JP4143484B2 - Two-component developer - Google Patents

Description

（式中、Ｒはエチレン又はプロピレン基を示し、ｘ，ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。）
【００７５】
さらに本発明において、結着樹脂としてポリエステルユニットとビニル系重合体ユニットを有しているハイブリッド樹脂を用いる場合、さらに良好な離型剤分散性と、低温定着性，耐オフセット性の向上が期待できる。
【００７６】
ビニル系樹脂を生成するためのビニル系モノマーとしては、次のようなものが挙げられる。スチレン；ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、α−メチルスチレン、ｐ−フェニルスチレン、ｐ−エチルスチレン、２，４−ジメチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−デシルスチレン、ｐ−ｎ−ドデシルスチレン、ｐ−メトキシスチレン、ｐ−クロルスチレン、３，４−ジクロルスチレン、ｍ−ニトロスチレン、ｏ−ニトロスチレン、ｐ−ニトロスチレンの如きスチレン及びその誘導体；エチレン、プロピレン、ブチレン、イソブチレンの如きスチレン不飽和モノオレフィン類；ブタジエン、イソプレンの如き不飽和ポリエン類；塩化ビニル、塩化ビニルデン、臭化ビニル、フッ化ビニルの如きハロゲン化ビニル類；酢酸ビニル、プロピオン酸ビニル、ベンゾエ酸ビニルの如きビニルエステル類；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸ｎ−オクチル、メタクリル酸ドデシル、メタクリル酸２−エチルヘキシル、メタクリル酸ステアリル、メタクリル酸フェニル、メタクリル酸ジメチルアミノエチル、メタクリル酸ジエチルアミノエチルの如きα−メチレン脂肪族モノカルボン酸エステル類；アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸ｎ−オクチル、アクリル酸ドデシル、アクリル酸２−エチルヘキシル、アクリル酸ステアリル、アクリル酸２−クロルエチル、アクリル酸フェニルの如きアクリル酸エステル類；ビニルメチルエーテル、ビニルエチルエーテル、ビニルイソブチルエーテルの如きビニルエーテル類；ビニルメチルケトン、ビニルヘキシルケトン、メチルイソプロペニルケトンの如きビニルケトン類；Ｎ−ビニルピロール、Ｎ−ビニルカルバゾール、Ｎ−ビニルインドール、Ｎ−ビニルピロリドンの如きＮ−ビニル化合物；ビニルナフタリン類；アクリロニトリル、メタクリロニトリル、アクリルアミドの如きアクリル酸もしくはメタクリル酸誘導体等が挙げられる。
【００７７】
さらに、マレイン酸、シトラコン酸、イタコン酸、アルケニルコハク酸、フマル酸、メサコン酸の如き不飽和二塩基酸；マレイン酸無水物、シトラコン酸無水物、イタコン酸無水物、アルケニルコハク酸無水物の如き不飽和二塩基酸無水物；マレイン酸メチルハーフエステル、マレイン酸エチルハーフエステル、マレイン酸ブチルハーフエステル、シトラコン酸メチルハーフエステル、シトラコン酸エチルハーフエステル、シトラコン酸ブチルハーフエステル、イタコン酸メチルハーフエステル、アルケニルコハク酸メチルハーフエステル、フマル酸メチルハーフエステル、メサコン酸メチルハーフエステルの如き不飽和二塩基酸のハーフエステル；ジメチルマレイン酸、ジメチルフマル酸の如き不飽和二塩基酸エステル；アクリル酸、メタクリル酸、クロトン酸、ケイヒ酸の如きα，β−不飽和酸；クロトン酸無水物、ケイヒ酸無水物の如きα，β−不飽和酸無水物、該α，β−不飽和酸と低級脂肪酸との無水物；アルケニルマロン酸、アルケニルグルタル酸、アルケニルアジピン酸、これらの酸無水物及びこれらのモノエステルの如きカルボキシル基を有するモノマーが挙げられる。
【００７８】
さらに、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレートなどのアクリル酸またはメタクリル酸エステル類；４−（１−ヒドロキシ−１−メチルブチル）スチレン、４−（１−ヒドロキシ−１−メチルヘキシル）スチレンの如きヒドロキシ基を有するモノマーが挙げられる。
【００７９】
本発明でいう結着樹脂のビニル系重合体ユニットは、ビニル基を２個以上有する架橋剤で架橋された架橋構造を有していてもよい。この場合に用いられる架橋剤としては、以下のものが挙げられる。
【００８０】
芳香族ジビニル化合物として例えば、ジビニルベンゼン、ジビニルナフタレンが挙げられ；アルキル鎖で結ばれたジアクリレート化合物類として例えば、エチレングリコールジアクリレート、１，３−ブチレングリコールジアクリレート、１，４−ブタンジオールジアクリレート、１，５−ペンタンジオールジアクリレート、１，６ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられ；エーテル結合を含むアルキル鎖で結ばれたジアクリレート化合物類としては、例えば、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコール＃４００ジアクリレート、ポリエチレングリコール＃６００ジアクリレート、ジプロピレングリコールジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられ；芳香族基及びエーテル結合を含む鎖で結ばれたジアクリレート化合物類として例えば、ポリオキシエチレン（２）−２，２−ビス（４−ヒドロキシフェニル）プロパンジアクリレート、ポリオキシエチレン（４）−２，２−ビス（４−ヒドロキシフェニル）プロパンジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられる。
【００８１】
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。
【００８２】
本発明ではビニル系重合体成分及び／又はポリエステル樹脂成分中に、両樹脂成分と反応し得るモノマー成分を含むことが好ましい。ポリエステル樹脂成分を構成するモノマーのうちビニル系重合体と反応し得るものとしては、例えば、フタル酸、マレイン酸、シトラコン酸、イタコン酸の如き不飽和ジカルボン酸又はその無水物などが挙げられる。ビニル系重合体成分を構成するモノマーのうちポリエステル樹脂成分と反応し得るものとしては、カルボキシル基又はヒドロキシ基を有するものや、アクリル酸もしくはメタクリル酸エステル類が挙げられる。
【００８３】
ビニル系重合体とポリエステル樹脂の反応生成物を得る方法としては、先に挙げたビニル系重合体及びポリエステル樹脂のそれぞれと反応しうるモノマー成分を含むポリマーが存在しているところで、どちらか一方もしくは両方の樹脂の重合反応をさせることにより得る方法が好ましい。
【００８４】
本発明のビニル重合体を製造する場合に用いられる重合開始剤としては、例えば、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２’−アゾビス（−２，４−ジメチルバレロニトリル）、２，２’−アゾビス（−２メチルブチロニトリル）、ジメチル−２，２’−アゾビスイソブチレート、１，１’−アゾビス（１−シクロヘキサンカルボニトリル）、２−（カーバモイルアゾ）−イソブチロニトリル、２，２’−アゾビス（２，４，４−トリメチルペンタン）、２−フェニルアゾ−２，４−ジメチル−４−メトキシバレロニトリル、２，２’−アゾビス（２−メチル−プロパン）、メチルエチルケトンパーオキサイド、アセチルアセトンパーオキサイド、シクロヘキサノンパーオキサイドの如きケトンパーオキサイド類、２，２−ビス（ｔ−ブチルパーオキシ）ブタン、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、１，１，３，３−テトラメチルブチルハイドロパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルクミルパーオキサイド、ジ−クミルパーオキサイド、α，α’−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン、イソブチルパーオキサイド、オクタノイルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、３，５，５−トリメチルヘキサノイルパーオキサイド、ベンゾイルパーオキサイド、ｍ−トリオイルパーオキサイド、ジ−イソプロピルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ジ−ｎ−プロピルパーオキシジカーボネート、ジ−２−エトキシエチルパーオキシカーボネート、ジ−メトキシイソプロピルパーオキシジカーボネート、ジ（３−メチル−３−メトキシブチル）パーオキシカーボネート、アセチルシクロヘキシルスルホニルパーオキサイド、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシネオデカノエイト、ｔ−ブチルパーオキシ２−エチルヘキサノエイト、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシベンゾエイト、ｔ−ブチルパーオキシイソプロピルカーボネート、ジ−ｔ−ブチルパーオキシイソフタレート、ｔ−ブチルパーオキシアリルカーボネート、ｔ−アミルパーオキシ２−エチルヘキサノエート、ジ−ｔ−ブチルパーオキシヘキサハイドロテレフタレート，ジ−ｔ−ブチルパーオキシアゼレートがあげられる。
【００８５】
次に、本発明の結着樹脂に用いられるハイブリッド樹脂の製造方法を説明する。以下の（１）〜（６）に示す製造方法等で本発明のハイブリッド樹脂が製造できる。
【００８６】
（１）ビニル系重合体、ポリエステル樹脂及びハイブリッド樹脂成分をそれぞれ製造後にブレンドする方法であり、ブレンドは有機溶剤（例えば、キシレン）に溶解・膨潤した後に有機溶剤を留去して製造される。尚、ハイブリッド樹脂成分は、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。
【００８７】
（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。
【００８８】
（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。
【００８９】
（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が製造される。この場合も適宜、有機溶剤を使用することができる。
【００９０】
（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）〜（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。
【００９１】
（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。
【００９２】
上記（１）〜（５）の製造方法において、ビニル系重合体ユニット及び／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。
【００９３】
なお、本発明のトナーに含有される結着樹脂は、上記ポリエステルとビニル系重合体との混合物、上記ハイブリッド樹脂とビニル系重合体との混合物、上記ポリエステル樹脂と上記ハイブリッド樹脂に加えてビニル系重合体の混合物を使用しても良い。好ましくはハイブリッド樹脂を含有することである。
【００９４】
本発明のトナーに含有される結着樹脂のガラス転移温度は４０〜９０℃が好ましく、より好ましくは４５〜８５℃である。結着樹脂の酸価は１〜４０ｍｇＫＯＨ／ｇであることが好ましい。
【００９５】
尚、本発明において、結着樹脂中のポリエステルユニットの占める割合は、５０〜１００（％）の範囲であるとよい。
【００９６】
次に、本発明に用いられる離型剤としては次のものが挙げられる。
【００９７】
低分子量ポリエチレン、低分子量ポリプロピレン、マイクロクリスタリンワックス、パラフィンワックス、フィッシャートロプシュワックスの如き脂肪族炭化水素系ワックス；酸化ポリエチレンワックスの如き脂肪族炭化水素系ワックスの酸化物；脂肪族炭化水素系ワックスのブロック共重合物；カルナバワックス、モンタン酸エステルワックス、キャンデリラワックス、ライスワックス、オゾケライト、みつろうの如き脂肪酸エステルを主成分とするワックス；及び脱酸カルナバワックスの如き脂肪酸エステルを一部または全部を脱酸化したものなどが挙げられる。
【００９８】
さらに、離型剤として、パルミチン酸、ステアリン酸、モンタン酸の如き飽和直鎖脂肪酸；ブラシジン酸、エレオステアリン酸、バリナリン酸の如き不飽和脂肪酸；ステアリルアルコール、アラルキルアルコール、ベヘニルアルコール、カルナウビルアルコール、セリルアルコール、メリシルアルコールの如き飽和アルコール；ソルビトールの如き多価アルコール；リノール酸アミド、オレイン酸アミド、ラウリン酸アミドの如き脂肪酸アミド；メチレンビスステアリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、ヘキサメチレンビスステアリン酸アミドの如き飽和脂肪酸ビスアミド；エチレンビスオレイン酸アミド、ヘキサメチレンビスオレイン酸アミド、Ｎ，Ｎ’−ジオレイルアジピン酸アミド、Ｎ，Ｎ’−ジオレイルセバシン酸アミドの如き不飽和脂肪酸アミド；ｍ−キシレンビスステアリン酸アミド、Ｎ，Ｎ’−ジステアリルイソフタル酸アミドの如き芳香族系ビスアミド；ステアリン酸カルシウム、ラウリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸マグネシウムの如き脂肪酸金属塩（一般に金属石けんといわれているもの）；脂肪族炭化水素系ワックスにスチレンやアクリル酸の如きビニルモノマーをグラフト化させたグラフトワックス；ベヘニン酸モノグリセリドの如き脂肪酸と多価アルコールの部分エステル化物；植物性油脂を水素添加することによって得られるヒドロキシル基を有するメチルエステル化合物などが挙げられる。
【００９９】
特に好ましく用いられるワックスとしては、分子鎖が短く、且つ立体障害が少なくモビリティに優れる、パラフィンワックスである。
【０１００】
ワックスの分子量分布では、メインピークが分子量３５０〜２４００の領域にあることが好ましく、４００〜２０００の領域にあることがより好ましい。このような分子量分布をもたせることによりトナーに好ましい熱特性を付与することができる。
【０１０１】
本発明に用いられる離型剤の添加量としては、結着樹脂１００質量部に対し、１〜１０質量部、好ましくは２〜８質量部含有させるとよい。１質量部より少ないと、溶融時にトナー表面に出て離型性を発揮させるには量が少ないため、かなりの熱量及び圧力が必要となるからである。逆に１０質量部を超えるとトナー中での離型剤量が多すぎ、透明性や帯電特性が劣ってしまうからである。
【０１０２】
次に、本発明のトナーに含有させる着色剤について説明する。
【０１０３】
本発明に用いられる着色剤としては、顔料及び／又は染料を用いることができる。
【０１０４】
マゼンタ用着色顔料としては、Ｃ．Ｉ．ピグメントレッド１，２，３，４，５，６，７，８，９，１０，１１，１２，１３，１４，１５，１６，１７，１８，１９，２１，２２，２３，３０，３１，３２，３７，３８，３９，４０，４１，４８，４９，５０，５１，５２，５３，５４，５５，５７，５８，６０，６３，６４，６８，８１，８３，８７，８８，８９，９０，１１２，１１４，１２２，１２３，１６３，２０２，２０６，２０７，２０９、Ｃ．Ｉ．ピグメントバイオレット１９、Ｃ．Ｉ．バットレッド１，２，１０，１３，１５，２３，２９，３５等が挙げられる。
【０１０５】
かかる顔料を単独で使用しても構わないが、染料と顔料と併用してその鮮明度を向上させた方がフルカラー画像の画質の点からより好ましい。
【０１０６】
マゼンタ用染料としては、Ｃ．Ｉ．ソルベントレッド１，３，８，２３，２４，２５，２７，３０，４９，８１，８２，８３，８４，１００，１０９，１２１、Ｃ．Ｉ．ディスパースレッド９、Ｃ．Ｉ．ソルベントバイオレット８，１３，１４，２１，２７、Ｃ．Ｉ．ディスパースバイオレット１等の油溶染料、Ｃ．Ｉ．ベーシックレッド１，２，９，１２，１３，１４，１５，１７，１８，２２，２３，２４，２７，２９，３２，３４，３５，３６，３７，３８，３９，４０、Ｃ．Ｉ．ベーシックバイオレット１，３，７，１０，１４，１５，２１，２５，２６，２７，２８等の塩基性染料が挙げられる。
【０１０７】
その他の着色顔料である、シアン用着色顔料としては、Ｃ．Ｉ．ピグメントブルー２，３，１５，１６，１７、Ｃ．Ｉ．バットブルー６、Ｃ．Ｉ．アシッドブルー４５又はフタロシアニン骨格にフタルイミドメチル基を１〜５個置換した銅フタロシアニン顔料等が挙げられる。
【０１０８】
また、イエロー用着色顔料としては、Ｃ．Ｉ．ピグメントイエロー１，２，３，４，５，６，７，１０，１１，１２，１３，１４，１５，１６，１７，２３，６５，７３，７４、８３、１５５、１８０、Ｃ．Ｉ．バットイエロー１，３，２０等が挙げられる。
【０１０９】
尚、着色剤の使用量は結着樹脂１００質量部に対して、０．１〜６０質量部、好ましくは０．５〜５０質量部含有させるとよい。
【０１１０】
また本発明のトナーは、公知の電荷制御剤と組み合わせて使用することもできる。
【０１１１】
本発明においては、必要に応じて有機金属化合物をトナーに含有して使用することができる。該有機金属化合物としては、芳香族オキシカルボン酸及び芳香族アルコキシカルボン酸から選択される芳香族カルボン酸誘導体の金属化合物であることが好ましく、その金属としては、２価以上の金属原子が好ましい。２価の金属としてＭｇ²⁺、Ｃａ²⁺、Ｓｒ²⁺、Ｐｂ²⁺、Ｆｅ²⁺、Ｃｏ²⁺、Ｎｉ²⁺、Ｚｎ²⁺、Ｃｕ²⁺が挙げられる。２価の金属としてはＺｎ²⁺、Ｃａ²⁺、Ｍｇ²⁺、Ｓｒ²⁺が好ましい。３価以上の金属としてはＡｌ³⁺、Ｃｒ³⁺、Ｆｅ³⁺、Ｎｉ³⁺が挙げられる。これらの金属の中で好ましいのはＡｌ³⁺、Ｃｒ³⁺であり、特に好ましいのはＡｌ³⁺である。
【０１１２】
具体的な金属化合物としては、以下の化合物が例示される。
【０１１３】
【化２】

【０１１４】
【化３】

【０１１５】
本発明においては、有機金属化合物として、ジ−ｔｅｒｔ−ブチルサリチル酸のアルミニウム化合物が特に好ましい。
【０１１６】
本発明に用いられる電荷制御剤の添加量としては、結着樹脂１００質量部に対し、０．３〜１０質量部、好ましくは０．５〜７質量部含有させるとよい。
【０１１７】
０．３未満であると帯電立ち上がりの効果が得られず、１０より多いと環境変動が大きくなるためである。
【０１１８】
また本発明のトナーは、流動化剤が含有されていてもよい。
【０１１９】
例えば、粉砕・分級工程を経た後、流動化剤などをヘンシェルミキサーの如き混合機で混合させると流動性が向上したトナーを得ることができる。
【０１２０】
流動化剤としては、着色剤含有結着樹脂粒子に添加することにより、流動性が添加前後を比較すると増加し得るものであれば、どのようなものでも使用可能である。例えば、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等のフッ素系樹脂粉末、酸化チタン微粉末、アルミナ微粉末、湿式製法シリカ、乾式製法シリカ等の微粉末シリカ、それらをシラン化合物、及び有機ケイ素化合物、チタンカップリング剤、シリコーンオイル等により表面処理を施した処理シリカ等がある。
【０１２１】
上記乾式製法シリカとは、ケイ素ハロゲン化合物の蒸気相酸化により生成された微粉体であり、いわゆる乾式法シリカ又はヒュームドシリカと称されるもので、従来公知の技術によって製造されるものである。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。
ＳｉＣｌ₄＋２Ｈ₂＋Ｏ₂→ＳｉＯ₂＋４ＨＣｌ
【０１２２】
また、この製造工程において、例えば塩化アルミニウム又は塩化チタン等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り、それらも包含する。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望ましく、特に好ましくは、０．００２〜０．２μｍの範囲内のシリカ微粉体を使用するのが良い。
【０１２３】
また上記酸化チタン微粉体としては、硫酸法、塩素法、揮発性チタン化合物例えばチタンアルコキシド，チタンハライド，チタンアセチルアセトネートの低温酸化法（熱分解，加水分解）により得られる酸化チタン微粒子が用いられる。結晶系としてはアナターゼ型，ルチル型，これらの混晶型，アモルファスのいずれのものも用いることができる。
【０１２４】
また、上記アルミナ微粉体としては、バイヤー法、改良バイヤー法、エチレンクロルヒドリン法、水中火花放電法、有機アルミニウム加水分解法、アルミニウムミョウバン熱分解法、アンモニウムアルミニウム炭酸塩熱分解法、塩化アルミニウムの火焔分解法により得られるアルミナ微粉体が用いられる。結晶系としてはα，β，γ，δ，ζ，η，θ，κ，χ，ρ型、これらの混晶型、アモルファスのいずれのものも用いられ、α，δ，γ，θ，混晶型，アモルファスのものが好ましく用いられる。
【０１２５】
また、上記の表面処理を施されたシリカとしては、無機微粉体と反応あるいは物理吸着する有機ケイ素化合物等で化学的、または物理的に処理することにより得られるものが用いられる。具体的には、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。そのような有機ケイ素化合物の例としては、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等が挙げられる。これらは１種あるいは２種以上の混合物で用いられる。
【０１２６】
また、本発明に用いられる流動化剤として、前述した乾式製法シリカを、アミノ基を有するカップリング剤或いは、シリコーンオイルで処理して用いてもかまわない。
【０１２７】
本発明に用いられる流動化剤は、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。トナー１００質量部に対して流動化剤０．０１〜８質量部、好ましくは０．１〜４質量部含有させるとよい。
【０１２８】
次に本発明で用いられるキャリアについて説明する。
【０１２９】
本発明に用いられるキャリア芯材としては次のものが挙げられる。表面酸化または未酸化の鉄、ニッケル、銅、亜鉛、コバルト、マンガン、マグネシウム、クロム、希土類等の金属及びそれらの合金または酸化物及びフェライトなどが使用できる。また、その製造方法として特別な制約はない。この中でも特にフェライトがより好ましい。
【０１３０】
またキャリアの表面はキャリアコアの質量に対して０．０１〜２．０質量％の樹脂被覆層を有することがトナーへの帯電付与性、耐スペント性を考慮すると好ましい。より好ましくは０．０５〜１．０質量％である。
【０１３１】
本発明の樹脂被覆キャリアは、平均粒径が２５〜６５μｍ、より好ましくは３０〜６５μｍである。樹脂被覆キャリアの平均粒径が２５μｍ未満の場合には、現像剤の現像担持体上での磁気力による穂立ちが不均一で、ベタ画像の均質性がなくなる。樹脂被覆キャリアの平均粒径が６５μｍを超える場合には、磁性による現像剤立ちが高く、この穂による現像剤の掃きむらが生じる。粒径１６μｍより小さいキャリア粒子が２％以下であり、６２μｍ以上のキャリア粒子が０．２〜４５％であり、８８μｍ以上のキャリア粒子が１２％以下であることが現像剤の流動性や帯電性を考慮すると好ましい。
【０１３２】
本発明のキャリアの被覆用に用いられる樹脂としては、シリコーン系樹脂、アクリル変性シリコーン樹脂、エポキシ系樹脂、ポリエステル系樹脂、スチレン・アクリル系樹脂、メラミン系樹脂、フッ素系樹脂、フッ素・アクリル系樹脂等、およびこれらの樹脂の混合物が挙げられるが、特に好ましくは、シリコーン系樹脂、アクリル変性シリコーン樹脂、フッ素系樹脂、フッ素・アクリル系樹脂等が挙げられる。
【０１３３】
アクリル変性シリコーン樹脂としては、メタクリル酸エステル変性シリコーン樹脂、アクリル酸エステル変性シリコーン樹脂、スチレン−メタクリル酸エステル変性シリコーン樹脂及びスチレン−アクリル酸エステル変性シリコーン樹脂が挙げられる。これらは単独で又は複数を混合して用いることができる。
【０１３４】
より具体的には、シリコーン樹脂は、従来から知られているいずれのシリコーン樹脂であってもよく、下記式に示されるオルガノシロキサン結合のみからなるストレートシリコーン樹脂及びアルキッド、ポリエステル、エポキシ、ウレタンなどで変性したシリコーン樹脂等が挙げられる。
【０１３５】
【化４】

【０１３６】
上記式中Ｒ₁は、水素原子、炭素数１〜４のアルキル基又はフェニル基、Ｒ₂及びＲ₃は水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、フェニル基、炭素数２〜４のアルケニル基、炭素数２〜４のアルケニルオキシ基、ヒドロキシ基、カルボキシル基、エチレンオキシド基、グリジニル基又は下記で示される基である。
【０１３７】
【化５】

【０１３８】
上記式中Ｒ₄、Ｒ₅は、ヒドロキシ基、カルボキシル基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数２〜４のアルケニル基、炭素数２〜４のアルケニルオキシ基、フェニル基、フェノキシ基、ｋ、ｌ、ｍ、ｎ、ｏ、ｐは１以上の正数を示す。
【０１３９】
上記各置換基は未置換のもののほか、例えばアミノ基、ヒドロキシ基、カルボキシル基、メルカプト基、アルキル基、フェニル基、エチレンオキシド基、ハロゲン原子のような置換基を有してもよい。例えば、市販品としてストレートシリコーン樹脂は、信越化学社製のＫＲ２７１、ＫＲ２５５、ＫＲ１５２、東レダウコーニング社製のＳＲ２４００、ＳＲ２４０５等があり、変性シリコーン樹脂は、信越化学社製のＫＲ２０６（アルキッド変性）、ＫＲ５２０８（アクリル変性）、ＥＳ１００１Ｎ（エポキシ変性）、ＫＲ３０５（ウレタン変性）、東レダウコーニング社製のＳＲ２１１５（エポキシ変性）、ＳＲ２１１０（アルキッド変性）などがある。
【０１４０】
本発明においてキャリアコート樹脂には、カップリング剤を含有しても良い。用いられるカップリング剤としては、シランカップリング剤が用いられるが、そのほかチタンカップリング剤、アルミニウムカップリング剤等も挙げられる。本発明に好ましく用いられるシランカップリング剤としては、例えばγ−（２−アミノエチル）アミノプロピルトリメトキシシラン、γ−（２−アミノエチル）アミノプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン塩酸塩、γ−グリシドキシプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、ビニルトリアセトキシシラン、γ−クロロプロピルトリメトキシシラン、ヘキサメチルジシラザン、γ−アニリノプロピルトリメトキシシラン、ビニルトリメトキシシラン、オクタデシルジメチル〔３−（トリメトキシシリル）プロピル〕アンモニウムクロライド、γ−クロロプロピルメチルジメトキシシラン、メチルトリクロロシラン、ジメチルジクロロシラン、トリメチルクロロシラン、（以上トーレ・シリコーン社製）、アリルトリエトキシシラン、３−アミノプロピルメチルジエトキシシラン、３−アミノプロピルトリメトキシシラン、ジメチルジエトキシシラン、１，３−ジビニルテトラメチルジシラザン、メタクリルオキシエチルジメチル（３−トリメトキシシリルプロピル）アンモニウムクロライド（以上チッソ社製）等が挙げられる。
【０１４１】
本発明の樹脂微粒子に用いられる樹脂としては、下記に例示する重合性単量体を用いて、単独重合、又は共重合した重合体が挙げられる。かかる重合性単量体としては、スチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メトキシスチレン、ｐ−エチルスチレン、αメチルスチレン、ｐ−ターシャリーブチルスチレンなどのスチレン系単量体；アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブチル、アクリル酸ｎ−プロピル、アクリル酸イソブチル、アクリル酸オクチル、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、などのアクリル酸エステル類；メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−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メチル、メタクリル酸ジエチルアミノエチル等のメタクリル酸エステル類；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の他アクリロニトリル、メタクリロニトリル、アクリルアミド等；の他、ビニル誘導体、具体的には例えばメチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ｎ−ブチルエーテル、イソブチルエーテル等のアルキルビニルエーテル類、β−クロルエチルビニルエーテル、フェニルビニルエーテル、ｐ−メチルフェニルエーテル、ｐ−クロルフェニルエーテル、ｐ−ブロムフェニルエーテル、ｐ−ニトロフェニルビニルエーテル、ｐ−メトキシフェニルビニルエーテル、２−ビニルピリジン、３−ビニルピリジン、４−ビニルピリジン、Ｎ−ビニルピロリドン、２−ビニルイミダゾール、Ｎ−メチル−２−ビニルイミダゾール、Ｎ−ビニルイミダゾール、ブタジエン等を挙げることができる。特にポリメタクリル酸メチルやメラミン樹脂がより好ましい。前記ＰＭＭＡ粒子は公知のものを使用でき、目的とする電子写真現像用トナーに必要な材料を選択できるが、架橋型ＰＭＭＡ粒子を用いることが好ましい。
【０１４２】
また本発明に用いられる樹脂微粒子の造粒方法としては、上記の重合体を粉砕処理する方法や、乳化重合、ソープフリー乳化重合、懸濁重合、分散重合等の粒子重合方法等を用いることができる。
【０１４３】
樹脂微粒子の添加量はキャリアに被膜する樹脂層に対して０．１〜５０質量％で用いることが好ましい。より好ましくは、１．０〜４５質量％において、更に良好な効果を付与することができる。
【０１４４】
キャリア表面に樹脂層をコーティング方法としては、樹脂を溶剤に希釈し、キャリアコアの表面に被覆するのが一般的である。ここに用いられる溶剤は、各樹脂に可溶なものであればよく、有機溶剤に可溶性樹脂である場合は、有機溶剤として、トルエン、キシレン、セルソルブブチルアセテート、メチルエチルケトン、メチルイソブチルケトン、メタノールが挙げられ、水溶性樹脂またはエマルジョンタイプである場合には、水を用いればよい。キャリア芯材表面に、溶剤で希釈された樹脂を被覆させる方法は、浸漬法、スプレー法、ハケ塗り法及び混練法の如き塗布方法により塗布され、その後、溶剤を揮発させる。なお、このような溶剤を用いた湿式法ではなく、乾式法によってキャリア芯材表面に樹脂粉を被覆することも可能である。
【０１４５】
樹脂をキャリア芯材表面に被覆後、焼き付けする場合は、外部加熱方式または内部加熱方式のいずれでもよく、例えば固定式または流動式電気炉、ロータリー式電気炉、バーナー炉でもよく、もしくはマイクロウェーブによる焼き付けでもよい。焼き付けの温度は使用する樹脂により異なるが、融点またはガラス転移点以上の温度は必要であり、また熱硬化性樹脂または縮合型樹脂では、十分硬化が進む温度まで上げる必要がある。
【０１４６】
このようにして、キャリア芯材表面に樹脂が被覆・焼き付けされた後、冷却され、解砕、粒度調整を経て樹脂コーティングキャリアが得られる。
【０１４７】
樹脂微粒子はキャリア表面に存在していれば良いが、含有方法としては樹脂コーティング時に溶剤中に分散させてキャリア被覆樹脂と共にキャリア表面に分散させることが好ましい。この時分散させる溶剤としては樹脂微粒子が膨潤しないものを選択することが好ましい。
【０１４８】
本発明において二成分系現像剤を調製する場合、その混合比率は現像剤中のトナー濃度として、２〜１５質量％、好ましくは４〜１３質量％にすると通常良好な結果が得られる。トナー濃度が２質量％未満では画像濃度が低下しやすく、１５質量％を超えるとカブリや機内飛散が発生しやすい。
【０１４９】
＜本発明のトナーの製造方法について＞
次に、本発明のトナーを製造する手順について説明する。
【０１５０】
まず、原料混合工程では、トナー内添剤として、少なくとも結着樹脂、着色剤、離型剤を所定量秤量して配合し、混合する。混合装置の一例としては、ダブルコン・ミキサー、Ｖ型ミキサー、ドラム型ミキサー、スーパーミキサー、ヘンシェルミキサー、ナウターミキサー等が挙げられる。
【０１５１】
更に、上記で配合し、混合したトナー原料を溶融混練して、結着樹脂類を溶融し、その中に着色剤等を分散させる。その溶融混練工程では、例えば、加圧ニーダー、バンバリィミキサー等のバッチ式練り機や、連続式の練り機を用いることができる。近年では、連続生産できる等の優位性から、１軸または２軸押出機が主流となっており、例えば、神戸製鋼所社製ＫＴＫ型２軸押出機、東芝機械社製ＴＥＭ型２軸押出機、ケイ・シー・ケイ社製２軸押出機、ブス社製コ・ニーダー等が一般的に使用される。更に、トナー原料を溶融混練することによって得られる着色樹脂組成物は、溶融混練後、２本ロール等で圧延され、水冷等で冷却する冷却工程を経て冷却される。
【０１５２】
そして一般的には上記で得られた着色樹脂組成物の冷却物は、次いで、粉砕工程で所望の粒径にまで粉砕される。粉砕工程では、まず、クラッシャー、ハンマーミル、フェザーミル等で粗粉砕され、更に、川崎重工業社製のクリプトロンシステム、日清エンジニアリング社製のスーパーローター等で粉砕される。その後、必要に応じて慣性分級方式のエルボージェット（日鉄鉱業社製）、遠心力分級方式のターボプレックス（ホソカワミクロン社製）等の分級機等の篩分機を用いて分級し、重量平均粒径３〜１１μｍの分級品を得る。
【０１５３】
必要に応じて、表面改質工程で表面改質＝球形化処理、例えば奈良機械製作所製のハイブリタイゼーションシステム、ホソカワミクロン社製のメカノフージョンシステムを行い、分級品とすることもできる。
【０１５４】
但し、本発明のトナーの好ましい製造工程としては、粉砕工程で機械式粉砕は用いず、エアージェット式粉砕機にて粉砕した後、図１及び図２に示す分級と機械式衝撃力を用いる表面改質処理を同時に行う装置Ａを用いて重量平均粒径３〜１１μｍの分級品を得ることである。
【０１５５】
尚、必要に応じて風力式篩のハイボルター（新東京機械社製）等の篩分機を用いても良い。更に、外添剤で処理する場合には、分級されたトナーと公知の各種外添剤を所定量配合し、ヘンシェルミキサー、スーパーミキサー等の粉体にせん断力を与える高速撹拌機を外添機として用いることができる。そして、撹拌・混合すれば、本発明のトナーを得ることができる。
【０１５６】
ここで本発明で用いられる上記装置Ａについて以下詳しく述べる。
【０１５７】
図１に示すように表面改質装置では、ケーシング３０、冷却水或いは不凍液を通水できるジャケット（図示しない）、表面改質手段である、ケーシング３０内にあって中心回転軸に取り付けられた、上面に角型のディスク或いは円筒型のピン４０を複数個有し、高速で回転する円盤上の回転体である分散ローター３６、分散ローター３６の外周に一定間隔を保持して配置されている表面に多数の溝が設けられているライナー３４（尚、ライナー表面上の溝はなくても構わない）、更に、表面改質された原料を所定粒径に分級するための手段である分級ローター３１、更に、冷風を導入するための冷風導入口３５、被処理原料を導入するための原料供給口３３、更に、表面改質時間を自在に調整可能となるように、開閉可能なように設置された排出弁３８、処理後の粉体を排出するための粉体排出口３７、更に、分級手段である分級ローター３１と表面改質手段である分散ローター３６−ライナー３４との間の空間を、分級手段へ導入される前の第一の空間４１と、分級手段により微粉を分級除去された粒子を表面処理手段へ導入するための第二の空間４２に仕切る案内手段である円筒形のガイドリング３９とから構成されている。分散ローター３６とライナー３４との間隙部分が表面改質ゾーンであり、分級ローター３１及びローター周辺部分が分級ゾーンである。
【０１５８】
このように上記回分式の表面改質装置は、所定粒径以下の微粉を装置外へ連続的に排出除去する分級手段と、機械式衝撃力を用いる表面処理手段、及び該分級手段と該表面処理手段との間の空間を該分級手段へ導入される前の第一の空間と該分級手段により微粉を分級除去された粒子を該表面処理手段へ導入するための第二の空間に仕切る案内手段とを有している。
【０１５９】
そして、この表面改質装置を用いて、微粉砕物を第一の空間に導入し、分級手段により所定粒径以下の微粉を装置外へ連続的に排出除去しながら、第二の空間を経由して、機械式衝撃力を用いる表面処理手段へ導入して表面改質処理を行い、再び第一の空間へ循環させることにより、一定時間分級と機械式衝撃力を用いる表面改質処理を繰り返す工程を施すと、所定粒径以下の微粉が除かれた、所望の形状及び性能を有する表面改質処理されたトナーを得ることができる。
【０１６０】
図１及び２を用いて、より具体的に工程を説明する。
【０１６１】
排出弁３８を閉とした状態で原料供給口３３から微粉砕品を投入すると、投入された微粉砕品は、まずブロワー（図示しない）により吸引され、分級ローター３１で分級される。その際、分級された所定粒径以下の微粉は装置外へ連続的に排出除去され、所定粒径以上の粗粉は遠心力によりガイドリング３９の内周（第二の空間４２）に沿いながら分散ローター３６により発生する循環流にのり表面改質ゾーンへ導かれる。表面改質ゾーンに導かれた原料は分散ローター３６とライナー３４間で機械式衝撃力を受け、表面改質処理される。表面改質された表面改質粒子は、機内を通過する冷風にのって、ガイドリング３９の外周（第一の空間４１）に沿いながら分級ゾーンに導かれ、分級ローター３１により、再度微粉は機外へ排出され、粗粉は、循環流にのり、再度表面改質ゾーンに戻され、繰り返し表面改質作用を受ける。一定時間経過後、排出弁３８を開とし、排出口３７より表面改質粒子を回収する。
【０１６２】
本発明者らが検討した結果、排出弁開放までの時間（サイクルタイム）と分散ローターの回転数が、球形度と表面離型剤量をコントロールする上で重要なことが分かった。球形度を上げるには、サイクルタイムを長くするか、分散ローターの周速を上げるのが効果的である。また表面離型剤量を低く抑えようとするなら、逆にサイクルタイムを短くするか、周速を下げることが有効である。その中でも特に分散ローターの周速がある一定以上にならないと効率的に球形化できないため、サイクルタイムを長くする必要があるが、その際、表面離型剤量との関係を考慮し、周速やサイクルタイムを設定する必要がある。本発明では、周速は１．２×１０⁵ｍｍ／ｓｅｃ以上であり、サイクルタイムは５〜６０秒が有効である。
【０１６３】
【実施例】
以下、本発明の具体的実施例について説明するが、本発明はこれらの実施例に限定されるものではない。
【０１６４】
尚、本発明における実施例で使用した測定法は以下のとおりである。
【０１６５】
１）トナーの平均円形度の測定
トナーの円相当径、円形度とは、トナー粒子の形状を定量的に表現する簡便な方法として用いたものであり、本発明ではシスメックス社製フロー式粒子像分析装置「ＦＰＩＡ−２１００」を用いて測定を行い、下式を用いて算出した。
【０１６６】
【数１】

【０１６７】
ここで、「粒子投影面積」とは二値化されたトナー粒子像の面積であり、「粒子投影像の周囲長」とは５１２×５１２の画像処理解像度（０．３μｍ×０．３μｍの画素）で画像処理した時の粒子像の周囲長と定義する。
【０１６８】
本発明における円形度はトナー粒子の凹凸の度合いを示す指標であり、トナー粒子が完全な球形の場合に１．０００を示し、表面形状が複雑になる程、円形度は小さな値となる。
【０１６９】
また、円形度頻度分布の平均値を意味する平均円形度Ｃは、粒度分布の分割点ｉでの円形度（中心値）をＣｉ、頻度をｆＣｉとすると、次式から算出される。
【０１７０】
【数２】

【０１７１】
なお、本発明で用いている測定装置である「ＦＰＩＡ−２１００」は、各粒子の円形度を算出後、平均円形度及び円形度標準偏差の算出に当たって、得られた円形度によって、粒子を円形度０．４〜１．０を６１分割したクラスに分け、分割点の中心値と頻度を用いて平均円形度及び円形度標準偏差の算出を行う算出法を用いている。しかしながら、この算出法で算出される平均円形度及び円形度標準偏差の各値と、上述した各粒子の円形度を直接用いる算出式によって算出される平均円形度及び円形度標準偏差の誤差は、非常に少なく、実質的には無視できる程度であり、本発明においては、算出時間の短縮化や算出演算式の簡略化の如きデータの取り扱い上の理由で、上述した各粒子の円形度を直接用いる算出式の概念を利用し、一部変更したこのような算出法を用いても良い。さらに本発明で用いている測定装置である「ＦＰＩＡ−２１００」は、従来よりトナーの形状を算出するために用いられていた「ＦＰＩＡ−１０００」と比較して、シースフローの薄層化（７μｍ→４μｍに）及び処理粒子画像の倍率の向上、さらに取り込んだ画像の処理解像度を向上（２５６×２５６→５１２×５１２）によりトナーの形状測定の精度が上がっており、それにより微粒子のより確実な補足を達成している装置である。従って、本発明のように、より正確に形状を測定する必要がある場合には、より正確に形状に関する情報が得られるＦＰＩＡ−２１００の方が有用である。
【０１７２】
具体的な測定方法としては、容器中に予め不純物などを除去したイオン交換水１０ｍｌを用意し、その中に分散剤として界面活性剤、好ましくはアルキルベンゼンスルホン酸塩を加えた後、更に測定試料を０．０２ｇ加え、均一に分散させる。分散させる手段としては、超音波分散機「Ｔｅｔｏｒａ１５０型」（日科機バイオス社製）を用い、２分間分散処理を行い、測定用の分散液とする。その際、該分散液の温度が４０℃以上とならない様に適宜冷却する。
【０１７３】
トナー粒子の形状測定には、測定時のトナー粒子濃度が３０００〜１万個／μｌとなる様に該分散液濃度を再調整し、上記フロー式粒子像測定装置を用い、０．６０μｍ以上１５９．２１μｍ未満の円相当径を有するトナー粒子を１０００個以上測定し、このデータを用いて、３μｍ以下のデータをカットして、トナー粒子の平均円形度を求める。
【０１７４】
測定の概略は、以下の通りである。
【０１７５】
試料分散液は、フラットで扁平なフローセル（厚み約２００μｍ）の流路（流れ方向に沿って広がっている）を通過させる。フローセルの厚みに対して交差して通過する光路を形成するように、ストロボとＣＣＤカメラが、フローセルに対して、相互に反対側に位置するように装着される。試料分散液が流れている間に、ストロボ光がフローセルを流れている粒子の画像を得るために１／３０秒間隔で照射され、その結果、それぞれの粒子は、フローセルに平行な一定範囲を有する２次元画像として撮影される。それぞれの粒子の２次元画像の面積から、同一の面積を有する円の直径を円相当径として算出する。それぞれの粒子の２次元画像の投影面積及び投影像の周囲長から上記の円形度算出式を用いて各粒子の円形度を算出する。
【０１７６】
２）メタノール４５体積％水溶液における透過率Ｂ
（ｉ）トナー分散液の調製
メタノール：水の体積混合比が４５：５５の水溶液を作製する。この水溶液１０ｍｌを３０ｍｌのサンプルビン（日電理化硝子：ＳＶ−３０）に入れ、トナー２０ｍｇを液面上に侵しビンのフタをする。その後、ヤヨイ式振とう器（モデル：ＹＳ−ＬＤ）により１５０ｒｐｍで５秒間振とうさせる。この時、振とうする角度は、振とう器の真上（垂直）を０度とすると、前方に１５度、後方に２０度、振とうする支柱が動くようにする。サンプルビンは支柱の先に取り付けた固定用ホルダー（サンプルビンの蓋が支柱中心の延長上に固定されたもの）に固定する。サンプルビンを取り出した後、３０秒静置後の分散液を測定用分散液とする。
【０１７７】
（ｉｉ）透過率測定
（ｉ）で得た分散液を１ｃｍ角の石英セルに入れて分光光度計ＭＰＳ２０００（島津製作所社製）を用いて、１０分後の分散液の波長６００ｎｍにおける透過率Ｂ（％）（次式参照）を測定する。
透過率Ｂ（％）＝Ｉ／Ｉ₀×１００ （Ｉ…入射光束…Ｉ₀透過光束）
【０１７８】
３）トナーの重量平均粒径の測定
本発明において、トナーの重量平均粒径及び粒度分布はコールターマルチサイザー（コールター社製）を用いることも可能である。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（コールターサイエンティフィックジャパン社製）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フォン酸塩を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、２．００μｍ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、重量平均粒径（Ｄ４）（各チャンネルの中央値をチャンネル毎の代表値とする）を求める。
【０１７９】
チャンネルとしては、２．００〜２．５２μｍ；２．５２〜３．１７μｍ；３．１７〜４．００μｍ；４．００〜５．０４μｍ；５．０４〜６．３５μｍ；６．３５〜８．００μｍ；８．００〜１０．０８μｍ；１０．０８〜１２．７０μｍ；１２．７０〜１６．００μｍ；１６．００〜２０．２０μｍ；２０．２０〜２５．４０μｍ；２５．４０〜３２．００μｍ；３２．００〜４０．３０μｍの１３チャンネルを用いる。
【０１８０】
４）トナーの最大吸熱ピークＴｓｃの測定
温度曲線：昇温Ｉ （３０℃〜２００℃、昇温速度１０℃／ｍｉｎ）
降温Ｉ （２００℃〜３０℃、降温速度１０℃／ｍｉｎ）
昇温ＩＩ（３０℃〜２００℃、昇温速度１０℃／ｍｉｎ）
トナーの最大吸熱ピークＴｓｃは、示差走査熱量計（ＤＳＣ測定装置）、ＤＣＳ−７（パーキンエルマー社製）やＤＳＣ２９２０（ＴＡインスツルメンツジャパン社製）を用いてＡＳＴＭ Ｄ３４１８−８２に準じて測定する。
【０１８１】
測定試料は５〜２０ｍｇ、好ましくは１０ｍｇを精密に秤量する。それをアルミパン中に入れ、リファレンスとして空のアルミパンを用い、測定範囲３０〜２００℃の間で、昇温速度１０℃／ｍｉｎで常温常湿下で測定を行う。
【０１８２】
トナーの最大吸熱ピークは、昇温ＩＩの過程で、トナーのＴｇの吸熱ピーク以上の領域のベースラインからの高さが一番高いものを、若しくはトナーのＴｇの吸熱ピークが別の吸熱ピークと重なり判別し難い場合、その重なるピークの極大ピークの高さが一番高いものを本発明のトナーの最大吸熱ピークとする。
【０１８３】
５）ＧＰＣ測定による分子量分布
トナーの樹脂成分におけるＧＰＣによる分子量分布は、下記の通り、トナーをＴＨＦ溶媒に溶解させて得られたＴＨＦ可溶成分を用いて、ＧＰＣにより測定する。
【０１８４】
すなわち、トナーをＴＨＦ中に入れ、数時間放置した後十分に振とうしＴＨＦと良く混ぜ（試料の合一体がなくなるまで）、更に１２時間以上静置する。このときＴＨＦ中への放置時間が２４時間以上となるようにする。その後、サンプル処理フィルタ（ポアサイズ ０．４５〜０．５μｍ、例えば、マイショリディスクＨ−２５−５ 東ソー社製、エキクロディスク２５ＣＲ ゲルマンサイエンスジャパン社製などが利用できる）を通過させたものを、ＧＰＣの試料とする。また試料濃度は、樹脂成分が０．５〜５ｍｇ／ｍｌとなるように調整する。
【０１８５】
上記の方法で調製された試料のＧＰＣの測定は、４０℃のヒートチャンバー中でカラムを安定化させ、この温度におけるカラムに溶媒としてテトラヒドロフラン（ＴＨＦ）を毎分１ｍｌの流速で流し、試料濃度として０．０５〜０．６質量％に調整した樹脂のＴＨＦ試料溶液を約５０〜２００μｌ注入して測定する。試料の分子量測定にあたっては、試料の有する分子量分布を数種の単分散ポリスチレン標準試料により作成された検量線の対数値とカウント数（リテンションタイム）との関係から算出する。検量線作成用の標準ポリスチレン試料としては、例えば東ソー社製或いはＰｒｅｓｓｕｒｅ Ｃｈｅｍｉｃａｌ Ｃｏ．製の分子量が６×１０²、２．１×１０³、４×１０⁴、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。
【０１８６】
カラムとしては、１０³〜２×１０⁶の分子量領域を的確に測定するために、市販のポリスチレンジェルカラムを複数本組み合わせるのが良く、例えば昭和電工社製のｓｈｏｄｅｘ ＧＰＣ ＫＦ−８０１，８０２，８０３，８０４，８０５，８０６，８０７の組み合わせや、Ｗａｔｅｒｓ社製のμ−ｓｔｙｒａｇｅｌ ５００、１０³、１０⁴、１０⁵の組み合わせを挙げることができる。
【０１８７】
６）集束イオンビーム加工観察装置によるキャリア表面の樹脂微粒子の観察方法
集束イオンビーム加工観察装置（ＦＩＢ）、ＦＢ−２０００Ｃ（日立製作所）を用い加工観察する。試料の作製は、試料台にカーボンペースト水溶液を塗布しその上に試料を少量載せる。その後白金蒸着を行わずに試料をＦＩＢ装置にセットして目的の試料の表面をビームを当て表面を削りながら観察する。
【０１８８】
７）トナーの摩擦帯電量の測定方法
摩擦帯電量を測定する装置の概略図を図３に示す。底に５００メッシュのスクリーン５３のある金属製の測定容器５２に、複写機又はプリンターの現像スリーブ上から採取した二成分系現像剤を約０．５〜１．５ｇ入れ金属製のフタ５４をする。この時の測定容器５２全体の質量を秤りＷ１（ｇ）とする。次に吸引機５１（測定容器５２と接する部分は少なくとも絶縁体）において、吸引口５７から吸引し風量調節弁５６を調整して真空計５５の圧力を２５０ｍｍＡｑとする。この状態で充分、好ましくは２分間吸引を行いトナーを吸引除去する。この時の電位計５９の電位をＶ（ボルト）とする。ここで５８はコンデンサーであり容量をＣ（ｍＦ）とする。また、吸引後の測定容器全体の重量を秤りＷ２（ｇ）とする。この試料の摩擦帯電量（ｍＣ／ｋｇ）は下式の如く算出される。
試料の摩擦帯電量（ｍＣ／ｋｇ）＝Ｃ×Ｖ／（Ｗ１−Ｗ２）
（但し、測定条件は２３℃，６０％ＲＨとする）
【０１８９】
８）定着可能領域
レーザージェット４１００（ヒューレットパッカード社製）の定着器の改造機を用い、定着ユニットは手動で定着温度が設定できるように改造した状態で定着試験を行う。画像はＣＬＣ５０００で単色モードで常温常湿度環境下（２３℃／６０％）において、紙上のトナー載り量を１．２ｍｇ／ｃｍ²になるよう現像コントラストを調整し、未定着画像を作成する。Ａ４（ＣＬＣ推奨紙であるＴＫＣＬＡ４）上に画像面積比率２５％で画像を形成する。常温常湿度環境下（２３℃／６０％）において１２０℃から順に１０℃ずつ上げ、オフセットや巻きつきが生じない温度幅を定着可能領域とする。
【０１９０】
９）クリーニング性評価
ＣＬＣ５０００での耐久一万枚のうちで、クリーニングされない残トナーのたて筋や斑点状が画像上に見えた時、クリーニング不良発生とする。
Ａ：画像欠陥はまったくない。
Ｂ：斑点状の模様が２〜３点発生で実用上問題なし。
Ｃ：斑点状あるいは筋状の模様が若干発生で実用上問題なし。
Ｄ：斑点状，筋状の模様、濃度ムラが発生している。
Ｅ：汚れの影響が大きく、濃度ムラ，帯電ムラも発生し、画像が乱れている。
【０１９１】
１０）カブリ測定
耐久試験においてのカブリを測定方法としては、シアン及びブラック画像の場合、画出し前の普通紙の平均反射率Ｄｒ（％）をアンバーフィルターを搭載したリフレクトメーター（東京電色株式会社製の「ＲＥＦＬＥＣＴＯＭＥＴＥＲ ＭＯＤＥＬ ＴＣ−６ＤＳ」）によって測定した。一方、普通紙上にベタ白画像を画出しし、次いでベタ白画像の反射率Ｄｓ（％）を測定した。カブリ（Ｆｏｇ［％］）は下記式
Ｆｏｇ［％］＝Ｄｒ［％］−Ｄｓ［％］
より算出した。また、マゼンタ及びブラック画像の場合はグリーンフィルター、そしてイエロー画像の場合はブルーフィルターで上記の測定を行って算出した。
【０１９２】
１１）Ｓｌ汚染
１０，０００枚複写した後の現像スリーブ表面の一部をエタノールで清浄に拭き取り、ベタ黒画像を複写し、エタノール拭き清掃前後の画像濃度を測定し、その差を算出することによりスリーブ汚染の評価を行い、下に示すランクに分類した。
【０１９３】
スリーブ汚染ランク
Ａ Δ０．０３未満
Ｂ Δ０．０３以上Δ０．１０未満
Ｃ Δ０．１０以上Δ０．２０未満
Ｄ Δ０．２０を超えるもの
【０１９４】
１２）キャリアの体積平均粒径の測定方法
キャリアの粒度測定：キャリアの粒度分布の測定装置としては、マイクロトラック粒度分析計（日機装株式会社）のＳＲＡタイプを使用し、０．７〜１２５μｍのレンジ設定で行って、キャリアの５０％平均粒径（Ｄ₅₀）及び粒度分布を求めた。
【０１９５】
１３）樹脂微粒子の体積平均粒径の測定方法
微粒子の粒径の測定には、コールター社製のＬＳ−２３０型レーザー回折式粒度分布測定装置にリキッドモジュールを取り付けたものを用いることができる。この装置によって０．０４〜２０００μｍの体積平均粒径を測定することが可能である。測定は、水１０ｃｃに微量の界面活性剤を添加し、これに微粒子１０ｍｇを加え、超音波分散機で１０分間分散した後、測定時間９０秒間、測定回数１回の条件で測定を行う。
【０１９６】
（ハイブリッド樹脂製造例）
ビニル系共重合体として、スチレン２．０ｍｏｌ、２−エチルヘキシルアクリレート０．２１ｍｏｌ、フマル酸０．１４ｍｏｌ、α−メチルスチレンの２量体０．０３ｍｏｌ、ジクミルパーオキサイド０．０５ｍｏｌを滴下ロートに入れる。また、ポリオキシプロピレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン７．０ｍｏｌ、ポリオキシエチレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン３．０ｍｏｌ、テレフタル酸３．０ｍｏｌ、無水トリメリット酸１．５ｍｏｌ、フマル酸５．０ｍｏｌ及び酸化ジブチル錫０．２ｇをガラス製４リットルの４つ口フラスコに入れ、温度計，撹拌棒，コンデンサー及び窒素導入管を取りつけマントルヒーター内においた。次にフラスコ内を窒素ガスで置換した後、撹拌しながら徐々に昇温し、１４５℃の温度で撹拌しつつ、先の滴下ロートよりビニル系樹脂の単量体、架橋剤及び重合開始剤を４時間かけて滴下した。次いで２００℃に昇温を行い、４時間反応せしめてハイブリッド樹脂を得た。ＧＰＣによる分子量測定の結果を表１に示す。
【０１９７】
（ポリエステル樹脂製造例）
ポリオキシプロピレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン３．６ｍｏｌ、ポリオキシエチレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン１．６ｍｏｌ、テレフタル酸１．７ｍｏｌ、無水トリメリット酸１．０ｍｏｌ、フマル酸２．４ｍｏｌ及び酸化ジブチル錫０．１２ｇをガラス製４リットルの４つ口フラスコに入れ、温度計，撹拌棒，コンデンサー及び窒素導入管を取りつけマントルヒーター内においた。窒素雰囲気下で、２１５℃で５時間反応させ、ポリエステル樹脂を得た。ＧＰＣによる分子量測定の結果を表１に示す。
【０１９８】
（スチレン−アクリル系共重合樹脂製造例）
・スチレン ７０質量部
・アクリル酸ｎ−ブチル ２４質量部
・マレイン酸モノブチル ６質量部
・ジ−ｔ−ブチルパーオキサイド １質量部
上記各成分を、４つ口フラスコ内でキシレン２００質量部を撹拌しながら容器内を十分に窒素で置換し１２０℃に昇温させた後３時間かけて滴下した。更にキシレン還流後下で重合を完了し、減圧下で溶媒を蒸留除去し、スチレン−アクリル樹脂を得た。ＧＰＣによる分子量測定の結果を表１に示す。
【０１９９】
【表１】

【０２００】
次に、本発明に用いたワックスを表２に示す。
【０２０１】
【表２】

【０２０２】
次に、本発明に用いたキャリアについて示す。
【０２０３】
＜キャリアの製造例＞
（キャリア１）
ＭｎＯを２８．０ｍｏｌ％、ＭｇＯを６．０ｍｏｌ％、Ｆｅ₂Ｏ₃を６５．２ｍｏｌ％及びＳｒＣＯ₃を０．８ｍｏｌ％湿式ボールミルで５時間粉砕、混合し、乾燥させた後、８５０℃で１時間保持し、仮焼成を行なった。これを湿式ボールミルで７時間粉砕し、３μｍ以下とした。このスラリーに分散剤およびバインダー（ポリビニルアルコール）を数質量％添加し、次いでスプレードライヤーにより造粒、乾燥し、電気炉にて、１２００℃で４時間保持し、本焼成を行なった。その後、解砕し、さらに分級して、体積平均粒径は４９.８μｍのキャリア芯材を得た。
【０２０４】
次に、
ストレートシリコーン（信越化学社製ＫＲ２５５（固形分換算））１００質量部
シラン系カップリング剤（γ−アミノプロピルエトキシシラン） ５質量部
ポリメタクリル酸メチル樹脂（体積平均粒径０．１０μｍ） １０質量部
をキシレン３００重量部と混合して、キャリア樹脂被覆溶液とした。
【０２０５】
この樹脂被覆溶液を用いて７０℃に加熱した流動床を用いて攪拌しながら、キャリア芯材に対して塗布および溶媒除去操作を行った。さらに、オーブンを用いて、２３０℃で２．５時間の処理を行い、解砕、篩による分級処理を行い、キャリア１を得た。
【０２０６】
（キャリア２）
ポリメタクリル酸メチル樹脂の体積平均粒径１．１０μｍの樹脂微粒子を使用すること以外はキャリア１と同様にしてキャリア２を得た。樹脂微粒子の粒径が大きいために、キャリア表面に分散して存在する微粒子が少なくなっている。
【０２０７】
（キャリア３）
ポリメタクリル酸メチル樹脂の体積平均粒径０．０５μｍの樹脂微粒子を使用し、キャリア芯材に対して被覆樹脂を塗布した後に、オーブンを用いて２５０℃にて処理すること意外はキャリア1と同様にしてキャリア３を得た。樹脂微粒子の粒径が小さくなっているためキャリア表面に分散して存在する微粒子が多くなっているが、オーブンで処理する温度を高くしているため、カップリング剤による架橋反応が進み、キャリア表面に分散して存在する樹脂微粒子が粒径の割には少なくなっている。
【０２０８】
（キャリア４）
被覆樹脂としてフッ素-アクリル樹脂（パーフルオロオクチルエチルアクリレート-メチルメタクリレート）、ポリメタクリル酸メチル樹脂に変えて、体積平均粒径０．１０μｍのメラミン樹脂微粒子を使用し、アミノシランカップリング剤を用いないこと以外はキャリア１と同様にしてキャリア４を得た。
【０２０９】
（キャリア５）
ポリメタクリル酸メチル樹脂を添加しないこと以外はキャリア１と同様にしてキャリア５を得た。
【０２１０】
本発明に用いたキャリアについて表３に示す。
【０２１１】
【表３】

【０２１２】
＜実施例１＞
以下の方法でトナー１を調製した。
【０２１３】
・ハイブリッド樹脂 １００質量部
・ワックスＡ ３質量部
・１，４−ジ−ｔ−ブチルサリチル酸アルミニウム化合物 １質量部
・シアン顔料（Ｐｉｇｍｅｎｔ Ｂｌｕｅ１５：３） ４質量部
上記の処方で十分にヘンシェルミキサーにより予備混合を行い、二軸押出し混練機で溶融混練し、冷却後ハンマーミルを用いて約１〜２ｍｍ程度に粗粉砕し、次いでエアージェット方式による微粉砕機で２０μｍ以下の粒径に微粉砕した。表３に示すように、さらに得られた微粉砕物を図１及び図２に示す分級と機械式衝撃力を用いる表面改質（球形化）処理を同時に行う装置Ａにて粉砕し、表４の製造条件にてシアン粒子１（分級品）を得た。
【０２１４】
上記シアン粒子に対して、針状酸化チタン微粉体（ＢＥＴ＝６２、イソブチルシランカップリング剤１０質量％処理）１．０質量％をヘンシェルミキサーにより外添してトナー１とした。該トナー１の重量平均粒径は７．０μｍ、平均円形度Ａは０．９３３であり、このときのメタノール４５体積％水溶液における透過率Ｂは、３１％であった。トナーの構成材料及び物性を表４に示す。
【０２１５】
さらに、トナー１と、キャリア１とを、トナー濃度が７．０質量％になるように混合し、現像剤１とした。現像剤の評価結果を表５に示す。
【０２１６】
この現像剤１で、カラー複写機ＣＬＣ−５０００（キヤノン製）のオイル塗布システム及び定着ローラーウェッブを除去し加熱ローラー及び加圧ローラーを１．２μｍのＰＦＡ表層を有するローラに変更し、オイル塗布機構をもたない定着器を取り付けたものを使用して、単色モードで常温常湿度環境下（２３℃／６０％）で画像面積比率３％のオリジナル原稿を用いて１００００枚の画だし試験の評価を行い、その後さらに２０００枚高画像面積比率２０％にて画だし評価を行った。また高温高湿環境下にて同様の評価を行った。
【０２１７】
表５に示すように、低画像面積比率でもその後の高画像面積比率においても安定した帯電を維持し、かつカブリもなく良好な結果が得られた。さらに定着温度領域も広く、クリーニング性にも問題なく、オリジナルを忠実に再現するシアン画像が得られた。
【０２１８】
＜実施例２＞
トナーの離型剤の添加量を多くすること以外は実施例１と同様にしてトナー２を得た。またトナー２とキャリア１を使用して現像剤２を得た。トナーの構成材料及び物性を表４に、現像剤の評価結果を表５に示す。若干メタノールに対するトナーの透過率が高くなっているため、高温高湿下における帯電立ち上がり性が若干悪化しているが実用上問題ないレベルであった。
【０２２０】
＜実施例４＞
トナーの離型剤の種類と球形化処理する時間を若干長くしたことを変えたトナー４とキャリア表面に存在する樹脂微粒子の数が少ないキャリア２を用いること以外は実施例１と同様にして現像剤４を得た。トナーの構成材料及び物性を表４に、現像剤の評価結果を表５に示す。若干メタノールに対するトナーの透過率が高くなっているが、キャリア表面の樹脂微粒子の量が若干少ないため高温高湿下での高面積画像を画だしした時にカブリが若干悪化しているが実用上問題のないレベルであった。
【０２２１】
＜実施例５＞
キャリア表面に存在する樹脂微粒子の数が多いキャリア３を用いること以外は実施例４と同様にして現像剤５を得た。トナーの構成材料及び物性を表４に、現像剤の評価結果を表５に示す。初期の帯電レベルも問題なく、樹脂微粒子を添加したキャリアと組み合わせることにより低画像面積から高画像面積まで幅広く帯電が安定していた。
【０２２２】
＜実施例６＞
トナーの離型剤の種類を変えたトナー５とキャリアのコート材料及び樹脂微粒子の種類を変えたキャリア４を用いる事以外実施例１と同様にして現像剤６を得た。トナーの構成材料及び物性を表４に、現像剤の評価結果を表５に示す。トナーの吸熱ピークが高いためにメタノールに対するトナーの透過率低くなりトリボの立ち上がりには良好だが、若干定着温度領域が小さくなっているが実用上は問題ない。
【０２２３】
＜実施例７＞
トナーの離型剤の種類を変えたトナー６とキャリア表面に存在する樹脂微粒子の数が多いキャリア３を用いること以外実施例１と同様にして現像剤７を得た。トナーの構成材料及び物性を表４に、現像剤の評価結果を表５に示す。メタノールに対するトナーの透過率低くなりトリボの立ち上がりには良好だが、若干定着温度領域が小さくなっているが実用上は問題ない。
【０２２４】
＜実施例８＞
トナーのメインバインダーをハイブリッド樹脂とポリエステル樹脂とを乾式ブレンド（５０：５０）したものに変えたトナー７とキャリア２を用いること以外は実施例１と同様にして現像剤８を得た。トナーの構成材料及び物性を表４に、現像剤の評価結果を表５に示す。トナーの帯電が若干高くなり、メタノールに対するトナーの透過率が若干高くなったがトリボの立ち上がりも、カブリも良好であった。
【０２２５】
＜参考例１＞
トナーのメインバインダーをハイブリッド樹脂とスチレンアクリル系共重合樹脂とを乾式ブレンド（７０：３０）したものに変えたトナー８とキャリア２を用いること以外は実施例１と同様にして現像剤９を得た。トナーの構成材料及び物性を表４に、現像剤の評価結果を表５に示す。若干定着性が悪化したが実用上は全く問題がないレベルであった。
【０２２６】
＜比較例１＞
トナーの離型剤の種類と粉砕方式をカウンタージェットミル（ホソカワミクロン製）という粉砕機を使用して、その後分級装置（エルボジェット分級機）を用いたトナー９とキャリア３とを組み合わせた事以外は実施例１と同様にして現像剤１０を得た。トナーの構成材料及び物性を表４に、現像剤の評価結果を表５に示す。メタノールに対するトナーの透過率が非常に悪いために帯電性もカブリも全く実用のレベルには至らなかった。
【０２２７】
＜比較例２＞
トナーのメインバインダーをスチレンアクリル系共重合樹脂としたものに変えたトナー１０とキャリア１を用いること以外は実施例１と同様にして現像剤１１を得た。トナーの構成材料及び物性を表４に、現像剤の評価結果を表５に示す。定着点がなく実用上不可であった。
【０２２８】
＜比較例３＞
トナーの離型剤をポリエチレンワックスに変えたトナー１１とキャリア１を用いること以外は実施例１と同様にして現像剤１２を得た。トナーの構成材料及び物性を表４に、現像剤の評価結果を表５に示す。定着点がなく実用上不可であった。
【０２２９】
＜比較例４＞
樹脂微粒子を含まないキャリア５を使用すること以外は実施例１と同様にして現像剤１３を得た。トナーの構成材料及び物性を表４に、現像剤の評価結果を表５に示す。高温高湿下において低面積画像を画だしした後に高面積画像を画だしすると帯電量が下がりカブリが悪化し実用上不可レベルであった。
【０２３０】
【表４】

【０２３１】
【表５】

【０２３２】
【発明の効果】
本発明は、トナーの離型剤の分散を最適にしさらにキャリアに樹脂微粒子を添加することにより、高精彩性を満足した画像を安定的に形成できる。具体的には、定着時の低温定着が可能であり、耐高温オフセットの問題も解消し、スリーブ汚染、キャリアスペントに対する許容幅も広く、クリーニング性にも優れ、低面積画像から高面積画像まで幅広くカブリ、濃度ムラのない高画質の画像が得られ、環境依存性に優れ、なおかつ高い耐久性能を有した二成分系現像剤を提供することができる。
【図面の簡単な説明】
【図１】表面改質処理装置の概略図である。
【図２】分散ローター及び配置されたライナーの説明図である。
【図３】トナーの摩擦帯電量を測定する装置の概略図である。
【符号の説明】
３１：分級ローター
３２：微粉回収
３３：原料供給口
３４：ライナー
３５：冷風導入口
３６：分散ローター
３７：製品排出口
３８：排出弁
３９：ガイドリング
４０：角型ディスク
４１：第一の空間
４２：第二の空間
５１：吸引機
５２：測定容器
５３：５００メッシュスクリーン
５４：金属製ふた
５５：真空計
５６：風量調節弁
５７：吸引口
５８：コンデンサー
５９：電位計[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a developer used when developing a latent image by an electrophotographic method, an electrostatic recording method, a toner jet method or the like.
[0002]
[Prior art]
In recent years, copying machines and printers have been strictly pursued for higher speed and higher reliability, and machines are configured with simpler elements in various respects. As a result, the performance required for the developer becomes higher, and if the improvement in the performance of the developer cannot be achieved, a superior machine cannot be realized.
[0003]
With regard to toner, in recent years, demand for high definition and high image quality of copiers has increased in the market, and in this technical field, attempts have been made to achieve high image quality color by reducing the particle size of toner. . The image area used in the conventional black-and-white copy is 10% or less, and it is almost a line image part such as a letter, a document, and a report as an image. As described above, solid images having gradation such as photographs, catalogs, maps, and paintings occupy a considerable frequency or area.
[0004]
When such continuous copying is performed using a document having a large image area, a copy with a high image density is usually obtained in the initial stage. However, the carrier coat is peeled off gradually, and a carrier spent is caused. Since the replenishment toner is developed in a sufficient state, it may cause fogging and toner scattering. In particular, recently, there has been a demand for image quality that satisfies both conventional black-and-white and color copies. In other words, it is desired to develop a developer that can maintain satisfactory image quality even when an image having a small image area and an image having a large image area are mixed in a color copying machine.
[0005]
In recent years, a method of adding a release agent such as low molecular weight polyethylene or low molecular weight polypropylene to the toner has been proposed for the purpose of reducing the size of the fixing device and improving the low-temperature fixing property. In order for such a release agent to function effectively during fixing, it is necessary to deposit the release agent on the toner surface. For this reason, during long-term copying, the release agent contaminates the carrier with which the toner strongly rubs, and the developability is lowered. Further, since the fluidity of the toner is extremely lowered due to the presence of the release agent on the toner surface, when the continuous copying is performed on a document having a large image area, the charge rising of the toner becomes very bad.
[0006]
On the other hand, as a full-color transfer material, in addition to ordinary paper and overhead projector film (OHP), there is an increasing need for various materials to be used on cardboard, card, postcard and other small-size paper. The transfer method using is becoming effective. In a system that normally uses an intermediate transfer member, it is necessary to transfer the developed color image of the toner from the photosensitive member to the intermediate transfer member, and then transfer it again from the intermediate transfer member onto the transfer material. It is necessary to increase the toner transfer efficiency more than before. In particular, in the case of using a full-color copying machine that transfers a plurality of toner images after development, the amount of toner on the photoconductor increases as compared with the case of one-color black toner used in a black-and-white copying machine. It is difficult to improve the transfer efficiency only with use.
[0007]
Therefore, as one of the techniques for increasing the transfer efficiency, the toner shape has been made close to a spherical shape in recent years. However, for example, a polymerization toner such as suspension polymerization or emulsion polymerization is a very effective technique for improving transfer efficiency. However, in a polymerized toner, the release agent is inevitably included, so that the release agent is difficult to come out on the toner surface, so that the fixing property is inferior. In addition, when the pulverized toner is spheroidized, the release agent easily elutes on the toner surface by a solvent or heat, and it tends to become richer than necessary, and there is a problem in controlling the amount of the release agent present on the toner surface. there were. In addition, it is not necessary to simply bring the toner close to a spherical shape. If the toner is too spherical, there is a problem that the toner slips through the cleaning portion and cannot be cleaned.
[0008]
Two-component developers share the functions of carrier agitation / conveyance / charging, etc., and the functions as a developer are separated, so that the controllability is good, and it is widely used at present. ing. In particular, it is suitably used in full-color image forming apparatuses such as full-color copying machines or full-color printers that require high image quality.
[0009]
As a magnetic carrier used for a two-component developer, an iron powder carrier, a ferrite carrier, or a magnetic material dispersion type resin carrier in which magnetic fine particles are dispersed in a binder resin is known. Among these, the iron powder carrier has a low carrier specific resistance, so that the charge of the electrostatic charge image leaks through the carrier and may disturb the electrostatic charge image, resulting in an image defect. Ferrite carriers and magnetic material-dispersed resin carriers are widely used.
[0010]
However, even when a ferrite carrier is used, a magnetic brush is applied to the toner image, and since the specific gravity is large, a load due to the weight of the carrier surface is large, so that a carrier spent such as toner component adhesion is likely to occur. If this becomes noticeable, the entire developer must be frequently replaced, which increases the running cost.
[0011]
In order to eliminate this carrier spent, a technique of applying a resin coat to the carrier has been used. However, in the resin coat carrier, the carrier coat component is worn out or destroyed. These damages cannot maintain the initial characteristics of the developer as the number of times of copying increases, and cause background fogging, in-machine contamination, image density fluctuation, and the like.
[0012]
On the other hand, the magnetic material-dispersed resin carrier has advantages such as low specific gravity and reduced stirring torque, and prevents carrier spent by reducing damage to the carrier during stirring. However, although the life of the developer can be extended, the toner charge rise is insufficient and fogging and toner scattering may occur particularly in an image having a large image area.
[0013]
Under such circumstances, for the purpose of enhancing the durability of the ferrite carrier, carrier spent is prevented by dispersing and containing thermosetting resin fine particles in the resin (for example, see Patent Document 1). However, with this carrier, at present, the demand for fixing properties and high image quality is increasing, and the performance is insufficient with respect to long life and chargeability.
[0014]
Further, the life is extended by regulating the carrier in which resin fine particles are dispersed and the amount of wax exposed on the toner surface (see, for example, Patent Document 2). However, the dispersion state of the resin fine particles on the surface of the carrier is not specified, and there are still problems with respect to charging stability and fogging in a large image area.
[0015]
Therefore, improvement from both the toner and the carrier has been an issue for the purpose of maintaining high image quality over a long period of time.
[0016]
[Patent Document 1]
JP-A-9-319161
[Patent Document 2]
Japanese Patent Laid-Open No. 9-319158
[0017]
[Problems to be solved by the invention]
An object of the present invention is to provide a two-component developer that solves the above-described problems, and can stably form an image satisfying high definition. Specifically, it can be fixed at low temperature during fixing, eliminates the problem of high-temperature offset resistance, has a wide tolerance for sleeve contamination and carrier spent, has excellent cleaning properties, and is widely used from low-area images to high-area images. An object of the present invention is to provide a two-component developer capable of obtaining a high-quality image free from fog and density unevenness, having excellent environmental stability and high durability.
[0018]
[Means for Solving the Problems]
The present invention can solve the above problems by adopting the following configuration.
[0019]
  In a two-component developer containing at least a binder resin, a colorant, a toner containing a release agent and a carrier,
(I) the binder resin includes at least a polyester unit;
(Ii) The transmittance B (%) of the toner in a 45 volume% methanol aqueous solution is in the range of 10 ≦ B ≦ 70,
(Iii) The endothermic curve in the differential thermal analysis (DSC) measurement of the toner has one or a plurality of endothermic peaks in the temperature range of 30 to 110 ° C., and the temperature Tsc of the maximum endothermic peak in the endothermic peak is 65 ° C. <Tsc <105 ° C.
(Iv) the carrierHas a carrier core and a resin coating layer covering the carrier core,Contains resin fine particlesAnd
(V) The average circularity A is in the range of 0.915 ≦ A ≦ 0.960 for the toner circle equivalent diameter of 3 μm or more.Ru
The present invention relates to a two-component developer.
[0020]
The transmittance B of the toner in a 45 volume% methanol aqueous solution is more preferably in the range of 15 ≦ B ≦ 50.
[0021]
The endothermic curve in the differential thermal analysis (DSC) measurement of the toner has one or a plurality of endothermic peaks in the temperature range of 30 to 110 ° C., and the temperature Tsc of the maximum endothermic peak in the endothermic peak is 70 ° C. < More preferably, Tsc <90 ° C.
[0022]
The binder resin may be (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl polymer unit, or (c) a mixture of a hybrid resin and a vinyl polymer, or (d It is preferably a resin selected from either a) a mixture of a polyester resin and a vinyl polymer, or (e) a mixture of a hybrid resin and a polyester resin.
[0023]
The molecular weight distribution measured by gel permeation chromatography (GPC) of the binder resin component preferably has a main peak in the region of molecular weight 3,500 to 30,000, more preferably molecular weight 5 It is more preferable that Mw / Mn is 5.0 or more.
[0024]
The glass transition temperature of the binder resin is preferably 40 to 90 ° C, more preferably 45 to 85 ° C. The acid value of the resin is preferably 1 to 40 mgKOH / g.
[0025]
The amount of the release agent added is preferably 1 to 10 parts by mass and more preferably 2 to 8 parts by mass with respect to 100 parts by mass of the binder resin.
[0026]
More preferably, the mold release agent is paraffin wax.
[0027]
The toner preferably contains a metal compound of an aromatic carboxylic acid as a charge control agent.
[0028]
The toner is subjected to a surface modification step using a batch type surface modification device, and fine particles having a predetermined particle diameter or less are continuously discharged and removed from the batch type surface modification device. And the surface treatment means using mechanical impact force, and the space between the classification means and the surface treatment means before the introduction to the classification means, and the classification means removes fine powder by the classification means. Guide means for partitioning the formed particles into a second space for introducing the particles into the surface treatment means,
The finely pulverized product is introduced into the first space, and mechanical impact force is used via the second space while continuously removing and removing fine powder having a predetermined particle size or less from the apparatus by the classification means. By introducing into the surface treatment means, performing surface modification treatment, and circulating again to the first space, by repeating the surface modification treatment using a fixed time classification and mechanical impact force, the particle size is less than a predetermined particle size. More preferably, the toner is obtained in the step of obtaining surface-modified particles from which fine powder has been removed.
[0029]
The toner preferably has an average circularity A in the range of 0.920 ≦ A ≦ 0.960 for particles having an equivalent circle diameter of 3 μm or more.
[0030]
The toner has a weight average particle diameter of 4 to 9 μm, contains 20 to 70% by number of toner having a particle diameter of 5.04 μm or less, and 3 to 40% by number of toner having a particle diameter of 4 μm or less. It is preferable that 3 to 60% by volume of toner having a particle size of 8 μm or more is contained, and 15% by volume or less of toner having a particle size of 10.08 μm or more is contained.
[0031]
The resin core is preferably a resin-coated carrier having 0.01 to 2.0% by mass of a resin coating layer on the surface of the carrier core, and 0.05 to 1.0% by mass. Is more preferable.
[0032]
In observation of the carrier with a focused ion beam (FIB) processing observation apparatus, the average particle diameter of the resin fine particles is 0.05 to 1.0 μm, and 1 to 200 particles / μm²Preferably 10 to 150 / μm²More preferably it is present.
[0033]
The resin particles added to the carrier are preferably crosslinkable resins.
[0034]
The thermal decomposition temperature of the resin fine particles added to the carrier is preferably 230 ° C. or higher, and more preferably 260 ° C. or higher.
[0035]
The amount of resin fine particles added to the carrier is preferably from 0.1 to 50% by mass, more preferably from 1.0 to 45% by mass, based on the carrier coating resin.
[0036]
The resin used for coating the carrier is more preferably a silicone resin, an acrylic-modified silicone resin, a fluorine resin, a fluorine / acrylic resin, or the like.
[0037]
The carrier preferably contains an amino group-containing silane coupling agent.
[0038]
The carrier has a weight average particle size of 25 to 65 μm, carrier particles smaller than 22 μm are 30% or less, carrier particles smaller than 16 μm are 2% or less, and carrier particles of 62 μm or more are 0.2 to 45 μm. %, And carrier particles of 88 μm or more are preferably 12% or less.
[0039]
DETAILED DESCRIPTION OF THE INVENTION
The inventors of the present invention have solved the various problems described above, and have reached the following invention in the course of earnestly studying to develop a two-component developer that meets the object of the present invention.
[0040]
The present invention relates to a two-component developer containing at least a binder resin, a colorant, a release agent and a carrier and a carrier, wherein the binder resin contains at least a polyester unit, and the toner permeates in an aqueous solution of 45% by volume of methanol. The rate B (%) is in the range of 10 ≦ B ≦ 70, and has one or more endothermic peaks in the temperature range of 30 to 110 ° C. in the endothermic curve in the differential thermal analysis (DSC) measurement of the toner. The temperature Tsc of the maximum endothermic peak in the endothermic peak is 65 ° C. <Tsc <105 ° C., and the carrier contains a resin coating layer and resin fine particles.
[0041]
The present invention defines the toner performance as described above, specifically, the amount of the release agent on the surface of the toner.
[0042]
By measuring the transmittance in a 45% by volume aqueous solution of methanol as a simple and accurate method for the release agent present on the toner surface, the entire toner particles can be grasped. This measurement method is to forcibly disperse the toner once in a mixed solvent to make the characteristics of the amount of the release agent present in each toner particle easy, and then measure the transmittance after a certain time, It is possible to accurately grasp the amount of the release agent present in the entire toner. That is, when a large amount of hydrophobic release agent is present on the surface of the toner, it is difficult to disperse in the solvent and aggregates and precipitates, so that the transmittance is as high as 70%. On the contrary, if the release agent is not present on the toner surface, the polyester unit of the binder resin that is hydrophilic occupies the toner surface, so that it is uniformly dispersed and the transmittance becomes a small value of less than 10%.
[0043]
In the present invention, the desired transmittance is characterized in that the transmittance B (%) in a 45 volume% methanol aqueous solution is in the range of 10 ≦ B ≦ 70, and preferably 15 ≦ B ≦ 50.
[0044]
If it is less than 10%, the release agent on the surface of the toner is so small that the releasing effect does not appear at the time of fixing. On the other hand, if it exceeds 70%, the release agent on the toner surface is too much, and the release agent is contaminated on the carrier, or the resistance is increased by, for example, fusing on the developing sleeve, so that the actual developing bias related to development is increased. Is reduced, and this leads to a decrease in image density.
[0045]
Here, as for the physical properties of the conventional toner, in a toner not using a release agent or a polymerized toner, since the hydrophobic release agent is not present on the toner surface, the transmittance becomes small and becomes less than 10%. Even if a release agent is used, if a small amount is used, or a toner having a melting point or maximum endothermic peak of 105 ° C. or higher is used, the transmittance decreases and becomes less than 10%, which is inferior to the fixing property. It will be enough.
[0046]
In addition, as described above, the present invention also defines other properties of the toner, specifically, the endothermic peak temperature of the toner.
[0047]
And in the endothermic curve in the differential thermal analysis (DSC) measurement of the release agent used in the present invention, it has one or a plurality of endothermic peaks in the temperature range of 30 to 110 ° C., and the maximum endothermic peak in the endothermic peak. The temperature Tsc is preferably 65 ° C. <Tsc <105 ° C., more preferably 70 ° C. <Tsc <90 ° C. When the temperature is 65 ° C. or lower, the toner has poor anti-blocking properties and causes fogging and toner scattering. On the other hand, if the temperature is 105 ° C. or higher, low-temperature fixing desired from the viewpoint of energy saving cannot be performed.
[0048]
The primary factor that determines the value of the maximum endothermic peak temperature Tsc of the toner is the release agent, and the endothermic peak value can be appropriately adjusted by considering the type of the release agent. .
[0049]
In the present invention, the carrier-containing component is also defined as described above.
[0050]
In the present invention, the carrier needs to contain resin fine particles.
[0051]
The present inventors consider the reason why the toner according to the present invention exhibits the effects of the present invention as follows.
[0052]
In the case of an output with a small image area, if the replacement of the toner is small, the toner is excessively charged, and the excessively charged toner strongly adheres to the carrier. On the contrary, in the case of an output with a large image area, the toner charge amount becomes small if the toner is frequently replaced. The difference in the number of contact between the toner and the carrier due to the difference in the image area can be mitigated by the presence of the resin fine particles on the carrier surface, so that the number of collisions of the toner with the carrier charge imparting portion can be reduced regardless of the toner replacement. It is thought that the effect to do is great. Accordingly, in the differential thermal analysis (DSC) measurement of the present invention, in the toner having an endothermic peak in the low temperature region, it is considered that the image defect due to the carrier spent does not occur even if the release agent exists on the toner surface.
[0053]
In the two-component developer of the present invention, in addition to the above requirements, a more preferable two-component developer can be obtained by defining the dispersion state of the resin fine particles on the carrier surface.
[0054]
In observation of the carrier surface, the average particle size of the resin fine particles is 0.05 to 1.0 μm, and 1 to 200 particles / μm.²Preferably 10 to 150 / μm²More preferably it is present.
[0055]
When the particle size of the resin fine particles is smaller than 0.05 μm, when the toner is replaced, a release agent present on the toner surface adheres to the carrier surface, and the charge rising of the toner is deteriorated to cause image defects such as fogging. If the particle size of the resin fine particles is larger than 1.0 μm, the effect of alleviating the collision of the resin fine particles with the carrier charge imparting portion cannot be obtained, and charispent occurs.
[0056]
The number of resin fine particles is 1 / μm.²If it is smaller than that, the effect of mitigating the collision of the resin fine particles with the carrier charge imparting layer cannot be obtained, and charispent is generated. 200 / μm²If the amount is larger than that, the charged portion existing on the surface of the carrier becomes very small, so that proper charge cannot be given to the toner.
[0057]
The resin particles added to the carrier are preferably crosslinkable resins. If the resin is not a crosslinkable resin, the resin fine particles are likely to be deteriorated by frictional heat when frictionally charged with the toner. The crosslinkable resin here refers to a resin having a three-dimensional network structure.
[0058]
The decomposition temperature of the resin fine particles added to the carrier is preferably 230 ° C. or higher, and more preferably 260 ° C. or higher. When the temperature is 230 ° C. or lower, when heat is applied in the step of coating the surface of the carrier, the spent resistance of the carrier is inferior because the surface does not exist in a particle state.
[0059]
In the two-component developer of the present invention, a more preferable two-component developer can be obtained by defining the shape of the toner in addition to the above requirements.
[0060]
In the present invention, the desired toner shape means that the average circularity A is in the range of 0.915 ≦ A ≦ 0.960, preferably 0.920 ≦ A ≦ 0, in the toner particles having an equivalent circle diameter of 3 μm or more. .945 range. If the value of A is less than 0.915, there are many irregularities on the toner surface, and the release agent present on the toner surface peels off when coming into contact with the carrier. An image defect occurs. On the other hand, if it is larger than 0.960, the amount of the release agent present on the toner surface is too large and the toner is not properly charged, so that fog and toner scattering occur.
[0061]
In the present invention, in order to obtain a toner having a desired shape and performance as described above, in the process of producing the toner, a process of applying a mechanical impact force while discharging the generated fine powder out of the system (in the process) The inventors have confirmed that it is effective to apply (details will be described below). In other words, even if the normal pulverization step and the spheronization step are performed alone or at the same time, if the generated fine powder is not discharged while being discharged out of the system, the considerably small fine powder generated during the pulverization aggregates again to make the shape uneven Therefore, a mechanical impact force is required more than necessary to obtain a desired sphericity, resulting in an excessive amount of heat and an increase in the amount of the release agent on the toner surface, which is harmful. Small fine powder is one of the major factors that worsen the spent on the carrier used in two-component development. If classification is performed without stopping the same air flow that applies mechanical impact force, the fine powder is efficiently discharged out of the system without re-aggregation. From the above, when a mechanical impact force is applied while discharging the generated fine powder out of the system, the toner shape, the fine powder amount, and the amount of the release agent can be controlled as desired. Thus, the toner of the present invention that satisfies the above requirements obtained by considering the balance between the degree of the sphere and the amount of the release agent on the surface of the toner is not merely spheroidized. The problems of the conventional toner can be solved.
[0062]
Next, the binder resin contained in the toner of the present invention will be described.
[0063]
The binder resin contained in the toner of the present invention includes (a) a polyester resin, or (b) a hybrid resin having a polyester unit and a vinyl polymer unit, or (c) a hybrid resin and a vinyl polymer. Or (d) a mixture of a polyester resin and a vinyl copolymer, or (e) a mixture of a hybrid resin and a polyester resin, or (f) a polyester resin and a hybrid resin, and a vinyl polymer. Resins selected from any of the mixtures are preferred.
[0064]
In the present invention, the “hybrid resin component” in the binder resin means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are formed by a transesterification reaction, preferably a vinyl polymer. Is used to form a graft copolymer (or block copolymer) having a backbone polymer and a polyester unit as a branch polymer.
[0065]
“Polyester unit” refers to a portion derived from polyester, and “vinyl polymer unit” refers to a portion derived from a vinyl polymer. The polyester monomer constituting the polyester unit is a polyvalent carboxylic acid component and a polyhydric alcohol component, and the vinyl polymer unit is a monomer component having a vinyl group. A monomer having a vinyl group, or a polyhydric alcohol component and a monomer having a vinyl group are defined as “polyester unit” components.
[0066]
The binder resin has a molecular weight distribution measured by gel permeation chromatography (GPC) having a main peak (MP) with a molecular weight of 3,500 to 30,000, more preferably a molecular weight of 5,000 to 20,000. The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 5.0 or more.
[0067]
When the main peak is in a region having a molecular weight of less than 3,500, the hot offset resistance of the toner is insufficient. On the other hand, when the main peak is in the region where the molecular weight exceeds 30,000, sufficient low-temperature fixability of the toner cannot be obtained, and application to high-speed fixing becomes difficult. Moreover, when Mw / Mn is less than 5.0, it becomes difficult to obtain good offset resistance.
[0068]
Next, the material of the binder resin will be described.
[0069]
When a polyester resin is used as the binder resin, alcohol and carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, or the like can be used as a raw material monomer.
[0070]
Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.
[0071]
Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.
[0072]
Examples of the carboxylic acid component include aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyrophosphate, or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, or the like Succinic acid substituted with an alkyl group having 6 to 12 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or the anhydride thereof;
[0073]
Among the above, in particular, a bisphenol derivative represented by the following general formula (1) as a diol component, a carboxylic acid component comprising a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof (for example, Polyester resins obtained by condensation polymerization of fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and the like as acid components are preferable because they have good charging characteristics.
[0074]
[Chemical 1]

(In the formula, 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.)
[0075]
Furthermore, in the present invention, when a hybrid resin having a polyester unit and a vinyl polymer unit is used as the binder resin, further improved release agent dispersibility, low-temperature fixability, and offset resistance can be expected. .
[0076]
The following are mentioned as a vinyl-type monomer for producing | generating a vinyl-type resin. Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Styrene and derivatives thereof such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated such as butadiene and isoprene Polyenes; vinyl chloride, vinyl chloride, vinyl bromide, fluoride Vinyl halides such as vinyl; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-methacrylate Α-methylene aliphatic monocarboxylic acid esters such as octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate Propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-acrylate Acrylic esters such as lorethyl and phenyl acrylate; 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 compounds such as N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.
[0077]
In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester unsaturated dibasic acid half ester; dimethylmaleic acid, dimethyl fumaric acid unsaturated dibasic acid ester; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.
[0078]
Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.
[0079]
The vinyl polymer unit of the binder resin referred to in the present invention may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. The following are mentioned as a crosslinking agent used in this case.
[0080]
Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butanediol di Examples include acrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and the above compounds in which acrylate is replaced by methacrylate; linked by an alkyl chain containing an ether bond. Examples of diacrylate compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 , Polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing acrylates of the above compounds with methacrylates; as diacrylate compounds linked by a chain containing an aromatic group and an ether bond, for example , 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.
[0081]
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.
[0082]
In the present invention, it is preferable that a monomer component capable of reacting with both resin components is contained in the vinyl polymer component and / or the polyester resin component. Examples of the monomer constituting the polyester resin component that can react with the vinyl polymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl polymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
[0083]
As a method of obtaining a reaction product of a vinyl polymer and a polyester resin, either a polymer containing a monomer component capable of reacting with each of the vinyl polymer and the polyester resin listed above is present, or either A method obtained by polymerizing both resins is preferred.
[0084]
Examples of the polymerization initiator used for producing the vinyl polymer 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, cyclohexane Ketone peroxides such as Sanone 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, -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 Benzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl peroxyhexa Idro terephthalate, di -t- butyl peroxy azelate and the like.
[0085]
Next, the manufacturing method of the hybrid resin used for the binder resin of this invention is demonstrated. The hybrid resin of the present invention can be produced by the production methods shown in the following (1) to (6).
[0086]
(1) A method in which a vinyl polymer, a polyester resin, and a hybrid resin component are blended after production. The blend is produced by dissolving and swelling in an organic solvent (for example, xylene) and then distilling off the organic solvent. The hybrid resin component is synthesized by separately producing a vinyl polymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and performing a transesterification reaction by heating. The ester compound used can be used.
[0087]
(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.
[0088]
(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.
[0089]
(4) After the production of the vinyl polymer unit and the polyester unit, a 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.
[0090]
(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.
[0091]
(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.
[0092]
In the production methods of (1) to (5) above, a polymer unit having a plurality of different molecular weights and crosslinking degrees can be used as the vinyl polymer unit and / or the polyester unit.
[0093]
The binder resin contained in the toner of the present invention includes a mixture of the polyester and a vinyl polymer, a mixture of the hybrid resin and a vinyl polymer, a vinyl resin in addition to the polyester resin and the hybrid resin. A mixture of polymers may be used. Preferably, a hybrid resin is contained.
[0094]
The glass transition temperature of the binder resin contained in the toner of the present invention is preferably 40 to 90 ° C, more preferably 45 to 85 ° C. The acid value of the binder resin is preferably 1 to 40 mgKOH / g.
[0095]
In the present invention, the proportion of the polyester unit in the binder resin is preferably in the range of 50 to 100 (%).
[0096]
Next, the following are mentioned as a mold release agent used for this invention.
[0097]
Low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, aliphatic hydrocarbon wax such as Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; block of aliphatic hydrocarbon wax Copolymers; waxes based on fatty acid esters such as carnauba wax, montanate wax, candelilla wax, rice wax, ozokerite, beeswax; and part or all of fatty acid esters such as deoxidized carnauba wax And the like.
[0098]
Furthermore, as release agents, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, and carnauvir alcohol Saturated alcohols such as ceryl alcohol and melyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide and lauric acid amide; Acid amides, saturated fatty acid bisamides such as hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N -Unsaturated fatty acid amides such as dioleyl sebacic acid amide; m-xylene bis stearic acid amide, aromatic bisamides such as N, N'-distearylisophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, stearic acid Fatty acid metal salt such as magnesium (generally called metal soap); Graft wax obtained by grafting vinyl monomer such as styrene or acrylic acid to aliphatic hydrocarbon wax; Fatty acid such as behenic acid monoglyceride and polyhydric alcohol And a partially esterified product of: methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and the like.
[0099]
A particularly preferably used wax is paraffin wax having a short molecular chain, less steric hindrance, and excellent mobility.
[0100]
In the molecular weight distribution of the wax, the main peak is preferably in the region of molecular weight 350-2400, more preferably in the region of 400-2000. By giving such a molecular weight distribution, preferable thermal characteristics can be imparted to the toner.
[0101]
The addition amount of the release agent used in the present invention is 1 to 10 parts by mass, preferably 2 to 8 parts by mass with respect to 100 parts by mass of the binder resin. If the amount is less than 1 part by mass, a sufficient amount of heat and pressure are required because the amount is small in order to come out on the toner surface at the time of melting and to exhibit the releasability. On the other hand, if the amount exceeds 10 parts by mass, the amount of the release agent in the toner is too large and the transparency and charging characteristics are inferior.
[0102]
Next, the colorant contained in the toner of the present invention will be described.
[0103]
As the colorant used in the present invention, pigments and / or dyes can be used.
[0104]
Examples of the color pigment for magenta include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.
[0105]
Such a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.
[0106]
Examples of the magenta dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic dyes such as basic violet 1,3,7,10,14,15,21,25,26,27,28 are listed.
[0107]
As other color pigments, cyan color pigments include C.I. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Examples thereof include Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
[0108]
Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 155, 180, C.I. I. Vat yellow 1, 3, 20 etc. are mentioned.
[0109]
In addition, the usage-amount of a coloring agent is 0.1-60 mass parts with respect to 100 mass parts of binder resin, Preferably it is good to make it contain 0.5-50 mass parts.
[0110]
The toner of the present invention can also be used in combination with a known charge control agent.
[0111]
In the present invention, an organic metal compound can be contained in the toner as needed. The organometallic compound is preferably a metal compound of an aromatic carboxylic acid derivative selected from aromatic oxycarboxylic acids and aromatic alkoxycarboxylic acids, and the metal is preferably a divalent or higher valent metal atom. Mg as a divalent metal²⁺, Ca²⁺, Sr²⁺, Pb²⁺, Fe²⁺, Co²⁺, Ni²⁺, Zn²⁺, Cu²⁺Is mentioned. Zn as a divalent metal²⁺, Ca²⁺, Mg²⁺, Sr²⁺Is preferred. Al for trivalent or higher metals³⁺, Cr³⁺, Fe³⁺, Ni³⁺Is mentioned. Among these metals, Al is preferable.³⁺, Cr³⁺And particularly preferred is Al.³⁺It is.
[0112]
Specific examples of the metal compound include the following compounds.
[0113]
[Chemical 2]

[0114]
[Chemical 3]

[0115]
In the present invention, the organometallic compound is particularly preferably an aluminum compound of di-tert-butylsalicylic acid.
[0116]
The addition amount of the charge control agent used in the present invention is 0.3 to 10 parts by mass, preferably 0.5 to 7 parts by mass with respect to 100 parts by mass of the binder resin.
[0117]
This is because if it is less than 0.3, the effect of charging rise cannot be obtained, and if it is more than 10, the environmental fluctuation increases.
[0118]
The toner of the present invention may contain a fluidizing agent.
[0119]
For example, a toner having improved fluidity can be obtained by mixing a fluidizing agent or the like with a mixer such as a Henschel mixer after the pulverization / classification step.
[0120]
Any fluidizing agent can be used as long as it can be added to the colorant-containing binder resin particles to increase the fluidity before and after the addition. For example, fluorinated resin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder, titanium oxide fine powder, alumina fine powder, wet process silica, fine process silica such as dry process silica, silane compound, and organic Examples include treated silica that has been surface-treated with a silicon compound, a titanium coupling agent, silicone oil, and the like.
[0121]
The dry process silica is a fine powder produced by vapor phase oxidation of a silicon halogen compound, and is called so-called dry process silica or fumed silica, and is manufactured by a conventionally known technique. 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.
SiCl_Four+ 2H₂+ O₂→ SiO₂+ 4HCl
[0122]
In this production process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. . The average primary particle size is preferably in the range of 0.001 to 2 μm, particularly preferably silica fine powder in the range of 0.002 to 0.2 μm. .
[0123]
As the titanium oxide fine powder, fine particles of titanium oxide obtained by a low-temperature oxidation method (thermal decomposition, hydrolysis) of sulfuric acid method, chlorine method, volatile titanium compounds such as titanium alkoxide, titanium halide and titanium acetylacetonate are used. . As the crystal system, any of anatase type, rutile type, mixed crystal type thereof, and amorphous type can be used.
[0124]
In addition, the alumina fine powder includes the buyer method, improved buyer method, ethylene chlorohydrin method, underwater spark discharge method, organoaluminum hydrolysis method, aluminum alum pyrolysis method, ammonium aluminum carbonate pyrolysis method, aluminum chloride Alumina fine powder obtained by flame decomposition method is used. As the crystal system, α, β, γ, δ, ζ, η, θ, κ, χ, ρ type, mixed crystal type, and amorphous type are used. Α, δ, γ, θ, mixed crystal A mold or an amorphous material is preferably used.
[0125]
Further, as the silica subjected to the above surface treatment, those obtained by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with inorganic fine powders are used. Specifically, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound. Examples of such organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchloro. Silane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisilo Xan, 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane containing 2 to 12 siloxane units per molecule and containing hydroxyl groups bonded to one Si at each terminal unit It is done. These are used alone or in a mixture of two or more.
[0126]
Further, as the fluidizing agent used in the present invention, the above-described dry process silica may be used after being treated with a coupling agent having an amino group or silicone oil.
[0127]
The fluidizing agent used in the present invention 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 fluidizing agent is added in an amount of 0.01 to 8 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the toner.
[0128]
Next, the carrier used in the present invention will be described.
[0129]
The following are mentioned as a carrier core material used for this invention. Metals such as surface oxidized or unoxidized iron, nickel, copper, zinc, cobalt, manganese, magnesium, chromium, rare earth and their alloys or oxides and ferrites can be used. Moreover, there is no special restriction | limiting as the manufacturing method. Among these, ferrite is particularly preferable.
[0130]
In addition, it is preferable that the surface of the carrier has a resin coating layer of 0.01 to 2.0% by mass with respect to the mass of the carrier core in view of charge imparting property and spent resistance to the toner. More preferably, it is 0.05-1.0 mass%.
[0131]
The resin-coated carrier of the present invention has an average particle size of 25 to 65 μm, more preferably 30 to 65 μm. When the average particle diameter of the resin-coated carrier is less than 25 μm, the rise of the developer due to the magnetic force on the developing carrier is not uniform, and the uniformity of the solid image is lost. When the average particle size of the resin-coated carrier exceeds 65 μm, the developer standing due to magnetism is high, and the developer sweeps unevenly due to the ears. Carrier particles smaller than 16 μm are 2% or less, carrier particles of 62 μm or more are 0.2 to 45%, and carrier particles of 88 μm or more are 12% or less. Is preferable.
[0132]
Examples of the resin used for coating the carrier of the present invention include silicone resins, acrylic-modified silicone resins, epoxy resins, polyester resins, styrene / acrylic resins, melamine resins, fluorine resins, fluorine / acrylic resins. And a mixture of these resins, particularly preferably silicone-based resins, acrylic-modified silicone resins, fluorine-based resins, fluorine-acrylic resins, and the like.
[0133]
Examples of the acrylic-modified silicone resin include methacrylic ester-modified silicone resins, acrylic ester-modified silicone resins, styrene-methacrylic ester-modified silicone resins, and styrene-acrylic ester-modified silicone resins. These may be used alone or in combination.
[0134]
More specifically, the silicone resin may be any conventionally known silicone resin, such as a straight silicone resin consisting only of an organosiloxane bond represented by the following formula and an alkyd, polyester, epoxy, urethane, etc. Examples thereof include modified silicone resins.
[0135]
[Formula 4]

[0136]
R in the above formula₁Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, R₂And R_ThreeIs a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a hydroxy group, a carboxyl group, An ethylene oxide group, a glycinyl group or a group shown below.
[0137]
[Chemical formula 5]

[0138]
R in the above formula_Four, R_FiveIs a hydroxy group, carboxyl group, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, alkenyl group having 2 to 4 carbon atoms, alkenyloxy group having 2 to 4 carbon atoms, phenyl group, phenoxy group , K, l, m, n, o, p are positive numbers of 1 or more.
[0139]
Each of the above substituents may have a substituent such as an amino group, a hydroxy group, a carboxyl group, a mercapto group, an alkyl group, a phenyl group, an ethylene oxide group, or a halogen atom in addition to an unsubstituted group. For example, commercially available straight silicone resins include KR271, KR255, KR152 manufactured by Shin-Etsu Chemical, SR2400, SR2405 manufactured by Toray Dow Corning, etc., and modified silicone resins include KR206 (alkyd modified) manufactured by Shin-Etsu Chemical, There are KR5208 (acrylic modification), ES1001N (epoxy modification), KR305 (urethane modification), SR2115 (epoxy modification) and SR2110 (alkyd modification) manufactured by Toray Dow Corning.
[0140]
In the present invention, the carrier coat resin may contain a coupling agent. As a coupling agent to be used, a silane coupling agent is used, but other examples include a titanium coupling agent and an aluminum coupling agent. Examples of the silane coupling agent preferably used in the present invention include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxy Silane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] an Nitric chloride, γ-chloropropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane (made by Torre Silicone), allyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltri Examples include methoxysilane, dimethyldiethoxysilane, 1,3-divinyltetramethyldisilazane, and methacryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride (manufactured by Chisso Corporation).
[0141]
Examples of the resin used for the resin fine particles of the present invention include a polymer obtained by homopolymerization or copolymerization using a polymerizable monomer exemplified below. Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methoxystyrene, p-ethylstyrene, α-methylstyrene, and p-tertiarybutylstyrene; acrylic Acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, n-propyl acrylate, isobutyl acrylate, octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, Acrylic esters such as phenyl acrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, methacrylic acid 2 Methacrylic acid esters such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminomethyl methacrylate, diethylaminoethyl methacrylate; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc. Other vinyl derivatives, specifically alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl ether, isobutyl ether, β-chloroethyl vinyl ether, phenyl vinyl ether, p-methylphenyl ether, p-chlorophenyl Ether, p-bromophenyl ether, p-nitrophenyl vinyl ether, p-methoxyphenyl vinyl ether, - vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, N- vinylpyrrolidone, 2-vinylimidazole, N- methyl-2-vinylimidazole, N- vinylimidazole, it may be mentioned butadiene. In particular, polymethyl methacrylate and melamine resin are more preferable. Known PMMA particles can be used, and materials necessary for the intended electrophotographic developing toner can be selected, but cross-linked PMMA particles are preferably used.
[0142]
In addition, as a granulation method of the resin fine particles used in the present invention, a method of pulverizing the above polymer, a particle polymerization method such as emulsion polymerization, soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, or the like may be used. it can.
[0143]
The addition amount of the resin fine particles is preferably 0.1 to 50% by mass with respect to the resin layer coated on the carrier. More preferably, a better effect can be imparted at 1.0 to 45% by mass.
[0144]
In general, the resin layer is coated on the carrier surface by diluting the resin in a solvent and coating the surface of the carrier core. The solvent used here may be one that is soluble in each resin. When the resin is soluble in an organic solvent, the organic solvent may be toluene, xylene, cellosolve butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, or methanol. In the case of a water-soluble resin or emulsion type, water may be used. The carrier core material is coated with a resin diluted with a solvent by a coating method such as a dipping method, a spray method, a brush coating method, or a kneading method, and then the solvent is volatilized. In addition, it is also possible to coat the resin powder on the surface of the carrier core material by a dry method instead of a wet method using such a solvent.
[0145]
When the resin is coated on the surface of the carrier core and then baked, either an external heating method or an internal heating method may be used, for example, a fixed or fluid electric furnace, a rotary electric furnace, a burner furnace, or by microwave It can be burned. The baking temperature varies depending on the resin to be used, but a temperature higher than the melting point or glass transition point is necessary, and in the case of a thermosetting resin or a condensation type resin, it is necessary to raise it to a temperature at which the curing proceeds sufficiently.
[0146]
In this way, after the resin is coated and baked on the surface of the carrier core material, the resin coating carrier is obtained through cooling, crushing and particle size adjustment.
[0147]
The resin fine particles may be present on the carrier surface. However, as a method of inclusion, it is preferable to disperse the resin fine particles in a solvent at the time of resin coating and to disperse the resin fine particles together with the carrier coating resin. As the solvent to be dispersed at this time, it is preferable to select a solvent in which the resin fine particles do not swell.
[0148]
When a two-component developer is prepared in the present invention, good results are usually obtained when the mixing ratio is 2 to 15% by mass, preferably 4 to 13% by mass, as the toner concentration in the developer. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.
[0149]
<Regarding the Toner Production Method of the Present Invention>
Next, a procedure for producing the toner of the present invention will be described.
[0150]
First, in the raw material mixing step, as a toner internal additive, at least a binder resin, a colorant, and a release agent are weighed and mixed and mixed. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer.
[0151]
Further, the toner raw materials blended and mixed as described above are melt-kneaded to melt the binder resin, and the colorant and the like are dispersed therein. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. In general, a twin-screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, or the like is used. Furthermore, the colored resin composition obtained by melt-kneading the toner raw material is rolled by a two-roll roll after melt-kneading, and then cooled through a cooling step of cooling by water cooling or the like.
[0152]
In general, the cooled colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization step, first, coarse pulverization is performed with a crusher, a hammer mill, a feather mill, or the like, and further, pulverization is performed with a kryptron system manufactured by Kawasaki Heavy Industries, Ltd., a super rotor manufactured by Nissin Engineering Co., Ltd., or the like. After that, if necessary, classification is performed using a classifier such as an inertia class elbow jet (manufactured by Nippon Steel Mining Co., Ltd.) or centrifugal class turbo plex (manufactured by Hosokawa Micron Co., Ltd.), and the weight average particle diameter A classified product of 3 to 11 μm is obtained.
[0153]
If necessary, it is possible to obtain a classified product by performing a surface modification = spheronization treatment in a surface modification step, for example, a hybridization system manufactured by Nara Machinery Co., Ltd. or a mechano-fusion system manufactured by Hosokawa Micron.
[0154]
However, as a preferable production process of the toner of the present invention, mechanical pulverization is not used in the pulverization process, and the surface using the classification and mechanical impact force shown in FIGS. 1 and 2 is used after pulverization with an air jet pulverizer. It is to obtain a classified product having a weight average particle diameter of 3 to 11 μm using the apparatus A that simultaneously performs the modification treatment.
[0155]
In addition, you may use sieving machines, such as a high volta of a wind-type sieve (made by Shin Tokyo Machine Co., Ltd.) as needed. Furthermore, when processing with an external additive, a high-speed stirrer that gives a shearing force to powder such as a Henschel mixer or a super mixer is blended with a predetermined amount of classified toner and various known external additives. Can be used as The toner of the present invention can be obtained by stirring and mixing.
[0156]
Here, the apparatus A used in the present invention will be described in detail below.
[0157]
As shown in FIG. 1, in the surface reforming apparatus, the casing 30, a jacket (not shown) through which cooling water or antifreeze liquid can be passed, and a surface reforming means, which is in the casing 30 and is attached to the central rotating shaft, Dispersion rotor 36, which is a rotating body on a disk that rotates at a high speed, and has a plurality of square disks or cylindrical pins 40 on the upper surface, and a surface that is arranged at a constant interval on the outer periphery of dispersion rotor 36 Liner 34 provided with a large number of grooves on the surface of the liner 34 (there is no need to have grooves on the liner surface), and further, a classification rotor 31 which is a means for classifying the surface-modified raw material into a predetermined particle size. Furthermore, a cold air introduction port 35 for introducing cold air, a raw material supply port 33 for introducing a raw material to be treated, and a surface modification time can be freely adjusted so that it can be opened and closed. The The space between the outlet valve 38, the powder discharge port 37 for discharging the processed powder, and the classification rotor 31 as the classification means and the dispersion rotor 36-the liner 34 as the surface modification means is classified. A cylindrical guide ring 39 which is a guide means for partitioning the first space 41 before being introduced into the means and the second space 42 for introducing the particles from which fine powder has been classified and removed by the classifying means into the surface treatment means. It consists of and. A gap portion between the dispersion rotor 36 and the liner 34 is a surface modification zone, and a classification rotor 31 and a rotor peripheral portion are classification zones.
[0158]
As described above, the batch type surface reforming apparatus includes a classifying means for continuously discharging and removing fine powder having a predetermined particle size or less to the outside of the apparatus, a surface treatment means using a mechanical impact force, and the classifying means and the surface. Guide for partitioning the space between the processing means into a first space before being introduced into the classification means and a second space for introducing the particles from which fine powder has been removed by the classification means into the surface treatment means Means.
[0159]
Then, using this surface modification device, the finely pulverized product is introduced into the first space, and the fine particles having a predetermined particle diameter or less are continuously discharged and removed from the device by the classifying means, while passing through the second space. Then, it is introduced into the surface treatment means using mechanical impact force, surface modification treatment is performed, and the surface modification treatment using mechanical impact force is repeated for a certain period of time by circulating again to the first space. By applying the step, it is possible to obtain a surface-modified toner having a desired shape and performance from which fine powder having a predetermined particle size or less is removed.
[0160]
The process will be described more specifically with reference to FIGS.
[0161]
When a finely pulverized product is introduced from the raw material supply port 33 with the discharge valve 38 closed, the charged finely pulverized product is first sucked by a blower (not shown) and classified by the classifying rotor 31. At that time, the classified fine powder having a predetermined particle diameter or less is continuously discharged and removed out of the apparatus, and the coarse powder having a predetermined particle diameter or more passes along the inner periphery (second space 42) of the guide ring 39 by centrifugal force. The circulating flow generated by the dispersion rotor 36 is guided to the surface modification zone. The raw material guided to the surface modification zone is subjected to a surface modification treatment by receiving a mechanical impact force between the dispersion rotor 36 and the liner 34. The surface-modified particles having undergone surface modification are guided to the classification zone along the outer periphery (first space 41) of the guide ring 39 on the cold air passing through the inside of the machine. The coarse powder discharged to the outside of the machine is put into a circulating flow, returned to the surface modification zone again, and repeatedly subjected to the surface modification action. After a certain period of time, the discharge valve 38 is opened and the surface modified particles are recovered from the discharge port 37.
[0162]
As a result of investigations by the present inventors, it has been found that the time until the discharge valve is opened (cycle time) and the rotational speed of the dispersion rotor are important in controlling the sphericity and the amount of the surface release agent. To increase the sphericity, it is effective to increase the cycle time or increase the peripheral speed of the dispersion rotor. In order to keep the amount of the surface release agent low, it is effective to shorten the cycle time or lower the peripheral speed. In particular, it is necessary to lengthen the cycle time because the spherical shape cannot be efficiently spheroidized unless the peripheral speed of the dispersed rotor exceeds a certain level. In this case, considering the relationship with the amount of surface release agent, the peripheral speed And cycle time need to be set. In the present invention, the peripheral speed is 1.2 × 10^FiveIt is mm / sec or more, and a cycle time of 5 to 60 seconds is effective.
[0163]
【Example】
Specific examples of the present invention will be described below, but the present invention is not limited to these examples.
[0164]
In addition, the measuring method used in the Example in this invention is as follows.
[0165]
1) Measurement of average circularity of toner
The equivalent circle diameter and circularity of the toner are used as a simple method for quantitatively expressing the shape of the toner particles. In the present invention, a flow type particle image analyzer “FPIA-2100” manufactured by Sysmex Corporation is used. And was calculated using the following formula.
[0166]
[Expression 1]

[0167]
Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is 512 × 512 image processing resolution (pixels of 0.3 μm × 0.3 μm). ) Is defined as the perimeter of the particle image when image processing is performed.
[0168]
In the present invention, the circularity is an index indicating the degree of unevenness of the toner particles, and is 1.000 when the toner particles are completely spherical. The more complicated the surface shape, the smaller the circularity.
[0169]
The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following equation, where the circularity (center value) at the division point i of the particle size distribution is Ci and the frequency is fCi.
[0170]
[Expression 2]

[0171]
In addition, “FPIA-2100”, which is a measuring apparatus used in the present invention, calculates the circularity of each particle, and then calculates the average circularity and the circularity standard deviation. The degree 0.4 to 1.0 is divided into 61 classes, and a calculation method is used in which the average circularity and the circularity standard deviation are calculated using the center value and frequency of the dividing points. However, the error of the average circularity and the circularity standard deviation calculated by the calculation formula using each value of the average circularity and the circularity standard deviation calculated by this calculation method and the circularity of each particle described above is In the present invention, the circularity of each particle described above is directly set for the reason of handling data such as shortening the calculation time and simplifying the calculation formula. Such a calculation method that is partially changed using the concept of the calculation formula to be used may be used. Furthermore, “FPIA-2100”, which is a measuring apparatus used in the present invention, has a thinner sheath flow (7 μm) than “FPIA-1000” that has been used to calculate the shape of the toner. (To 4 μm) and the processing particle image magnification, and the processing resolution of the captured image is improved (256 × 256 → 512 × 512), so that the accuracy of toner shape measurement is improved, thereby making sure the fine particles are more reliable. A device that has achieved supplementation. Therefore, when it is necessary to measure the shape more accurately as in the present invention, the FPIA-2100 that can obtain information on the shape more accurately is more useful.
[0172]
As a specific measurement method, 10 ml of ion-exchanged water from which impurities have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein. Add 0.02 g and disperse uniformly. As a means for dispersion, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios Co., Ltd.) is used, and dispersion treatment is performed for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more.
[0173]
For the measurement of the shape of the toner particles, the dispersion concentration is readjusted so that the toner particle concentration at the time of measurement is 3000 to 10,000 particles / μl, and the flow type particle image measuring device is used to measure 0.65 μm or more and 159 More than 1000 toner particles having a circle-equivalent diameter of less than 21 μm are measured, and using this data, data of 3 μm or less is cut to determine the average circularity of the toner particles.
[0174]
The outline of the measurement is as follows.
[0175]
The sample dispersion is passed through a flow path (expanded along the flow direction) of a flat and flat flow cell (thickness: about 200 μm). The strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other so as to form an optical path that passes through the thickness of the flow cell. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter. The circularity of each particle is calculated from the projected area of the two-dimensional image of each particle and the perimeter of the projected image using the above circularity calculation formula.
[0176]
2) Transmittance B in methanol 45 volume% aqueous solution
(I) Preparation of toner dispersion
An aqueous solution having a volume mixing ratio of methanol: water of 45:55 is prepared. 10 ml of this aqueous solution is placed in a 30 ml sample bottle (Nippon Denka Glass: SV-30), and 20 mg of toner is impregnated on the liquid surface to cover the bottle. Then, it is made to shake for 5 seconds at 150 rpm with a Yayoi type shaker (model: YS-LD). At this time, the angle of shaking is such that the shaking column moves 15 degrees forward and 20 degrees backward, assuming that the vertical (vertical) of the shaker is 0 degree. The sample bottle is fixed to a fixing holder (with the sample bottle lid fixed on the extension at the center of the column) attached to the tip of the column. After removing the sample bottle, the dispersion after standing for 30 seconds is used as a measurement dispersion.
[0177]
(Ii) Transmittance measurement
The dispersion obtained in (i) is placed in a 1 cm square quartz cell, and using a spectrophotometer MPS2000 (manufactured by Shimadzu Corporation), transmittance B (%) at a wavelength of 600 nm of the dispersion after 10 minutes (the following formula) Measure).
Transmittance B (%) = I / I₀× 100 (I: Incident luminous flux ... I₀Transmitted light)
[0178]
3) Measurement of weight average particle diameter of toner
In the present invention, a Coulter Multisizer (manufactured by Coulter, Inc.) can be used for the weight average particle diameter and particle size distribution of the toner. As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) 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 electrolytic aqueous 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 a dispersion process for about 1 to 3 minutes with an ultrasonic disperser, and the volume and the number of toners of 2.00 μm or more are measured by using the 100 μm aperture as the aperture by the measuring device. The distribution and the number distribution are calculated to determine the weight average particle diameter (D4) (the median value of each channel is the representative value for each channel).
[0179]
As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00 μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00-40.30 μm are used.
[0180]
4) Measurement of maximum endothermic peak Tsc of toner
Temperature curve: Temperature increase I (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (200 ° C-30 ° C, temperature drop rate 10 ° C / min)
Temperature increase II (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)
The maximum endothermic peak Tsc of the toner is measured according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device), DCS-7 (manufactured by PerkinElmer) or DSC2920 (manufactured by TA Instruments Japan).
[0181]
The sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg. The sample is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rise rate of 10 ° C./min at room temperature and humidity in a measurement range of 30 to 200 ° C.
[0182]
The maximum endothermic peak of the toner is the one having the highest height from the baseline in the region above the Tg endothermic peak of the toner in the process of temperature increase II, or the endothermic peak of the Tg of the toner is different from the endothermic peak. When it is difficult to determine the overlap, the maximum endothermic peak of the toner of the present invention is defined as the highest peak of the overlapping peak.
[0183]
5) Molecular weight distribution by GPC measurement
The molecular weight distribution by GPC in the resin component of the toner is measured by GPC using a THF-soluble component obtained by dissolving the toner in a THF solvent as described below.
[0184]
That is, the toner is put in THF, left for several hours, and then sufficiently shaken to mix well with THF (until the sample is no longer united), and then left to stand for 12 hours or more. At this time, the standing time in THF is set to be 24 hours or longer. Thereafter, a sample processing filter (pore size 0.45 to 0.5 μm, for example, Mysori Disc H-25-5 manufactured by Tosoh Corporation, Excro Disc 25CR manufactured by Gelman Science Japan Co., Ltd., etc.) can be used. A sample of GPC is used. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.
[0185]
The GPC measurement of the sample prepared by the above method was performed by stabilizing the column in a heat chamber at 40 ° C., and flowing tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min as a solvent at this temperature. About 50 to 200 μl of a THF sample solution of resin adjusted to 0.05 to 0.6% by mass is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts (retention time). Examples of standard polystyrene samples for preparing a calibration curve include those manufactured by Tosoh Corporation or Pressure Chemical Co. Made molecular weight 6 × 10²2.1 × 10^Three4 × 10^Four1.75 × 10^Four5.1 × 10^Four1.1 × 10^Five3.9 × 10^Five8.6 × 10^Five2 × 10⁶4.48 × 10⁶It is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
[0186]
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, such as the combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807 manufactured by Showa Denko KK [Mu] -styragel 500, 10 manufactured by Waters^Three10^Four10^FiveCan be mentioned.
[0187]
6) Observation method of resin fine particles on carrier surface by focused ion beam processing observation device
Processing observation is performed using a focused ion beam processing observation apparatus (FIB) and FB-2000C (Hitachi). The sample is prepared by applying a carbon paste aqueous solution on a sample stage and placing a small amount of the sample thereon. Thereafter, the sample is set in an FIB apparatus without performing platinum deposition, and the surface of the target sample is observed while applying a beam to the surface and scraping the surface.
[0188]
7) Measuring method of triboelectric charge amount of toner
A schematic diagram of an apparatus for measuring the triboelectric charge amount is shown in FIG. About 0.5 to 1.5 g of a two-component developer collected from the developing sleeve of a copying machine or printer is placed in a metal measuring container 52 having a 500-mesh screen 53 at the bottom, and a metal lid 54 is placed. . The total mass of the measurement container 52 at this time is weighed and is defined as W1 (g). Next, in the suction device 51 (at least the insulator is in contact with the measurement container 52), the suction is performed through the suction port 57 and the air volume control valve 56 is adjusted so that the pressure of the vacuum gauge 55 is 250 mmAq. In this state, the toner is removed by suction for 2 minutes. The potential of the electrometer 59 at this time is set to V (volt). Here, 58 is a capacitor, and the capacity is C (mF). Moreover, the weight of the whole measurement container after suction is weighed and is defined as W2 (g). The triboelectric charge amount (mC / kg) of this sample is calculated as follows.
Sample triboelectric charge (mC / kg) = C × V / (W1-W2)
(However, the measurement conditions are 23 ° C. and 60% RH)
[0189]
8) Fixable area
The fixing unit is subjected to a fixing test using a laser jet 4100 (manufactured by Hewlett-Packard Co.) fixing machine and the fixing unit is modified so that the fixing temperature can be manually set. The image is 1.2 mg / cm on the amount of toner on the paper in a single color mode with CLC5000 in a normal temperature and humidity environment (23 ° C./60%).²The development contrast is adjusted to create an unfixed image. An image is formed on A4 (TKCLA4 which is a CLC recommended paper) with an image area ratio of 25%. In a room temperature and normal humidity environment (23 ° C./60%), the temperature range is raised by 10 ° C. in order from 120 ° C., and the temperature range in which no offset or wrapping occurs is defined as the fixable region.
[0190]
9) Evaluation of cleaning performance
Out of 10,000 sheets with the CLC 5000, when the remaining toner's warp streaks or spots appear on the image, the cleaning failure occurs.
A: There are no image defects.
B: There are no practical problems with the occurrence of 2 to 3 spots.
C: Some spots or streaks are generated and there is no practical problem.
D: Spots, streaks, and uneven density occur.
E: The influence of dirt is large, density unevenness and charging unevenness are also generated, and the image is disturbed.
[0191]
10) Fog measurement
As a method for measuring fog in the endurance test, in the case of cyan and black images, an average reflectance Dr (%) of plain paper before image output is a reflectometer equipped with an amber filter (manufactured by Tokyo Denshoku Co., Ltd.). REFLECTOMETER MODEL TC-6DS "). On the other hand, a solid white image was drawn on plain paper, and then the reflectance Ds (%) of the solid white image was measured. Fog (Fog [%]) is the following formula
Fog [%] = Dr [%] − Ds [%]
Calculated from Further, the above measurement was performed using a green filter for magenta and black images, and a blue filter for yellow images.
[0192]
11) Sl contamination
Wipe a portion of the developing sleeve surface after copying 10,000 sheets with ethanol, copy a solid black image, measure the image density before and after cleaning with ethanol, and calculate the difference to evaluate sleeve contamination. And classified into the ranks shown below.
[0193]
Sleeve contamination rank
A Less than Δ0.03
B Δ0.03 or more and less than Δ0.10
C Δ0.10 or more and less than Δ0.20
More than D Δ0.20
[0194]
12) Measuring method of volume average particle diameter of carrier
Carrier particle size measurement: SRA type of Microtrac particle size analyzer (Nikkiso Co., Ltd.) is used as a measuring device for carrier particle size distribution, and it is carried out with a range setting of 0.7 to 125 μm. Diameter (D₅₀) And particle size distribution.
[0195]
13) Measuring method of volume average particle diameter of resin fine particles
For the measurement of the particle size of the fine particles, a LS-230 type laser diffraction particle size distribution measuring device manufactured by Coulter, Inc., to which a liquid module is attached can be used. With this apparatus, it is possible to measure a volume average particle diameter of 0.04 to 2000 μm. The measurement is performed by adding a small amount of a surfactant to 10 cc of water, adding 10 mg of fine particles thereto, dispersing for 10 minutes with an ultrasonic disperser, and then measuring for 90 seconds for one measurement.
[0196]
(Example of hybrid resin production)
As a vinyl copolymer, 2.0 mol of styrene, 0.21 mol of 2-ethylhexyl acrylate, 0.14 mol of fumaric acid, 0.03 mol of α-methylstyrene dimer, and 0.05 mol of dicumyl peroxide are put into a dropping funnel. . In addition, 7.0 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane; 0 mol, 3.0 mol of terephthalic acid, 1.5 mol of trimellitic anhydride, 5.0 mol of fumaric acid and 0.2 g of dibutyltin oxide are placed in a 4-liter four-necked flask made of glass, a thermometer, a stirring rod, a condenser and nitrogen The introduction tube was installed and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and while stirring at a temperature of 145 ° C., the monomer of the vinyl resin, the crosslinking agent and the polymerization initiator were added from the previous dropping funnel. It was dripped over 4 hours. Next, the temperature was raised to 200 ° C. and reacted for 4 hours to obtain a hybrid resin. The results of molecular weight measurement by GPC are shown in Table 1.
[0197]
(Example of polyester resin production)
3.6 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1.6 mol of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1.7 mol of terephthalic acid, 1.0 mol of trimellitic anhydride, 2.4 mol of fumaric acid and 0.12 g of dibutyltin oxide are placed in a 4-liter 4-necked flask made of glass, a thermometer, a stir bar, a condenser and a nitrogen inlet tube Was installed in a mantle heater. Under a nitrogen atmosphere, reaction was performed at 215 ° C. for 5 hours to obtain a polyester resin. The results of molecular weight measurement by GPC are shown in Table 1.
[0198]
(Production example of styrene-acrylic copolymer resin)
・ 70 parts by mass of styrene
・ N-butyl acrylate 24 parts by mass
・ 6 parts by weight of monobutyl maleate
・ Di-t-butyl peroxide 1 part by mass
While stirring 200 parts by mass of xylene in a four-necked flask, the above components were sufficiently replaced with nitrogen and heated to 120 ° C., and then dropped over 3 hours. Further, the polymerization was completed under reflux of xylene, and the solvent was distilled off under reduced pressure to obtain a styrene-acrylic resin. The results of molecular weight measurement by GPC are shown in Table 1.
[0199]
[Table 1]

[0200]
Next, Table 2 shows the waxes used in the present invention.
[0201]
[Table 2]

[0202]
Next, the carrier used in the present invention will be described.
[0203]
<Example of carrier production>
(Carrier 1)
MnO 28.0 mol%, MgO 6.0 mol%, Fe₂O_Three65.2 mol% and SrCO_ThreeWas pulverized, mixed and dried in a 0.8 mol% wet ball mill for 5 hours, and then held at 850 ° C. for 1 hour to perform preliminary firing. This was pulverized with a wet ball mill for 7 hours to 3 μm or less. A dispersant and a binder (polyvinyl alcohol) were added to this slurry by several mass%, then granulated and dried with a spray dryer, and held in an electric furnace at 1200 ° C. for 4 hours to perform main firing. Thereafter, it was crushed and further classified to obtain a carrier core material having a volume average particle diameter of 49.8 μm.
[0204]
next,
100 parts by weight of straight silicone (KR255 manufactured by Shin-Etsu Chemical Co., Ltd.)
Silane coupling agent (γ-aminopropylethoxysilane) 5 parts by mass
Polymethyl methacrylate resin (volume average particle size 0.10 μm) 10 parts by mass
Was mixed with 300 parts by weight of xylene to prepare a carrier resin coating solution.
[0205]
The carrier core material was coated and solvent-removed while stirring using a fluidized bed heated to 70 ° C. using this resin coating solution. Furthermore, the carrier 1 was obtained by performing a treatment for 2.5 hours at 230 ° C. using an oven, and performing a pulverization and a classification treatment with a sieve.
[0206]
(Carrier 2)
Carrier 2 was obtained in the same manner as carrier 1 except that resin fine particles having a volume average particle diameter of 1.10 μm of polymethyl methacrylate resin were used. Due to the large particle size of the resin fine particles, there are few fine particles dispersed and present on the carrier surface.
[0207]
(Carrier 3)
Uses resin fine particles of polymethyl methacrylate resin with a volume average particle size of 0.05 μm, and after applying the coating resin to the carrier core material, it is the same as carrier 1 except that it is treated at 250 ° C. using an oven. Thus, carrier 3 was obtained. Since the particle size of the resin fine particles is small, there are many fine particles dispersed and present on the carrier surface. However, since the temperature at which the treatment is performed in the oven is high, the crosslinking reaction proceeds with the coupling agent, and the carrier surface. The resin fine particles dispersed and present in the resin are less than the particle size.
[0208]
(Carrier 4)
Instead of fluorine-acrylic resin (perfluorooctylethyl acrylate-methyl methacrylate) or polymethyl methacrylate resin as the coating resin, use melamine resin fine particles with a volume average particle size of 0.10 μm and no aminosilane coupling agent. Except for the above, Carrier 4 was obtained in the same manner as Carrier 1.
[0209]
(Carrier 5)
Carrier 5 was obtained in the same manner as carrier 1, except that no polymethyl methacrylate resin was added.
[0210]
Table 3 shows the carriers used in the present invention.
[0211]
[Table 3]

[0212]
<Example 1>
Toner 1 was prepared by the following method.
[0213]
・ 100 parts by mass of hybrid resin
・ 3 parts by weight of wax A
・ 1,4-di-tert-butylsalicylic acid aluminum compound 1 part by mass
Cyan pigment (Pigment Blue 15: 3) 4 parts by mass
Preliminarily mixed with a Henschel mixer with the above formulation, melt-kneaded with a twin screw extruder kneader, cooled and roughly crushed to about 1 to 2 mm using a hammer mill, and then with an air jet fine pulverizer Finely pulverized to a particle size of 20 μm or less. As shown in Table 3, the finely pulverized product obtained was further pulverized by the apparatus A that simultaneously performs the classification and surface modification (spheronization) treatment using mechanical impact force shown in FIGS. Cyan particles 1 (classified product) were obtained under the following production conditions.
[0214]
Toner 1 was prepared by externally adding 1.0% by mass of acicular titanium oxide fine powder (BET = 62, treated with 10% by mass of isobutylsilane coupling agent) to the cyan particles using a Henschel mixer. The toner 1 had a weight average particle diameter of 7.0 μm and an average circularity A of 0.933, and the transmittance B in a 45 volume% methanol aqueous solution at this time was 31%. Table 4 shows the constituent materials and physical properties of the toner.
[0215]
Further, the toner 1 and the carrier 1 were mixed so that the toner concentration became 7.0% by mass, whereby a developer 1 was obtained. Table 5 shows the evaluation results of the developer.
[0216]
With this developer 1, the oil application system and fixing roller web of the color copying machine CLC-5000 (manufactured by Canon) are removed, and the heating roller and pressure roller are changed to a roller having a PFA surface layer of 1.2 μm, and an oil application mechanism Evaluation of 10000-sheet printing test using an original document with an image area ratio of 3% in a single-color mode under normal temperature and humidity (23 ° C / 60%) After that, the image was further printed and evaluated at 20% high image area ratio of 2000 sheets. The same evaluation was performed in a high temperature and high humidity environment.
[0217]
As shown in Table 5, stable charge was maintained both at a low image area ratio and at a subsequent high image area ratio, and good results without fogging were obtained. Furthermore, a cyan image that faithfully reproduces the original was obtained with a wide fixing temperature range and no problem in cleaning properties.
[0218]
<Example 2>
Toner 2 was obtained in the same manner as in Example 1 except that the amount of toner release agent added was increased. Further, a developer 2 was obtained using toner 2 and carrier 1. Table 4 shows the constituent materials and physical properties of the toner, and Table 5 shows the evaluation results of the developer. Since the transmittance of the toner with respect to methanol is slightly high, the charge rising property under high temperature and high humidity is slightly deteriorated, but it is at a level that causes no practical problem.
[0220]
<Example 4>
Develop in the same manner as in Example 1 except that the toner 4 and the carrier 2 having a small number of resin fine particles existing on the surface of the carrier are used, except that the type of the toner release agent and the spheroidizing time are slightly increased. Agent 4 was obtained. Table 4 shows the constituent materials and physical properties of the toner, and Table 5 shows the evaluation results of the developer. Although the toner transmittance to methanol is slightly higher, the amount of resin fine particles on the carrier surface is slightly smaller, so the fog is slightly worse when a high-area image under high temperature and high humidity is drawn. There was no level.
[0221]
<Example 5>
Developer 5 was obtained in the same manner as in Example 4 except that carrier 3 having a large number of resin fine particles present on the carrier surface was used. Table 4 shows the constituent materials and physical properties of the toner, and Table 5 shows the evaluation results of the developer. There was no problem in the initial charging level, and the charging was stable in a wide range from a low image area to a high image area by combining with a carrier to which resin fine particles were added.
[0222]
<Example 6>
A developer 6 was obtained in the same manner as in Example 1 except that the toner 5 in which the type of the toner release agent was changed and the carrier 4 in which the type of the carrier coating material and the resin fine particles were changed were used. Table 4 shows the constituent materials and physical properties of the toner, and Table 5 shows the evaluation results of the developer. Since the toner has a high endothermic peak, the transmittance of the toner with respect to methanol is low, and it is good for the rising of the tribo. However, although the fixing temperature region is slightly reduced, there is no practical problem.
[0223]
<Example 7>
A developer 7 was obtained in the same manner as in Example 1 except that the toner 6 having a different type of toner release agent and the carrier 3 having a large number of resin fine particles present on the carrier surface were used. Table 4 shows the constituent materials and physical properties of the toner, and Table 5 shows the evaluation results of the developer. Although the transmittance of the toner with respect to methanol is low and it is good for starting up the tribo, the fixing temperature region is slightly reduced, but there is no practical problem.
[0224]
<Example 8>
A developer 8 was obtained in the same manner as in Example 1 except that the toner 7 and the carrier 2 in which the main binder of the toner was changed to a dry blend (50:50) of a hybrid resin and a polyester resin were used. Table 4 shows the constituent materials and physical properties of the toner, and Table 5 shows the evaluation results of the developer. The charge of the toner was slightly higher and the transmittance of the toner to methanol was slightly higher, but the rise of the tribo and the fog were good.
[0225]
  <Reference example 1>
  The developer 9 is obtained in the same manner as in Example 1 except that the toner 8 and the carrier 2 are used in which the main binder of the toner is changed to a dry blend (70:30) of a hybrid resin and a styrene acrylic copolymer resin. It was. Table 4 shows the constituent materials and physical properties of the toner, and Table 5 shows the evaluation results of the developer. Although the fixing property was slightly deteriorated, there was no problem in practical use.
[0226]
<Comparative Example 1>
Except for the combination of toner 9 and carrier 3 using a classifier (elbow jet classifier) using a pulverizer called a counter jet mill (manufactured by Hosokawa Micron) as the type of toner release agent and pulverization method. In the same manner as in Example 1, developer 10 was obtained. Table 4 shows the constituent materials and physical properties of the toner, and Table 5 shows the evaluation results of the developer. Since the transmittance of the toner with respect to methanol is very poor, neither charging property nor fogging has reached a practical level.
[0227]
<Comparative example 2>
A developer 11 was obtained in the same manner as in Example 1 except that the toner 10 and the carrier 1 were used in which the main binder of the toner was changed to a styrene acrylic copolymer resin. Table 4 shows the constituent materials and physical properties of the toner, and Table 5 shows the evaluation results of the developer. There was no fixing point and it was impractical.
[0228]
<Comparative Example 3>
A developer 12 was obtained in the same manner as in Example 1 except that the toner 11 and the carrier 1 in which the toner release agent was changed to polyethylene wax were used. Table 4 shows the constituent materials and physical properties of the toner, and Table 5 shows the evaluation results of the developer. There was no fixing point and it was impractical.
[0229]
<Comparative example 4>
A developer 13 was obtained in the same manner as in Example 1 except that the carrier 5 containing no resin fine particles was used. Table 4 shows the constituent materials and physical properties of the toner, and Table 5 shows the evaluation results of the developer. When a high-area image was drawn after drawing a low-area image under high temperature and high humidity, the charge amount decreased and fogging deteriorated.
[0230]
[Table 4]

[0231]
[Table 5]

[0232]
【The invention's effect】
In the present invention, an image satisfying high definition can be stably formed by optimizing the dispersion of the toner release agent and adding resin fine particles to the carrier. Specifically, it can be fixed at low temperature during fixing, eliminates the problem of high-temperature offset resistance, has a wide tolerance for sleeve contamination and carrier spent, has excellent cleaning properties, and is widely used from low-area images to high-area images. A high-quality image free from fog and density unevenness can be obtained, and a two-component developer having excellent environmental dependence and high durability can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic view of a surface modification treatment apparatus.
FIG. 2 is an explanatory view of a dispersion rotor and a disposed liner.
FIG. 3 is a schematic view of an apparatus for measuring the triboelectric charge amount of toner.
[Explanation of symbols]
31: Classification rotor
32: Fine powder recovery
33: Raw material supply port
34: Liner
35: Cold air inlet
36: Distributed rotor
37: Product outlet
38: Discharge valve
39: Guide ring
40: Square disk
41: First space
42: Second space
51: Suction machine
52: Measuring container
53: 500 mesh screen
54: Metal lid
55: Vacuum gauge
56: Air flow control valve
57: Suction port
58: Condenser
59: Electrometer

Claims (3)

In a two-component developer containing at least a binder resin, a colorant, a toner containing a release agent and a carrier,
(I) the binder resin includes at least a polyester unit;
(Ii) The transmittance B (%) of the toner in a 45 volume% methanol aqueous solution is in the range of 10 ≦ B ≦ 70,
(Iii) The endothermic curve in the differential thermal analysis (DSC) measurement of the toner has one or a plurality of endothermic peaks in the temperature range of 30 to 110 ° C., and the temperature Tsc of the maximum endothermic peak in the endothermic peak is 65 ° C. <Tsc <105 ° C.
(Iv) The carrier has a carrier core and a resin coating layer that covers the carrier core, and the resin coating layer contains resin fine particles ;
(V) said in the toner circle-equivalent diameter 3μm or more particles, the average circularity A is a two-component developer, wherein the range der Rukoto of 0.915 ≦ A ≦ 0.960. In observation by the focused ion beam (FIB) processing observation apparatus of the carrier, the average particle diameter of the resin fine particles 0.05 to 1.0 [mu] m, according to claim 1, characterized in that there 1-200 pieces / [mu] m ² The two-component developer described in 1.   The two-component developer according to claim 1 or 2, wherein the release agent is paraffin wax.

Images