as shown in Table 3, and the cyan toners a2 to a15 were obtained by appropriately changing the melt kneading temperature, the number of rotations of the dispersion rotor during the surface treatment, and the treatment time. Table 4 shows the physical properties of the obtained toners a2 to a15.
[0198]
Each cyan toner was mixed with a carrier in the same manner as the cyan toner a1 to obtain cyan developers a2 to a15.
[0199]
<Production Examples of Cyan Toners b1 to b15 and Cyan Developers b1 to b15>
  Cyan toners a1 to a15Cyan toners b1 to b15 and cyan developers b1 to b15 were obtained using the same method as in the toner a production example except that the amount of colorant used was changed as shown in Table 3. . Table 5 shows the physical properties of the obtained cyan toners b1 to b15.
[0200]
<Production Example of Magenta Toner a1 and Magenta Developer a1>
In the production example of cyan toner a1, C.I. I. A magenta toner a1 and a magenta developer a1 were obtained using the same method as in the above production example except that 1 part of Pigment Red 122 was used. Table 4 shows the physical properties of Magenta Toner a1 obtained.
[0201]
<Production Example of Magenta Toner a2 and Magenta Developer a2>
In the production example of cyan toner a11, C.I. I. A magenta toner a2 and a magenta developer a2 were obtained using the same method as in the above production example except that 1 part of Pigment Red 122 was used. Table 4 shows the physical properties of Magenta Toner a2.
[0202]
<Production Example of Magenta Toner b and Magenta Developer b>
In the production example of magenta toner a1, magenta toner b and magenta developer b were obtained using the same method as in the above production example, except that the amount of colorant used was changed to 6 parts. Table 5 shows the physical properties of Magenta Toner b obtained.
[0203]
<Production example of yellow toner b and yellow developer b>
In the production example of cyan toner a1, C.I. I. A yellow toner b and a yellow developer b were obtained in the same manner as in the above production example except that 9 parts of Pigment Yellow 180 were used. Table 5 shows the physical properties of the resulting yellow toner b.
[0204]
<Example of production of black toner b and black developer b>
A black toner b and a black developer b were obtained in the same manner as in the above production example except that 5 parts of carbon black was used as a colorant in the production example of the cyan toner a1. Table 5 shows the physical properties of Toner b thus obtained.
[0205]
[Table 2]

[0206]
[Table 3]

[0207]
[Table 4]

[0208]
[Table 5]

[0209]
<Example 1>
Using the image forming apparatus and the developing apparatus shown in FIGS. 4 and 6, using plain paper (color laser copier paper TKCLA4; manufactured by Canon), an image of cyan toner a1 is output in the printer mode, and the following items are evaluated. Went. The image forming apparatus and the developing apparatus are as described in the embodiment of the invention.
[0210]
(1) Measurement of fixing temperature range
The fixing device 9 shown in FIG. 4 was allowed to freely set the fixing temperature, and a cyan developer a1 was set in the developing device 41a shown in FIG. The image area ratio at this time is 25%, and the applied toner amount per unit area is 1.5 mg / cm.²Set to. Fixing start temperature and offset start temperature are measured by adjusting the process speed to 150 mm / s and the fixing device set temperature at a temperature range of 140 to 220 ° C every 5 ° C, and outputting a fixed image at each temperature. The fixed image thus obtained was 4.9 kPa (50 g / cm²The fixing temperature at which the density reduction rate before and after the rubbing was 10% or less was defined as the fixing start temperature. Further, the set temperature was further raised from the fixing start temperature, and the temperature at which the high temperature offset occurred was determined as the offset start temperature.
[0211]
A cyan developer a1 was set in the developing device 41a, and a cyan developer b1 was set in the developing device 41b, and a 12-gradation patch image was formed in the printer mode. The maximum amount of toner applied per unit area is 1.5 mg / cm in total for toner a and toner b.²Was set to be.
[0212]
(2) Measurement of transfer efficiency
As an image for measuring transfer efficiency, a solid image with an image area ratio of 5% was developed and transferred before and after the end of 10,000 sheets, and the amount of toner before transfer on the photoreceptor (per unit area) and on the recording member Each toner amount (per unit area) was measured and determined by the following equation. The durability test was performed with the image area ratio of 25%.
[0213]
[Equation 9]
Transfer rate (%)
= (Toner amount on recording member) / (toner amount before transfer on photoreceptor) × 100
[0214]
(3) Glossiness measurement
Regarding the measurement of glossiness (gloss), a VG-10 gloss meter (manufactured by Nippon Denshoku) was used, and the image used in the measurement of the fixing temperature region was fixed at 185 ° C. as a sample. It was. As a measurement, first, the voltage was set to 6 V with a constant voltage device. Next, the light projecting angle and the light receiving angle were adjusted to 60 °. Using the zero point adjustment and standard plate, after the standard setting, the sample image was placed on the sample stage, and further, three sheets of white paper were overlapped and measured, and the numerical value indicated on the marking portion was read in% units. At this time, the S and S / 10 switch SW was set to S, and the angle and sensitivity switch SW was set to 45-60.
[0215]
Further, a 12-tone image output using toner a and toner b was measured, and the difference between the maximum value and the minimum value of glossiness was calculated and evaluated according to the following evaluation criteria.
[0216]
a: Gross difference is less than 4
b: Gross difference is 4 or more and less than 7
c: Gross difference of 7 or more and less than 10
d: Gross difference is 10 or more
[0217]
(4) Roughness of the image during fixing
A fine line image (7 lines / 1 mm) was fixed, and the resolution was observed using a magnifying glass, and the degree of toner scattering and the decrease in resolution were confirmed and evaluated. That is, the number of distinguishable lines was evaluated according to the following criteria. At this time, the number of lines that can be discriminated was an average value of 10 vertical lines and 10 horizontal lines. The fixing temperature was measured by the fixing start temperature of each toner.
[0218]
A: 7
B: 5-6
C: 3-4
D: 2 or less
[0219]
The cyan developer a1 of this example showed excellent fixability and transfer efficiency, and there was no feeling of image roughness during fixing. Table 6 shows the evaluation results using only developer a1, and Table 7 shows the evaluation results using a combination of developer a1 and developer b1.
[0220]
<Example 2>
Evaluation was performed in the same manner as in Example 1 except that cyan developer a2 was used instead of cyan developer a1, and cyan developer b2 was used instead of cyan developer b1. When the cyan developer a2 was used, the fixing start temperature was slightly high, but there was no problem. Also in Example 2, excellent transfer efficiency was exhibited, and there was no feeling of image roughness during fixing. Similarly, there was no problem in the combination of developer a2 and developer b2. Table 6 shows the evaluation results using only the developer a2, and Table 7 shows the evaluation results using a combination of the developer a2 and the developer b2.
[0221]
<Example 3>
Evaluation was performed in the same manner as in Example 1 except that cyan developer a3 was used instead of cyan developer a1, and cyan developer b3 was used instead of cyan developer b1. In the cyan developer a3, the toner was considerably spheroidized, or the image roughness at the time of fixing was slightly deteriorated, but there was no problem. Fixability and transfer efficiency were very good. Similarly, there was no problem in the combination of developer a3 and developer b3. Table 6 shows the evaluation results using only developer a3, and Table 7 shows the evaluation results using a combination of developer a3 and developer b3.
[0222]
<Example 4>
Evaluation was performed in the same manner as in Example 1 except that cyan developer a4 was used instead of cyan developer a1, and cyan developer b4 was used instead of cyan developer b1. In the cyan developer a4, the transfer efficiency was lowered because the sphericity of the toner was slightly low, but there was no problem. The cyan developer a4 exhibited excellent fixability, and there was no feeling of image roughness during fixing. Similarly, there was no problem in the combination of developer a4 and developer b4. Table 6 shows the evaluation results using only developer a4, and Table 7 shows the evaluation results using a combination of developer a4 and developer b4.
[0223]
<Example 5>
Evaluation was performed in the same manner as in Example 1 except that cyan developer a5 was used instead of cyan developer a1, and cyan developer b5 was used instead of cyan developer b1. In the cyan developer a5, since the maximum value of the DSC maximum endothermic peak was small, the transfer efficiency was slightly lower than the initial value, but there was no problem. The cyan developer a5 exhibited excellent fixability, and there was no feeling of image roughness during fixing. Similarly, there was no problem in the combination of developer a5 and developer b5. Table 6 shows the results of evaluation using only developer a5, and Table 7 shows the results of evaluation using a combination of developer a5 and developer b5.
[0224]
<Example 6>
Evaluation was performed in the same manner as in Example 1 except that cyan developer a6 was used instead of cyan developer a1, and cyan developer b6 was used instead of cyan developer b1. In the cyan developer a6, the maximum value of the DSC maximum endothermic peak of the toner was large, so the low-temperature fixability was slightly deteriorated. There was no feeling of roughness of the image at the time of fixing. The transfer efficiency was very good. Similarly, there was no problem in the combination of developer a6 and developer b6. Table 6 shows the results of evaluation using only developer a6, and Table 7 shows the results of evaluation using a combination of developer a6 and developer b6.
[0225]
<Example 7>
Evaluation was performed in the same manner as in Example 1 except that cyan developer a7 was used instead of cyan developer a1, and cyan developer b7 was used instead of cyan developer b1. For cyan developer a7, toner deformation amount R₂₀₀Became relatively large. Therefore, the transfer efficiency was slightly lower than the initial level, but was at a usable level. R₅₀₀Although it became slightly larger and the feeling of image sticking at the time of fixing was slightly worse, there was no problem. The combination of developer a7 and developer b7 was also at a usable level. Table 6 shows the evaluation results using only developer a7, and Table 7 shows the evaluation results using a combination of developer a7 and developer b7.
[0226]
<Reference example 1>
  Evaluation was performed in the same manner as in Example 1 except that cyan developer a8 was used instead of cyan developer a1, and cyan developer b8 was used instead of cyan developer b1. For cyan developer a8, toner deformation amount R₂₀₀Became relatively small. For this reason, toner scattering slightly occurred during fixing, and the image roughness was slightly deteriorated, but it was at a usable level. Further, since the viscoelastic property of the toner is relatively large, the low-temperature fixability is slightly deteriorated, and the fixing temperature range is slightly narrowed. Further, although the glossiness was slightly lowered, there was no problem. There was no problem with the transfer efficiency. Further, in the combination of developer a8 and developer b8, the glossiness of the image was slightly non-uniform, but was at a usable level. Table 6 shows the evaluation results using only developer a8, and Table 7 shows the evaluation results using a combination of developer a8 and developer b8.
[0227]
<Reference example 2>
  Evaluation was performed in the same manner as in Example 1 except that cyan developer a9 was used instead of cyan developer a1, and cyan developer b9 was used instead of cyan developer b1. For cyan developer a9, toner deformation amount R₂₀₀Became relatively large. Therefore, the transfer efficiency was slightly lower than the initial level, but was at a usable level. R₅₀₀Although it became slightly larger and the feeling of image sticking at the time of fixing was slightly worse, there was no problem. Also, since the viscoelastic properties of the toner are relatively small, the fixing temperature range is narrowed andYoOffset is likely to occur. Further, with the combination of developer a9 and developer b9, the glossiness of the image was slightly non-uniform, but was at a usable level. The evaluation results using only developer a9 are shown in Table 6, and the evaluation results using combinations of developer a9 and developer b9 are shown in Table 7.
[0228]
<Example 10>
The one-component development method was evaluated using cyan toners a1 and b1. As the apparatus, an LBP-2040 (Canon) fixing unit was removed and a fixing device as shown in FIG. The same evaluation as in Example 1 was performed using the above toner and apparatus. The fixable temperature and the feeling of image roughness at the time of fixing were the same as in Example 1. The transfer efficiency was 91% before the endurance test and 91% after the endurance test for 4000 sheets. Even with the combination of toner a1 and toner b1, the transfer efficiency was very good with the same result.
[0229]
<Example 11>
In this embodiment, the electrophotographic apparatus shown in FIGS. 4 and 6 is used, and glossy paper (color laser copier glossy cardboard as a recording member) is formed by a combination of a developing device and a developer shown in the following (a) and (b). An image was formed on the MS-701) using the original chart. Thus, a significant difference in the combination of the developers (a) and (b) was examined.
[0230]
(A): The cyan developer a1 was developed in the developing unit 41a, the magenta developer a1 and the developing units 43a and 44a were left empty in the developing unit 42a. The cyan developer b1 and 42b were set in the developing device 41b, the magenta developer b was set in the developing device 43b, the yellow developer b and the developing device 44b and the black developer b were set in the developing device 43b.
[0231]
(B): The cyan developer a11 was developed in the developing device 41a, the magenta developer a2 and the developing devices 43a and 44a were left empty in the developing device 42a. The cyan developer b1 and 42b were set in the developing device 41b, the magenta developer b was set in the developing device 43b, the yellow developer b and the developing device 44b and the black developer b were set in the developing device 43b.
[0232]
As a result, (a) outputs an image such as a photograph that has a smooth change in density, suppresses graininess and roughness, and has no uneven gloss over the entire area from the low density part to the high density part. I was able to. On the other hand, (b) has a narrow fixing temperature range. In addition, the change in density from the low density part to the high density part was smooth, but the low density part was noticeable. Also, the gloss was not uniform and the image was uncomfortable.
[0233]
<Comparative example 1>
Evaluation was performed in the same manner as in Example 1 except that the cyan developer a10 was used instead of the cyan developer a1 and the cyan developer b10 was used instead of the cyan developer b1. In the evaluation of the glossiness, in this comparative example, fixing could not be performed at 185 ° C., and therefore, evaluation was performed using a material fixed at 175 ° C. For cyan developer a10, toner deformation amount R₂₀₀Therefore, the transfer efficiency tends to decrease. R₅₀₀And the feeling of image roughness during fixing became worse. Also, the fixing temperature range was narrowed. In addition, the evaluation results similarly deteriorated in the combination of developer a10 and developer b10. Table 6 shows the evaluation results using only developer a10, and Table 7 shows the evaluation results using a combination of developer a10 and developer b10.
[0234]
<Comparative example 2>
Evaluation was performed in the same manner as in Example 1 except that cyan developer a11 was used instead of cyan developer a1, and cyan developer b11 was used instead of cyan developer b1. In the evaluation of glossiness, in this comparative example, fixing could not be performed at 185 ° C., so that evaluation was performed using what was fixed at 195 ° C. With cyan developer 11, toner deformation amount R₂₀₀Therefore, the feeling of image roughness during fixing was also deteriorated. In particular, when the developer a11 and the developer b11 were used in combination, the glossiness of the image was non-uniform. Furthermore, the low-temperature fixability deteriorated, and the fixing temperature range narrowed. Also, the transfer efficiency was low from the beginning. Table 6 shows the evaluation results using only developer a11, and Table 7 shows the evaluation results using a combination of developer a11 and developer b11.
[0235]
<Comparative Example 3>
Evaluation was performed in the same manner as in Example 1 except that cyan developer a12 was used instead of cyan developer a1, and cyan developer b12 was used instead of cyan developer b1. In the evaluation of glossiness, in this comparative example, fixing could not be performed at 185 ° C., so that evaluation was performed using what was fixed at 195 ° C. With the cyan developer 12, the toner deformation amount R₂₀₀Therefore, the feeling of image roughness during fixing was also deteriorated. The combination of developer a12 and developer b12 was particularly noticeable. R₅₀₀Also, the glossiness of the image was not uniform when the developer a12 and developer b12 were used in combination. L^*(A) -L^*Since (b) was larger than 40, the density change from the low density part to the high density part could not be reproduced smoothly. Furthermore, the low-temperature fixability deteriorated, and the fixing temperature range narrowed. Also, the transfer efficiency was low from the beginning. Table 6 shows the results of evaluation using only developer a12, and Table 7 shows the results of evaluation using a combination of developer a12 and developer b12.
[0236]
<Comparative example 4>
Evaluation was performed in the same manner as in Example 1 except that cyan developer a13 was used instead of cyan developer a1, and cyan developer b13 was used instead of cyan developer b1. In the evaluation of the glossiness, since it was not possible to fix at 185 ° C. in this comparative example, the evaluation was made using the one fixed at 165 ° C. For cyan developer a13, toner deformation amount R₂₀₀Therefore, the transfer efficiency tends to decrease. R₅₀₀And the feeling of image roughness during fixing became worse. Also, the fixing temperature range was narrowed. Furthermore, when used in combination with developer a13 and developer b13, L^*(A) -L^*Since (b) was smaller than 10, the color reproduction space from low density to high density was difficult to expand. Table 6 shows the evaluation results using only developer a13, and Table 7 shows the evaluation results using a combination of developer a13 and developer b13.
[0237]
<Comparative Example 5>
Evaluation was performed in the same manner as in Example 1 except that cyan developer a14 was used instead of cyan developer a1, and cyan developer b14 was used instead of cyan developer b1. In the evaluation of glossiness, in this comparative example, fixing could not be performed at 185 ° C., so that evaluation was performed using what was fixed at 195 ° C. With cyan developer a14, toner deformation amount R₂₀₀Therefore, the feeling of image roughness at the time of fixing became very poor. Further, since the viscoelastic property of the toner is large, the low-temperature fixability is deteriorated, and the fixing temperature range is remarkably narrowed. Further, even when the developer a14 and the developer b14 were used in combination, the difference in glossiness was not so great, but the image was hardly glossy and the image quality was very poor. L^*(A) -L^*Since (b) was larger than 40, the density change from the low density part to the high density part could not be reproduced smoothly. Table 6 shows the results of evaluation using only developer a14, and Table 7 shows the results of evaluation using a combination of developer a14 and developer b14.
[0238]
<Comparative Example 6>
Evaluation was performed in the same manner as in Example 1 except that cyan developer a15 was used instead of cyan developer a1, and cyan developer b15 was used instead of cyan developer b1. With the cyan developer 15, the viscoelastic property of the toner was too small, so that the winding occurred immediately and there was no fixing point. For this reason, it was impossible to measure the feeling of roughness and glossiness of the image at the time of fixing. Also, the transfer efficiency tended to decrease. The evaluation results similarly deteriorated even in the combination of developer a15 and developer b15. Table 6 shows the evaluation results using only developer a15, and Table 7 shows the evaluation results using a combination of developer a15 and developer b15.
[0239]
[Table 6]

[0240]
[Table 7]

[0241]
【The invention's effect】
According to the present invention, it is possible to provide a toner and an image forming method capable of reducing graininess and roughness from a low density region to a high density region. Further, it is possible to provide a toner and an image forming method that have a wide fixing temperature range even when a large amount of toner is placed on a recording member, maintain an excellent image even after continuous copying, and have excellent offset resistance.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of an example of a surface modification apparatus preferably used in the present invention.
FIG. 2 is a schematic plan view of an example of a surface modification apparatus preferably used in the present invention.
FIG. 3 is a schematic configuration diagram showing an example of a fixing device preferably used in the image forming method of the present invention.
FIG. 4 is a schematic cross-sectional view showing an example of an image forming apparatus that can suitably implement the image forming method of the present invention.
5 is a schematic block diagram of the exposure apparatus 3 in FIG.
6 is a schematic configuration diagram of the developing device of FIG. 6;
FIG. 7 is a schematic cross-sectional view showing an example of a two-component developer preferably used in the present invention.
[Explanation of symbols]
1 Photoconductor
2 Primary charger
3 Exposure equipment
4, 4a, 4b Developing device
5 Transcript
6 Cleaning device
7 Pre-exposure lamp
8 Conveyor belt
9 Fixing device
10 Paper cassette
11, 12 Paper feed roller
13 Registration roller
14 Suction roller
15 Paper discharge roller
21 Document reading unit
41a, 41b, 42a, 42b, 43a, 43b, 44a, 44b Developer
50 Fixing roller
51 Halogen lamp
52 belt
53-55 support rollers
A Printer section
B Image reading unit
P Recording member

Claims (9)

A light magenta toner containing at least a binder resin, a colorant, and a wax,
Lightness L ^* in the powder state is 45 to 75,
In the viscoelastic properties, the storage elastic modulus (G ′ ₁₂₀ ) at a temperature of 120 ° C. is 5 × 10 ² to 1 × 10 ⁵ [Pa], and the storage elastic modulus (G ′ ₁₈₀ ) at a temperature of 180 ° C. is 10 to 5 × 10 ³ [Pa]
Deformation amount (R ₂₀₀ ) when pressure of 4.0 × 10 ³ Pa is applied at 120 ° C. to a sample in which the toner is pressure-molded into a pellet and the height (gap) is adjusted to 10.000 mm. Is 47 to 63%, and the deformation amount (R ₅₀₀ ) when a pressure of 1.0 × 10 ⁴ Pa is applied to the sample at 120 ° C. is 65 to 85%, and the toner is a non-magnetic toner. A light-colored magenta toner. A light cyan toner containing at least a binder resin, a colorant, and a wax,
  Lightness L in powder state ^* Is 45-75,
  In the viscoelastic properties, the storage elastic modulus (G ′) at a temperature of 120 ° C. ₁₂₀ ) Is 5 × 10 ² ~ 1x10 ^Five [Pa] and storage elastic modulus (G ′) at a temperature of 180 ° C. ₁₈₀ ) Is 10-5 × 10 ^Three [Pa]
  The toner was pressure-molded into pellets, and the height (gap) was adjusted to 10.000 mm. ^Three Deformation amount when pressure of Pa is applied (R ₂₀₀ ) Is 47-63% and the sample is 1.0 × 10 6 at a temperature of 120 ° C. ^Four Deformation amount when pressure of Pa is applied (R ₅₀₀ ) Is 65 to 85%, and the toner is a non-magnetic toner. In the endothermic curve obtained by differential scanning calorimetry (DSC) measurement of the toner, one or a plurality of endothermic peaks exist in the temperature range of 30 to 200 ° C., and the maximum endothermic peak in the endothermic peak has a maximum value of 65. The toner according to claim 1, wherein the toner is in a range of ˜105 ° C. The toner according to claim 1, wherein the wax contains at least an aliphatic hydrocarbon wax. The toner according to claim 1, wherein the toner has an average circularity A of 0.940 to 0.970 in particles having an equivalent circle diameter of 3 μm or more. An image forming method for forming an image on a recording member by heating and pressing and fixing a toner image made of toner formed on the recording member by a fixing means,
  The fixing unit includes a rotatable fixing roller, a fixing belt that is pressed against and contacts the fixing roller, and rotates while forming a nip portion as the fixing roller rotates, and a heating unit that heats the nip portion. And fixing the toner image on the recording member by nipping and conveying the recording member at the nip portion by the rotation of the fixing roller and the fixing belt,
  The width of the nip portion in the rotation direction of the fixing roller is 10 mm or more;
  The image forming method according to claim 1, wherein the toner is the light color magenta toner according to claim 1. An image forming method for forming an image on a recording member by heating and pressing and fixing a toner image made of toner formed on the recording member by a fixing means,
  The fixing unit includes a rotatable fixing roller, a fixing belt that is pressed against and contacts the fixing roller, and rotates while forming a nip portion as the fixing roller rotates, and a heating unit that heats the nip portion. And fixing the toner image on the recording member by nipping and conveying the recording member at the nip portion by the rotation of the fixing roller and the fixing belt,
  The width of the nip portion in the rotation direction of the fixing roller is 10 mm or more;
  The light-colored magenta toner (magenta toner a) according to claim 1 and at least a binder resin, a colorant, and a wax as the toner, and the lightness L of the magenta toner a in a powder state. ^* (A) Lower brightness L ^* (B), magenta toner b which is a non-magnetic toner,
  Lightness L of the magenta toner a ^* (A) and lightness L of the magenta toner b ^* (B) satisfies the relationship of the following formula (1).
  10 ≦ L ^* (A) -L ^* (B) ≦ 40 An image forming method for forming an image on a recording member by heating and pressing and fixing a toner image made of toner formed on the recording member by a fixing means,
  The fixing unit includes a rotatable fixing roller, a fixing belt that is pressed against and contacts the fixing roller, and rotates while forming a nip portion as the fixing roller rotates, and a heating unit that heats the nip portion. And fixing the toner image on the recording member by nipping and conveying the recording member at the nip portion by the rotation of the fixing roller and the fixing belt,
  The width of the nip portion in the rotation direction of the fixing roller is 10 mm or more;
  The image forming method according to claim 2, wherein the toner is the light cyan toner according to claim 2. An image forming method for forming an image on a recording member by heating and pressing and fixing a toner image made of toner formed on the recording member by a fixing means,
  The fixing unit includes a rotatable fixing roller, a fixing belt that is pressed against and contacts the fixing roller, and rotates while forming a nip portion as the fixing roller rotates, and a heating unit that heats the nip portion. And fixing the toner image on the recording member by nipping and conveying the recording member at the nip portion by the rotation of the fixing roller and the fixing belt,
  The width of the nip portion in the rotation direction of the fixing roller is 10 mm or more;
  The light-colored cyan toner (cyan toner a) according to claim 2 and at least a binder resin, a colorant, and a wax as the toner, and the lightness L of the cyan toner a in a powder state. ^* (A) Lower brightness L ^* (B), a cyan toner b which is a non-magnetic toner,
  Lightness L of cyan toner a ^* (A) and lightness L of the cyan toner b ^* (B) satisfies the relationship of the following formula (1).
  10 ≦ L ^* (A) -L ^* (B) ≦ 40

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