JP4532792B2 - Toner, image forming method, and process cartridge - Google Patents

Description

【００５８】
次に、本発明のトナーにおいて、結着樹脂として使用されるハイブリッド樹脂成分について説明する。
【００５９】
本発明のトナーにおいて、トナー粒子に含有されるハイブリッド樹脂は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。ハイブリッド樹脂成分の存在は¹³Ｃ−ＮＭＲ測定により確認することができる。¹³Ｃ−ＮＭＲスペクトルの分解能を阻害する磁性体を含有する磁性トナーでは、トナーを濃塩酸水溶液中に添加して室温で７０乃至８０時間撹拌することにより磁性体を溶解したものを使用することにより、測定することができる。また、カーボンブラック、有機顔料を含有するトナーは、そのままの状態で測定試料とすることができる。以下にビニル系重合体としてスチレンとアクリル酸エステルを用いた場合の測定結果の一例を表２に示す。
【００６０】
【表２】

【００６１】
本発明のトナーにおいて、ポリエステルユニットのアルコール成分としては、エチレングリコール、プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、２，３−ブタンジオール、ジエチレングリコール、トリエチレングリコール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、２−エチル１，３−ヘキサンジオール、水素添加ビスフェノールＡ、下記式（３）で示されるビスフェノール誘導体、また下記式（４）で示されるジオール類が挙げられる。
【００６２】
【化１】

［式中、Ｒはエチレンまたはプロピレン基を示し、ｘ及びｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。］
【００６３】
【化２】

［式中、Ｒ’はエチレン、プロピレンまたはターシャリブチレン基を示す。］
【００６４】
本発明のトナーにおいて、ポリエステルユニットの酸成分としては、フタル酸、無水フタル酸、イソフタル酸及びテレフタル酸の如き芳香族ジカルボン酸；コハク酸、アジピン酸、セバシン酸及びアゼライン酸の如きアルキルジカルボン酸または酸無水物；炭素数６〜１８のアルキル基で置換されたコハク酸もしくはその酸無水物；フマル酸、マレイン酸及びシトラコン酸の如き不飽和ジカルボン酸またはその酸無水物；が挙げられる。
【００６５】
本発明のトナーにおいて、ビニル系重合体ユニットを形成するためのビニルモノマーとしては、スチレン；ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ｐ−メトキシスチレン、ｐ−フェニルスチレン、ｐ−クロルスチレン、３，４−ジクロルスチレン、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エチレン不飽和モノオレフィン；ブタジエンの如き不飽和ポリエン；塩化ビニル、塩化ビニリデン、臭化ビニル、弗化ビニルの如きハロゲン化ビニル；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酸；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；アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸プロピル、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；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；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；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；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；前述のα，β−不飽和酸のエステル、二塩基酸のジエステルが挙げられる。
【００６６】
また、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；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ル基を有するビニル系モノマーが挙げられる。これらは、単独もしくは２種以上を使用してビニル系重合体ユニットを構成するものである。
【００６７】
本発明のトナーにおいて、ハイブリッド樹脂成分のポリエステルユニットは三価以上の多価カルボン酸またはその無水物、または、三価以上の多価アルコールで架橋された架橋構造を有しているものが好ましい。三価以上の多価カルボン酸またはその無水物としては、１，２，４−ベンゼントリカルボン酸、１，２，４，−シクロヘキサントリカルボン酸、１，２，４−ナフタレントリカルボン酸、ピロメリット酸及びこれらの酸無水物または低級アルキルエステルが挙げられる。三価以上の多価アルコールとしては、１，２，３−プロパントリオール、トリメチロールプロパン、ヘキサントリオール、ペンタエリスリトールが挙げられる。好ましくは１，２，４−ベンゼントリカルボン酸及びその酸無水物である。
【００６８】
本発明のトナーにおいて、ハイブリッド樹脂成分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。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、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、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、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、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；ポリエステル型ジアクリレート類として、商品ＭＡＮＤＡ（日本化薬）が挙げられる。
【００６９】
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。
【００７０】
これらの架橋剤は、他のモノマー成分１００質量部に対して、０．０１〜１０質量部（さらに好ましくは０．０３〜５質量部）用いるのが良い。
【００７１】
これらの架橋性モノマーのうち、トナーの定着性、耐オフセット性の点から好適に用いられるものとして、芳香族ジビニル化合物（特にジビニルベンゼン）、芳香族基及びエーテル結合を１含む鎖で結ばれたジアクリレート化合物が挙げられる。
【００７２】
本発明ではビニル系共重合体ユニット及び／又はポリエステルユニット中に、両樹脂ユニットと反応し得るモノマー成分を含むことが好ましい。ポリエステル樹脂ユニットを構成するモノマーのうちビニル系重合体ユニットと反応し得るものとしては、フマル酸、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が挙げられる。ビニル系重合体ユニットを構成するモノマーのうちポリエステルユニット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が挙げられる。
【００７３】
ビニル系重合体ユニットとポリエステルユニット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ユニット及びポリエステルユニットのそれぞれと反応しうるモノマー成分を含むポリマーユニットが存在しているところで、どちらか一方もしくは両方のポリマーユニットの重合反応をさせることにより得る方法が好ましい。
【００７４】
本発明のビニル系重合体ユニットを製造する場合に用いられる重合開始剤としては、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あげられる。
【００７５】
本発明のトナーの結着樹脂は、上述したビニル系重合体ユニットとポリエステルユニットとを有しているハイブリッド樹脂成分を少なくとも有していれば良いが、ハイブリッド樹脂成分に加えて、ビニル系重合体及びポリエステル樹脂を含有している樹脂組成物であることが、本発明のトナーに含有されている含イオウ樹脂の分散を好適な状態に保持し、トナーの現像性と定着性を共に満足することが可能となる点で好ましい。
【００７６】
本発明のトナーの結着樹脂は、ハイブリッド樹脂成分または、ハイブリッド樹脂成分及びポリエステル樹脂としてポリエステルユニットを５０乃至９５質量％含有するものが好ましく、より好ましくは６０乃至９０質量％含有するものが良く、更に好ましくは６５乃至８５質量％含有するものが良い。ポリエステルユニットの含有量が５０質量％未満となる場合にはトナーの低温定着性及び耐高温オフセット性が低下する場合があり好ましくなく、９５質量％超となる場合にはトナーの耐高温オフセット性が低下する場合があり好ましくない。
【００７７】
このようなハイブリッド樹脂成分、ビニル系重合体及びポリエステル樹脂を有する樹脂組成物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。
【００７８】
（１）ビニル系樹脂、ポリエステル樹脂及びハイブリッド樹脂成分をそれぞれ製造後にブレンドする方法である。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するものであり、好ましくは、このブレンド工程でワックスを添加して製造される。ハイブリッド樹脂成分は、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なって合成されるエステル化合物を用いることができる。
【００７９】
（２）ビニル系重合体ユニット製造後に、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成分を製造する方法である。ハイブリッド樹脂成分はビニル系重合体ユニット（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／また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。好ましくは、この工程でワックスを添加する。
【００８０】
（３）ポリエステルユニット製造後に、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成分を製造する方法である。ハイブリッド樹脂成分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／またはビニル系重合体ユニットとの反応により製造される。好ましくは、この工程でワックスを添加する。
【００８１】
（４）ビニル系重合体ユニット及びポリエステルユニット製造後に、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／また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成分を製造される。この場合も適宜、有機溶剤を使用することができる。好ましくは、この工程でワックスを添加する。
【００８２】
（５）ハイブリッド樹脂成分を製造後、ビニル系モノマー及び／また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、ハイブリッド樹脂成分は上記（２）乃至（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。さらに、適宜、有機溶剤を使用することができる。好ましくは、この工程でワックスを添加する。
【００８３】
（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成分が製造される。さらに、適宜、有機溶剤を使用することができる。好ましくは、この工程でワックスを添加する。
【００８４】
上記（１）乃至（５）の製造方法において、ビニル系重合体ユニット及び／また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。
【００８５】
上記の（１）〜（６）の製造方法の中でも、特に（３）の製造方法が、ビニル系重合体ユニットの分子量制御が容易であり、ハイブリッド樹脂成分の生成を制御することができ、かつワックスを添加する場合にはその分散状態を制御できる点で好ましい。
【００８６】
本発明のトナーの重量平均粒径は４乃至１２μｍであり、粒径１０．１μｍ以上の粒子を３０体積％未満含有するものが好ましく、より好ましくは重量平均粒径５乃至９μｍであり、粒径１０．１μｍ以上の粒子を２０体積％未満含有するのが良く、更に好ましくは重量平均粒径５．５乃至８μｍであり、粒径１０．１μｍ以上の粒子を１０体積％未満含有するのが良い。トナーの重量平均粒径が１２μｍ超であり、粒径１０．１μｍ以上の粒子を３０体積％以上含有する場合には、トナーの帯電性が不均一性になる場合があり好ましくない。
【００８７】
トナーが磁性トナーの場合は、磁性トナーに使用される磁性体は、異種元素を含有するマグネタイト、マグヘマタイト、フェライトの如き磁性酸化物及びその混合物が好ましく用いられる。
【００８８】
例えば、リチウム、ベリリウム、ボロン、マグネシウム、アルミニウム、ケイ素、リン、イオウ、ゲルマニウム、チタン、ジルコニウム、錫、鉛、亜鉛、カルシウム、バリウム、バナジウム、クロム、マンガン、コバルト、銅、ニッケル、ガリウム、インジウム、銀、パラジウム、金、白金、タングステン、モリブデン、ニオブ、オスミニウム、ストロンチウム、イットリウム、テクネチウム、ルテニウム、ロジウム及びビスマスから選ばれる少なくとも一つ以上の元素を含有する磁性酸化鉄である。リチウム、ベリリウム、ボロン、マグネシウム、アルミニウム、ケイ素、リン、ゲルマニウム、チタン、ジルコニウム、錫、イオウ、カルシウム、バリウム、バナジウム、クロム、マンガン、コバルト、銅、ニッケル、ストロンチウム、ビスマス及び亜鉛が好ましい。特に好ましくは、異種元素としてマグネシウム、アルミニウム、ケイ素、リン及びジルコニウムから選択される元素を含有する磁性酸化鉄である。これらの元素は酸化鉄結晶格子に取り込まれても良いし、酸化物として酸化鉄中に取り込まれていても良いし、表面に酸化物あるいは水酸化物として存在しても良いが、酸化物として含有されるのが好ましい。
【００８９】
これらの元素は、磁性体生成時に各々の元素の塩を混在させｐＨ調整により、粒子中に取り込むことが出来る。また、磁性体粒子生成後にｐＨ調整、あるいは各々の元素の塩を添加しｐＨ調整することにより粒子表面に析出させることが出来る。
【００９０】
これらの元素を含有する磁性体は、ハイブリッド樹脂との親和性が良好であり特定の酸価を有するハイブリッド樹脂ではより効果的であるばかりでなく、本発明のトナーに用いられる含イオウ樹脂を本発明に好適な状態に分散するにも好影響を与える。また、これらの磁性体は粒度分布を狭くすることが可能であり、かつハイブリッド樹脂への分散性も良好であることからトナーの帯電均一化及び安定化を改善する効果も有する。
【００９１】
これらの異種元素の含有率は、磁性酸化鉄の鉄元素を基準として０．０５から１０質量％であるのが良く、より好ましくは０．１〜７質量％含有するのが良く、さらに好ましくは０．２〜５質量％含有するのが良く、特に好ましくは、０．３〜４質量％含有するのが良い。含有量が０．０５質量％未満となる場合には、上記、これらの元素の含有効果が少なく、良好な分散性、帯電均一性が得られにくい。また、１０質量％より多くなると電荷の放出が多くなり帯電不足が生じやすく、画像濃度の低下、カブリの増加を生じやすいので好ましくない。
【００９２】
また、これらの異種元素の含有分布において、磁性体の粒子の表面近傍に多く存在しているのが好ましい。例えば、酸化鉄に含有される鉄元素の溶解率が２０質量％のときに、異種元素の溶解率が、全異種元素の存在量の２０〜１００質量％であるのが良く、より好ましくは２５〜１００質量％であるのが良く、特に好ましくは３０〜１００質量％であるのが良い。異種元素の表面存在量を多くすることにより分散効果及び電気的拡散効果をより向上することができる。
【００９３】
磁性体の個数平均粒径は０．０５〜１．０μｍが好ましく、さらには０．１〜０．５μｍのものが好ましい。磁性体のＢＥＴ比表面積は２〜４０ｍ²／ｇが好ましく、さらには４〜２０ｍ²／ｇのものが好ましい。磁性体の磁気特性は、磁場７９５．８ｋＡ／ｍで測定した飽和磁化が１０〜２００Ａｍ²／ｋｇが好ましく、さらには７０〜１００Ａｍ²／ｋｇがより好ましい。残留磁化は１〜１００Ａｍ²／ｋｇが好ましく、さらには２〜２０Ａｍ²／ｋｇが好ましい。抗磁力は１〜３０ｋＡ／ｍが好ましく、さらには２〜１５ｋＡ／ｍがより好ましい。これらの磁性体は結着樹脂１００質量部に対して２０〜２００質量部添加して用いられる。
【００９４】
本発明のトナーには任意の適当な顔料または染料を着色剤として使用できる。顔料としては、カーボンブラック、アニリンブラック、アセチレンブラック、ナフトールイエロー、ハンザイエロー、ローダミンイエロー、アリザリンイエロー、ベンガラ、フタロシアニンブルーが挙げられる。顔料は、結着樹脂１００質量部に対して０．１〜２０質量部添加するのが良く、より好ましくは０．２〜１０質量部添加するのが良い。染料としては、アゾ系染料、アントラキノン系染料、キサンテン系染料、メチン系染料が挙げられる。染料は、結着樹脂１００質量部に対して０．１〜２０質量部添加するのが良く、より好ましくは０．３〜１０質量部添加するのが良い。
【００９５】
本発明のトナーにおいて、シリカ、アルミナ、酸化チタンの如き無機酸化物の微粉体、カーボンブラック、フッ化カーボンの如き微粒径の無機微粉体がトナー粒子に外添されている。
【００９６】
シリカ微粉体、アルミナ微粉体または酸化チタン微粉体は、トナー粒子表面に分散させた時に細かい粒子となるほうがトナーへの流動性付与効果が高く好ましい。これらの無機微粉体は個数平均粒径が５〜１００ｎｍであるのが好ましく、より好ましくは５〜５０ｎｍであるのが良い。
【００９７】
これらの無機微粉体の添加量は、トナー粒子１００質量部に対して、０．０３〜５質量部使用すると、適切なトナー粒子表面被覆率になる。
【００９８】
本発明のトナーは、さらに、フッ化ビニリデン微粉末、ポリテトラフルオロエチレン微粉末の如きフッ素系樹脂粉末を外添しても良い。
【００９９】
好ましい無機微粉体としては、ケイ素ハロゲン化合物の蒸気相酸化により生成された乾式法シリカ又はヒュームドシリカである。例えば、四塩化ケイ素ガスの酸水素焔中における熱分解酸化反応を利用するもので、基礎となる反応式は次の様なものである。
【０１００】
【化３】
ＳｉＣｌ₄＋２Ｈ₂＋Ｏ₂→ＳｉＯ₂＋４ＨＣｌ
【０１０１】
この製造工程において、塩化アルミニウム又は塩化チタン等の他の金属ハロゲン化合物をケイ素ハロゲン化合物と共に用いることによってシリカと他の金属酸化物の複合微粉体を得ることも可能である。その粒径は、平均の一次粒径として、０．００１〜２μｍの範囲内であることが好ましく、特に好ましくは、０．００２〜０．２μｍの範囲内にあり、個数平均径が５〜１００ｎｍであるシリカ微粉体を使用するのが良い。
【０１０２】
ケイ素ハロゲン化合物の蒸気相酸化により生成された市販のシリカ微粉体としては、例えば以下の様な商品名で市販されているものがある。
【０１０３】
ＡＥＲＯＳＩＬ（日本アエロジル社）１３０、２００、３００、３８０、ＴＴ６００、ＭＯＸ１７０、ＭＯＸ８０、ＣＯＫ８４；Ｃａ−Ｏ−ＳｉＬ（ＣＡＢＯＴ Ｃｏ．社）Ｍ−５、ＭＳ−７、ＭＳ−７５、ＨＳ−５、ＥＨ−５；（ＷＡＣＫＥＲ−ＣＨＥＭＩＥ ＧＭＢＨ社）ＨＤＫ、Ｎ２０、１５、Ｎ２０Ｅ、Ｔ３０、Ｔ４０；Ｄ−Ｃ Ｆｉｎｅ Ｓｉｌｉｃａ（ダウコーニングＣｏ．社）；Ｆｒａｎｓｏｌ（Ｆｒａｎｓｉｌ社）
【０１０４】
疎水化方法としては、シリカ微粉体と反応あるいは物理吸着する有機ケイ素化合物で化学的に処理することによって付与される。好ましい方法としては、ケイ素ハロゲン化合物の蒸気相酸化により生成されたシリカ微粉体を有機ケイ素化合物で処理する。
【０１０５】
有機ケイ素化合物としては、ヘキサメチルジシラザン、トリメチルシラン、トリメチルクロルシラン、トリメチルエトキシシラン、ジメチルジクロルシラン、メチルトリクロルシラン、アリルジメチルクロルシラン、アリルフェニルジクロルシラン、ベンジルジメチルクロルシラン、ブロムメチルジメチルクロルシラン、α−クロルエチルトリクロルシラン、β−クロルエチルトリクロルシラン、クロルメチルジメチルクロルシラン、トリオルガノシリルメルカプタン、トリメチルシリルメルカプタン、トリオルガノシリルアクリレート、ビニルジメチルアセトキシシラン、ジメチルエトキシシラン、ジメチルジメトキシシラン、ジフェニルジエトキシシラン、ヘキサメチルジシロキサン、１，３−ジビニルテトラメチルジシロキサン、１，３−ジフェニルテトラメチルジシロキサンおよび１分子当り２から１２個のシロキサン単位を有し末端に位置する単位にそれぞれ１個宛のＳｉに結合した水酸基を含有するジメチルポリシロキサンがある。さらに、ジメチルシリコーンオイルの如きシリコーンオイルが挙げられる。これらは１種あるいは２種以上の混合物で用いられる。
【０１０６】
無機微粉体は、ＢＥＴ法で測定した窒素吸着による比表面積が３０ｍ²／ｇ以上、好ましくは５０ｍ²／ｇ以上のものが良好な結果を与える。無機微粉体は、トナー粒子１００質量部に対して０．０１〜８質量部、より好ましくは０．０３〜５質量部、さらに好ましくは０．１〜４質量部使用するのが良い。
【０１０７】
本発明のトナーに用いられる無機微粉体の疎水化度は、メタノールウェッタビリティーは３０％以上であるのが好ましく、より好ましくは５０％以上であるのが良い。疎水化処理処理剤としては、含ケイ素表面処理剤であるシラン化合物とシリコーンオイルが好ましい。
【０１０８】
例えば、ジメチルジメトキシシラン、トリメチルエトキシシラン、ブチルトリメトキシシラン等のアルキルアルコキシシラン；ジメチルジクロルシラン、トリメチルクロルシラン、アリルジメチルクロルシラン、ヘキサメチレンジメチルクロルシラン、アリルフェニルジメチルクロルシラン、ベンジルジメチルクロルシラン、ビニルトリエトキシシラン、γ−メタクリルオキシプロピルトリメトキシシラン、ジビニルクロルシラン、ジメチルビニルクロルシランの如きシランカップリング剤を用いることができる。
【０１０９】
本発明のトナーは、キャリアと混合して二成分現像剤として使用してもよい。キャリアの抵抗値は、キャリア表面の凹凸度合い、被覆する樹脂量を調整して１０⁶〜１０¹⁰Ω・ｃｍにするのがよい。
【０１１０】
キャリア表面を被覆する樹脂としては、スチレン−アクリル酸エステル共重合体、スチレン−メタクリル酸エステル共重合体、アクリル酸エステル共重合体、メタクリル酸エステル共重合体、シリコーン樹脂、フッ素樹脂、ポリアミド樹脂、アイオノマー樹脂、ポリフェニレンサルファイト樹脂あるいは、これらの樹脂の混合物を使用することができる。
【０１１１】
キャリアコアの磁性材料としては、フェライト、鉄過剰型フェライト、マグネタイト、γ−酸化鉄等の酸化物、鉄、コバルト、ニッケルのような金属あるいはこれらの合金を用いることができる。また、これらの磁性材料に含有される元素としては、鉄、コバルト、ニッケル、アルミニウム、銅、鉛、マグネシウム、錫、亜鉛、アンチモン、ベリリウム、ビスマス、カルシウム、マンガン、セレン、チタン、タングステン、バナジウムが挙げられる。
【０１１２】
本発明のトナーにおいて、各種特性付与を目的として種々の添加剤を使用することができ、例えば、以下に示す添加剤である。
【０１１３】
（１）研磨剤としては、金属酸化物（チタン酸ストロンチウム、酸化セリウム、酸化アルミニウム、酸化マグネシウム、酸化クロム）、窒化物（窒化ケイ素）、炭化物（炭化ケイ素）、金属塩（硫酸カルシウム、硫酸バリウム、炭酸カルシウム）がある。
【０１１４】
（２）滑剤としては、フッ素系樹脂粉末（ポリフッ化ビニリデン、ポリテトラフルオロエチレン）、脂肪族金属塩（ステアリン酸亜鉛、ステアリン酸カルシウム）がある。
【０１１５】
（３）導電性粒子としては、金属酸化物（酸化錫、酸化亜鉛）、カーボンブラックがある。
【０１１６】
これらの添加剤は、トナー粒子１００質量部に対して０．０５〜１０質量部添加されるのが良く、より好ましくは０．１〜５質量部添加するのが良い。これらの添加剤は単独または複数種を混合して使用してもよい。
【０１１７】
磁性トナーの場合には、２種以上の無機酸化物あるいは金属酸化物の無機微粉体を用いることが現像の耐久安定性及び放置後の現像安定性の観点から好ましい。非磁性一成分現像方法の場合には、酸化チタン微粉体またはアルミナ微粉体を用いるのが、流動性向上及び画像均一性の観点から好ましい。
【０１１８】
本発明に係るトナー粒子を製造するには、上述したトナー粒子構成材料をボールミル、ヘンシェルミキサーの如き混合機を用いて十分に混合してから、熱ロールニーダー、エクストルダーの如き熱混練機を用いてよく混練し、冷却固化後、機械的に粗粉砕し、次にジェット気流または機械的に微砕粉し、これを分級することによりトナー粒子を得る方法が好ましい。これ以外の製造法としては、結着樹脂を構成すべきモノマーに所定の材料を混合しして乳化懸濁液とした後に、重合してトナー粒子を得る重合トナー製造法；コア材、シェル材からなるマイクロカプセルトナーにおいて、コア材あるいはシェル材、あるいはこれらの両方に所定の材料を含有させる方法；結着樹脂溶液中に構成材料を分散した後に、噴霧乾燥することによりトナー粒子を得る方法が挙げられる。さらに所望の添加剤とトナー粒子とをヘンシェルミキサーの如き混合機により十分に混合することにより、本発明のトナーを製造することができる。
【０１１９】
次に、本発明のトナーが好ましく用いられる画像形成法について説明する。
【０１２０】
本発明の画像形成方法に適用できる現像手段について説明する。
【０１２１】
図１において、公知のプロセスにより形成された静電荷像を担持する像担持体（例えば電子写真感光ドラム）７は、矢印Ｂ方向に回転される。現像剤担持体としての現像スリーブ１４は、ホッパー９から供給されたトナー１０を担持して、矢印Ａ方向に回転することにより、現像スリーブ１４と感光ドラム７とが対向した現像部Ｄにトナー１０を搬送する。現像スリーブ１４内には、トナー１０が磁性トナーである場合には、現像スリーブ１４上に磁気的に吸引及び保持するために、磁界発生手段（磁石）１１が配置されている。トナー１０は現像スリーブ１４との摩擦により、感光ドラム７上の静電荷像を現像可能な摩擦帯電電荷を得る。現像スリーブ１４は基体１２上に樹脂層１３が設けられている。
【０１２２】
現像部Ｄに搬送されるトナー１０の層厚を規制するために、磁性トナーである場合には強磁性金属からなる規制磁性ブレード８が、現像スリーブ１４の表面から２００〜３００μｍのギャップ幅を持って現像スリーブ１４に臨むように、ホッパー９から垂下されている。磁石１１の磁極Ｎ１からの磁力線がブレード８に集中することにより、現像スリーブ１４上にトナー１０の薄層が形成される。ブレード８としては非磁性ブレードを使用することもできる。また、磁性ブレードのかわりに、ウレタンゴム、シリコーンゴム、チップブレードの如き弾性ブレードが用いられる。
【０１２３】
現像スリーブ１４上に形成されるトナー１０の薄層の厚みは、現像部Ｄにおける現像スリーブ１４と感光ドラム７との間の最小間隙よりも更に薄いものであることが好ましい。このようなトナー薄層は静電荷像を現像する方式の現像装置（即ち非接触型現像装置）に、特に有効である。しかし、現像部において、トナー層の厚みが現像スリーブ１４と感光ドラム７との間の最小間隙以上の厚みである現像装置（即ち接触型現像装置）にも、適用することができる。
【０１２４】
以下、非接触型現像装置の例を説明する。
【０１２５】
上記現像スリーブ１４には、これに担持されたトナー１０を飛翔させるために、電源１５により現像バイアス電圧が印加される。この現像バイアス電圧として直流電圧を使用するときは、静電荷像の画像部（トナー１０が付着して可視化される領域）の電位と背景部の電位との間の値の電圧が、現像スリーブ１４に印加されることが好ましい。一方、現像画像の濃度を高め或は階調性を向上するために、現像スリーブ１４に交番バイアス電圧を印加して、現像部Ｄに向きが交互に反転する振動電界を形成してもよい。この場合、上記画像部の電位と背景部の電位の値を有する直流電圧成分が重畳された交番バイアス電圧を現像スリーブ１４に印加することが好ましい。
【０１２６】
また、高電位部と低電位部を有する静電荷像の高電位部にトナーを付着させて可視化する正規現像では、静電荷像の極性と逆極性に帯電するトナーを使用する。一方、静電荷像の低電位部にトナーを付着させて可視化する、反転現像では、トナーは静電荷像の極性と同極性に帯電するトナーを使用する。高電位と低電位というのは、絶対値による表現である。トナー１０は現像スリーブ１４との摩擦により静電荷像を現像するための極性に帯電する。
【０１２７】
現像装置では、現像スリーブ１４上のトナー１０の層厚を規制する部材として、ウレタンゴム，シリコーンゴムの如きゴム弾性を有する材料、或はリン青銅，ステンレス鋼の如き金属弾性を有する材料で形成された弾性板１７を使用し、この弾性板１７を現像スリーブ１４に圧接させている。このような現像装置では、現像スリーブ８上に更に薄いトナー層を形成することができる。図２の現像装置のその他の構成は、図１に示した現像装置と基本的に同じで、図２において図１に付した符号と同一の符号は同一の部材を示す。
【０１２８】
上記のようにして現像スリーブ１４上にトナー層を形成する図２に示すような現像装置は、弾性板１７によりトナーを現像スリーブ１４上に擦りつけるため、トナーの摩擦帯電量も多くなり、画像濃度の向上が図られる。また、非磁性一成分トナーにおいても、このような現像装置が用いられる。
【０１２９】
本発明に用いられる現像剤担持体である現像スリーブは、円筒状基体と、該基体表面を被覆する被膜層（樹脂層）を有することも好ましい。その構成は図３に示したようなものである。該樹脂層１は、結着樹脂４、場合によっては導電性物質２、充填剤３及び固体潤滑剤５を含有し、円筒状基体６上に被覆されている。導電性物質２が含有されている場合、樹脂層１は導電性なのでトナーの過剰帯電が防止できる。また充填剤３が含有されている場合には、トナーによる該樹脂層１の摩耗を防ぎ、更に充填剤３の帯電付与性により、トナーの帯電も好適にコントロールできる。また、固体潤滑剤５が含有される場合には、トナーと現像スリーブとの離型性が向上され、その結果トナーの現像スリーブ上への融着が防止できる。
【０１３０】
現像スリーブにおいて、樹脂層に導電性物質を含有させる場合、該樹脂層の体積抵抗が１０⁶Ω・ｃｍ以下、好ましくは１０³Ω・ｃｍ以下であるものがよい。樹脂層の体積抵抗が１０⁶Ω・ｃｍを超える場合には、トナーのチャージアップが発生しやすくなり、ブロッチの発生や現像特性の劣化を引き起こすことがある。
【０１３１】
また、該樹脂層の表面粗さは、ＪＩＳ中心線平均粗さ（Ｒａ）で０．２〜３．５μｍの範囲にあることが好ましい。Ｒａが０．２μｍ未満ではスリーブ近傍のトナーの帯電量が高くなりやすく、鏡映力によりトナーがスリーブ上に引きつけられ、新たなトナーがスリーブから帯電付与を受けられず、現像性が低下しやすい。Ｒａが３．５μｍを超えると、スリーブ上のトナーコート量が増加しすぎてトナーが十分な帯電量を得られず、かつ不均一な帯電となりやすく、画像濃度の低下や濃度ムラの原因となりやすい。
【０１３２】
次に図３を参照しながら該樹脂層１を構成する各材料について説明する。
【０１３３】
導電性物質２としては、アルミニウム、銅、ニッケル、銀の如き金属粉体；酸化アンチモン、酸化インジウム、酸化スズの如き金属酸化物；カーボンファイバー、カーボンブラック、グラファイトの如き炭素同素体が挙げられる。このうちカーボンブラックは特に電気伝導性に優れ、高分子材料に充填して導電性を付与したり、添加量のコントロールで、ある程度任意の導電度を得ることができるために好適に用いられる。カーボンブラックの個数平均粒径は０．００１〜１．０μｍ、好ましくは０．０１〜０．８μｍのものが良い。カーボンブラックの個数平均粒径が１μｍを超える場合には、樹脂層の体積抵抗を制御しづらくなり好ましくない。
【０１３４】
導電性物質の使用量としては、結着樹脂１００質量部に対して、好ましくは０．１〜３００質量部であり、より好ましくは１〜１００質量部である。
【０１３５】
充填剤３としては、公知のトナー用ネガ帯電性荷電制御剤、あるいはポジ帯電性荷電制御剤を添加しても良い。このほかの充填剤として、アルミナ、アスベスト、ガラス繊維、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、硫酸バリウム、シリカ、ケイ酸カルシウムの如き無機化合物；フェノール樹脂、エポキシ樹脂、メラミン樹脂、シリコーン樹脂、ＰＭＭＡ、メタクリレートのターポリマー（例えばポリスチレン／ｎ−ブチルメタクリレート／シランターポリマー）、スチレン−ブタジエン系共重合体、ポリカプロラクトン；ポリカプロラクタム、ポリビニルピリジン、ポリアミドの如き含窒素化合物；ポリフッ化ビニリデン、ポリ塩化ビニル、ポリテトラフルオロエチレン、ポリテトラクロロフルオロエチレン、ペルフルオロアルコキシル化エチレン、ポリテトラフルオロアルコキシエチレン、フッ素化エチレンプロピレン−ポリテトラフルオロエチレン共重合体、トリフルオロクロロエチレン−塩化ビニル共重合体といった高度にハロゲン化された重合体；ポリカーボネート、ポリエステルが挙げられる。このうちシリカ及びアルミナが、それ自身の硬さ及びトナーに対する帯電制御性を有するので好ましく用いられる。
【０１３６】
充填剤の使用量としては、結着樹脂１００質量部に対して、好ましくは０．１〜５００質量部、より好ましくは１〜２００質量部である。
【０１３７】
固体潤滑剤５としては、二硫化モリブデン、窒化硼素、グラファイト、フッ化グラファイト、銀−セレン化ニオブ、塩化カルシウム−グラファイト、滑石が挙げられる。このうちグラファイトは潤滑性と共に導電性を有し、高すぎる電荷を有するトナーを減少させ、現像に好適な帯電量を持たせる働きがあることから好適に用いられる。
【０１３８】
固体潤滑剤の使用量としては、結着樹脂１００質量部に対して、好ましくは０．１〜３００質量部であり、より好ましくは１〜１５０質量部である。
【０１３９】
場合によっては、該導電性物質２、該充填剤３や固体潤滑剤５が分散される結着樹脂４としては、フェノール系樹脂、エポキシ系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、ポリオレフィン系樹脂、シリコーン系樹脂、フッ素系樹脂、スチレン系樹脂、アクリル系樹脂の如き樹脂が用いられる。特に熱硬化性もしくは光硬化性の樹脂が好ましい。
【０１４０】
現像スリーブ表面の樹脂層中の導電性物質、或いは充填剤や固体潤滑剤を表面に好適に露出させるために、または、表面を平滑化処理して均一な凹凸表面を作るために、後述の磨き加工等の手段により表面を平滑化処理することにより、さらに好ましい性能を付与することが可能である。特に、ベタ黒やハーフトーン画像に発生する縦スジ現象や初期の画像濃度の立ち上がりに効果があり、特に高温高湿下での効果が大きい。フェルトや砥粒の付着した帯状研磨材での磨き加工を施すことで、スリーブの表面凹凸を均一に仕上げることができるので、スリーブ上のトナーコート量が均一化し、その結果スリーブとの摩擦帯電を受けたトナーのみが現像領域に搬送されるようになる。従って、上記効果が得られるものと考えられる。
【０１４１】
上記のように平滑化処理を施した後も、コート層表面はＪＩＳ Ｂ ０６０１におけるＲａで０．２〜３．５μｍの範囲の凹凸を保持していることが好ましく、より好ましくは０．３〜２．５μｍ程度である。理由は前記と同様である。
【０１４２】
円筒基体６としては、非磁性金属円筒管、樹脂円筒が好ましく用いられる。例えば、ステンレス円筒管、アルミニウム円筒管、銅合金円筒管の如き非磁性の円筒管が用いられる。円筒管を作製する方法としては、引き抜き法や押し出し法があり、更に円筒管自体の寸法精度を上げる場合には、切削や研磨を施して所定の寸法精度とする。円筒管の真直度は３０μｍ以下であることが好ましく、さらには２０μｍ以下が好ましく良好な画像が得られる。また必要に応じて適度な凹凸を表面に付与するためにサンドブラストや研磨により粗面を形成してもよい。ブラストに用いられる砥粒は定形粒子でも不定形粒子でも構わない。
【０１４３】
次に、本発明の画像形成方法の一例を図４に示す。図４は接触帯電手段及び接触転写手段を有する画像形成装置を示す。
【０１４４】
光導電層８０１ａ及び導電性基層８０１ｂを有する回転ドラム型の感光体８０１は、図面上時計の針の回転方向に所定の周速（プロセススピード）で回転される。導電性弾性層８０２ａ及び芯金８０２ｂを有している接触帯電手段である帯電ローラー８０２は、帯電バイアス電源８０３によりバイアスが印加されている。帯電ローラー８０２は、感光体８０１に押圧力により圧接されており、感光体８０１の回転に伴い従動回転する。
【０１４５】
帯電ローラー８０２にバイアスＶ₂が印加されることで感光体８０１の表面が所定の極性・電位に帯電される。次いで画像露光８０４によって静電荷像が形成され、現像手段８０５によりトナー画像として順次可視化されていく。
【０１４６】
現像手段８０５を構成する現像スリーブには、現像バイアス印加手段８１３よりバイアスＶ₁が印加される。現像により潜像保持体上に形成されたトナー像は、転写バイアス電源８０７により転写バイアスＶ₃が印加された転写材８０８を感光体８０１に押圧する当接転写手段としての転写ローラー８０６（導電性弾性層８０６ａ，芯金８０６ｂ）により転写材８０８に静電転写され、転写材上のトナー像は、加熱ローラー８１１ａ及び加圧ローラー８１１ｂを有する加熱加圧手段８１１により加熱加圧定着される。トナー画像転写後の感光体８０１面では転写残りトナーの如き付着汚染物質を、感光体８０１にカウンター方向に圧接した弾性クリーニングブレードを具備したクリーニング装置８０９で清浄面化され、更に除電露光装置８１０により除電されて、繰り返して作像される。
【０１４７】
一次帯電手段としては、以上のごとく接触帯電手段として帯電ローラー８０２を用いて説明したが、帯電ブレード、帯電ブラシの如き接触帯電手段でもよく、更に、非接触のコロナ帯電手段でもよい。接触帯電手段の方が帯電工程におけるオゾンの発生が少ない。転写手段としては、以上のごとく転写ローラー８０６を用いて説明したが転写ブレード又は転写ベルトの如き接触帯電手段でもよく、更に非接触のコロナ転写手段でもよい。当接転写手段の方が転写工程におけるオゾンの発生が少ない。
【０１４８】
更に、本発明の画像形成方法に適用できる別の定着法について図５に示す定着手段を用いて説明する。図５は、トナー画像を担持している記録材５１９を固定支持された加熱体５１１と、該加熱体に対向圧接し且つフィルム５１５を介して該記録材を該加熱体に密着させる加圧部材５１８とにより加熱定着する手段を示す。
【０１４９】
図５に示す定着装置において加熱体５１１は、従来の熱ロールに比べて熱容量が小さく、線状の加熱部を有するものであって、加熱部の最高温度は１００〜３００℃であることが好ましい。
【０１５０】
また、加熱体５１１と加圧部材としての加圧ローラー５１８との間に位置する定着フィルム５１５は、厚さ１〜１００μｍの耐熱性のシートであることが好ましく、これら耐熱性シートとしては耐熱性の高い、ポリエステル，ＰＥＴ（ポリエチレンテレフタレート），ＰＦＡ（テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体），ＰＴＦＥ（ポリテトラフルオロエチレン），ポリイミド，ポリアミドの如きポリマーシートの他、アルミニウムの如き金属シート及び、金属シートとポリマーシートから構成されたラミネートシートが用いられる。
【０１５１】
より好ましい定着フィルムの構成としては、これら耐熱性シートが離型層及び／又は低抵抗層を有していることである。
【０１５２】
５１１は、装置に固定支持された低熱容量線状加熱体であって、一例として厚み１．０ｍｍ，幅１０ｍｍ，長手長２４０ｍｍのアルミナ基板５１２に抵抗材料５１３を幅１．０ｍｍに塗工したもので、長手方向両端より通電される。通電はＤＣ１００Ｖの周期２０ｍｓｅｃのパルス状波形で検温素子５１４によりコントロールされた所望の温度、エネルギー放出量に応じたパルスをそのパルス幅を変化させて与える。略パルス幅は０．５ｍｓｅｃ〜５ｍｓｅｃとなる。この様にエネルギー及び温度を制御された加熱体５１１に当接して、図中矢印方向に定着フィルム５１５は移動する。
【０１５３】
この定着フィルムの一例として厚み２０μｍの耐熱フィルム（例えば、ポリイミド，ポリエーテルイミド，ＰＥＳ，ＰＦＡに少なくとも画像当接面側にＰＴＦＥ，ＰＡＦの如き弗素樹脂）に導電剤を添加した離型層を１０μｍコートしたエンドレスフィルムである。一般的には総厚は１００μｍ未満、より好ましく４０μｍ未満が良い。フィルムの駆動は駆動ローラー５１６と従動ローラー５１７による駆動とテンションにより矢印方向に皺を生じることなく移動する。
【０１５４】
５１８は、シリコーンゴムの如き離型性の良いゴム弾性層を有する加圧ローラーで、総圧３９．２〜１９６Ｎ（４〜２０ｋｇ）でフィルムを介して加熱体を加圧し、フィルムと圧接回転する。記録材５１９上の未定着トナー５２０は、入口ガイド５２１により定着部に導かれ、上述の加熱により定着画像を得るものである。
【０１５５】
定着フィルム５１５は、エンドレスベルトで説明したが、シート送り出し軸及び巻き取り軸を使用し、定着フィルムは有端のフィルムであってもよい。
【０１５６】
図６に、本発明のプロセスカートリッジの一具体例を示す。プロセスカートリッジは、現像手段と静電荷像担持体とを少なくとも一体的にカートリッジ化し、プロセスカートリッジは、画像形成装置本体（例えば、複写機、レーザービームプリンター）に着脱可能なように形成される。
【０１５７】
図６では、現像手段７０９、ドラム状の静電荷像担持体（感光体ドラム）７０１、クリーニングブレード７０８ａを有するクリーナ７０８、一次帯電器（帯電ローラー）７４２を一体としたプロセスカートリッジ７５０が例示される。
【０１５８】
図６では、現像手段７０９は弾性ブレード７１１ａとトナー容器７６０内に磁性トナー７１０を有し、該磁性トナー７１０を用い、現像時には、バイアス印加手段からのバイアスにより感光ドラム７０１と現像スリーブ７０４との間に所定の電界が形成され、現像工程が好適に実施されるためには、感光ドラム７０１と現像スリーブ７０４との間の距離は非常に大切である。
【０１５９】
本発明のトナーに係る物性の測定方法を以下に記載する。
【０１６０】
（１）トナー及び結着樹脂の酸価測定
ＪＩＳ Ｋ００７０に記載の測定方法に準拠して行う。
測定装置 ：電位差自動滴定装置 ＡＴ−４００（京都電子社製）
装置の校正：トルエン１２０ｍｌとエタノール３０ｍｌの混合溶媒を使用する。測定温度 ：２５℃
試料調製 ：トナー１．０ｇ又は結着樹脂０．５ｇをトルエン１２０ｍｌに添加して室温（約２５℃）で約１０時間マグネチックスターラーを用いて撹拌して溶解する。更にエタノール３０ｍｌを添加して試料溶液とする。
【０１６１】
（２）ＴＨＦ可溶分の分子量測定
結着樹脂又はトナーのテトラヒドロフラン（ＴＨＦ）可溶分のＴＨＦを溶媒としたＧＰＣによる分子量分布は次の条件で測定し、分子量１０００以上を測定するものとする。
【０１６２】
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ＴＨＦを毎分１ｍｌの流速で流し、ＴＨＦ試料溶液を約１００μｌ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値との関係から算出した。検量線作成用の標準ポリスチレン試料としては、例えば東ソー社製あるいは昭和電工社製の分子量が１０²〜１０⁷程度のものを用い、少なくとも１０点の標準ポリスチレン試料を用いるのが適当である。また、検出器にはＲＩ（屈折率）検出器を用いる。なお、カラムをしては、市販のポリスチレンジェルカラムを複数本組合せるのが良く、例えば昭和電工社製のｓｈｏｄｅｘ ＧＰＣ ＫＦ−８０１、８０２、８０３、８０４、８０５、８０６、８０７、８００Ｐの組合せや、東ソー社製のＴＳＫｇｅｌ Ｇ１０００Ｈ（Ｈ_XL）、Ｇ２０００Ｈ（Ｈ_XL）、Ｇ３０００Ｈ（Ｈ_XL）、Ｇ４０００Ｈ（Ｈ_XL）、Ｇ５０００Ｈ（Ｈ_XL）、Ｇ６０００Ｈ（Ｈ_XL）、Ｇ７０００Ｈ（Ｈ_XL）、ＴＳＫｇｕｒｄ ｃｏｌｕｍｎの組合せを挙げることができる。
【０１６３】
上記の方法で得られたＧＰＣによる分子量分布から、分子量８００以上の分子量積分値に対する分子量５０万以上の分子量積分値の割合を算出することによって、分子量５０万以上の成分の含有量を求める。
【０１６４】
試料は以下の様にして作製する。
【０１６５】
試料をＴＨＦ中に入れ、数時間放置した後、十分振とうしＴＨＦとよく混ぜ（試料の合一体が無くなるまで）、更に１２時間以上静置する。その時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ー（ポアサイズ０．２〜０．５μｍ、例えばマイショリディスクＨ−２５−２（東ソー社製）などが使用できる。）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。
【０１６６】
（３）テトラヒドロフラン（ＴＨＦ）不溶分の測定
ＴＨＦ不溶分を測定しようとするトナー試料を０．５乃至１．０ｇを精秤し、円筒ろ紙（東洋濾紙社製、Ｎｏ．８６Ｒ、寸法は外形２８ｍｍ×高さ１００ｍｍ）に入れてソックスレー抽出器にかけ、抽出溶媒であるＴＨＦは２００ｍｌ使用する。抽出はオイルバスの温度を１２０乃至１３０℃に制御して使用し、１回の還流に要する時間は１２０乃至１５０秒になるように調整する。抽出時間は１０時間とする。抽出終了後は円筒濾紙を７０℃で１０時間減圧乾燥し、下記式からＴＨＦ不溶分を算出する。
【０１６７】
【数１】

〔式中、Ｗ１はトナー試料の質量、Ｗ２は結着樹脂のＴＨＦ可溶成分、Ｗ３はトナーに含有される結着樹脂以外の成分（例えば、磁性体、ワックス、外添剤等である）を表す。〕
【０１６８】
（４）トナーのＤＳＣ曲線及びワックスの吸熱ピーク温度の測定
示差走査熱量計（ＤＳＣ測定装置），ＤＳＣ−７（パーキンエルマー社製）を用いてＡＳＴＭ Ｄ３４１８−８２に準じて測定する。
【０１６９】
測定試料は２〜１０ｍｇ、好ましくは５ｍｇを精密に秤量する。
【０１７０】
こ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、測定温度範囲３０〜２００℃の間で、昇温速度１０℃／ｍｉｎで測定を行う。
【０１７１】
この昇温過程で、温度３０〜２００℃の範囲におけるトナーのＤＳＣ曲線及びＤＳＣ曲線におけるワックスのメインピークの吸熱ピークが得られる。この吸熱メインピークの温度をもってワックスの融点とする。
【０１７２】
（５）トナー及び結着樹脂のガラス転移温度（Ｔｇ）の測定
示差走査熱量計（ＤＳＣ測定装置），ＤＳＣ−７（パーキンエルマー社製）を用いてＡＳＴＭ Ｄ３４１８−８２に準じて測定する。
【０１７３】
測定試料は５〜２０ｍｇ、好ましくは１０ｍｇを精密に秤量し、こ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、測定温度範囲３０〜２００℃の間で、昇温速度１０℃／ｍｉｎで測定を行う。この昇温過程で、温度４０〜１００℃の範囲におけるメインピークの吸熱ピークが得られる。
【０１７４】
吸熱ピーク前後の２本のベースラインの中間点の線と示差熱曲線との交点を本発明におけるガラス転移温度Ｔｇとする。
【０１７５】
（６）ワックスの分子量分布の測定
ＧＰＣ測定装置：ＧＰＣ−１５０Ｃ（ウォーターズ社）
カラム：ＧＭＨ−ＨＴ３０ｃｍ２連（東ソー社製）
温度：１３５℃
溶媒：ｏ−ジクロロベンゼン（０．１％アイオノール添加）
流速：１．０ｍｌ／ｍｉｎ
試料：０．１５％の試料を０．４ｍｌ注入
以上の条件で測定し、試料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較正曲線を使用する。さらに、Ｍａｒｋ−Ｈｏｕｗｉｎｋ粘度式から導き出される換算式でポリエチレン換算することによって算出される。
【０１７６】
（７）結着樹脂原料又はトナーの結着樹脂成分の分子量分布測定
ＧＰＣによるクロマトグラムの分子量は次の条件で測定される。
【０１７７】
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の流速で流す。試料が結着樹脂原料の場合は、結着樹脂原料をロールミルに素通し（１３０℃，１５分）したものを用いる。試料がトナーの場合は、トナーをＴＨＦに溶解後０．２μｍフィルターで濾過し、その濾液を試料として用いる。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製された検量線の対数値とカウント数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、Ｐｒｅｓｓｕｒｅ Ｃｈｅｍｉｃａｌ Ｃｏ．製あるいは、東洋ソーダ工業社製の分子量が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。
【０１７８】
カラムとしては、１０³〜２×１０⁶の分子量領域を適確に測定するために、市販のポリスチレンゲルカラムを複数組合せるのが良く、例えば、Ｗａｔｅｒｓ社製のμ−ｓｔｙｒａｇｅｌ ５００，１０³，１０⁴，１０⁵の組合せや、昭和電工社製のｓｈｏｄｅｘ ＫＡ−８０１，８０２，８０３，８０４，８０５，８０６，８０７の組合せが好ましい。
【０１７９】
（８）トナーの粒度分布の測定
本発明のトナーの粒度分布測定は、コールターカウンターＴＡ−ＩＩ型あるいはコールターマルチサイザー（ベックマン・コールター社製）を用いる。電解液は、１級塩化ナトリウムを用いて１％ＮａＣｌ水溶液を調製する。例えば、ＩＳＯＴＯＮ Ｒ−ＩＩ（ベックマン・コールター社製）が使用できる。測定法としては、前記電解水溶液１００〜１５０ｍｌ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０．１〜５ｍｌ加え、更に測定試料を２〜２０ｍｇ加える。試料を懸濁した電解液は、超音波分散器で約１〜３分間分散処理を行ない、前記測定装置により、アパーチャーとして１００μｍアパーチャーを用いて、２μｍ以上のトナーの体積、個数を測定して体積分布と個数分布とを算出した。それから本発明に係る体積分布から求めた重量基準（各チャンネルの代表値とする）の重量平均径（Ｄ４）を求めた。
【０１８０】
チャンネルとしては、２．００〜２．５２μｍ未満；２．５２〜３．１７μｍ未満；３．１７〜４．００μｍ未満；４．００〜５．０４μｍ未満；５．０４〜６．３５μｍ未満；６．３５〜８．００μｍ未満；８．００〜１０．０８μｍ未満；１０．０８〜１２．７２μｍ未満；１２．７２〜１６．００μｍ未満；１６．００〜２０．０２μｍ未満；２０．０２〜２５．４０μｍ未満；２５．４０〜３２．００μｍ未満；３２．００〜４０．３０μｍ未満の１３チャンネルを用いる。
【０１８１】
（９）トナーに含有されるイオウ原子含有量の測定
トナーに含有されるイオウ原子含有量は、堀場製作所（株）製のＥＭＩＡ−３２０を用いて測定する。
【０１８２】
酸素気流中でトナーを燃焼し赤外線吸収方法でトナーにおける含イオウ樹脂のイオウ原子を二酸化イオウとし、二酸化イオウの量からイオウ原子を定量する。
【０１８３】
（１０）磁性酸化鉄中の異種元素含有量の測定
磁性酸化鉄中の元素は、蛍光Ｘ線分析装置ＳＹＳＴＥＭ３０８０（理学電気工業社製）を使用し、ＪＩＳ Ｋ０１１９蛍光Ｘ線分析通則に従って、蛍光Ｘ線分析を行うことにより測定することができる。
【０１８４】
（１１）磁性酸化鉄中の異種元素含有分布の測定
磁性酸化鉄中の異種元素の含有分布については、塩酸又はフッ酸溶解しながらの元素量をプラズマ発光分布（ＩＣＰ）により測定定量し、各元素の全溶時の濃度に対する各溶解時の各元素濃度からその溶解率を求めることにより得られる。
【０１８５】
（１２）磁性酸化鉄の個数平均粒径の測定
磁性酸化鉄の個数平均粒径の測定は、透過型電子顕微鏡により拡大率４万倍で拡大撮影した写真を用いて、ランダムに３００個の磁性体を選びデジタイザーで測定することにより求めることができる。
【０１８６】
（１３）磁性酸化鉄の磁気特性の測定
磁性酸化鉄の磁気特性は、振動試料型磁力計ＶＳＭ−３Ｓ−１５（東英工業社製）を用いて外部磁場７９５．８ｋＡ／ｍの下で測定する。
【０１８７】
（１４）磁性酸化鉄及び外添剤のＢＥＴ方で測定した比表面積の測定
磁性酸化鉄及び外添剤の比表面積は、ＢＥＴ法に従って、比表面積測定装置オートソーブ１（湯浅アイオニクス社製）を用いて試料表面に窒素ガスを吸着させ、ＢＥＴ多点法を用いて比表面積を算出する。
【０１８８】
【実施例】
以下、実施例によって本発明を説明するが、本発明はこれらの実施例に限定されるものではない。
【０１８９】
含イオウ樹脂の製造：
製造例１
還流管，撹拌機，温度計，窒素導入管，滴下装置及び減圧装置を備えた加圧可能な反応容器に、溶媒としてメタノール２００質量部、２−ブタノン１５０質量部及び２−プロパノール５０質量部を添加し、モノマーとしてスチレン７８質量部、アクリル酸ｎ−ブチル１５質量部、２−アクリルアミド−２−メチルプロパンスルホン酸７質量部を添加して撹拌しながら７０℃まで加熱した。重合開始剤である２，２’−アゾビス（２−メチルブチロニトリル）１質量部を２−ブタノン２０質量部で希釈した溶液を１時間かけて滴下して５時間撹拌を継続し、更に２，２’−アゾビス（２−メチルブチロニトリル）１質量部を２−ブタノン２０質量部で希釈した溶液を３０分かけて滴下して更に５時間撹拌して重合を終了した。重合溶媒を減圧留去した後に得られた重合体を１５０メッシュのスクリーンを装着したカッターミルを用いて１００μｍ以下に粗粉砕した。
【０１９０】
得られた含イオウ共重合体はガラス転移温度（Ｔｇ）が７４℃、重量平均分子量（Ｍｗ）が２７０００、酸価が２３ｍｇＫＯＨ／ｇであった。これを含イオウ共重合体（Ｓ−１）とする。
【０１９１】
製造例２
製造例１において、モノマーをスチレン７０質量部、アクリル酸ｎ−ブチル１３質量部、２−アクリルアミド−２−メチルプロパンスルホン酸７質量部、ジビニルベンゼン０．０５質量部とし、重合開始剤である２，２’−アゾビス（２−メチルブチロニトリル）１質量部を９０分かけて滴下した以外は同様にして、含イオウ共重合体（Ｓ−２）を得た。
【０１９２】
得られた含イオウ共重合体（Ｓ−２）はＴｇが５８℃であり、重量平均分子量（Ｍｗ）が１７４０００、酸価が２６ｍｇＫＯＨ／ｇであった。
【０１９３】
製造例３
製造例１において、重合開始剤である２，２’−アゾビス（２−メチルブチロニトリル）４質量部とした以外は、同様にして、含イオウ共重合体（Ｓ−３）を得た。
【０１９４】
得られた含イオウ共重合体（Ｓ−３）はＴｇが５７℃、重量平均分子量（Ｍｗ）が４８００、酸価が２２ｍｇＫＯＨ／ｇであった。
【０１９５】
製造例４
製造例１において、重合溶媒をトルエン８００質量部、イソプロパノール１００質量部とし、モノマーをスチレン７１質量部、アクリル酸ｎ−ブチル２６質量部、２−アクリルアミド−２−メチルプロパンスルホン酸３質量部とし、重合開始剤である２，２’−アゾビス（２−メチルブチロニトリル）２質量部として、還流温度で７時間重合反応を行った以外は同様にして、含イオウ共重合体（Ｓ−４）を得た。
【０１９６】
得られた含イオウ共重合体（Ｓ−４）はＴｇが３８℃、重量平均分子量（Ｍｗ）が２２０００、酸価が１１ｍｇＫＯＨ／ｇであった。
【０１９７】
製造例５
製造例１において、重合溶媒をメタノール５０質量部、キシレン１０００質量部とし、モノマーをスチレン９００質量部、２−アクリルアミド−２−メチルプロパンスルホン酸１００質量部とし、重合開始剤を２，２’−アゾビス（２，４−ジメチルバレロニトリル）６０質量部として、６０℃で１０時間重合反応を行った以外は同様にして、含イオウ共重合体（Ｓ−５）を得た。
【０１９８】
得られた含イオウ共重合体（Ｓ−５）はＴｇが９６℃、重量平均分子量（Ｍｗ）が９６００、酸価が２９ｍｇＫＯＨ／ｇであった。
【０１９９】
製造例６
製造例１において、モノマーをスチレン７０質量部、メタクリル酸ｎ−ブチル１８質量部、２−アクリルアミド−２−メチルプロパンスルホン酸１２質量部とした以外は同様にして、含イオウ共重合体（Ｓ−６）を得た。
【０２００】
得られた含イオウ共重合体（Ｓ−６）はＴｇが７８℃、重量平均分子量（Ｍｗ）が１０５００、酸価が３７ｍｇＫＯＨ／ｇであった。
【０２０１】
製造例７
製造例１において、重合溶媒をキシレン２００質量部として、第１段階の重合反応として、スチレン４３質量部、２−アクリルアミド−２−メチルプロパンスルホン酸７質量部及び重合開始剤として１，１−ビス（ｔ−ブチルペルオキシ）−２−メチルシクロヘキサン３質量部を滴下してその温度で８時間保持した。次に第２段階の重合反応として、反応容器を１２０℃まで加熱してスチレン３０質量部、アクリル酸ｎ−ブチル２０質量部、及びキシレン５０質量部からなるモノマー組成物を１時間かけて滴下し、その温度を５時間保持し重合反応を終了した。キシレンを減圧留去することにより含イオウ共重合体（Ｓ−７）を得た。
【０２０２】
得られた含イオウ共重合体（Ｓ−７）はＴｇが７７℃、重量平均分子量（Ｍｗ）が２６０００、酸価が２４ｍｇＫＯＨ／ｇであった。
【０２０３】
製造例８
製造例１において、重合溶媒及び重合開始剤を添加せずにモノマーであるスチレン７０質量部、アクリル酸ｎ−ブチル２７質量部、２−アクリルアミド−２−メチルプロパンスルホン酸３質量部を仕込み、１２０℃まで昇温して塊状重合を８時間行った。次いで、キシレン５０質量部を添加して１１０℃まで冷却し、ｔ−ブチルペルオキシ−２−エチルヘキサノエート１質量部を溶解したキシレン溶液５０質量部を６時間かけて滴下し、更に１時間撹拌した以外は同様にして、含イオウ共重合体（Ｓ−８）を得た。
【０２０４】
含イオウ共重合体（Ｓ−８）はＴｇが５６℃、重量平均分子量（Ｍｗ）が２７１０００、酸価が８ｍｇＫＯＨ／ｇであった。
【０２０５】
製造例９
製造例１において、モノマーを４−ｔ−ブチルスチレン９３質量部、２−アクリルアミド−２−メチルプロパンスルホン酸７質量部からなるモノマー混合物を使用した以外は同様にして、含イオウ共重合体（Ｓ−９）を得た。
【０２０６】
含イオウ共重合体（Ｓ−９）はＴｇが１３３℃、重量平均分子量（Ｍｗ）が１４０００、酸価が１９ｍｇＫＯＨ／ｇであった。
【０２０７】
製造例１０
製造例１において、重合溶媒をメタノール３００質量部、トルエン１００質量部とし、モノマーをスチレン５４０質量部、２−アクリルアミド−２−メチルプロパンスルホン酸６０質量部とし、重合開始剤をラウロイルパーオキサイド６０質量部として、還流温度で１０時間重合反応を行った以外は同様にして、含イオウ共重合体（Ｓ−１０）を得た。
【０２０８】
含イオウ共重合体（Ｓ−１０）はＴｇが２８℃、重量平均分子量（Ｍｗ）が１９００、酸価が３６ｍｇＫＯＨ／ｇであった。
【０２０９】
表３は、含イオウ共重合体（Ｓ−１）〜（Ｓ−１０）の物性を示すものである。
【０２１０】
樹脂製造例１
（１）ポリエステル樹脂の製造
・テレフタル酸 ：６．１ｍｏｌ
・無水ドデセニルコハク酸 ：３．０ｍｏｌ
・フマル酸 ：０．８ｍｏｌ
・無水トリメリット酸 ：３．１ｍｏｌ
・ＰＯ−ＢＰＡ（プロポキシ化ビスフェノールＡ） ：７．２ｍｏｌ
・ＥＯ−ＢＰＡ（エトキシ化ビスフェノールＡ） ：３．０ｍｏｌ
上記ポリエステルモノマーをエステル化触媒とともにオートクレーブに仕込み、減圧装置，水分離装置，窒素ガス導入装置，温度測定装置及び撹拌装置を付し、窒素ガス雰囲気下で２１０℃まで加熱しながら縮重合反応を行い、ポリエステル樹脂（ＰＥ）を得た。得られたポリエステル樹脂（ＰＥ）は、メインピーク分子量が７１５０であり、Ｍｗが２５０００であり、Ｍｗ／Ｍｎが３．４であり、酸価が２９．３ｍｇＫＯＨ／ｇであり、Ｔｇが６０℃であった。
【０２１１】
（２）ハイブリッド樹脂成分の製造
上記ポリエステル樹脂（ＥＲ）８０質量部をキシレン１００質量部に溶解・膨潤した。次に、スチレン１５質量部、アクリル酸２−エチルヘキシル５質量部、ワックス（１）７質量部及びエステル化触媒としてジブチルスズオキサイド０．１質量部を添加してキシレンの還流温度まで加熱してポリエステル樹脂のカルボン酸とアクリル酸２−エチルヘキシルとのエステル交換反応を開始した。更にラジカル重合開始剤としてｔ−ブチルハイドロパーオキサイド１質量部をキシレン３０質量部に溶解したキシレン溶液を約１時間かけて滴下した。その温度で６時間保持してラジカル重合反応を終了し、減圧下２１０℃まで加熱して脱溶剤することで、ポリエステル樹脂の水酸基とビニル系重合体ユニットの共重合モノマーであるアクリル酸２−エチルヘキシルとのエステル交換反応を行うことにより、ポリエステル樹脂と、ビニル系重合体と、ポリエステルユニットとビニル系重合体ユニットがエステル結合することにより生成したハイブリッド樹脂とを有する結着樹脂とワックス（１）とが均一に混合した樹脂組成物（Ｈ−１）を得た。
【０２１２】
得られた樹脂組成物（Ｈ−１）は、酸価が２８ｍｇＫＯＨ／ｇであり、Ｔｇが５９℃であり、メインピーク分子量は７３００、重量平均分子量（Ｍｗ）は４３，０００、Ｍｗ／Ｍｎは８．５、ＴＨＦ不溶分を約１３質量％含有量していた。
【０２１３】
樹脂製造例２〜５
樹脂製造例１において、ワックス（１）のかわりに、表４に示すワックス（２）〜（５）を各々７質量部添加した以外は同様にして樹脂組成物（Ｈ−２）〜（Ｈ−５）を得た。
【０２１４】
樹脂製造例６
樹脂製造例１において、ワックス（１）のかわりに、表４に示すワックス（１）３質量部とワックス（３）３質量部を添加した以外は同様にして樹脂組成物（Ｈ−６）を得た。
【０２１５】
樹脂製造例７
樹脂製造例１において、ワックス（１）のかわりに、表４に示すワックス（３）３質量部とワックス（５）３質量部を添加した以外は同様にして樹脂組成物（Ｈ−７）を得た。
【０２１６】
樹脂製造例８
樹脂製造例１において、ハイブリット樹脂製造時にワックス（１）を添加しない以外は同様にして樹脂組成物（Ｈ−８）を得た。
【０２１７】
樹脂製造例９
製造例１で使用したポリエステル樹脂を構成するモノマーを下記に示すものを使用した以外は同様にして、樹脂組成物（Ｈ−９）を得た。
・テレフタル酸 ：６．０ｍｏｌ
・無水ドデセニルコハク酸 ：１．０ｍｏｌ
・フマル酸 ：２．０ｍｏｌ
・無水トリメリット酸 ：６．０ｍｏｌ
・ＰＯ−ＢＰＡ ：７．０ｍｏｌ
・ＥＯ−ＢＰＡ ：３．０ｍｏｌ
得られた樹脂組成物（Ｈ−９）は、酸価が４６ｍｇＫＯＨ／ｇであり、Ｔｇは５７℃であり、メインピーク分子量は１０６００、重量平均分子量（Ｍｗ）は１６７０００、Ｍｗ／Ｍｎは４２であり、ＴＨＦ不溶分を約１５質量％含有していた。
【０２１８】
樹脂製造例１０
製造例１で使用したポリエステル樹脂（１）を９０質量部とし、ビニル系モノマーをスチレン７質量部とアクリル酸２−エチルヘキシル３質量部とした以外は同様にして、樹脂組成物（Ｈ−１０）を得た。
【０２１９】
得られた樹脂組成物（Ｈ−１０）は、酸価は３５ｍｇＫＯＨ／ｇであり、Ｔｇは６１℃であり、メインピーク分子量は８３００、重量平均分子量（Ｍｗ）は４１９０００、Ｍｗ／Ｍｎは１８であり、ＴＨＦ不溶分を約１２質量％含有していた。
【０２２０】
樹脂製造例１１
製造例１で使用したポリエステル樹脂（１）を５０質量部とし、ビニル系モノマーをスチレン３５質量部とアクリル酸２−エチルヘキシル１５質量部とした以外は、製造例１と同様にして、樹脂組成物（Ｈ−１１）を得た。
【０２２１】
得られた樹脂組成物（Ｈ−１１）は、酸価が１６ｍｇＫＯＨ／ｇであり、Ｔｇが６０℃であり、メインピーク分子量が６４００、重量平均分子量（Ｍｗ）が１３６万、Ｍｗ／Ｍｎは２１５であり、ＴＨＦ不溶分を約６質量％含有していた。
【０２２２】
樹脂製造例１２
下記に示すポリエステルモノマー及びビニル系モノマーをエステル化触媒とともに、減圧装置、水分離装置、窒素ガス導入装置、温度測定装置及び撹拌装置を装備した４つ口フラスコに窒素雰囲気下にて１３０℃の温度で撹拌しつつ、滴下ロートから４時間かけて滴下した。
ポリエステルモノマー
・ＰＯ−ＢＰＡ（プロポキシ化ビスフェノールＡ） ３．０ｍｏｌ
・ＥＯ−ＢＰＡ（エトキシ化ビスフェノールＡ） １．３ｍｏｌ
・テレフタル酸 １．７ｍｏｌ
・無水トリメリット酸 １．２ｍｏｌ
・無水ドデセニルコハク酸 １．５ｍｏｌ
ビニル系モノマー
・スチレン ４．５ｍｏｌ
・アクリル酸２−エチルヘキシル ０．５６ｍｏｌ
・アゾビスイソブチロニトリル（ビニル重合開始剤） ０．１２ｍｏｌ
４つ口フラスコを１３０℃に保持したままさらに３時間加熱し（ビニル系重合反応終了）、次に２３０℃に昇温して減圧しながら縮重合反応を行った。反応終了後容器から取り出し、冷却、粉砕し、ポリエステル樹脂、ビニル系重合体及び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からなる樹脂組成物（Ｈ−１２）を得た。樹脂組成物（Ｈ−１２）は、酸価が２２ｍｇＫＯＨ／ｇであり、Ｔｇが６０．５℃であり、メインピーク分子量が８７００、重量平均分子量（Ｍｗ）が７５０００、Ｍｗ／Ｍｎが２０、ＴＨＦ不溶分の含有量は２２質量％であった。
【０２２３】
比較製造例
減圧装置，水分離装置，窒素ガス導入管，温度測定装置及び撹拌装置を装着したオートクレーブに、スチレン８４質量部と２−エチルヘキシルアクリレート１６質量部からなるスチレン共重合体（ＳＲ）（数平均分子量８０００、Ｍｗ／Ｍｎ＝２．７）２００質量部の存在下、テレフタル酸２５０質量部、トリメリット酸３０質量部、ＥＯ−ＢＰＡ１９３質量部、ＰＯ−ＢＰＡ８４０質量部及びジブチルスズオキサイド２質量部を仕込み、窒素雰囲気下、減圧しながら２００℃まで加熱しながら縮重合反応を行うことにより、比較用樹脂組成物（ＲＨ−１）を得た。
【０２２４】
得られた比較用樹脂組成物（ＲＨ−１）は、酸価は１ｍｇＫＯＨ／ｇであり、Ｔｇは６１．４℃でありピーク分子量は２０８００、重量平均分子量（Ｍｗ）は４５０００、Ｍｗ／Ｍｎは６．３であり、ＴＨＦ不溶分の含有量が１質量％以下であり、ハイブリッド樹脂は含有されていなかった。
【０２２５】
実施例１
・樹脂組成物（Ｈ−１） １００質量部
・含イオウ重合体（Ｓ−１） ２質量部
・荷電制御剤（３，５−ジ−ｔｅｒｔブチルサリチル酸２モルとアルミニウム原子からなる有機アルミニウム化合物） １質量部
・磁性酸化鉄（平均粒径０．１８μｍ、保磁力１０．７ｋＡ／ｍ、残留磁化１１．２Ａｍ²／ｋｇ、飽和磁化８１．５Ａｍ²／ｋｇ） ９０質量部
上記混合物を、１３０℃に加熱された二軸混練機で溶融混練し、冷却した混合物をハンマーミルで粗粉砕した。粗粉砕物をターボミルＴ−２５０型（ターボ工業社製）で微粉砕し、得られた微粉砕物を風力分級機で分級し、重量平均径７．７μｍ、１０．１μｍ以上の粒子が、６．６体積％である磁性トナー粒子を得た。
【０２２６】
この磁性トナー粒子１００質量部に対して、疎水性乾式シリカ微粉体（ＢＥＴ比表面積；２００ｍ²／ｇ）１．０質量部をヘンシェルミキサーにて外添して磁性トナー（１）を得た。磁性トナー（１）の各物性を表５に示す。磁性トナー（１）を用いて現像性及び定着性の評価を行った。
【０２２７】
トナーの現像性評価は、電子写真プロセス及び加熱加圧定着方式を採用しているキヤノン製デジタル複写機ｉＲ−６０００を使用して、高温高湿環境（３０℃，８０％）で１０万枚の耐久画像評価試験を行い、画像のカブリ、画質及び画像濃度の安定性を評価した。
【０２２８】
画像のカブリ測定と評価ランク
カブリ測定用反射測定機ＲＥＦＬＥＣＴＭＥＴＥＲ（東京電色（株））にて、カブリを評価する画像の白部（非画像部）の反射率（％）及び未使用紙の反射率（％）を測定し、両者の差（未使用紙反射率−画像白部の反射率）をカブリ（％）とする。
ランク５：カブリ０．１％未満
ランク４：カブリ０．１以上〜０．５％未満
ランク３：カブリ０．５以上〜１．５％未満
ランク２：カブリ１．５以上〜２．０％未満
ランク１：カブリ２．０％以上
【０２２９】
画質の評価法と評価ランク
ランク５：原稿に忠実な画像である。
ランク４：画像をルーペで拡大すると、多少飛び散りが見られる
ランク３：画像をルーペで拡大すると、飛び散り、乱れが見られる
ランク２：目視により、飛び散り、画像の乱れが見られる
ランク１：原稿を再現していない。
【０２３０】
トナーの画像濃度安定性
トナーの画像濃度安定性は、キヤノン製デジタル複写機ｉＲ−６０００を使用して、常温常湿環境（２３℃，６０％）にて１０万枚の耐久試験を行い、最後の画像濃度（Ｆ）を測定しておく。複写機から現像器を取り外して、高温高湿室（３０℃，８０％）環境に４８時間放置する。現像器を高温高湿環境に放置する際には、結露防止のために現像器は梱包し、５時間以上調温・調湿後に開封する。放置後、常温常湿環境に現像器を取り出し、ｉＲ−６０００に現像器を設置する。現像スリーブを１分間回転させた後、評価画像を１０枚サンプリングし、画像濃度の平均値を放置後濃度（Ｒ）とし、放置前画像濃度（Ｆ）と放置後画像濃度（Ｒ）の差（（Ｆ）−（Ｒ））によりトナー帯電性能を評価した。評価ランクを以下に示す。
ランク５：（Ｆ）−（Ｒ）の値が０〜０．０５未満
ランク４：（Ｆ）−（Ｒ）の値が０．０５以上〜０．１０未満
ランク３：（Ｆ）−（Ｒ）の値が０．１０以上〜０．１５未満
ランク２：（Ｆ）−（Ｒ）の値が０．１５以上〜０．２０未満
ランク１：（Ｆ）−（Ｒ）の値が０．２０以上
【０２３１】
トナーの定着性評価
トナーの定着性は、キヤノン製複写機ＮＰ６０８５の定着器を取り外し、外部駆動装置及び定着器の温度制御装置を取り付けた定着試験装置にて、定着器の温度を変えてハーフトーン画像部（画像濃度：０．６）を通紙して、定着性試験を行った。
【０２３２】
定着下限温度は、定着画像に、４９００Ｎ／ｍ²（５０ｇ／ｃｍ²）の荷重をかけ、柔和な薄紙により定着画像を擦り、その前後の画像濃度の低下率が２０％以下になった温度とした。定着上限温度は、目視で転写紙上にホットオフセットが発生した温度を観察することにより評価した。
【０２３３】
これらの評価した結果を表７に示す如く、極めて良好な結果が得られた。
【０２３４】
参考例２、３、実施例４、参考例５、６、実施例７
表３に示す含イオウ共重合体を使用した以外は実施例１と同様にして磁性トナー（２）〜（７）を製造した。得られた磁性トナーの各物性を表５と６に示す。磁性トナーを実施例１と同様に評価した。結果を表７に示す。
【０２３５】
実施例８〜１３
実施例１において、結着樹脂として樹脂組成物（Ｈ−２）〜（Ｈ−７）を使用した以外は実施例１と同様にして磁性トナー（８）〜（１３）を製造した。得られた磁性トナーの各物性を表５と６に示す。磁性トナーを実施例１と同様に評価した。結果を表７に示す。
【０２３６】
実施例１４
実施例１において、結着樹脂として樹脂組成物（Ｈ−８）を使用し、混練時にワックス（３）７質量部を添加した以外は実施例１と同様にして磁性トナー（１４）を製造した。得られた磁性トナーの各物性を表５と６に示す。磁性トナーを実施例１と同様に評価した。結果を表７に示す。
【０２３７】
実施例１５〜１７
実施例１において、結着樹脂及びトナー粒度を変更した以外は実施例１と同様にして、表５に示す磁性トナー（１５）〜（１７）を製造した。得られた磁性トナーの各物性を表５と６に示す。磁性トナーを実施例１と同様に評価した。結果を表７に示す。
【０２３８】
実施例１８〜２０
実施例１において、含イオウ共重合体の添加量を変える以外は同様にして磁性トナー（１８）〜（２０）を製造した。得られた磁性トナーの各物性を表５と６に示す。磁性トナーの評価結果を表７に示す。
【０２３９】
参考例２１
実施例１において、荷電制御剤（３，５−ジ−ｔ−ブチルサリチル酸２モルとアルミニウム原子１モルからなる有機アルミニウム化合物）を使用しなかった以外は実施例１と同様にして、表５と６に示す磁性トナー（２１）を製造した。実施例１と同様に評価した。結果を表７に示す。
【０２４０】
参考例２２〜２４
実施例１において、含イオウ重合体（Ｓ−８）〜（Ｓ−１０）を使用した以外は同様にして磁性トナー（２２）〜（２４）を製造した。得られた磁性トナーの各物性を表５と６に示す。磁性トナーの評価結果を表７に示す。
【０２４１】
比較例１
実施例１において、比較用結着樹脂（ＲＨ−１）を使用した以外は同様にして比較磁性トナー（１）を製造した。得られた比較磁性トナーの各物性を表５と６に示し、評価結果を表７に示す。
【０２４２】
比較例２
実施例１において、含イオウ共重合体を含有せず、また、荷電制御剤として、（３，５−ジ−ｔ−ブチルサリチル酸と亜鉛原子からなる有機亜鉛化合物を用いる以外は同様にして比較磁性トナー（２）を製造した。得られた比較磁性トナー（２）の各物性を表５と６に示し、評価結果を表７に示す。
【０２４３】
比較例３
樹脂製造例１において製造されたポリエステル樹脂（ＰＥ）（Ｍｗ＝２５０００）を結着樹脂として使用する以外は、実施例１４と同様にして比較磁性トナー（３）を製造した。得られた比較磁性トナー（３）の各物性を表５と６に示し、評価結果を表７に示す。
【０２４４】
比較例４
比較製造例で使用したスチレン−２−エチルヘキシルアクリレート共重合体（ＳＲ）（共重合質量比＝８４：１６；Ｍｎ＝８０００，Ｍｗ／Ｍｎ＝２．７）を結着樹脂として使用する以外は、実施例１４と同様にして比較磁性トナー（４）を製造した。得られた比較磁性トナー（４）の各物性を表５と６に示し、評価結果を表７に示す。
【０２４５】
実施例２５
実施例１において、結着樹脂を樹脂組成物（Ｈ−１２）にかえる以外は実施例１と同様にして磁性トナー（２５）を製造した。得られた磁性トナーの各物性知を表５と６に示す。磁性トナーを実施例１と同様に評価した。結果を表７に示す。
【０２４６】
【表３】

【０２４７】
【表４】

【０２４８】
【表５】

【０２４９】
【表６】

【０２５０】
【表７】

【０２５１】
【発明の効果】
本発明は、摩擦帯電の立ち上がり特性が改善され、帯電安定性に優れ、多数枚耐久性に優れ、高画像濃度を維持でき、低温定着性及び耐高温オフセット性に優れているトナーを提供し得る。
【図面の簡単な説明】
【図１】本発明のトナーが使用される画像形成装置に使用される、現像剤担持体が組み込まれる現像剤補給系現像装置の一例（規制部材に磁性ブレードを使用）を示す概略図である。
【図２】本発明のトナーが使用される画像形成装置に使用される、現像剤担持体が組み込まれる現像剤補給系現像装置の一例（規制部材に弾性ブレードを使用）を示す概略図である。
【図３】本発明のトナーが使用される画像形成装置に適用される現像装置の現像剤担持体の一部分の断面の概略図である。
【図４】本発明のトナーを適用し得る画像形成方法の概略的説明図である。
【図５】本発明の画像形成方法に適用し得る定着装置の概略図である。
【図６】本発明のプロセスカートリッジの一例を示す概略的説明図である。
【符号の説明】
７ 感光体
８ 層規制部材
９ ホッパー
１０ トナー
１１ マグネット
１４ 現像スリーブ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a toner used in a recording method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and a toner jet recording method, an image forming method using the toner, and a process cartridge having the toner.
[0002]
[Prior art]
The electrophotographic method generally uses a photoconductive material, forms an electrostatic charge image on a photoreceptor by various means, and then develops the electrostatic charge image with toner, and if necessary, a transfer material such as paper. After the toner image is transferred to the toner image, the toner image is fixed by heating, pressure, heating and pressurization or solvent vapor to obtain a fixed image of the toner image.
[0003]
The developing methods applied to these electrophotographic methods are roughly classified into a dry developing method and a wet developing method. The former is further divided into a method using a two-component developer and a method using a one-component developer.
[0004]
As a toner to be applied to these dry development methods, particles obtained by finely pulverizing a colorant dispersed in a binder resin to about 5 to 15 μm are used. As the magnetic toner which is a one-component developer, a toner containing magnetic fine particles as a colorant is used. In the two-component developer, a toner containing a pigment such as carbon black as a colorant is mixed with carrier particles such as iron powder or magnetic ferrite particles.
[0005]
In order to impart charge to the toner particles, a dye, pigment or polymer compound is added as a charge control agent, and as a positive friction charge control agent, nigrosine dye, azine dye, copper phthalocyanine pigment, quaternary ammonium salt, etc. As the negative triboelectric charge control agent, a monoazo dye organometallic compound, a salicylic acid, naphthoic acid, dicarboxylic acid organometallic compound, and a charge control resin which is a polymer having a sulfonic acid group are used.
[0006]
In Japanese Patent Application Laid-Open No. 57-171345, a toner containing a specific amount of an unsaturated polyester resin using a copolymer of a styrene monomer, a (meth) acrylic monomer, and an unsaturated polyester resin as a binder resin. Although disclosed, there is a long-awaited desire to further improve the charging stability of the toner.
[0007]
Japanese Patent Laid-Open No. 62-195681 discloses a toner containing a polyester resin containing a specific amount of vinyl resin having a specific molecular weight and glass transition temperature as a main component of a binder resin. There is a long-awaited desire to further improve stability.
[0008]
Japanese Patent Application Laid-Open No. 11-153858 discloses a toner binder made of a resin obtained by reacting a polyester resin having a specific molecular weight with a vinyl polymer having a specific structure, and a toner using the binder. Therefore, further improvement in the charging stability of the toner is awaited.
[0009]
Japanese Patent Application Laid-Open No. 2000-56511 discloses a toner in which the binder resin contains a hybrid resin component, contains a specific amount of insoluble matter that does not dissolve in a specific solvent, and the tetrahydrofuran-soluble component has a specific molecular weight distribution. However, there is a long-awaited improvement in the rise of charging in a high-temperature and high-humidity environment.
[0010]
Japanese Patent Application Laid-Open No. 63-184762 discloses a toner containing a copolymer obtained by copolymerizing a specific acrylamide sulfonic acid monomer and styrene in order to impart stable charging characteristics to the toner. There is no description about the combination of a resin component and this copolymer.
[0011]
In Japanese Patent No. 2623684, in order to improve the rising of the charge amount of a toner, a thermoplastic resin is used as a binder resin, and a copolymer of a sulfonic acid group-containing acrylamide monomer and a vinyl monomer having a specific structure is charged. A toner contained as a control resin is disclosed, but there is no description about a combination of the charge control resin and a hybrid resin component.
[0012]
In JP-A-2000-56518, a sulfonic acid group-containing (meth) acrylamide copolymer having a specific glass transition temperature is used as a charge control resin in order to provide a toner having excellent charging stability and low environmental dependency. Although the toner to be contained is disclosed, there is no description about the combination of the charge control resin and the hybrid resin component.
[0013]
[Problems to be solved by the invention]
An object of the present invention is to provide a toner that solves the above problems. An object of the present invention is to provide a toner, an image forming method, or a process cartridge having improved fogging, charging stability, environmental dependency of charging, and rising characteristics of charging.
[0014]
An object of the present invention is to provide a toner, an image forming method, or a process cartridge that has less fogging, excellent charging stability, and has both good fixability and high-temperature offset resistance.
[0015]
An object of the present invention is to provide a toner, an image forming method, or a process cartridge containing a sulfur-containing polymer having good dispersibility of the toner in a binder resin and excellent initial charge rising characteristics of the toner regardless of the environment. To do.
[0016]
[Means for Solving the Problems]
  The present invention relates to a toner having inorganic particles and toner particles containing at least a binder resin, a colorant, a sulfur-containing resin and a wax.
(A) The sulfur-containing resin is a copolymer of an acrylamide sulfonic acid monomer and a vinyl monomer, and has a weight average molecular weight of 17,000 to 100,000,
(B) the binder resin contains a hybrid resin component having a vinyl polymer unit and a polyester unit;
(C)The toner particles are produced by melt-kneading the binder resin containing the hybrid resin component, the colorant, the sulfur-containing resin and the mixture containing at least the wax, and then pulverizing the mixture.
(d) The THF soluble content of the binder resin in the toner has a peak at a molecular weight of 2000 to 15000 in the molecular weight distribution measured by gel permeation chromatography (GPC), and the Z average molecular weight (Mz) is 2.0 × 10.⁸The toner is characterized in that the ratio (Mz / Mw) of the Z average molecular weight (Mz) to the weight average molecular weight (Mw) is 20 to 120.
[0017]
  The present invention further includes (I) a developing step of developing a toner image by developing an electrostatic image carried on an image carrier for carrying an electrostatic image with a negative triboelectrically charged toner;
(II) a transfer step in which the toner image formed on the image carrier is transferred to a recording material with or without an intermediate transfer member; and
(III) a fixing step in which the toner image transferred to the recording material is heat-fixed on the recording material;
In an image forming method having
  The toner isThe toner has the above configuration.The present invention relates to an image forming method.
[0018]
  Furthermore, the present invention has at least an image carrier, a developing unit for developing the electrostatic image formed on the image carrier with dry toner, and a container for holding the dry toner,
  The image carrier, the developing means, and the container are process cartridges having a configuration in which they are supported integrally.
  The process cartridge is detachable from the image forming apparatus main body,
  The toner isThe toner has the above configuration.The present invention relates to a process cartridge.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
According to the study by the present inventors, in order to obtain a toner that exhibits good fixing performance and has good charging characteristics over a long period of time without being influenced by the environment, a polyester unit and vinyl are used as the binder resin for the toner. It has been found that this can be achieved by using a hybrid resin having a polymer unit and containing a sulfur-containing resin.
[0020]
  According to studies by the present inventors, in order for the toner to exhibit good charging characteristics, a binder resin andIt is a negative charge control resin as described above.The combination with sulfur-containing resin was found to be important.
[0021]
In the toner particles, when the sulfur-containing resin is present in a state of being compatible with the binder resin, the rising of the charge of the toner is not improved, and the toner resin is present in a state of being completely phase-separated in the binder resin. This is because the environmental stability of toner charging is not improved.
[0022]
In the toner of the present invention, the glass transition temperature (Tg) of the sulfur-containing resin may be 30 to 120 ° C., preferably 50 to 100 ° C., and more preferably 72 to 95 ° C. In any case where the glass transition temperature (Tg) of the sulfur-containing resin is less than 30 ° C. or more than 120 ° C., it is difficult to control the dispersion state of the sulfur-containing resin to a state suitable for the toner of the present invention. It is difficult to show a good charging performance.
[0023]
In the toner of the present invention, the weight average molecular weight (Mw) of the sulfur-containing resin may be 2000 to 200,000, preferably 17000 to 100,000, and more preferably 27,000 to 50,000. When the weight average molecular weight (Mw) is less than 2,000, the sulfur-containing resin is compatible with the binder resin or is finely dispersed, so that the charging characteristics are hardly improved, and the toner fluidity and transferability are reduced. Since it falls, it is not preferable. In addition, when the weight average molecular weight (Mw) exceeds 200,000, the sulfur-containing resin may be phase-separated from the binder resin and may be completely liberated from the toner particles, increasing the fog density or stabilizing the environment of charging. The properties may decrease, which is not preferable.
[0024]
In the toner of the present invention, the acid value of the toner is preferably 1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g, and still more preferably 10 to 20 mgKOH / g. In any case where the acid value of the toner is less than 1 mgKOH / g or more than 40 mgKOH / g, the dispersion of the sulfur-containing resin is not necessarily in a suitable state, and the image density may decrease due to durability. It is not preferable.
[0025]
In the toner of the present invention, the acid value of the binder resin is preferably 1 to 50 mgKOH / g, more preferably 5 to 40 mgKOH / g, and still more preferably 10 to 30 mgKOH / g. In any case where the acid value of the binder resin is less than 1 mg KOH / g or more than 50 mg KOH / g, it is difficult to adjust the acid value of the toner to a range suitable for the toner of the present invention.
[0026]
In the toner of the present invention, the binder resin contained in the toner particles preferably contains 1 to 50% by mass of THF insolubles, more preferably 5 to 40% by mass, and still more preferably. It is good to contain 10 thru | or 30 mass%. When the THF-insoluble content contained in the toner binder resin is less than 1% by mass or more than 50% by mass, it is difficult to keep the sulfur-containing resin contained in the toner in an optimum state, and the fixing member is more durable. It is not preferable because toner adhesion to the toner may become apparent.
[0027]
  In the toner of the present invention, the THF soluble content isGel permeation chromatography (GPC)In the chromatogram by measurement, it has a main peak in the region of molecular weight 2000 to 15000, and Z average molecular weight (Mz) is 2.0 × 10.⁸The ratio (Mz / Mw) of the Z average molecular weight (Mz) to the weight average molecular weight (Mw) is preferably 20 to 120, and more preferably has a main peak in the region of the molecular weight 4000 to 12000, Average molecular weight (Mz) is 1.5 × 10⁸The ratio (Mz / Mw) of the Z average molecular weight (Mz) to the weight average molecular weight (Mw) is 30 to 100, and more preferably the molecular weight is 6000 to10,000With a main peak and a Z average molecular weight (Mz) of 1.0 × 10⁸This is the case where the ratio (Mz / Mw) of the Z average molecular weight (Mz) to the weight average molecular weight (Mw) is 40 to 80. When having a main peak at a molecular weight of less than 2000 and a ratio (Mz / Mw) of less than 20, and having a main peak at a molecular weight of more than 15000 and a ratio (Mz / Mw) of more than 120, the Z average molecular weight ( Mz) is 2.0 × 10⁸In any of the cases where the temperature is excessive, it is difficult to keep the sulfur-containing resin contained in the toner in a suitable state, and the image density may decrease due to durability, which is not preferable.
[0028]
In the toner of the present invention, the sulfur-containing resin is mainly added as a charge control agent, but also has an effect of controlling the dispersion state of the colorant (particularly the magnetic substance) contained in the toner, and has a sulfonic acid group. The polymer or copolymer is preferably a sulfur-containing polymer or copolymer having an acrylamide sulfonic acid monomer unit, particularly preferably a 2-acrylamido-2-methylpropane sulfonic acid monomer. It is a sulfur-containing polymer or copolymer having a unit, and can effectively exhibit the effect of controlling the dispersion state of the colorant (particularly the magnetic material).
[0029]
In the toner of the present invention, the sulfur-containing resin is preferably contained in an amount of 0.01 to 20 parts by weight, more preferably 0.5 to 5 parts by weight, even more preferably 100 parts by weight of the binder resin. Is preferably contained in an amount of 0.7 to 2 parts by mass. In any case where the content of the sulfur-containing resin is less than 0.01 parts by mass or more than 20 parts by mass, it is difficult to control charging of the toner.
[0030]
In the toner of the present invention, the sulfur-containing resin is preferably contained in an amount of 20 ppm to 5% by mass, more preferably 50 ppm to 1% by mass, more preferably 50% to 1% by mass, based on the mass of the toner. It is preferable to contain 100 ppm to 0.5 mass%. In any case where the sulfur atom content is less than 20 ppm or more than 5% by mass, it is difficult to control charging of the toner.
[0031]
In the toner of the present invention, the sulfur-containing resin is a polymer compound mainly composed of an aromatic vinyl monomer and a (meth) acrylic acid ester monomer, a polymer compound represented by the formula (1), and / or these polymer compounds and polyester. It can also contain as a reaction product.
[0032]
Formula (1):
R-X
(In the formula, R is a polymer block mainly composed of an aromatic vinyl monomer unit and a (meth) acrylic acid ester monomer unit, and X is a polymer block containing a monomer unit having a sulfonic acid group as a constituent component. X may further have a monomer unit having a carboxylic acid group or a phosphoric acid group.)
[0033]
A polymer compound mainly composed of an aromatic vinyl monomer unit and a (meth) acrylic acid ester monomer unit and a polymer block represented by R in the formula (1) include an aromatic vinyl monomer unit and a (meth) acrylic acid ester monomer unit. As the aromatic vinyl monomer, styrene is preferable, and the (meth) acrylate monomer is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl acrylate Acrylate ester monomers such as hexyl, octyl acrylate, lauryl acrylate, stearyl acrylate are preferred, and copolymers obtained by polymerizing styrene and 2-ethylhexyl acrylate or styrene and (n) butyl acrylate Obtained by polymerizing It is particularly preferred is a copolymer. In this case, the styrene monomer unit is contained in an amount of 60 to 90% by mass, preferably 65 to 85% by mass, more preferably 70 to 80% by mass, and 2-ethylhexyl acrylate monomer unit or (n) butyl acrylate. The monomer unit is contained in an amount of 5 to 25% by mass, preferably 7 to 22% by mass, more preferably 10 to 20% by mass. When the content of the styrene monomer unit is less than 60% by mass and the content of the (meth) acrylic acid ester monomer unit exceeds 25% by mass and when the content of the styrene monomer unit exceeds 90% by mass, the (meth) acrylic acid ester In any case where the monomer unit content is less than 5% by mass, it is difficult to keep the sulfur-containing resin in the toner binder resin in a suitable state.
[0034]
In the formula (1), the polymer block represented by X is a polymer compound containing a monomer unit having a sulfonic acid group as a constituent component. As the monomer having a sulfonic acid group, an acrylamide sulfonic acid derivative monomer is preferable, and a 2-acrylamido-2-methylpropanesulfonic acid monomer is particularly preferable. X may further have a monomer unit having a carboxylic acid group or a phosphoric acid group. As the monomer having a carboxylic acid group, acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic acid monoester, vinyl benzoic acid or hydroxycarboxylic acid esters of (meth) acrylic acid are preferred, and the monomer having a sulfonic acid group Is 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, a maleic acid amide derivative having a sulfonic acid group, a maleimide derivative having a sulfonic acid group, a sulfonic acid group Preferred are styrene derivatives having
[0035]
In the formula (1), when a monomer unit having a carboxylic acid group is contained as a constituent component, it contains 2 to 20% by mass, preferably 10 to 17% by mass, more preferably 7 to 15% by mass. If the content of the monomer unit having a carboxylic acid group is less than 2% by mass, it is difficult to impart sufficient frictional charging ability to the toner, and if it exceeds 20% by mass, It is not preferable because it is difficult to disperse uniformly. Further, the polymer block represented by R is copolymerized with a monomer unit having a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group as a substituent at 5% by mass or less copolymerized with the polymer block represented by X. You may do it.
[0036]
In the toner of the present invention, the polymer compound represented by the formula (1) can also form a reaction product with polyester. The reaction product with polyester is an addition polymerization of unsaturated polyester and the above-mentioned aromatic vinyl monomer, (meth) acrylic acid ester monomer or a monomer having a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group as a substituent. A polymer compound and / or a charge control agent produced by esterification of a hydroxyl group of a polyester and / or polyester with a carboxylic acid group, a sulfonic acid group or a phosphate group of the polymer compound constituting the charge control agent When a monomer having a hydroxyl group is copolymerized with the constituting polymer compound, it is a polymer compound produced by esterification of a carboxylic acid group of polyester and a hydroxyl group of the polymer compound, and constitutes a charge control agent. The polymer compound can contain 1 to 98% by mass of a reaction product with this polyester.
[0037]
In the toner of the present invention, the polymer compound represented by the formula (1) has a mass ratio of 90:10 to 30:70 of a monomer that forms a polymer block represented by R and a monomer that forms a polymer block represented by X. What is obtained by polymerization is preferred, more preferably polymerized at a mass ratio of 85:15 to 35:65, and still more preferably polymerized at a mass ratio of 80:20 to 40:60 It is. When the monomer forming the polymer block represented by R exceeds 90% by mass, it is difficult to impart sufficient triboelectric chargeability to the toner, and when it is less than 30% by mass, the toner is dispersed in the binder resin. It is not preferable because it tends to be uneven.
[0038]
In the toner of the present invention, the sulfur-containing polymer and the sulfur-containing copolymer can be produced by various polymerization methods. However, as a preferable polymerization method, a polymerization solvent is not used, or a bulk polymer using a small amount of polymerization solvent is used. This is a case of manufacturing by a combination method or a solution polymerization method. As the reaction solvent, solvents such as methanol, ethanol, propanol, 2-propanol, propanone, 2-butanone and dioxane can be used. When these solvents are mixed and used, it is preferable to mix methanol, 2-butanone and 2-propanol in a mass ratio of 2: 1: 1 to 1: 5: 5. As a polymerization initiator, t-butyl peroxy-2-ethylhexanoate, cumyl perpivalate, t-butyl peroxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-t-butyl Peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2 , 4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis-4-cyanovaleric acid, 1,1′-azobis (cyclohexane- 1-carbonitrile), 1,1′-di (t-butylperoxy) 3-methylcyclohexane, , 1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1′-di (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t- Butylperoxy) cyclohexane, 1,4-bis (t-butylperoxycarbonyl) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) Valerate, 2,2-bis (t-butylperoxy) butane, 1,3-bis (t-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) Hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di-t- Tildiperoxyisophthalate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutamate Di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, diethylene glycol-bis (t-butyl) Peroxycarbonate), di-t-butylperoxytrimethyladipate, tris (t-butylperoxy) triazine, vinyltris (t-butylperoxy) silane. These can be used alone or in combination. Preferably, 2,2′-azobis (2-methylbutyronitrile), 4,4′-azobis-4-cyanovaleric acid, 1,1′-di (t-butylperoxy) 3-methylcyclohexane, , 1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane may be used alone or in combination. These polymerization initiators are preferable in that the molecular weight of the sulfur-containing polymer or copolymer can be adjusted to a range suitable for the toner of the present invention, and the unreacted monomer can be reduced to increase the polymerization addition rate.
[0039]
For the polymer compound represented by formula (1), the monomer type to be copolymerized, the composition ratio or the polymerization solvent is appropriately selected, and the monomer is continuously supplied to the polymerization system to utilize the difference in copolymerization reactivity of the monomers. Either a state in which the same type of monomer is localized in the polymer chain (also referred to as a polymer block in the present invention) is formed, or two peroxide groups or azo groups having different half-life temperatures are present in the molecule. It can be produced by changing the monomer composition and polymerization temperature to be polymerized using a polymerization initiator having at least one polymerization initiator. In the former production method, the composition of the polymer block represented by R and X changes continuously with the progress of the polymerization reaction, which may affect the dispersibility and developability of the toner in the binder resin. The latter production method is preferable in that the change in the composition of the polymer block represented by R and C is relatively small.
[0040]
In the toner of the present invention, it is preferable to add an organoaluminum compound and / or an organoiron compound as a charge control agent.
[0041]
The organoaluminum compound is a compound obtained by reacting an aromatic diol, aromatic hydroxycarboxylic acid, aromatic monocarboxylic acid or aromatic polycarboxylic acid with an aluminum compound (for example, an organoaluminum complex compound (complex, complex salt) or organoaluminum). Salt), preferably an organoaluminum compound composed of 2 mol of 3,5-di-tert-butylsalicylic acid and 1 mol of aluminum element. The organoaluminum compound is preferably contained in the toner in an amount of 0.02 to 2% by mass as an aluminum element, more preferably 0.05 to 1.5% by mass, and still more preferably 0.1 to 2% by mass. It is good to contain 1% by mass. When the organoaluminum compound contained in the toner has an aluminum element content of less than 0.02% by mass, the effect of addition is small. Further, the high temperature resistant offset of the toner may be reduced. If it exceeds 2% by mass, the toner is likely to be charged up, and the low-temperature fixability of the toner may be lowered.
[0042]
The organic iron compound is preferably a compound obtained by reacting a monoazo compound and an iron compound, and the organic iron compound preferably contains 0.02 to 2% by mass as an iron element in the toner, more preferably 0. 0.05 to 1.5% by mass is preferable, and 0.1 to 1% by mass is more preferable. When the organic iron compound contained in the toner is less than 0.02% by mass as an iron element, the toner image density stability in a high-temperature and high-humidity environment of the toner is liable to decrease and exceeds 2% by mass However, the stability of the image density of the toner in a room temperature and low humidity environment is liable to be lowered, which is not preferable.
[0043]
In the toner of the present invention, as the charge control agent, an organoaluminum compound interacts with the carboxyl group of the binder resin in the melt kneading step of the toner, and performs a kind of complex formation reaction presumed to be a ligand exchange reaction, Although it is preferable in terms of forming THF-insoluble matter in the binder resin of the toner, it has been difficult to control the amount of THF-insoluble matter produced so far. When sulfur-containing resins are present, there is no confirmation, but not only the amount of THF-insoluble matter produced by the synergistic effect of the organoaluminum compound, binder resin and sulfur-containing resin can be controlled, but the wax dispersion state is suitable. It becomes possible to be in a state.
[0044]
  The wax contained in the toner of the present invention has a main peak at a molecular weight of 300 to 20000, and preferably has a ratio (Mw / Mn) of 1.0 to 20, more preferably a main peak at a molecular weight of 500 to 5000. And the ratio (Mw / Mn) should be 1.1 to 18, more preferably molecular weight 700 to10,000It has a main peak and the ratio (Mw / Mn) is preferably 1.2 to 15. When the molecular weight indicating the main peak of the wax is less than 300, the dispersed particle diameter of the wax in the toner particles tends to be small, the molecular weight indicating the main peak is more than 20000, and the ratio (Mw / Mn) is more than 20. Is unfavorable because the dispersed particle size tends to be large, and in either case, it is difficult to control the dispersed state of the wax to a good state.
[0045]
The toner of the present invention preferably has an endothermic main peak in a temperature range of 70 to 150 ° C., more preferably a temperature range of 75 to 130 ° C., in a DSC curve measured by a differential scanning calorimeter (DSC) of the toner. It is preferable to have an endothermic main peak, more preferably an endothermic main peak in a temperature range of 80 to 110 ° C., and an endothermic subpeak or endothermic shoulder at the same time. When the toner has an endothermic main peak outside the above temperature range, it is difficult to satisfy a good balance between low-temperature fixability, hot offset resistance and blocking resistance.
[0046]
The toner of the present invention may contain two or more different waxes. The wax composition in which two or more kinds of waxes are mixed has a main peak at a molecular weight of 300 to 7000 and a ratio (Mw / Mn) of 1.2 to 15, more preferably a molecular weight of 350 to 4000. Having a main peak at a ratio (Mw / Mn) of 1.5 to 12, more preferably having a main peak at a molecular weight of 400 to 4000 and a ratio (Mw / Mn) of 2 to 10. There should be. In the wax composition, when the main peak molecular weight is less than 300 and the ratio (Mw / Mn) is less than 1.2, the main peak molecular weight exceeds 7000 and the ratio (Mw / Mn) exceeds 15; It is difficult to control the dispersion state of the wax composition well.
[0047]
The wax contained in the toner of the present invention is preferably a hydrocarbon wax, a polyethylene wax or a polypropylene wax.
[0048]
The wax contained in the toner of the present invention is preferably a wax such as a synthetic hydrocarbon obtained from a distillation residue of hydrocarbons obtained by an aging method using carbon monoxide / hydrogen as a raw material or by hydrogenation thereof. Furthermore, the thing which fractionated the hydrocarbon wax by the use of the press perspiration method, the solvent method, the vacuum distillation, or the fractional crystal method is more preferably used.
[0049]
The wax contained in the toner of the present invention has a structure represented by the formula (2).
[0050]
Formula (2):
CH_Three-(CH₂-CH₂)_x-CH₂-CH₂-A
(In the formula, A represents a hydroxyl group or a galboxyl group, and x represents an integer of 20 to 60, preferably A represents a hydroxyl group and x represents an integer of 30 to 50)
[0051]
  The wax contained in the toner of the present invention is acid-modified polyethylene.waxIn this case, it is preferable that the acid value is 1 to 20 mgKOH / g and the polyethylene is modified with a monomer selected from at least one of maleic acid, maleic acid half ester, and maleic anhydride. More preferably, those having an acid value of 1.5 to 15 mg KOH / g are preferred.
[0052]
  The wax contained in the toner of the present invention is acid-modified polypropylene.waxIn this case, it is preferable that the acid value is 1 to 20 mgKOH / g and the polyethylene is modified with a monomer selected from at least one of maleic acid, maleic acid half ester, and maleic anhydride. More preferably, it has 1.5 to 15 mg KOH / g.
[0053]
When the toner of the present invention contains two types of waxes, it is preferable to use the above-mentioned wax as at least one type of wax.
[0054]
In the toner of the present invention, the wax is added to and dispersed in the toner in the kneading step. Preferably, the wax is added in the production step of the binder resin, so that the control of the dispersed state of the wax is further facilitated.
[0055]
In the toner of the present invention, when two or more kinds of different waxes are contained, the wax added in the production step of the binder resin is preferably a hydrocarbon wax, a polyethylene polymer, a polypropylene polymer, 1 to It is preferable to use acid-modified polypropylene having an acid value of 20 mgKOH / g and acid-modified polyethylene having an acid value of 1 to 20 mgKOH / g.
[0056]
The preferred wax combination when the toner of the present invention contains a mixture of two kinds of waxes and the main peak molecular weight, weight average molecular weight (Mw) and number average molecular weight (Mn) of the wax when they are mixed in the same mass. An example of the ratio (Mw / Mn) is shown in Table 1 below.
[0057]
[Table 1]

[0058]
Next, the hybrid resin component used as the binder resin in the toner of the present invention will be described.
[0059]
In the toner of the present invention, the hybrid resin contained in the toner particles has a polyester unit and a vinyl polymer unit. The presence of the hybrid resin component¹³This can be confirmed by C-NMR measurement.¹³In the case of a magnetic toner containing a magnetic substance that inhibits the resolution of the C-NMR spectrum, the toner is added to a concentrated hydrochloric acid aqueous solution and stirred at room temperature for 70 to 80 hours to use a magnetic toner dissolved therein. Can be measured. The toner containing carbon black and organic pigment can be used as a measurement sample as it is. Table 2 shows an example of measurement results when styrene and acrylate are used as vinyl polymers.
[0060]
[Table 2]

[0061]
In the toner of the present invention, the alcohol component of the polyester unit includes ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5. -Pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl 1,3-hexanediol, hydrogenated bisphenol A, bisphenol derivatives represented by the following formula (3), and represented by the following formula (4) Diols are mentioned.
[0062]
[Chemical 1]

[Wherein, R represents an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10. ]
[0063]
[Chemical 2]

[Wherein, R ′ represents an ethylene, propylene or tertiary ribylene group. ]
[0064]
In the toner of the present invention, the acid component of the polyester unit includes aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid and terephthalic acid; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, or Acid anhydrides; succinic acid substituted with an alkyl group having 6 to 18 carbon atoms or an acid anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, and citraconic acid, or acid anhydrides thereof.
[0065]
In the toner of the present invention, the vinyl monomer for forming the vinyl polymer unit may be styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p- Chlorstyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene Styrene derivatives such as styrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene; ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene; vinyl chloride Halogens such as vinylidene chloride, vinyl bromide and vinyl fluoride Vinyl ester acid such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate , Isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, acrylic acid Acrylic esters such as phenyl; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N- N-vinyl compounds such as vinylindole and N-vinylpyrrolidone; vinylnaphthalene; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; esters of the aforementioned α, β-unsaturated acids, diesters of dibasic acids Is mentioned.
[0066]
Also, 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 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 Monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy Examples thereof include vinyl monomers having a hydroxyl group such as acrylic acid or methacrylic acid esters such as propyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, and 4- (1-hydroxy-1-methylhexyl) styrene. . These constitute a vinyl polymer unit alone or in combination of two or more.
[0067]
In the toner of the present invention, the polyester unit of the hybrid resin component preferably has a crosslinked structure crosslinked with a trivalent or higher polyvalent carboxylic acid or an anhydride thereof, or a trivalent or higher polyhydric alcohol. Examples of the trivalent or higher polyvalent carboxylic acid or its anhydride include 1,2,4-benzenetricarboxylic acid, 1,2,4, -cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, and These acid anhydrides or lower alkyl esters are mentioned. Examples of the trihydric or higher polyhydric alcohol include 1,2,3-propanetriol, trimethylolpropane, hexanetriol, and pentaerythritol. 1,2,4-benzenetricarboxylic acid and its acid anhydride are preferred.
[0068]
In the toner of the present invention, the vinyl polymer unit of the hybrid resin component may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include divinylbenzene and divinylnaphthalene as aromatic divinyl compounds; diacrylate compounds linked by an alkyl chain, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of the above compounds with methacrylates; Examples of diacrylate compounds linked by an alkyl chain include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyethylene glycol # 40. Examples include diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing the acrylate of the above compound with methacrylate; as diacrylate compounds linked by a chain containing an aromatic group and an ether bond. , Polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and acrylates of the above compounds Is replaced with methacrylate; examples of polyester-type diacrylates include the product MANDA (Nippon Kayaku).
[0069]
Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallylcia Examples include nurate and triallyl trimellitate.
[0070]
These crosslinking agents may be used in an amount of 0.01 to 10 parts by mass (more preferably 0.03 to 5 parts by mass) with respect to 100 parts by mass of other monomer components.
[0071]
Among these crosslinkable monomers, those which are preferably used from the viewpoint of toner fixing property and offset resistance, are bonded with a chain containing an aromatic divinyl compound (particularly divinylbenzene), an aromatic group and an ether bond. A diacrylate compound is mentioned.
[0072]
In this invention, it is preferable that the monomer component which can react with both resin units is contained in a vinyl-type copolymer unit and / or a polyester unit. Examples of monomers that can react with the vinyl polymer unit among the monomers constituting the polyester resin unit include unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl polymer unit, those capable of reacting with the polyester unit include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid ester.
[0073]
As a method for obtaining a reaction product of a vinyl polymer unit and a polyester unit, there is a polymer unit containing a monomer component capable of reacting with each of the vinyl polymer unit and the polyester unit mentioned above, A method obtained by polymerizing one or both polymer units is preferred.
[0074]
Examples of the polymerization initiator used in producing the vinyl polymer unit of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvalero). Nitrile), 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, cyclo Ketone peroxides such as xanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroper Oxide, di-t-butyl peroxide, t-butylcumyl 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 peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxy Oxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl peroxyhex Hydro terephthalate, di -t- butyl peroxy azelate and the like.
[0075]
The binder resin of the toner of the present invention may have at least the hybrid resin component having the vinyl polymer unit and the polyester unit described above. In addition to the hybrid resin component, the vinyl polymer And a resin composition containing a polyester resin, the dispersion of the sulfur-containing resin contained in the toner of the present invention is maintained in a suitable state, and both the developability and the fixability of the toner are satisfied. Is preferable in that it becomes possible.
[0076]
The binder resin of the toner of the present invention preferably contains 50 to 95% by mass, more preferably 60 to 90% by mass of a polyester unit as a hybrid resin component or a hybrid resin component and a polyester resin. More preferably, the content is 65 to 85% by mass. When the content of the polyester unit is less than 50% by mass, the low-temperature fixability and high-temperature offset resistance of the toner may be deteriorated, and when it exceeds 95% by mass, the high-temperature offset resistance of the toner is not preferable. It may decrease and is not preferable.
[0077]
As a manufacturing method which can prepare the resin composition which has such a hybrid resin component, a vinyl-type polymer, and a polyester resin, the manufacturing method shown to the following (1)-(6) can be mentioned, for example.
[0078]
(1) A method in which a vinyl resin, a polyester resin, and a hybrid resin component are blended after production. The blend is obtained by dissolving and swelling in an organic solvent (for example, xylene) and then distilling off the organic solvent. Preferably, the blend is produced by adding wax in this blending step. The hybrid resin component is synthesized by separately producing a vinyl polymer and a polyester resin, then dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and performing a transesterification reaction by heating. An ester compound can be used.
[0079]
(2) A method of producing a polyester unit and a hybrid resin component in the presence of a vinyl polymer unit in the presence of the vinyl polymer unit. The hybrid resin component is produced by a reaction between a vinyl polymer unit (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. Preferably, wax is added in this step.
[0080]
(3) A method for producing a vinyl polymer unit and a hybrid resin component in the presence of the polyester unit after the production. The hybrid resin component is produced by a reaction between a polyester unit (a polyester monomer can be added if necessary) and a vinyl monomer and / or vinyl polymer unit. Preferably, wax is added in this step.
[0081]
(4) After the production of the vinyl polymer unit and the polyester unit, the hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. Also in this case, an organic solvent can be appropriately used. Preferably, wax is added in this step.
[0082]
(5) After producing the hybrid resin component, vinyl polymer units and / or polyester units (alcohol, carboxylic acid) are added to carry out addition polymerization and / or polycondensation reaction to produce vinyl polymer units and polyester units. Is done. In this case, as the hybrid resin component, 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 used as appropriate. Preferably, wax is added in this step.
[0083]
(6) A vinyl polymer unit, a polyester unit, and a hybrid resin component 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 used as appropriate. Preferably, wax is added in this step.
[0084]
In the production methods (1) to (5), the vinyl polymer unit and / or the polyester unit can use a plurality of polymer units having different molecular weights and crosslinking degrees.
[0085]
Among the production methods (1) to (6) above, in particular, the production method (3) can easily control the molecular weight of the vinyl polymer unit, can control the production of the hybrid resin component, and When a wax is added, it is preferable in that the dispersion state can be controlled.
[0086]
The toner of the present invention has a weight average particle diameter of 4 to 12 μm and preferably contains less than 30% by volume of particles having a particle diameter of 10.1 μm or more, more preferably a weight average particle diameter of 5 to 9 μm. It is preferable to contain less than 20% by volume of particles of 10.1 μm or more, more preferably 5.5 to 8 μm in weight average particle size, and less than 10% by volume of particles having a particle size of 10.1 μm or more. . When the toner has a weight average particle size of more than 12 μm and contains 30% by volume or more of particles having a particle size of 10.1 μm or more, the chargeability of the toner may become non-uniform.
[0087]
When the toner is a magnetic toner, the magnetic material used for the magnetic toner is preferably a magnetic oxide such as magnetite, maghematite or ferrite containing a different element and a mixture thereof.
[0088]
For example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, sulfur, germanium, titanium, zirconium, tin, lead, zinc, calcium, barium, vanadium, chromium, manganese, cobalt, copper, nickel, gallium, indium, Magnetic iron oxide containing at least one element selected from silver, palladium, gold, platinum, tungsten, molybdenum, niobium, osmium, strontium, yttrium, technetium, ruthenium, rhodium and bismuth. Preference is given to lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, titanium, zirconium, tin, sulfur, calcium, barium, vanadium, chromium, manganese, cobalt, copper, nickel, strontium, bismuth and zinc. Particularly preferred is magnetic iron oxide containing an element selected from magnesium, aluminum, silicon, phosphorus and zirconium as a different element. These elements may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, and may exist on the surface as an oxide or hydroxide, It is preferable to contain.
[0089]
These elements can be incorporated into the particles by mixing the salts of the respective elements at the time of magnetic substance production and adjusting the pH. Moreover, it can be made to deposit on the particle | grain surface by adjusting pH after magnetic body particle | grain production | generation, or adding salt of each element and adjusting pH.
[0090]
The magnetic substance containing these elements has good affinity with the hybrid resin and is not only more effective with the hybrid resin having a specific acid value, but also the sulfur-containing resin used in the toner of the present invention. It also has a positive effect on dispersion in a state suitable for the invention. In addition, these magnetic materials can narrow the particle size distribution and have good dispersibility in the hybrid resin, and thus have an effect of improving toner charge uniformity and stabilization.
[0091]
The content of these different elements is preferably 0.05 to 10% by mass, more preferably 0.1 to 7% by mass, and still more preferably based on the iron element of magnetic iron oxide. It is good to contain 0.2-5 mass%, Most preferably, it is good to contain 0.3-4 mass%. When the content is less than 0.05% by mass, the above-described effects of containing these elements are small, and it is difficult to obtain good dispersibility and charging uniformity. On the other hand, if it exceeds 10% by mass, the discharge of electric charges increases and insufficient charging tends to occur, and image density is lowered and fog is likely to increase.
[0092]
Further, in the content distribution of these different elements, it is preferable that they exist in the vicinity of the surface of the magnetic particles. For example, when the dissolution rate of the iron element contained in the iron oxide is 20% by mass, the dissolution rate of the different element may be 20 to 100% by mass of the total amount of the different element, more preferably 25%. It is good that it is ˜100% by mass, particularly preferably 30˜100% by mass. By increasing the surface abundance of the different elements, the dispersion effect and the electrical diffusion effect can be further improved.
[0093]
The number average particle size of the magnetic material is preferably 0.05 to 1.0 μm, more preferably 0.1 to 0.5 μm. BET specific surface area of magnetic material is 2-40m²/ G is preferable, and further 4 to 20 m²/ G is preferred. The magnetic properties of the magnetic material are such that the saturation magnetization measured at a magnetic field of 795.8 kA / m is 10 to 200 Am.²/ Kg is preferable, and further 70 to 100 Am²/ Kg is more preferable. Residual magnetization is 1-100 Am²/ Kg is preferable, and further 2 to 20 Am²/ Kg is preferred. The coercive force is preferably 1 to 30 kA / m, and more preferably 2 to 15 kA / m. These magnetic materials are used by adding 20 to 200 parts by mass with respect to 100 parts by mass of the binder resin.
[0094]
Any suitable pigment or dye can be used as the colorant in the toner of the present invention. Examples of the pigment include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine yellow, alizarin yellow, bengara, and phthalocyanine blue. The pigment may be added in an amount of 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, with respect to 100 parts by mass of the binder resin. Examples of the dye include azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes. The dye is preferably added in an amount of 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, with respect to 100 parts by mass of the binder resin.
[0095]
In the toner of the present invention, fine particles of inorganic oxide such as silica, alumina and titanium oxide, and fine inorganic particles of fine particle size such as carbon black and carbon fluoride are externally added to the toner particles.
[0096]
The fine silica powder, fine alumina powder, or fine titanium oxide powder is preferably finer when dispersed on the toner particle surface because the effect of imparting fluidity to the toner is higher. These inorganic fine powders preferably have a number average particle diameter of 5 to 100 nm, more preferably 5 to 50 nm.
[0097]
When the amount of these inorganic fine powders used is 0.03 to 5 parts by mass with respect to 100 parts by mass of the toner particles, an appropriate toner particle surface coverage is obtained.
[0098]
The toner of the present invention may further be externally added with a fluororesin powder such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder.
[0099]
A preferred inorganic fine powder is dry-process silica or fumed silica produced by vapor phase oxidation of a silicon halide compound. For example, a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame is used, and the basic reaction formula is as follows.
[0100]
[Chemical Formula 3]
SiCl_Four+ 2H₂+ O₂→ SiO₂+ 4HCl
[0101]
In this production process, it is also possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with a silicon halide. The average primary particle size is preferably in the range of 0.001 to 2 μm, particularly preferably in the range of 0.002 to 0.2 μm, and the number average diameter is 5 to 100 nm. It is preferable to use silica fine powder.
[0102]
Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include those sold under the following trade names.
[0103]
AEROSIL (Nippon Aerosil Co., Ltd.) 130, 200, 300, 380, TT600, MOX170, MOX80, COK84; Ca-O-SiL (CABOT Co.) M-5, MS-7, MS-75, HS-5, EH -5; (WACKER-CHEMIE GMBH) HDK, N20, 15, N20E, T30, T40; DC Fine Silica (Dow Corning Co.); Francol (Fransil)
[0104]
As a hydrophobizing method, it is applied by chemically treating with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound.
[0105]
Examples of organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, and bromomethyldimethyl. Chlorsilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyl Diethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3 -Diphenyltetramethyldisiloxane and dimethylpolysiloxanes containing 2 to 12 siloxane units per molecule and containing hydroxyl groups bonded to one Si each in the terminal unit. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These are used alone or in a mixture of two or more.
[0106]
The inorganic fine powder has a specific surface area of 30 m by nitrogen adsorption measured by the BET method.²/ G or more, preferably 50 m²/ G or more gives good results. The inorganic fine powder is used in an amount of 0.01 to 8 parts by mass, more preferably 0.03 to 5 parts by mass, and still more preferably 0.1 to 4 parts by mass with respect to 100 parts by mass of the toner particles.
[0107]
As for the degree of hydrophobicity of the inorganic fine powder used in the toner of the present invention, the methanol wettability is preferably 30% or more, and more preferably 50% or more. As the hydrophobizing treatment agent, a silane compound and silicone oil which are silicon-containing surface treatment agents are preferable.
[0108]
For example, alkylalkoxysilanes such as dimethyldimethoxysilane, trimethylethoxysilane, butyltrimethoxysilane; dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethylenedimethylchlorosilane, allylphenyldimethylchlorosilane, benzyldimethylchlorosilane Silane coupling agents such as vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, divinylchlorosilane, and dimethylvinylchlorosilane can be used.
[0109]
The toner of the present invention may be mixed with a carrier and used as a two-component developer. The carrier resistance value is 10 by adjusting the degree of unevenness of the carrier surface and the amount of resin to be coated.⁶-10^TenIt should be Ω · cm.
[0110]
As the resin covering the carrier surface, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, acrylic acid ester copolymer, methacrylic acid ester copolymer, silicone resin, fluororesin, polyamide resin, An ionomer resin, a polyphenylene sulfite resin, or a mixture of these resins can be used.
[0111]
As the magnetic material for the carrier core, oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof can be used. The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. Can be mentioned.
[0112]
In the toner of the present invention, various additives can be used for the purpose of imparting various properties. For example, the following additives are used.
[0113]
(1) As abrasives, metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide), nitride (silicon nitride), carbide (silicon carbide), metal salts (calcium sulfate, barium sulfate) , Calcium carbonate).
[0114]
(2) Examples of the lubricant include fluorine-based resin powder (polyvinylidene fluoride, polytetrafluoroethylene) and aliphatic metal salts (zinc stearate, calcium stearate).
[0115]
(3) Examples of the conductive particles include metal oxides (tin oxide and zinc oxide) and carbon black.
[0116]
These additives may be added in an amount of 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner particles. These additives may be used alone or in combination of two or more.
[0117]
In the case of a magnetic toner, it is preferable to use inorganic fine powders of two or more kinds of inorganic oxides or metal oxides from the viewpoints of development durability stability and development stability after standing. In the case of the non-magnetic one-component development method, it is preferable to use titanium oxide fine powder or alumina fine powder from the viewpoint of improving fluidity and image uniformity.
[0118]
In order to produce the toner particles according to the present invention, the above-described toner particle constituent materials are sufficiently mixed using a mixer such as a ball mill or a Henschel mixer, and then a thermal kneader such as a hot roll kneader or an extruder is used. A method in which toner particles are obtained by kneading thoroughly, cooling and solidifying, mechanically coarsely pulverizing, then jetting or mechanically pulverizing powder, and classifying the powder is preferable. As other production methods, a polymerized toner production method in which a predetermined material is mixed with a monomer to constitute a binder resin to obtain an emulsion suspension, and then polymerized to obtain toner particles; a core material, a shell material In a microcapsule toner comprising: a method of containing a predetermined material in a core material or a shell material, or both of them; a method of obtaining toner particles by dispersing a constituent material in a binder resin solution and then spray drying Can be mentioned. Furthermore, the toner of the present invention can be produced by sufficiently mixing the desired additive and toner particles with a mixer such as a Henschel mixer.
[0119]
Next, an image forming method in which the toner of the present invention is preferably used will be described.
[0120]
The developing means applicable to the image forming method of the present invention will be described.
[0121]
  In FIG. 1, an image carrying an electrostatic charge image formed by a known process.BurdenThe holder (for example, electrophotographic photosensitive drum) 7 is rotated in the direction of arrow B. The developing sleeve 14 as a developer carrying member carries the toner 10 supplied from the hopper 9 and rotates in the direction of arrow A, so that the developing sleeve D and the photosensitive drum 7 face the developing portion D where the developing sleeve D faces the toner 10. Transport. In the developing sleeve 14, when the toner 10 is a magnetic toner, in order to be magnetically attracted and held on the developing sleeve 14,Magnetic field generation means (magnet)11 is arranged. The toner 10 obtains a triboelectric charge capable of developing the electrostatic image on the photosensitive drum 7 by friction with the developing sleeve 14. The developing sleeve 14 is provided with a resin layer 13 on the base 12.
[0122]
In order to regulate the layer thickness of the toner 10 transported to the developing section D, the regulating magnetic blade 8 made of a ferromagnetic metal has a gap width of 200 to 300 μm from the surface of the developing sleeve 14 in the case of magnetic toner. Then, it is suspended from the hopper 9 so as to face the developing sleeve 14. A magnetic force line from the magnetic pole N <b> 1 of the magnet 11 concentrates on the blade 8, whereby a thin layer of the toner 10 is formed on the developing sleeve 14. A nonmagnetic blade can also be used as the blade 8. In place of the magnetic blade, an elastic blade such as urethane rubber, silicone rubber, or chip blade is used.
[0123]
The thickness of the thin layer of toner 10 formed on the developing sleeve 14 is preferably thinner than the minimum gap between the developing sleeve 14 and the photosensitive drum 7 in the developing portion D. Such a toner thin layer is particularly effective for a developing device that develops an electrostatic image (that is, a non-contact developing device). However, the present invention can also be applied to a developing device (that is, a contact-type developing device) in which the thickness of the toner layer is equal to or greater than the minimum gap between the developing sleeve 14 and the photosensitive drum 7 in the developing unit.
[0124]
Hereinafter, an example of a non-contact type developing device will be described.
[0125]
A developing bias voltage is applied to the developing sleeve 14 by a power source 15 in order to cause the toner 10 carried on the developing sleeve 14 to fly. When a DC voltage is used as the developing bias voltage, a voltage having a value between the potential of the image portion of the electrostatic charge image (the region visualized by the toner 10 attached) and the potential of the background portion is the developing sleeve 14. It is preferable to be applied to. On the other hand, in order to increase the density of the developed image or improve the gradation, an alternating bias voltage may be applied to the developing sleeve 14 to form an oscillating electric field whose direction is alternately reversed in the developing portion D. In this case, it is preferable to apply to the developing sleeve 14 an alternating bias voltage in which a DC voltage component having values of the image portion potential and the background portion potential is superimposed.
[0126]
In normal development in which toner is attached to a high potential portion of an electrostatic charge image having a high potential portion and a low potential portion for visualization, toner charged to a polarity opposite to that of the electrostatic charge image is used. On the other hand, in reversal development in which toner is attached to a low potential portion of an electrostatic charge image and visualized, the toner is charged with the same polarity as that of the electrostatic charge image. High potential and low potential are expressed by absolute values. The toner 10 is charged to a polarity for developing an electrostatic charge image by friction with the developing sleeve 14.
[0127]
In the developing device, the member that regulates the layer thickness of the toner 10 on the developing sleeve 14 is formed of a rubber elastic material such as urethane rubber or silicone rubber, or a metal elastic material such as phosphor bronze or stainless steel. The elastic plate 17 is used, and the elastic plate 17 is pressed against the developing sleeve 14. In such a developing device, a thinner toner layer can be formed on the developing sleeve 8. 2 is basically the same as the developing device shown in FIG. 1, and the same reference numerals as those in FIG. 1 in FIG. 2 denote the same members.
[0128]
The developing device as shown in FIG. 2 that forms the toner layer on the developing sleeve 14 as described above rubs the toner on the developing sleeve 14 by the elastic plate 17, so that the amount of toner triboelectric charge increases, and the image The concentration is improved. Such a developing device is also used for non-magnetic one-component toner.
[0129]
The developing sleeve which is a developer carrying member used in the present invention preferably has a cylindrical substrate and a coating layer (resin layer) covering the surface of the substrate. The configuration is as shown in FIG. The resin layer 1 contains a binder resin 4, optionally a conductive material 2, a filler 3 and a solid lubricant 5, and is coated on a cylindrical substrate 6. When the conductive material 2 is contained, since the resin layer 1 is conductive, the toner can be prevented from being overcharged. Further, when the filler 3 is contained, the abrasion of the resin layer 1 by the toner is prevented, and further, the charging of the toner can be suitably controlled by the charge imparting property of the filler 3. When the solid lubricant 5 is contained, the releasability between the toner and the developing sleeve is improved, and as a result, the toner can be prevented from being fused onto the developing sleeve.
[0130]
In the developing sleeve, when a conductive material is contained in the resin layer, the volume resistance of the resin layer is 10⁶Ω · cm or less, preferably 10^ThreeWhat is below ohm * cm is good. The volume resistance of the resin layer is 10⁶If it exceeds Ω · cm, the toner is likely to be charged up, which may cause blotch and deterioration of development characteristics.
[0131]
Moreover, it is preferable that the surface roughness of this resin layer exists in the range of 0.2-3.5 micrometers in JIS centerline average roughness (Ra). When Ra is less than 0.2 μm, the charge amount of the toner near the sleeve tends to be high, the toner is attracted onto the sleeve by the mirroring force, and new toner cannot be charged from the sleeve, and the developability tends to be lowered. . If Ra exceeds 3.5 μm, the toner coat amount on the sleeve will increase too much, and the toner will not be able to obtain a sufficient charge amount, and will tend to be unevenly charged, which tends to cause a decrease in image density and uneven density. .
[0132]
Next, each material which comprises this resin layer 1 is demonstrated, referring FIG.
[0133]
Examples of the conductive material 2 include metal powders such as aluminum, copper, nickel, and silver; metal oxides such as antimony oxide, indium oxide, and tin oxide; and carbon allotropes such as carbon fiber, carbon black, and graphite. Among these, carbon black is particularly preferred because it is excellent in electrical conductivity and can be filled with a polymer material to impart conductivity, or can have a certain degree of conductivity by controlling the amount added. The number average particle size of carbon black is 0.001 to 1.0 μm, preferably 0.01 to 0.8 μm. When the number average particle diameter of the carbon black exceeds 1 μm, it is difficult to control the volume resistance of the resin layer, which is not preferable.
[0134]
The amount of the conductive substance used is preferably 0.1 to 300 parts by mass, more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the binder resin.
[0135]
As the filler 3, a known negative charge control agent for toner or a positive charge control agent for toner may be added. Other fillers include inorganic compounds such as alumina, asbestos, glass fiber, calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, silica, calcium silicate; phenol resin, epoxy resin, melamine resin, silicone resin, PMMA, Methacrylate terpolymer (eg polystyrene / n-butyl methacrylate / silane terpolymer), styrene-butadiene copolymer, polycaprolactone; nitrogen-containing compounds such as polycaprolactam, polyvinylpyridine, polyamide; polyvinylidene fluoride, polyvinyl chloride, Polytetrafluoroethylene, polytetrachlorofluoroethylene, perfluoroalkoxylated ethylene, polytetrafluoroalkoxyethylene, fluorinated ethylene propylene-polytetrafluoroethylene Oroechiren copolymer, trifluorochloroethylene - polymers were highly halogenated such vinyl chloride copolymers; polycarbonates, and polyester. Of these, silica and alumina are preferably used because they have their own hardness and charge controllability to the toner.
[0136]
As a usage-amount of a filler, Preferably it is 0.1-500 mass parts with respect to 100 mass parts of binder resin, More preferably, it is 1-200 mass parts.
[0137]
Examples of the solid lubricant 5 include molybdenum disulfide, boron nitride, graphite, graphite fluoride, silver-niobium selenide, calcium chloride-graphite, and talc. Of these, graphite is preferably used because it has conductivity as well as lubricity, has a function of reducing toner having an excessively high charge, and having a charge amount suitable for development.
[0138]
The amount of the solid lubricant used is preferably 0.1 to 300 parts by mass and more preferably 1 to 150 parts by mass with respect to 100 parts by mass of the binder resin.
[0139]
In some cases, as the binder resin 4 in which the conductive material 2, the filler 3 and the solid lubricant 5 are dispersed, a phenol resin, an epoxy resin, a polyamide resin, a polyester resin, a polycarbonate resin, Resins such as polyolefin resin, silicone resin, fluorine resin, styrene resin, and acrylic resin are used. In particular, a thermosetting or photocurable resin is preferable.
[0140]
In order to expose the conductive material, filler or solid lubricant in the resin layer on the surface of the developing sleeve suitably on the surface, or to smooth the surface to create a uniform uneven surface, polishing described later By smoothing the surface by means such as processing, it is possible to impart more desirable performance. In particular, it is effective in the vertical streaking phenomenon that occurs in solid black and halftone images and the rise of the initial image density, and is particularly effective under high temperature and high humidity. By applying a polishing process with a belt-like abrasive with felt or abrasive grains, the surface irregularity of the sleeve can be finished uniformly, so that the toner coat amount on the sleeve is made uniform, resulting in frictional charging with the sleeve. Only the received toner is conveyed to the development area. Therefore, it is considered that the above effect can be obtained.
[0141]
Even after performing the smoothing treatment as described above, it is preferable that the surface of the coat layer retains unevenness in the range of 0.2 to 3.5 μm as Ra in JIS B 0601, and more preferably 0.3 to It is about 2.5 μm. The reason is the same as described above.
[0142]
As the cylindrical substrate 6, a nonmagnetic metal cylindrical tube or a resin cylinder is preferably used. For example, a non-magnetic cylindrical tube such as a stainless cylindrical tube, an aluminum cylindrical tube, or a copper alloy cylindrical tube is used. As a method of manufacturing the cylindrical tube, there are a drawing method and an extrusion method. When the dimensional accuracy of the cylindrical tube itself is further increased, cutting and polishing are performed to obtain a predetermined dimensional accuracy. The straightness of the cylindrical tube is preferably 30 μm or less, more preferably 20 μm or less, and a good image can be obtained. Further, if necessary, a rough surface may be formed by sandblasting or polishing in order to impart appropriate irregularities to the surface. Abrasive grains used for blasting may be either regular particles or irregular particles.
[0143]
Next, an example of the image forming method of the present invention is shown in FIG. FIG. 4 shows an image forming apparatus having contact charging means and contact transfer means.
[0144]
A rotating drum type photoreceptor 801 having a photoconductive layer 801a and a conductive base layer 801b is rotated at a predetermined peripheral speed (process speed) in the clockwise direction of the hands in the drawing. A charging roller 802, which is a contact charging unit having a conductive elastic layer 802a and a cored bar 802b, is biased by a charging bias power source 803. The charging roller 802 is pressed against the photoconductor 801 by a pressing force, and is driven to rotate as the photoconductor 801 rotates.
[0145]
Bias V on charging roller 802₂Is applied to charge the surface of the photoconductor 801 to a predetermined polarity and potential. Next, an electrostatic charge image is formed by the image exposure 804 and is sequentially visualized as a toner image by the developing unit 805.
[0146]
A developing sleeve constituting the developing unit 805 has a bias V from a developing bias applying unit 813.₁Is applied. A toner image formed on the latent image holding member by development is transferred to a transfer bias V by a transfer bias power source 807._ThreeIs transferred electrostatically to the transfer material 808 by a transfer roller 806 (conductive elastic layer 806a, cored bar 806b) as a contact transfer means for pressing the transfer material 808 to which the photosensitive member 801 is applied, and a toner image on the transfer material. Is heated and pressurized and fixed by a heating and pressing means 811 having a heating roller 811a and a pressing roller 811b. On the surface of the photoconductor 801 after the toner image transfer, adhering contaminants such as toner remaining after transfer are cleaned by a cleaning device 809 having an elastic cleaning blade pressed against the photoconductor 801 in the counter direction. Static electricity is removed and images are created repeatedly.
[0147]
The primary charging means has been described using the charging roller 802 as the contact charging means as described above, but may be a contact charging means such as a charging blade or a charging brush, or may be a non-contact corona charging means. The contact charging means generates less ozone in the charging process. As described above, the transfer unit has been described using the transfer roller 806, but may be a contact charging unit such as a transfer blade or a transfer belt, or may be a non-contact corona transfer unit. The contact transfer means generates less ozone in the transfer process.
[0148]
Further, another fixing method applicable to the image forming method of the present invention will be described with reference to a fixing unit shown in FIG. FIG. 5 shows a heating member 511 fixedly supported by a recording material 519 carrying a toner image, and a pressure member that is pressed against the heating member and in close contact with the heating member through a film 515. Reference numeral 518 denotes a heat fixing unit.
[0149]
In the fixing device shown in FIG. 5, the heating body 511 has a smaller heat capacity than a conventional heat roll and has a linear heating portion, and the maximum temperature of the heating portion is preferably 100 to 300 ° C. .
[0150]
The fixing film 515 located between the heating body 511 and the pressure roller 518 as a pressure member is preferably a heat-resistant sheet having a thickness of 1 to 100 μm. In addition to polymer sheets such as polyester, PET (polyethylene terephthalate), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), PTFE (polytetrafluoroethylene), polyimide, and polyamide, metal sheets such as aluminum, A laminate sheet composed of a metal sheet and a polymer sheet is used.
[0151]
A more preferable fixing film structure is that these heat-resistant sheets have a release layer and / or a low resistance layer.
[0152]
Reference numeral 511 denotes a low heat capacity linear heating element fixedly supported by the apparatus. As an example, an alumina substrate 512 having a thickness of 1.0 mm, a width of 10 mm, and a longitudinal length of 240 mm is coated with a resistance material 513 to a width of 1.0 mm. Thus, power is supplied from both ends in the longitudinal direction. The energization is performed by changing the pulse width of a pulse corresponding to a desired temperature and energy release amount controlled by the temperature measuring element 514 with a pulse waveform with a cycle of 20 msec of DC 100V. The approximate pulse width is 0.5 msec to 5 msec. In this way, the fixing film 515 moves in the direction of the arrow in contact with the heating body 511 whose energy and temperature are controlled.
[0153]
As an example of this fixing film, a release layer in which a conductive agent is added to a heat-resistant film having a thickness of 20 μm (for example, fluorine resin such as PTFE or PAF at least on the image contact surface side of polyimide, polyetherimide, PES, or PFA) is 10 μm. It is a coated endless film. In general, the total thickness is less than 100 μm, more preferably less than 40 μm. The driving of the film moves without causing wrinkles in the direction of the arrow due to driving and tension by the driving roller 516 and the driven roller 517.
[0154]
Reference numeral 518 denotes a pressure roller having a rubber elastic layer with good releasability such as silicone rubber, which presses the heating body through the film at a total pressure of 39.2 to 196 N (4 to 20 kg) and rotates in pressure contact with the film. . The unfixed toner 520 on the recording material 519 is guided to the fixing unit by the entrance guide 521, and a fixed image is obtained by the heating described above.
[0155]
Although the fixing film 515 has been described as an endless belt, a sheet feeding shaft and a take-up shaft may be used, and the fixing film may be an end film.
[0156]
FIG. 6 shows a specific example of the process cartridge of the present invention. In the process cartridge, the developing means and the electrostatic charge image carrier are at least integrally formed as a cartridge, and the process cartridge is formed so as to be detachable from the main body of the image forming apparatus (for example, a copying machine or a laser beam printer).
[0157]
FIG. 6 illustrates a process cartridge 750 in which a developing unit 709, a drum-shaped electrostatic charge image carrier (photosensitive drum) 701, a cleaner 708 having a cleaning blade 708a, and a primary charger (charging roller) 742 are integrated. .
[0158]
In FIG. 6, the developing unit 709 includes an elastic blade 711 a and a magnetic toner 710 in a toner container 760, and the magnetic toner 710 is used, and at the time of development, the photosensitive drum 701 and the developing sleeve 704 are biased by a bias from the bias applying unit. The distance between the photosensitive drum 701 and the developing sleeve 704 is very important in order that a predetermined electric field is formed between them and the developing process is suitably performed.
[0159]
A method for measuring physical properties of the toner of the present invention will be described below.
[0160]
(1) Measurement of acid value of toner and binder resin
The measurement is performed according to the measurement method described in JIS K0070.
Measuring apparatus: Automatic potentiometric titrator AT-400 (manufactured by Kyoto Electronics Co., Ltd.)
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol. Measurement temperature: 25 ° C
Sample preparation: 1.0 g of toner or 0.5 g of binder resin is added to 120 ml of toluene and dissolved by stirring with a magnetic stirrer at room temperature (about 25 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to prepare a sample solution.
[0161]
(2) Molecular weight measurement of THF-soluble matter
The molecular weight distribution by GPC using THF as a solvent for the binder resin or toner in tetrahydrofuran (THF) is measured under the following conditions, and a molecular weight of 1000 or more is measured.
[0162]
The column is stabilized in a heat chamber at 40 ° C., and THF as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml per minute, and about 100 μl of the THF sample solution is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count value. As a standard polystyrene sample for preparing a calibration curve, for example, a molecular weight of 10 manufactured by Tosoh Corporation or Showa Denko KK is 10²-10⁷It is appropriate to use a standard polystyrene sample of at least 10 points. An RI (refractive index) detector is used as the detector. In addition, as a column, it is preferable to combine a plurality of commercially available polystyrene gel columns. TSKgel G1000H (H_XL), G2000H (H_XL), G3000H (H_XL), G4000H (H_XL), G5000H (H_XL), G6000H (H_XL), G7000H (H_XL), A combination of TSKgull column.
[0163]
The content of the component having a molecular weight of 500,000 or more is obtained by calculating the ratio of the molecular weight integral value having a molecular weight of 500,000 or more to the molecular weight integral value having a molecular weight of 800 or more from the molecular weight distribution by GPC obtained by the above method.
[0164]
The sample is prepared as follows.
[0165]
Place the sample in THF and let stand for several hours, then shake well and mix well with THF (until the sample is no longer united) and let stand for more than 12 hours. At that time, the standing time in THF should be 24 hours or more. Thereafter, a sample processed filter (pore size 0.2 to 0.5 μm, for example, Mysori Disc H-25-2 (manufactured by Tosoh Corporation) can be used) is used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.
[0166]
(3) Measurement of tetrahydrofuran (THF) insoluble matter
0.5 to 1.0 g of a toner sample to be measured for THF-insoluble content is precisely weighed and placed in a cylindrical filter paper (No. 86R, manufactured by Toyo Roshi Kaisha Co., Ltd., dimensions are 28 mm x 100 mm height). Soxhlet extractor And 200 ml of THF as the extraction solvent is used. The extraction is performed by controlling the temperature of the oil bath at 120 to 130 ° C., and the time required for one reflux is adjusted to be 120 to 150 seconds. The extraction time is 10 hours. After completion of extraction, the cylindrical filter paper is dried under reduced pressure at 70 ° C. for 10 hours, and the THF-insoluble matter is calculated from the following formula.
[0167]
[Expression 1]

[W1 is the mass of the toner sample, W2 is a THF soluble component of the binder resin, and W3 is a component other than the binder resin contained in the toner (for example, magnetic substance, wax, external additive, etc.) Represents. ]
[0168]
(4) Measurement of DSC curve of toner and endothermic peak temperature of wax
It measures according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device) and DSC-7 (manufactured by Perkin Elmer).
[0169]
The measurement sample is precisely weighed in an amount of 2 to 10 mg, preferably 5 mg.
[0170]
This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 10 ° C./min within a measurement temperature range of 30 to 200 ° C.
[0171]
In this temperature raising process, the DSC curve of the toner in the temperature range of 30 to 200 ° C. and the endothermic peak of the wax main peak in the DSC curve are obtained. The temperature of this endothermic main peak is taken as the melting point of the wax.
[0172]
(5) Measurement of glass transition temperature (Tg) of toner and binder resin
It measures according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device) and DSC-7 (manufactured by Perkin Elmer).
[0173]
A sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg, put in an aluminum pan, and an empty aluminum pan is used as a reference. Measure in min. In this temperature raising process, an endothermic peak of the main peak in the temperature range of 40 to 100 ° C. is obtained.
[0174]
The intersection of the intermediate point line between the two baselines before and after the endothermic peak and the differential heat curve is defined as the glass transition temperature Tg in the present invention.
[0175]
(6) Measurement of molecular weight distribution of wax
GPC measuring device: GPC-150C (Waters)
Column: GMH-HT 30 cm 2 series (manufactured by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% ionol added)
Flow rate: 1.0 ml / min
Sample: 0.4ml injection of 0.15% sample
Measurement is performed under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used in calculating the molecular weight of the sample. Furthermore, it calculates by converting into polyethylene by the conversion formula derived from the Mark-Houwink viscosity formula.
[0176]
(7) Measurement of molecular weight distribution of binder resin raw material or binder resin component of toner
The molecular weight of the chromatogram by GPC is measured under the following conditions.
[0177]
The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min. When the sample is a binder resin raw material, a material obtained by passing the binder resin raw material through a roll mill (130 ° C., 15 minutes) is used. When the sample is toner, the toner is dissolved in THF, filtered through a 0.2 μm filter, and the filtrate is used as a sample. Measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6 mass%. 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. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Manufactured by Toyo Soda Industry Co., Ltd.²2.1 × 10^Three, 4 × 10^Three, 1.75 × 10^Four, 5.1 × 10^Four1.1 × 10^Five, 3.9 × 10^Five8.6 × 10^Five, 2 × 10⁶, 4.48 × 10⁶It is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
[0178]
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, for example, μ-stergel 500, 10 manufactured by Waters.^Three, 10^Four, 10^FiveAnd combinations of shodex KA-801, 802, 803, 804, 805, 806 and 807 manufactured by Showa Denko KK are preferred.
[0179]
(8) Measurement of toner particle size distribution
The particle size distribution of the toner of the present invention is measured using a Coulter Counter TA-II type or Coulter Multisizer (manufactured by Beckman Coulter). As the electrolytic solution, a 1% NaCl aqueous solution is prepared using first grade sodium chloride. For example, ISOTON R-II (manufactured by Beckman Coulter) can be used. As a measuring method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the aqueous electrolytic solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measuring device is used to measure the volume and number of toners of 2 μm or more using a 100 μm aperture as the aperture. Distribution and number distribution were calculated. Then, the weight average diameter (D4) based on the weight distribution (representative value of each channel) obtained from the volume distribution according to the present invention was obtained.
[0180]
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.72 μm; less than 12.72 to less than 16.00 μm; less than 16.00 to less than 20.02 μm; Use 13 channels less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm.
[0181]
(9) Measurement of sulfur atom content in toner
The sulfur atom content contained in the toner is measured using EMIA-320 manufactured by HORIBA, Ltd.
[0182]
The toner is burned in an oxygen stream, and the sulfur atom of the sulfur-containing resin in the toner is changed to sulfur dioxide by an infrared absorption method, and the sulfur atom is determined from the amount of sulfur dioxide.
[0183]
(10) Measurement of different element content in magnetic iron oxide
Elements in magnetic iron oxide can be measured by performing fluorescent X-ray analysis using a fluorescent X-ray analyzer SYSTEM3080 (manufactured by Rigaku Denki Kogyo Co., Ltd.) according to JIS K0119 general X-ray fluorescence analysis rules.
[0184]
(11) Measurement of heterogeneous element content distribution in magnetic iron oxide
Regarding the distribution of heterogeneous elements in magnetic iron oxide, the amount of elements dissolved in hydrochloric acid or hydrofluoric acid is measured and quantified by plasma emission distribution (ICP), and each element at the time of dissolution relative to the concentration at the time of total dissolution of each element. It is obtained by determining the dissolution rate from the concentration.
[0185]
(12) Measurement of number average particle diameter of magnetic iron oxide
Measurement of the number average particle diameter of magnetic iron oxide can be obtained by randomly selecting 300 magnetic bodies and measuring with a digitizer using a photograph taken at a magnification of 40,000 with a transmission electron microscope. .
[0186]
(13) Measurement of magnetic properties of magnetic iron oxide
The magnetic properties of magnetic iron oxide are measured under an external magnetic field of 795.8 kA / m using a vibrating sample magnetometer VSM-3S-15 (manufactured by Toei Kogyo Co., Ltd.).
[0187]
(14) Measurement of specific surface area measured by BET method of magnetic iron oxide and external additive
The specific surface area of the magnetic iron oxide and the external additive is determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics) according to the BET method, and using the BET multipoint method. Is calculated.
[0188]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
[0189]
Production of sulfur-containing resin:
Production Example 1
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 200 parts by mass of methanol, 150 parts by mass of 2-butanone and 50 parts by mass of 2-propanol were used as solvents. Then, 78 parts by mass of styrene, 15 parts by mass of n-butyl acrylate, and 7 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added as monomers and heated to 70 ° C. with stirring. A solution obtained by diluting 1 part by mass of 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator with 20 parts by mass of 2-butanone was added dropwise over 1 hour, and stirring was continued for 5 hours. , 2′-azobis (2-methylbutyronitrile) diluted with 20 parts by mass of 2-butanone was added dropwise over 30 minutes and stirred for another 5 hours to complete the polymerization. The polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less using a cutter mill equipped with a 150 mesh screen.
[0190]
The obtained sulfur-containing copolymer had a glass transition temperature (Tg) of 74 ° C., a weight average molecular weight (Mw) of 27000, and an acid value of 23 mgKOH / g. This is referred to as a sulfur-containing copolymer (S-1).
[0191]
Production Example 2
In Production Example 1, the monomer is 70 parts by mass of styrene, 13 parts by mass of n-butyl acrylate, 7 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid, 0.05 parts by mass of divinylbenzene, and 2 is a polymerization initiator. , 2′-azobis (2-methylbutyronitrile) was added dropwise over 90 minutes in the same manner to obtain a sulfur-containing copolymer (S-2).
[0192]
The obtained sulfur-containing copolymer (S-2) had a Tg of 58 ° C., a weight average molecular weight (Mw) of 174,000, and an acid value of 26 mgKOH / g.
[0193]
Production Example 3
A sulfur-containing copolymer (S-3) was obtained in the same manner as in Production Example 1, except that 4 parts by mass of 2,2'-azobis (2-methylbutyronitrile) as a polymerization initiator was used.
[0194]
The obtained sulfur-containing copolymer (S-3) had a Tg of 57 ° C., a weight average molecular weight (Mw) of 4800, and an acid value of 22 mgKOH / g.
[0195]
Production Example 4
In Production Example 1, the polymerization solvent is 800 parts by mass of toluene, 100 parts by mass of isopropanol, the monomer is 71 parts by mass of styrene, 26 parts by mass of n-butyl acrylate, and 3 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid. Sulfur-containing copolymer (S-4) was prepared in the same manner except that the polymerization reaction was conducted for 7 hours at reflux temperature as 2 parts by mass of 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator. Got.
[0196]
The obtained sulfur-containing copolymer (S-4) had a Tg of 38 ° C., a weight average molecular weight (Mw) of 22000, and an acid value of 11 mgKOH / g.
[0197]
Production Example 5
In Production Example 1, the polymerization solvent is 50 parts by mass of methanol and 1000 parts by mass of xylene, the monomers are 900 parts by mass of styrene, 100 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid, and the polymerization initiator is 2,2′-. A sulfur-containing copolymer (S-5) was obtained in the same manner except that the polymerization reaction was carried out at 60 ° C. for 10 hours as 60 parts by mass of azobis (2,4-dimethylvaleronitrile).
[0198]
The obtained sulfur-containing copolymer (S-5) had a Tg of 96 ° C., a weight average molecular weight (Mw) of 9600, and an acid value of 29 mgKOH / g.
[0199]
Production Example 6
In the same manner as in Production Example 1, except that the monomer was 70 parts by mass of styrene, 18 parts by mass of n-butyl methacrylate, and 12 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid. 6) was obtained.
[0200]
The obtained sulfur-containing copolymer (S-6) had a Tg of 78 ° C., a weight average molecular weight (Mw) of 10500, and an acid value of 37 mgKOH / g.
[0201]
Production Example 7
In Production Example 1, the polymerization solvent is 200 parts by mass of xylene, the first stage polymerization reaction is 43 parts by mass of styrene, 7 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid, and 1,1-bis is used as the polymerization initiator. 3 parts by mass of (t-butylperoxy) -2-methylcyclohexane was added dropwise and held at that temperature for 8 hours. Next, as a second stage polymerization reaction, the reaction vessel is heated to 120 ° C., and a monomer composition comprising 30 parts by mass of styrene, 20 parts by mass of n-butyl acrylate, and 50 parts by mass of xylene is added dropwise over 1 hour. The temperature was maintained for 5 hours to complete the polymerization reaction. Xylene was distilled off under reduced pressure to obtain a sulfur-containing copolymer (S-7).
[0202]
The obtained sulfur-containing copolymer (S-7) had a Tg of 77 ° C., a weight average molecular weight (Mw) of 26000, and an acid value of 24 mgKOH / g.
[0203]
Production Example 8
In Production Example 1, 70 parts by mass of styrene as a monomer, 27 parts by mass of n-butyl acrylate, and 3 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were charged without adding a polymerization solvent and a polymerization initiator. The temperature was raised to 0 ° C. and bulk polymerization was carried out for 8 hours. Next, 50 parts by mass of xylene was added and cooled to 110 ° C., 50 parts by mass of a xylene solution in which 1 part by mass of t-butylperoxy-2-ethylhexanoate was dissolved was added dropwise over 6 hours, and further stirred for 1 hour. Except that, a sulfur-containing copolymer (S-8) was obtained in the same manner.
[0204]
The sulfur-containing copolymer (S-8) had a Tg of 56 ° C., a weight average molecular weight (Mw) of 271,000, and an acid value of 8 mgKOH / g.
[0205]
Production Example 9
A sulfur-containing copolymer (S) was prepared in the same manner as in Production Example 1, except that a monomer mixture consisting of 93 parts by mass of 4-t-butylstyrene and 7 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid was used. -9) was obtained.
[0206]
The sulfur-containing copolymer (S-9) had a Tg of 133 ° C., a weight average molecular weight (Mw) of 14,000, and an acid value of 19 mgKOH / g.
[0207]
Production Example 10
In Production Example 1, the polymerization solvent is 300 parts by mass of methanol, 100 parts by mass of toluene, the monomer is 540 parts by mass of styrene, 60 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid, and the polymerization initiator is 60 parts by mass of lauroyl peroxide. As a part, a sulfur-containing copolymer (S-10) was obtained in the same manner except that the polymerization reaction was carried out at reflux temperature for 10 hours.
[0208]
The sulfur-containing copolymer (S-10) had a Tg of 28 ° C., a weight average molecular weight (Mw) of 1900, and an acid value of 36 mgKOH / g.
[0209]
Table 3 shows the physical properties of the sulfur-containing copolymers (S-1) to (S-10).
[0210]
Resin production example 1
(1) Manufacture of polyester resin
・ Terephthalic acid: 6.1 mol
・ Dodecenyl succinic anhydride: 3.0 mol
・ Fumaric acid: 0.8 mol
・ Trimellitic anhydride: 3.1 mol
PO-BPA (propoxylated bisphenol A): 7.2 mol
EO-BPA (ethoxylated bisphenol A): 3.0 mol
The above polyester monomer is charged into an autoclave together with an esterification catalyst, and a polycondensation reaction is performed while heating to 210 ° C. in a nitrogen gas atmosphere with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device. A polyester resin (PE) was obtained. The obtained polyester resin (PE) has a main peak molecular weight of 7150, Mw of 25000, Mw / Mn of 3.4, an acid value of 29.3 mgKOH / g, and Tg of 60 ° C. there were.
[0211]
(2) Manufacture of hybrid resin components
80 parts by mass of the polyester resin (ER) was dissolved and swollen in 100 parts by mass of xylene. Next, 15 parts by mass of styrene, 5 parts by mass of 2-ethylhexyl acrylate, 7 parts by mass of wax (1) and 0.1 part by mass of dibutyltin oxide as an esterification catalyst were added and heated to the reflux temperature of xylene to obtain a polyester resin. The transesterification reaction of the carboxylic acid and 2-ethylhexyl acrylate was started. Further, a xylene solution prepared by dissolving 1 part by mass of t-butyl hydroperoxide in 30 parts by mass of xylene as a radical polymerization initiator was dropped over about 1 hour. The radical polymerization reaction is terminated by holding at that temperature for 6 hours, and the solvent is removed by heating to 210 ° C. under reduced pressure, whereby 2-ethylhexyl acrylate, which is a copolymerization monomer of the hydroxyl group of the polyester resin and the vinyl polymer unit, is obtained. A binder resin having a polyester resin, a vinyl polymer, a hybrid resin formed by ester bonding of the polyester unit and the vinyl polymer unit, and a wax (1). Obtained the resin composition (H-1) which mixed uniformly.
[0212]
The obtained resin composition (H-1) has an acid value of 28 mgKOH / g, a Tg of 59 ° C., a main peak molecular weight of 7300, a weight average molecular weight (Mw) of 43,000, and Mw / Mn of 8.5, about 13% by mass of THF-insoluble content.
[0213]
Resin production examples 2-5
In Resin Production Example 1, resin compositions (H-2) to (H-) were similarly prepared except that 7 parts by mass of each of the waxes (2) to (5) shown in Table 4 was added instead of the wax (1). 5) was obtained.
[0214]
Resin production example 6
In Resin Production Example 1, a resin composition (H-6) was prepared in the same manner except that 3 parts by mass of wax (1) and 3 parts by mass of wax (3) shown in Table 4 were added instead of wax (1). Obtained.
[0215]
Resin production example 7
In Resin Production Example 1, a resin composition (H-7) was prepared in the same manner except that 3 parts by mass of wax (3) and 3 parts by mass of wax (5) shown in Table 4 were added instead of wax (1). Obtained.
[0216]
Resin production example 8
In Resin Production Example 1, a resin composition (H-8) was obtained in the same manner except that the wax (1) was not added during the production of the hybrid resin.
[0217]
Resin production example 9
A resin composition (H-9) was obtained in the same manner except that the monomers constituting the polyester resin used in Production Example 1 were as follows.
・ Terephthalic acid: 6.0 mol
・ Dodecenyl succinic anhydride: 1.0 mol
・ Fumaric acid: 2.0 mol
・ Trimellitic anhydride: 6.0 mol
・ PO-BPA: 7.0 mol
・ EO-BPA: 3.0 mol
The obtained resin composition (H-9) has an acid value of 46 mgKOH / g, Tg of 57 ° C., a main peak molecular weight of 10600, a weight average molecular weight (Mw) of 167,000, and Mw / Mn of 42. Yes, it contained about 15% by mass of THF-insoluble matter.
[0218]
Resin production example 10
Resin composition (H-10) was similarly prepared except that the polyester resin (1) used in Production Example 1 was 90 parts by mass, the vinyl monomer was 7 parts by mass of styrene and 3 parts by mass of 2-ethylhexyl acrylate. Got.
[0219]
The obtained resin composition (H-10) has an acid value of 35 mgKOH / g, Tg of 61 ° C., a main peak molecular weight of 8300, a weight average molecular weight (Mw) of 419000, and Mw / Mn of 18. Yes, it contained about 12% by mass of THF-insoluble matter.
[0220]
Resin production example 11
Resin composition as in Production Example 1 except that the polyester resin (1) used in Production Example 1 is 50 parts by mass and the vinyl monomer is 35 parts by mass of styrene and 15 parts by mass of 2-ethylhexyl acrylate. (H-11) was obtained.
[0221]
The obtained resin composition (H-11) has an acid value of 16 mgKOH / g, a Tg of 60 ° C., a main peak molecular weight of 6400, a weight average molecular weight (Mw) of 1,360,000, and Mw / Mn of 215. It contained about 6% by mass of THF-insoluble matter.
[0222]
Resin production example 12
A polyester monomer and a vinyl monomer shown below together with an esterification catalyst, a four-necked flask equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device at a temperature of 130 ° C. in a nitrogen atmosphere The mixture was added dropwise from the dropping funnel over 4 hours while stirring.
Polyester monomer
・ PO-BPA (propoxylated bisphenol A) 3.0 mol
・ EO-BPA (ethoxylated bisphenol A) 1.3 mol
・ Terephthalic acid 1.7mol
・ Trimellitic anhydride 1.2 mol
・ Dodecenyl succinic anhydride 1.5 mol
Vinyl monomer
・ Styrene 4.5 mol
・ 2-ethylhexyl acrylate 0.56mol
・ Azobisisobutyronitrile (vinyl polymerization initiator) 0.12 mol
The four-necked flask was further heated for 3 hours while maintaining the temperature at 130 ° C. (end of the vinyl polymerization reaction), and then the condensation polymerization reaction was performed while the temperature was raised to 230 ° C. and the pressure was reduced. After completion of the reaction, it was taken out from the container, cooled and pulverized to obtain a resin composition (H-12) comprising a polyester resin, a vinyl polymer, and a hybrid resin having a polyester unit and a vinyl polymer unit. The resin composition (H-12) has an acid value of 22 mgKOH / g, a Tg of 60.5 ° C., a main peak molecular weight of 8700, a weight average molecular weight (Mw) of 75000, Mw / Mn of 20, THF The insoluble content was 22% by mass.
[0223]
Comparative production example
A styrene copolymer (SR) consisting of 84 parts by mass of styrene and 16 parts by mass of 2-ethylhexyl acrylate (number average molecular weight 8000) is placed in an autoclave equipped with a decompression device, a water separation device, a nitrogen gas inlet tube, a temperature measuring device and a stirring device. Mw / Mn = 2.7) In the presence of 200 parts by mass, 250 parts by mass of terephthalic acid, 30 parts by mass of trimellitic acid, 193 parts by mass of EO-BPA, 840 parts by mass of PO-BPA and 2 parts by mass of dibutyltin oxide were charged. A comparative resin composition (RH-1) was obtained by performing a condensation polymerization reaction while heating to 200 ° C. under reduced pressure in an atmosphere.
[0224]
The obtained comparative resin composition (RH-1) has an acid value of 1 mgKOH / g, Tg of 61.4 ° C., a peak molecular weight of 20800, a weight average molecular weight (Mw) of 45,000, and Mw / Mn of It was 6.3, the THF-insoluble content was 1% by mass or less, and no hybrid resin was contained.
[0225]
Example 1
-Resin composition (H-1) 100 mass parts
・ Sulfur-containing polymer (S-1) 2 parts by mass
Charge control agent (organoaluminum compound consisting of 2 mol of 3,5-di-tert-butylsalicylic acid and aluminum atoms) 1 part by mass
Magnetic iron oxide (average particle size 0.18 μm, coercive force 10.7 kA / m, remanent magnetization 11.2 Am²/ Kg, saturation magnetization 81.5Am²/ Kg) 90 parts by mass
The above mixture was melt-kneaded with a twin-screw kneader heated to 130 ° C., and the cooled mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized with a turbo mill T-250 type (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified with an air classifier. Particles having a weight average diameter of 7.7 μm, 10.1 μm or more Magnetic toner particles having a volume of 6% by volume were obtained.
[0226]
Hydrophobic dry silica fine powder (BET specific surface area: 200 m) with respect to 100 parts by mass of the magnetic toner particles²/ G) 1.0 part by mass was externally added with a Henschel mixer to obtain a magnetic toner (1). Table 5 shows the physical properties of the magnetic toner (1). The developing property and the fixing property were evaluated using the magnetic toner (1).
[0227]
The toner developability was evaluated by using a Canon digital copying machine iR-6000, which employs an electrophotographic process and a heat and pressure fixing method, in a high-temperature and high-humidity environment (30 ° C., 80%). Durability image evaluation tests were conducted to evaluate image fogging, image quality, and image density stability.
[0228]
Image fog measurement and evaluation rank
Measure the reflectivity (%) of the white part (non-image part) of the image to be evaluated for fog and the reflectivity (%) of the unused paper with a reflection measuring machine REFECTMETETER (Tokyo Denshoku Co., Ltd.). The difference between the two (unused paper reflectance-image white portion reflectance) is defined as fog (%).
Rank 5: fog less than 0.1%
Rank 4: fog 0.1 or more and less than 0.5%
Rank 3: fog 0.5 to less than 1.5%
Rank 2: fog 1.5 to less than 2.0%
Rank 1: fog 2.0% or more
[0229]
Image quality evaluation method and evaluation rank
Rank 5: The image is faithful to the original.
Rank 4: When the image is enlarged with a magnifying glass, some scattering is seen
Rank 3: When the image is enlarged with a magnifying glass, scattering and turbulence are seen
Rank 2: Scattering and image distortion can be seen by visual inspection.
Rank 1: The original is not reproduced.
[0230]
Image density stability of toner
The toner image density stability was determined by conducting a durability test of 100,000 sheets in a normal temperature and humidity environment (23 ° C., 60%) using a Canon digital copying machine iR-6000. The final image density (F) Measure it. The developing unit is removed from the copying machine and left in a high-temperature and high-humidity chamber (30 ° C., 80%) environment for 48 hours. When leaving the developing device in a high temperature and high humidity environment, the developing device is packed to prevent condensation, and then opened after temperature control and humidity control for 5 hours or more. After leaving, the developing device is taken out in a normal temperature and humidity environment, and the developing device is installed in iR-6000. After rotating the developing sleeve for 1 minute, 10 evaluation images are sampled, and the average value of the image density is defined as the density after leaving (R), and the difference between the image density before leaving (F) and the image density after leaving (R) (R) The toner charging performance was evaluated by (F)-(R)). The evaluation rank is shown below.
Rank 5: The value of (F)-(R) is from 0 to less than 0.05
Rank 4: The value of (F)-(R) is 0.05 or more and less than 0.10
Rank 3: The value of (F)-(R) is 0.10 or more and less than 0.15
Rank 2: The value of (F)-(R) is 0.15 or more and less than 0.20
Rank 1: (F)-(R) value is 0.20 or more
[0231]
Toner fixability evaluation
Toner fixability is determined by removing the fixing device of Canon copier NP6085 and changing the temperature of the fixing device with a fixing test device to which an external drive device and a temperature control device for the fixing device are attached. : 0.6), and the fixing property test was conducted.
[0232]
The minimum fixing temperature is 4900 N / m for fixed images.²(50 g / cm²), The fixed image was rubbed with soft thin paper, and the temperature before and after that was such that the rate of decrease in image density was 20% or less. The fixing upper limit temperature was evaluated by visually observing the temperature at which hot offset occurred on the transfer paper.
[0233]
As shown in Table 7, the evaluation results are very good.
[0234]
  Reference Examples 2, 3, Example 4, Reference Examples 5, 6, and Example 7
  Magnetic toners (2) to (7) were produced in the same manner as in Example 1 except that the sulfur-containing copolymer shown in Table 3 was used. The physical properties of the obtained magnetic toner are shown in Tables 5 and 6. The magnetic toner was evaluated in the same manner as in Example 1. The results are shown in Table 7.
[0235]
Examples 8-13
Magnetic toners (8) to (13) were produced in the same manner as in Example 1 except that the resin compositions (H-2) to (H-7) were used as binder resins in Example 1. The physical properties of the obtained magnetic toner are shown in Tables 5 and 6. The magnetic toner was evaluated in the same manner as in Example 1. The results are shown in Table 7.
[0236]
Example 14
In Example 1, the magnetic toner (14) was produced in the same manner as in Example 1 except that the resin composition (H-8) was used as the binder resin and 7 parts by mass of the wax (3) was added during kneading. . The physical properties of the obtained magnetic toner are shown in Tables 5 and 6. The magnetic toner was evaluated in the same manner as in Example 1. The results are shown in Table 7.
[0237]
Examples 15-17
In Example 1, magnetic toners (15) to (17) shown in Table 5 were produced in the same manner as in Example 1 except that the binder resin and the toner particle size were changed. The physical properties of the obtained magnetic toner are shown in Tables 5 and 6. The magnetic toner was evaluated in the same manner as in Example 1. The results are shown in Table 7.
[0238]
Examples 18-20
In Example 1, magnetic toners (18) to (20) were produced in the same manner except that the addition amount of the sulfur-containing copolymer was changed. The physical properties of the obtained magnetic toner are shown in Tables 5 and 6. Table 7 shows the evaluation results of the magnetic toner.
[0239]
  Reference Example 21
  In Example 1, except that the charge control agent (organoaluminum compound consisting of 2 mol of 3,5-di-t-butylsalicylic acid and 1 mol of aluminum atom) was not used, A magnetic toner (21) shown in FIG. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 7.
[0240]
  Reference Examples 22-24
  Magnetic toners (22) to (24) were produced in the same manner as in Example 1 except that the sulfur-containing polymers (S-8) to (S-10) were used. The physical properties of the obtained magnetic toner are shown in Tables 5 and 6. Table 7 shows the evaluation results of the magnetic toner.
[0241]
Comparative Example 1
A comparative magnetic toner (1) was produced in the same manner as in Example 1 except that the comparative binder resin (RH-1) was used. The physical properties of the obtained comparative magnetic toner are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.
[0242]
Comparative Example 2
In Example 1, it does not contain a sulfur-containing copolymer, and as a charge control agent, a comparative magnetism is similarly obtained except that an organozinc compound composed of (3,5-di-t-butylsalicylic acid and a zinc atom is used. Toner (2) was produced, the physical properties of the comparative magnetic toner (2) obtained are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.
[0243]
Comparative Example 3
A comparative magnetic toner (3) was produced in the same manner as in Example 14 except that the polyester resin (PE) (Mw = 25000) produced in Resin Production Example 1 was used as the binder resin. The physical properties of the comparative magnetic toner (3) obtained are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.
[0244]
Comparative Example 4
Except for using the styrene-2-ethylhexyl acrylate copolymer (SR) (copolymerization mass ratio = 84: 16; Mn = 8000, Mw / Mn = 2.7) used in the comparative production example as a binder resin, Comparative magnetic toner (4) was produced in the same manner as in Example 14. The physical properties of the comparative magnetic toner (4) obtained are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.
[0245]
Example 25
In Example 1, a magnetic toner (25) was produced in the same manner as in Example 1 except that the binder resin was changed to the resin composition (H-12). The physical properties of the obtained magnetic toner are shown in Tables 5 and 6. The magnetic toner was evaluated in the same manner as in Example 1. The results are shown in Table 7.
[0246]
[Table 3]

[0247]
[Table 4]

[0248]
[Table 5]

[0249]
[Table 6]

[0250]
[Table 7]

[0251]
【The invention's effect】
INDUSTRIAL APPLICABILITY The present invention can provide a toner having improved triboelectric charge-up characteristics, excellent charging stability, excellent multi-sheet durability, high image density, and excellent low-temperature fixability and high-temperature offset resistance. .
[Brief description of the drawings]
FIG. 1 is a schematic view showing an example of a developer supply system developing device (a magnetic blade is used as a regulating member) used in an image forming apparatus in which the toner of the present invention is used and incorporating a developer carrier. .
FIG. 2 is a schematic diagram showing an example of a developer supply system developing device (using an elastic blade as a regulating member) used in an image forming apparatus in which the toner of the present invention is used, in which a developer carrier is incorporated. .
FIG. 3 is a schematic cross-sectional view of a part of a developer carrying member of a developing device applied to an image forming apparatus in which the toner of the present invention is used.
FIG. 4 is a schematic explanatory diagram of an image forming method to which the toner of the present invention can be applied.
FIG. 5 is a schematic view of a fixing device applicable to the image forming method of the present invention.
FIG. 6 is a schematic explanatory view showing an example of a process cartridge according to the present invention.
[Explanation of symbols]
7 Photoconductor
8 layer regulating member
9 Hopper
10 Toner
11 Magnet
14 Development sleeve

Claims (16)

In a toner having toner particles and inorganic fine powder containing at least a binder resin, a colorant, a sulfur-containing resin and a wax,
(A) The sulfur-containing resin is a copolymer of an acrylamide sulfonic acid monomer and a vinyl monomer, and has a weight average molecular weight of 17,000 to 100,000,
(B) the binder resin contains a hybrid resin component having a vinyl polymer unit and a polyester unit;
(C) The toner particles are produced by melt-kneading the binder resin containing the hybrid resin component, the colorant, the sulfur-containing resin and the mixture containing at least the wax, and then pulverizing the mixture. And
( D ) The THF soluble content of the binder resin in the toner has a peak at a molecular weight of 2000 to 15000 in the molecular weight distribution measured by gel permeation chromatography (GPC), and the Z average molecular weight (Mz) is 2.0. A toner, which is 10 ⁸ or less and has a ratio (Mz / Mw) of Z average molecular weight (Mz) to weight average molecular weight (Mw) of 20 to 120.   The toner according to claim 1, wherein the sulfur-containing resin is a copolymer of 2-acrylamido-2-methylpropanesulfonic acid and a vinyl monomer.   The toner according to claim 1, wherein the toner contains 0.5 to 5 parts by mass of the sulfur-containing resin with respect to 100 parts by mass of the binder resin.   4. The toner according to claim 1, wherein the sulfur-containing resin has a weight average molecular weight (Mw) of 27,000 to 50,000.   The toner according to any one of claims 1 to 4, wherein the sulfur-containing resin has a glass transition temperature (Tg) of 50 to 100 ° C.   The toner according to any one of claims 1 to 4, wherein the sulfur-containing resin has a glass transition temperature (Tg) of 72 to 95 ° C.   The toner according to claim 1, wherein the binder resin of the toner contains 50 to 95% by mass of a polyester unit.   7. The toner according to claim 1, wherein the binder resin of the toner contains 65 to 85% by mass of a polyester unit. The THF soluble content of the binder resin of the toner has a peak at a molecular weight of 4000 to 12000 in the molecular weight distribution measured by gel permeation chromatography (GPC), and the Z average molecular weight (Mz) is 1.5 ×. The toner according to claim 1, wherein the toner is 10 ⁸ or less, and a ratio (Mz / Mw) of a Z average molecular weight (Mz) to a weight average molecular weight (Mw) is 30 to 100. The THF soluble content of the binder resin of the toner has a peak at a molecular weight of 6000 to 10,000 in the molecular weight distribution measured by gel permeation chromatography (GPC), and the Z average molecular weight (Mz) is 1.0 ×. The toner according to claim 1, wherein the toner is 10 ⁸ or less, and a ratio (Mz / Mw) of a Z average molecular weight (Mz) to a weight average molecular weight (Mw) is 40 to 80.   11. The wax contained in the toner has a main peak at a molecular weight of 700 to 5,000, and a ratio (Mw / Mn) of 1.2 to 15. toner.   12. The toner according to claim 1, wherein at least one endothermic peak is observed in the toner when the temperature is raised by a differential scanning calorimeter (DSC) in a temperature range of 70 to 150.degree. Toner.   12. The toner according to claim 1, wherein at least one endothermic peak is observed in the toner when the temperature is raised by a differential scanning calorimeter (DSC) in a temperature range of 75 to 130 ° C. 12. Toner.   14. The toner according to claim 1, wherein the toner has a weight average diameter of 5.5 to 8 μm, and contains less than 10% by volume of particles having a particle diameter of 10.1 μm or more in the particle size distribution of the toner. The toner described. (I) a developing step of developing a toner image by developing the electrostatic image carried on the image carrier for carrying the electrostatic image with a negative triboelectrically charged toner;
(II) a transfer step in which the toner image formed on the image carrier is transferred to a recording material via or without an intermediate transfer member; and (III) the toner image transferred to the recording material is recorded. Fixing process for heat fixing to the material;
In an image forming method having
The image forming method according to claim 1, wherein the toner is the toner according to claim 1. At least an image carrier, a developing unit for developing the electrostatic image formed on the image carrier with dry toner, and a container for holding the dry toner,
The image carrier, the developing means, and the container are process cartridges having a configuration in which they are supported integrally.
The process cartridge is detachable from the image forming apparatus main body,
The process cartridge according to claim 1, wherein the toner is the toner according to claim 1.

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