JP3780202B2 - Full-color toner and method for producing the same - Google Patents

Description

【００５７】
さらに結着樹脂としてポリエステルユニットとビニル系共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、さらに良好なワックス分散性と、低温定着性，耐オフセット性の向上が期待できる。本発明に用いられる「ハイブリッド樹脂成分」とは、ビニル系重合体ユニットとポリエステルユニットが化学的に結合された樹脂を意味する。具体的には、ポリエステルユニットと（メタ）アクリル酸エステルの如きカルボン酸エステル基を有するモノマーを重合したビニル系重合体ユニットとがエステル交換反応によって形成されるものであり、好ましくはビニル系重合体を幹重合体、ポリエステルユニットを枝重合体としたグラフト共重合体（あるいはブロック共重合体）を形成するものである。
【００５８】
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。
【００５９】
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。
【００６０】
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。
【００６１】
本発明のトナーにおいて、結着樹脂のビニル系重合体ユニットは、ビニル基を２個以上有する架橋剤で架橋された架橋構造を有していてもよいが、この場合に用いられる架橋剤は、芳香族ジビニル化合物として例えば、ジビニルベンゼン、ジビニルナフタレンが挙げられ；アルキル鎖で結ばれたジアクリレート化合物類として例えば、エチレングリコールジアクリレート、１，３−ブチレングリコールジアクリレート、１，４−ブタンジオールジアクリレート、１，５−ペンタンジオールジアクリレート、１，６ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられ；エーテル結合を含むアルキル鎖で結ばれたジアクリレート化合物類としては、例えば、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコール＃４００ジアクリレート、ポリエチレングリコール＃６００ジアクリレート、ジプロピレングリコールジアクリレート及び以上の化合物のアクリレートをメタ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。
【００６２】
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。
【００６３】
本発明ではビニル系共重合体成分及び／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共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。ビニル系共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。
【００６４】
ビニル系樹脂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樹脂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。
【００６５】
本発明のビニル系共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。
【００６６】
本発明のトナーに用いられるハイブリッド樹脂を調製できる製造方法としては、例えば、以下の（１）〜（６）に示す製造方法を挙げることができる。
【００６７】
（１）ビニル系樹脂、ポリエステル樹脂及びハイブリッド樹脂成分をそれぞれ製造後にブレンドする方法であり、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。
【００６８】
（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。
【００６９】
（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。
【００７０】
（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。
【００７１】
（５）ハイブリッド樹脂成分を製造後、ビニル系モノマー及び／またはポリエステルモノマー（アルコール、カルボン酸）を添加して付加重合及び／又は縮重合反応を行うことによりビニル系重合体ユニット及びポリエステルユニットが製造される。この場合、ハイブリッド樹脂成分は上記（２）乃至（４）の製造方法により製造されるものを使用することもでき、必要に応じて公知の製造方法により製造されたものを使用することもできる。さらに、適宜、有機溶剤を使用することができる。
【００７２】
（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。
【００７３】
上記（１）乃至（５）の製造方法において、ビニル系重合体ユニット及び／またはポリエステルユニットは複数の異なる分子量、架橋度を有する重合体ユニットを使用することができる。
【００７４】
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共重合体との混合物、上記ハイブリッド樹脂とビニル系共重合体との混合物、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共重合体の混合物を使用しても良い。
【００７５】
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。樹脂の酸価は１〜４０ｍｇＫＯＨ／ｇであることが好ましい。
【００７６】
本発明のトナーは、その帯電性をさらに安定化させる為に必要に応じて荷電制御剤を用いることができる。荷電制御剤は、結着樹脂１００質量部当り０．１〜１０質量部、好ましくは０．１〜５質量部使用するのが好ましい。今日、当該技術分野で知られている荷電制御剤としては、以下のものが挙げられる。例えば有機金属錯体、キレート化合物が有効である。モノアゾ金属錯体、芳香族ヒドロキシカルボン酸、金属錯体、芳香族ジカルボン酸系の金属錯体が挙げられる。他には、芳香族ハイドロキシカルボン酸、芳香族モノ及びポリカルボン酸及びその金属塩、無水物、エステル類、ビスフェノールのフェノール誘導体類が挙げられる。特に適しているものは芳香族カルボン酸誘導体の金属化合物である。
【００７７】
また、本発明に用いられるフルカラー用トナーの着色剤としては、ワックスを表面に担持することで、ワックスと共に均一分散するためＢＥＴが重要となってくる。顔料のＢＥＴが３０ｍ²／ｇより小さいとワックスを担持する表面積が少ないため、遊離若しくは凝集したワックスが存在してしまう。また顔料のＢＥＴが２００ｍ²／ｇより大きいと顔料の表面の因子が強くなり、顔料自体の帯電性が強く表れて帯電阻害の要因となるためである。
【００７８】
顔料の種類としては例えば次の様なものが挙げられる。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。
【００７９】
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。かかる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。
【００８０】
その他の着色顔料として、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である。
【００８１】
イエロー用着色顔料としては、Ｃ．Ｉ．ピグメントイエロー１，２，３，４，５，６，７，１０，１１，１２，１３，１４，１５，１６，１７，２３，６５，７３，８３、Ｃ．Ｉ．バットイエロー１，３，２０等が挙げられる。
【００８２】
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質量部である。
【００８３】
本発明に用いられる黒色着色剤としてカーボンブラック，磁性体、及び上記に示すイエロー／マゼンタ／シアン着色剤を用い黒色に調色されたものが利用できる。
【００８４】
本発明のトナーは、粉砕・分級後、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ことにより、トナーの流動性を向上して用いることができる。
【００８５】
負帯電性流動化剤としては、着色剤含有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、それらをシランカップリング剤、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。
【００８６】
例えば乾式製法シリカとしては、ケイ素ハロゲン化合物の蒸気相酸化により生成された微粉体であり、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
【００８７】
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。
【００８８】
本発明に用いられるケイ素ハロゲン化合物の蒸気相酸化により生成された市販のシリカ微粉体としては、例えば以下の様な商品名で市販されているものがある。

【００８９】
さらには、該ケイ素ハロゲン化合物の気相酸化により生成されたシリカ微粉体に疎水化処理した処理シリカ微粉体を用いることが、より好ましい。該処理シリカ微粉体において、メタノール疎水化度が３０〜８０の範囲の値を示すようにシリカ微粉体を処理したものが特に好ましい。
【００９０】
疎水化方法としては、シリカ微粉体と反応あるいは物理吸着する有機ケイ素化合物等で化学的に処理することによって付与される。好ましい方法としては、ケイ素ハロゲン化合物の蒸気相酸化により生成されたシリカ微粉体を有機ケイ素化合物で処理する。
【００９１】
そのような有機ケイ素化合物の例は、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ある。これらは１種あるいは２種以上の混合物で用いられる。
【００９２】
本発明に用いられる流動化剤として、前述した乾式法シリカを、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たものを本発明の目的を達成するために必要に応じて用いてもかまわない。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質量部使用するのが良い。
【００９３】
本発明のトナーを二成分系現像剤に用いる場合は、トナーは磁性キャリアと混合して使用される。磁性キャリアとしては、例えば表面酸化又は未酸化の鉄、ニッケル、銅、亜鉛、コバルト、マンガン、クロム、希土類の如き金属粒子、それらの合金粒子、酸化物粒子及びフェライト等が使用できる。
【００９４】
上記磁性キャリア粒子の表面を樹脂で被覆した被覆キャリアは、現像スリーブに交流バイアスを印加する現像法において特に好ましい。被覆方法としては、樹脂の如き被覆材を溶剤中に溶解もしくは懸濁せしめて調製した塗布液を磁性キャリアコア粒子表面に付着せしめる方法、磁性キャリアコア粒子と被覆材とを粉体で混合する方法等、従来公知の方法が適用できる。
【００９５】
磁性キャリアコア粒子表面への被覆材料としては、シリコーン樹脂、ポリエステル樹脂、スチレン系樹脂、アクリル系樹脂、ポリアミド、ポリビニルブチラール、アミノアクリレート樹脂が挙げられる。これらは、単独或いは複数で用いる。
【００９６】
上記被覆材料の処理量は、キャリアコア粒子に対し０．１〜３０質量％（好ましくは０．５〜２０質量％）が好ましい。これらキャリアの平均粒径は１０〜１００μｍ、好ましくは２０〜７０μｍを有することが好ましい。
【００９７】
本発明のトナーと磁性キャリアとを混合して二成分系現像剤を調製する場合、その混合比率は現像剤中のトナー濃度として、２〜１５質量％、好ましくは４〜１３質量％にすると通常良好な結果が得られる。トナー濃度が２質量％未満では画像濃度が低下しやすく、１５質量％を超えるとカブリや機内飛散が発生しやすい。
【００９８】
本発明における測定法について以下に説明する。
【００９９】
１）透明性について
ＯＨＴシート上にトナーが０．７〜０．７５ｍｇ／ｃｍ²になるよう調整した状態で、定着させて得られた数値を用い、透明性を評価した。以下に透過率の測定方法を述べる。
【０１００】
透過率の測定は、島津自記分光光度計ＵＶ２２００（島津製作所社製）を使用し、ＯＨＰフィルム単独の透過率を１００％とし、
マゼンタトナーの場合：６５０ｎｍ
シアントナーの場合：５００ｎｍ
イエロートナーの場合：６００ｎｍ
での最大吸収波長における透過率を測定する。
○：色むらがなく、透過率が５０％以上
△：色むらが殆どなく、透過率が４０〜５０％以内
×：色むらがあり、透過率が４０％以下
【０１０１】
２）トナーの摩擦帯電量の測定方法
図１は摩擦帯電量を測定する装置の説明図である。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質量を秤り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。
【０１０２】
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）
【０１０３】
３）離型剤及びトナーの極大吸熱ピークの測定
示差熱分析測定装置（ＤＳＣ測定装置）、ＤＳＣ−７（パーキンエルマー社製）を用い測定する。測定試料は５〜２０ｍｇ、好ましくは１０ｍｇを精密に秤量する。これをアルミパン中に入れ、リファレンスとして空のアルミパンを用い、測定温度範囲３０〜２００℃の間で、昇温速度１０℃／ｍｉｎで常温常湿下で測定を行う。この昇温過程で、温度３０〜１６０℃の範囲におけるメインピークの吸熱ピークが得られる。吸熱ピークとは、言うまでもなく、その中で極大の値を示す温度のことである。
【０１０４】
４）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。
【０１０５】
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。
【０１０６】
上記の方法で調製された試料のＧＰＣの測定は、４０℃のヒートチャンバー中でカラムを安定化させ、この温度におけるカラムに溶媒としてテトラヒドロフラン（ＴＨＦ）を毎分１ｍｌの流速で流し、試料濃度として０．０５〜０．６質量％に調整した樹脂のＴＨＦ試料溶液を約５０〜２００μｌ注入して測定する。試料の分子量測定にあたっては、試料の有する分子量分布を数種の単分散ポリスチレン標準試料により作成された検量線の対数値とカウント数（リテンションタイム）との関係から算出する。検量線作成用の標準ポリスチレン試料としては、例えば東ソー社製或いはＰｒｅｓｓｕｒｅ Ｃｈｅｍｉｃａｌ Ｃｏ．製の分子量が６×１０²、２．１×１０³、４×１０³、１．７５×１０⁴、５．１×１０⁴、１．１×１０⁵、３．９×１０⁵、８．６×１０⁵、２×１０⁶、４．４８×１０⁶のものを用い、少なくとも１０点程度の標準ポリスチレン試料を用いるのが適当である。検出器にはＲＩ（屈折率）検出器を用いる。
【０１０７】
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。
【０１０８】
５）トナー粒度分布の測定
本発明において、トナーの平均粒径及び粒度分布はコールターカウンターＴＡ−ＩＩ型（コールター社製）を用いて行うが、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た。それから本発明に係る体積分布から求めた重量基準の重量平均粒径（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）を求めた。
【０１０９】
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。
【０１１０】
６）メタノール疎水化度測定
トナーの疎水化度（メタノールウェッタビリティー）における降下開始点は、粉体濡れ性試験機（ＷＥＴ−１００Ｐ、レスカ社製）を用いて測定することができる。１００ｍｌのビーカーに純水（イオン交換水または市販の精製水）４２ｍｌとメタノール１８ｍｌを入れ、ふたをして超音波分散器などを用いて均一分散させる。トナー０．５ｇを精秤して添加し、スターラーを２５０ｒｐｍさせながら撹拌し、メタノールを１．３ｍｌ／ｍｉｎで添加していく。水溶液にトナーが沈降、分散しはじめると溶液の透過度が低下するので、この時のメタノール／（メタノール＋水）の割合（％）を、トナー疎水化度の降下開始点とする。
【０１１１】
【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。
【０１１２】
（ハイブリッド樹脂製造例１）
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１．９ｍｏｌ、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（１）を得た。ＧＰＣによる分子量測定の結果を表１に示す。
【０１１３】
（ハイブリッド樹脂製造例２）
フマル酸５．０ｍｏｌに代えてマレイン酸４．５ｍｏｌとイタコン酸３．０ｍｏｌを使用すること、ジクミルパーオキサイド０．０５ｍｏｌに代えてイソブチルパーオキサイド０．１ｍｏｌを使用すること以外は、ハイブリッド樹脂製造例１と同様に反応させ、ハイブリッド樹脂（３）を得た。ＧＰＣによる分子量測定の結果を表１に示す。
【０１１４】
（ハイブリッド樹脂製造例３）
スチレン３．８ｍｏｌ、α−メチルスチレンの２量体０．０８ｍｏｌ、ジクミルパーオキサイド０．１ｍｏｌを使用すること以外は、ハイブリッド樹脂製造例１と同様に反応させ、ハイブリッド樹脂（２）を得た。ＧＰＣによる分子量測定の結果を表１に示す。
【０１１５】
（ハイブリッド樹脂製造例４）
フマル酸５．０ｍｏｌに代えてマレイン酸３．０ｍｏｌとイタコン酸３．８ｍｏｌを使用すること、ジクミルパーオキサイド０．０５ｍｏｌに代えてイソブチルパーオキサイド０．１３ｍｏｌを使用すること以外は、ハイブリッド樹脂製造例１と同様に反応させ、ハイブリッド樹脂（３）を得た。ＧＰＣによる分子量測定の結果を表１に示す。
【０１１６】
（ハイブリッド樹脂製造例５）
スチレン３．５ｍｏｌ、α−メチルスチレンの２量体０．１３ｍｏｌ、ジクミルパーオキサイド０．１４ｍｏｌを使用すること以外は、ハイブリッド樹脂製造例１と同様に反応させ、ハイブリッド樹脂（２）を得た。ＧＰＣによる分子量測定の結果を表１に示す。
【０１１７】
（ポリエステル樹脂製造例６）
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１．４ｍｏｌ、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（１）を得た。ＧＰＣによる分子量測定の結果を表１に示す。
【０１１８】
【表１】

【０１１９】
本実施例に用いたワックスを表２に記載した。
【０１２０】
【表２】

【０１２１】
＜実施例１＞
表３に示すように、以下の方法でトナー１を調製した。
【０１２２】
（第一工程）
・ワックス（Ａ） ５０質量部
・シアン顔料 ５０質量部
（Ｐｉｇｍｅｎｔ Ｂｌｕｅ１５：３ ＢＥＴ＝７２ｍ²／ｇ）
上記の原材料をまずニーダー型ミキサーに仕込み、混合しながら非加圧下で昇温させる。材料自体の温度を１００℃で３０分間加熱溶融混練させ、第一の工程を終了した後、冷却、簡便に粉砕して混練物を得た。
【０１２３】
（第二の混練工程）
・上記第一工程の混練物 １００質量部
・ハイブリッド樹脂（１） １００質量部
上記の原材料をまずニーダー型ミキサーに仕込み、混合しながら非加圧下で昇温させる。材料自体の温度を１１０℃で１５分間加熱溶融混練させ、第二の工程を終了した後、冷却、粉砕して混練物を得た。
【０１２４】

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材料温度を１３０℃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。さらに得られた微粉砕物を分級して、粒度分布における重量平均径が７．０μｍになるように選択してシアン粒子（分級品）を得た。
【０１２５】
流動性向上及び帯電特性付与を目的として、ｉ−Ｃ₄Ｈ₉Ｓｉ（ＯＣＨ₃）₃：２３質量部で処理した疎水性酸化アルミニウム（ＢＥＴ１７０ｍ²／ｇ）を、上記シアン粒子１００質量部に対して、１．０質量部を合せてトナー１とした。トナー１の重量平均径は７．０μｍであった。
【０１２６】
さらに、トナー１と、シリコーン樹脂で表面被覆した磁性フェライトキャリア粒子（平均粒径４５μｍ）とを、トナー濃度が７質量％になるように混合し、二成分系現像剤１とした。トナーの測定結果を表４に示す。
【０１２７】
この現像剤１で、カラー複写機ＣＬＣ−１１３０（キヤノン製）の定着ユニットのオイル塗布機構を取り外した改造機（プロセススピード２００ｍｍ／ｓｅｃ）を用い、単色モードで低温低湿環境下（１５℃／１０％）、で画像面積比率７％のオリジナル原稿を用いて１万枚の耐刷試験と、高温高湿環境下（３０℃／８０％）による帯電測定と、常温常湿度環境下（２３℃／６０％）での定着試験を行った。さらに定着可能領域の評価については、定着ユニットを手動で定着温度が設定できるように改造した。
【０１２８】
１万枚の耐久後でも初期と画像濃度の変動も小さく、カブリのないオリジナルを忠実に再現するシアン画像が得られた。複写機内での搬送、現像剤濃度検知も良好で安定した画像濃度が得られた。定着温度設定１７０℃にして１万枚の繰り返し複写でも定着ローラーへのオフセットはまったく生じなかった。なお、定着ローラーへのオフセットの発生状況は、繰り返し複写後の定着ローラーの表面を目視により観察することによって行った。
【０１２９】
またトナー１は、表３に示すように透明性に優れ、且つ低温低湿環境下と高温高湿環境下での環境安定性を調べたところ、表４に示すように帯電差が小さく良好なものであった。
【０１３０】
トナー１の保存安定性を調べた結果、良好なデータを示した。すなわち、サンプルトナーの耐ブロッキング性に関しては、５０℃のオーブン内にて２週間放置することにより評価した。評価としては目視による凝集性のレベルより判定した。
【０１３１】
（耐ブロッキング性の評価基準）
○：凝集体が全く見られなく流動性が非常に良い
△：若干の凝集体は見られるがすぐにほぐれる
×：現像剤撹拌装置では凝集体が十分にほぐれない。
【０１３２】
＜実施例２＞
実施例１において、第一工程全量のうち離型剤と着色剤の比率が、７０質量％を使用したこと以外は実施例１とほぼ同様にして、トナー２を作製し、同様にして現像剤２を得た。トナーの測定結果を表４に示す。トナー２では若干透明性が劣り、カブリと耐久濃度変動が見られたが実用レベル内であった。
【０１３３】
＜実施例３〜６＞
実施例１において、表３に示すように樹脂２、３またはワックスＢ，Ｃを用いたことを除いて、あとはほぼ同様にしてトナー３〜６を得た。実施例１と同様に耐久試験したところ、表４に示すように帯電の環境差、透明性、ブロッキング特性、濃度変動幅、カブリ、そして定着オフセットにおいて、実施例１と比べ劣る点も見られたが、実用レベル内であった。
【０１３４】
＜実施例７＞
実施例１において、樹脂１を樹脂６を用いたことを除いて、あとはほぼ同様にしてトナー７を得た。帯電の環境差と耐久濃度変動はやや悪化するものの、実用上問題となるレベルではなかった。実施例１と同様に耐久試験したところ、ほぼ同様の結果が得られた。
【０１３５】
＜実施例８＞
実施例７において、アゾ系のクロム錯体（オリエントＳ−３４）を４．０質量部用いたことを除いて、あとはほぼ同様にしてトナー８を得た。帯電の環境差と耐久濃度変動はやや悪化するもの実用上問題となるレベルではなかった。実施例１と同様に耐久試験したところ、ほぼ同様の結果が得られた。
【０１３６】
＜実施例９＞
実施例７において、着色剤にＰｉｇｍｅｎｔ Ｒｅｄ ５７：１（ＢＥＴ＝３２ｍ²／ｇ）を用いたことを除いて，あとはほぼ同様にしてトナー９を得た。帯電の環境差と耐久濃度変動はやや悪化するものの、実用上では問題となるレベルではなかった。実施例１と同様に耐久試験したところ、ほぼ同様の結果が得られた。
【０１３７】
＜実施例１０＞
実施例１において、ワックスＤを用いたことを除いて、あとはほぼ同様にしてトナー１０を得た。トナー１０では若干透明性が劣り、カブリと耐久濃度変動が見られたが実用レベル内であった。
【０１３８】
＜実施例１１〜１２＞
表３に示すように、実施例１において、工程１の温度を変えたことを除いて、あとはほぼ同様にしてトナー１１〜１２を得た。表４に示すように透明性、ブロッキング特性、濃度変動幅、カブリにおいて、実施例１と比べ劣る点も見られたが、実用レベル内であった。
【０１３９】
＜実施例１３＞
表３に示すように、実施例１において、工程２の温度を変えたことを除いて、あとはほぼ同様にしてトナー１３を得た。表４に示すように帯電の環境差とブロッキング特性、濃度変動幅、定着オフセットにおいて、実施例１と比べ劣る点も見られたが、実用レベル内であった。
【０１４０】
＜実施例１４＞
表３に示すように、実施例１において、工程３の温度を変えたことを除いて、あとはほぼ同様にしてトナー１４を得た。表４に示すように透明性、ブロッキング特性、濃度変動幅、カブリにおいて、実施例１と比べ劣る点も見られたが、実用レベル内であった。
【０１４１】
＜比較例１＞
表３に示すように、実施例１において、工程１にワックスＡの代わりに樹脂１を５０質量部入れて、ニーダー型ミキサーに仕込み、混合しながら非加圧下で昇温させる。材料自体の温度を１００℃で３０分間加熱溶融混練させた後、冷却、簡便に粉砕して混練物を得た。そしてこの混練物をさらに３本ロールにて、１００℃で３０分間加熱溶融混練させて第一の工程を終了した後、冷却、簡便に粉砕して混練物を得た。
【０１４２】
第二工程はなく、第三工程において以下の配合によりトナー１５を得た。

【０１４３】
表４に示すようにブロッキング特性は実用範囲であるものの、透明性、濃度変動幅、カブリにおいて、実施例１と比べかなり劣る点が見られ、実用的に使用できるものではなかった。
【０１４４】
＜比較例２＞
表３に示すように、実施例１において、工程１では
・ハイブリッド樹脂（５） １００．０質量部
・ワックスＡ ５０．０質量部
・シアン顔料（Ｐｉｇｍｅｎｔ Ｂｌｕｅ１５：３） ５０．０質量部
をニーダー型ミキサーに仕込み、混合しながら非加圧下で昇温させる。材料自体の温度を１００℃で３０分間加熱溶融混練させた後、冷却、簡便に粉砕して混練物を得た。
【０１４５】
第二工程はなく、第三工程において以下の配合によりトナー１６を得た。

【０１４６】
表４に示すように透明性、ブロッキング特性、濃度変動幅、カブリ、定着オフセットにおいて、実施例１と比べかなり劣る点が見られ、実用的に使用できるものではなかった。
【０１４７】
＜比較例３＞
表３に示すように、実施例１において、結着樹脂を変えたことを除いて、あとはほぼ同様にしてトナー１７を得た。表４に示すように定着オフセットが悪く、実用的に使用できるものではなかった。
【０１４８】
＜比較例４〜５＞
表３に示すように、実施例１において、工程２の温度を変えたことを除いて、あとはほぼ同様にしてトナー１８、１９を得た。表４に示すように濃度変動幅とカブリにおいて、実施例１と比べかなり劣る点が見られ、実用的に使用できるものではなかった。
【０１４９】
＜比較例６＞
表３に示すように、実施例１において、工程３の温度を変えたことを除いて、あとはほぼ同様にしてトナー２０を得た。表４に示すように透明性、ブロッキング、濃度変動幅とカブリにおいて、実施例１と比べかなり劣る点が見られ、実用的に使用できるものではなかった。
【０１５０】
＜比較例７＞
表３に示すように、実施例１において、顔料のＢＥＴを変えたことを除いて、あとはほぼ同様にしてトナー２１を得た。表４に示すように濃度変動幅とカブリにおいて、実施例１と比べかなり劣る点が見られ、実用的に使用できるものではなかった。
【０１５１】
＜比較例８＞
表３に示すように、実施例１において、顔料のＢＥＴを変えたことを除いて、あとはほぼ同様にしてトナー２２を得た。表４に示すように帯電の環境差と濃度変動幅とカブリにおいて、実施例１と比べかなり劣る点が見られ、実用的に使用できるものではなかった。
【０１５２】
＜比較例９＞
表３に示すように、実施例１において、ワックスＥに変えたことを除いて、あとはほぼ同様にしてトナー２３を得た。表４に示すように特にブロッキングにおいて、実施例１と比べかなり劣る点が見られ、実用的に使用できるものではなかった。
【０１５３】
＜比較例１０＞
表３に示すように、実施例１において、樹脂２とワックスＦに変えたことを除いて、あとはほぼ同様にしてトナー２４を得た。表４に示すように定着オフセットにおいて、実施例１と比べかなり劣る点が見られ、実用的に使用できるものではなかった。
【０１５４】
＜比較例１１＞
表３に示すように、実施例１において、ワックスＡの添加部数を２．３部に変えたことを除いて、あとはほぼ同様にしてトナー２５を得た。表４に示すように定着オフセットにおいて、実施例１と比べかなり劣る点が見られ、実用的に使用できるものではなかった。
【０１５５】
＜比較例１２＞
表３に示すように、実施例１において、ワックスＡの添加部数を１０．５部に変えたことを除いて、あとはほぼ同様にしてトナー２５を得た。表４に示すように定着オフセットにおいて、実施例１と比べかなり劣る点が見られ、実用的に使用できるものではなかった。
【０１５６】
＜実施例１５＞
実施例７において、着色剤にＰｉｇｍｅｎｔ Ｙｅｌｌｏｗ １５５（ＢＥＴ＝８０ｍ²／ｇ）を用いたことを除いて、あとはほぼ同様にしてトナー２７を得た。トナー１とトナー９及びトナー２７を用いてフルカラー画像評価を行ったところ、一万枚後の濃度変動及びカブリも良好であり、透明性も良好であった。
【０１５７】
【表３】

【０１５８】
【表４】

【０１５９】
【発明の効果】
本発明のフルカラー用トナー及びその製造方法は、着色剤と離型剤の分散性を向上させ、高速複写の低温定着と帯電安定性に優れ、耐ブロッキングに優れたフルカラー用トナーを提供できるものである。
【図面の簡単な説明】
【図１】トナーの摩擦帯電量を測定する装置の説明図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and a toner jet method, particularly a toner suitable for oilless heat roll fixing, and a manufacturing method thereof. The present invention relates to a full-color toner that improves dispersibility of a colorant and a release agent, is excellent in low-temperature fixing for high-speed copying, and has excellent blocking resistance.
[0002]
[Prior art]
The full-color toner is obtained by mixing, melting and kneading a binder resin, a colorant, and if necessary, a release agent, a charge control agent and the like, cooling and solidifying, pulverizing and classifying. Furthermore, if necessary, a fluidity imparting agent, a charge control agent, a cleaning aid, a transfer aid and the like are adhered and fixed to the toner surface, and coarse powder is removed by sieving.
[0003]
In the toner, it is necessary that components such as a colorant and a release agent are uniformly and finely dispersed in the binder resin, which is more important in recent demands for full color and high image quality. It is increasing.
[0004]
For example, if poor dispersion in which the colorant is unevenly distributed in the binder resin or a state in which the colorant is uniformly dispersed but the dispersion unit is large occurs, particles with uneven composition are mixed in the toner. A large difference may occur, or the charge amount distribution may be broadened, resulting in reverse polarity. Further, if the colorant does not stay inside the toner but is liberated and exists on the surface, the powder flowability of the toner is remarkably lowered, which may cause a transfer failure or the like.
[0005]
In addition, as a toner mounted on a full-color copying machine, it is necessary that the toners are sufficiently mixed in the heat and pressure fixing process without impairing the color reproducibility and the transparency of the OHP image.
[0006]
Compared to a general black toner for black-and-white copying machines, a full-color toner is preferably a binder resin containing a polyester resin having sharp melt properties.
[0007]
However, when a sharp melt binder resin is used, when a binder resin and a colorant are mixed, melted and kneaded to obtain a toner, it is difficult to obtain a high shearing force, and thus it is difficult to achieve a high dispersion of the colorant. There is a harmful effect. That is, the dispersion state of the colorant or the like in the binder resin depends on these kneading steps. For example, it is difficult to obtain a desired toner by simply melt-kneading the above raw materials with a conventional kneading method such as a screw-type extrusion continuous kneader, a two-roll mill, a three-roll mill, or a pressure and heat kneader. Manufacturing methods such as batches have been proposed.
[0008]
For example, as a method of obtaining a pigment resin colored product (masterbatch) having excellent dispersibility, an aqueous pigment paste and a resin are kneaded to transfer the aqueous phase pigment to the resin phase, and then remove water. A method for producing a pigment resin composition has been proposed.
[0009]
Further, JP-A-2-175770, JP-A-5-34978, and JP-A-7-261459 in combination with a specific resin can be mentioned.
[0010]
Japanese Patent Laid-Open No. 6-148937 has been proposed as a production method in which water as a dispersion aid is added and the pigment and the resin are heated and kneaded under pressure or normal pressure, and then the water is removed.
[0011]
However, these methods are very effective means only for dispersing the colorant, but they cannot be used as a master batch for the demand for high dispersion of the release agent.
[0012]
On the other hand, with regard to the release agent, for the purpose of preventing the toner from adhering to the surface of the conventional fixing roller, the release agent is formed of silicone rubber or fluorine-based resin having excellent releasability, and a release agent such as silicone oil or fluorine oil is further formed on the surface. The surface of a roller is coated with a thin liquid film having high properties.
[0013]
However, this method is extremely effective in preventing toner offset, but has a problem that the fixing device is complicated because an apparatus for supplying the liquid for preventing offset is necessary. .
[0014]
In addition, since OHP has a low oil absorption capability unlike paper, a copy OHP obtained at present cannot avoid a solid feeling due to oil application, and a great problem remains in the quality of the obtained image.
[0015]
Therefore, instead of using a silicone oil supply device, instead of supplying an anti-offset liquid from the toner during heating, a release agent such as low molecular weight polyethylene or low molecular weight polypropylene is used in the toner. At the same time, a method of melt-kneading all at once has been proposed. For example, the technology is disclosed in Japanese Patent Application Laid-Open No. 1-109359, Japanese Patent Application Laid-Open No. 3-168649, Japanese Patent Application Laid-Open No. 8-101526, Japanese Patent Application Laid-Open No. 8-220808, and the like.
[0016]
However, in these methods of adding a mold release agent, the dispersion is not very good with unmodified polyolefins and paraffins, and there are also some modified types such as acid-modified and ester waxes, which are slightly improved in dispersion. The dispersibility control is not sufficient.
[0017]
When the binder resin contains a polyester resin, it is difficult to disperse because the release agent is hardly dissolved, and a relatively large release agent domain is formed in the polyester resin, and the toner is pulverized in this domain part during pulverization. The release agent is likely to be exposed or released on the toner surface, that is, the charge imparting ability as the toner is lowered, causing a reduction in image density, or contaminating the surface of the photoreceptor to cause image loss (streak). In addition, the charging performance varies greatly depending on the environment, and the durability and stability are poor. When the release agent is liberated, the offset resistance of the toner is not sufficient, which adversely affects powder flowability and storage stability.
[0018]
In Japanese Patent Publication No. 7-120074, there is a proposal to disperse a colorant and a wax in advance, but since the binder resin is styrene-acrylic, the compatibility with a release agent such as wax is good. The release agent can be dispersed relatively easily. However, as described above, in a full-color toner, a resin containing a polyester resin having poor compatibility with a release agent such as wax is preferable. Therefore, there is a demand for a combination of a manufacturing method and a material that optimizes the balance of the colorant and the release agent for the resin including the polyester resin, in addition to making the colorant and the release agent highly dispersed.
[0019]
In Japanese Patent Application Laid-Open No. 11-190914, the temperature relationship between the softening temperature or outflow start temperature of the binder resin and the melting point of the release agent is defined, but the binder resin, the release agent, and the colorant are used. Since melt-kneading is performed collectively, the binder resin and the release agent are limited to substantially the same temperature characteristics so as not to separate.
[0020]
In recent years, full-color toners are required to have low-temperature fixing performance at high speed because of the relationship between high output speed and power consumption. Therefore, in order to express the release performance from a low temperature, a release agent having a low melting point is required, which means that the binder resin reaches a low softening temperature. Lowering the softening temperature of the binder resin is likely to cause a reduction in blocking resistance, image density fluctuations due to toner charge changes due to external additive driving in high-speed continuous copying, and image blurring due to poor fluidity. It will be.
[0021]
[Problems to be solved by the invention]
An object of the present invention is to provide a full-color toner that can be fixed without applying a large amount of oil or without applying any oil, and a manufacturing method thereof.
[0022]
An object of the present invention is to provide a full-color toner excellent in low-temperature fixing property even in high-speed copying, excellent in storage stability and blocking resistance, and a production method.
[0023]
An object of the present invention is to provide a full-color toner having a high chroma and brightness, excellent OHP transparency, and excellent colorant dispersion and a production method.
[0024]
An object of the present invention is to provide a full-color toner excellent in the environmental stability of charging by controlling the degree of hydrophobicity of the toner surface, excellent in durability stability having sufficient frictional charging properties, and a manufacturing method.
[0025]
An object of the present invention is to provide a full-color toner having a wide fixable temperature by highly dispersing a release agent, having no fusing in and around the developing device, and having good cleaning properties, and a production method. .
[0026]
[Means for Solving the Problems]
The above object is achieved by allowing various materials to exist on the toner surface in a well-balanced manner, and is achieved by the following configuration.
[0027]
That is, the present invention provides a full-color toner having at least a binder resin, a colorant, and a release agent.
(I) The content of the release agent with respect to 100 parts by mass of the binder resin is 2.5 to 10 parts by mass,
(Ii) The descent start point in the methanol hydrophobization degree of the toner is in the range of 35 ≦ methanol / (methanol + water) ≦ 60 (volume%), (iii) the resin has at least a polyester resin, iv) The maximum endothermic peak temperature Tsc measured by DSC of the release agent is 70 ° C. <Tsc <100 ° C., (v) the BET of the colorant is 30 to 200 m ² / G (Vi) the colorant is surface-treated with the release agent The present invention relates to a full color toner.
[0028]
Further, the present invention provides a method for producing a full color toner having at least a binder resin, a colorant, and a release agent.
The toner has (i) a content of the release agent of 2.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin, and (ii) a start point of decrease in the degree of methanol hydrophobization of the toner is 35 ≦ Methanol / (methanol + water) ≦ 60 (volume%), (iii) the resin has at least a polyester resin, and (iv) the maximum endothermic peak temperature Tsc measured by DSC of the release agent is 70 ° C. <Tsc <100 ° C. (v) BET of the colorant is 30 to 200 m ² / G,
The toner production process includes (1): a first process in which at least a release agent and a colorant are melt-mixed; and (2): a melt mixture produced in (1) and a binder resin. The present invention relates to a method for producing a full-color toner comprising two steps and (3): a third step of melt-mixing the molten mixture produced in (2) and at least a binder resin.
[0029]
DETAILED DESCRIPTION OF THE INVENTION
The present inventors have so far been excellent in charging environmental stability, have sufficient triboelectric chargeability in high-speed copying, have excellent durability stability, and have excellent colorant dispersion and transparency, and in high-speed fixing. However, a toner that has a high release effect and does not require the application of silicone oil to the fixing roller was examined, but none of the conventional methods simultaneously satisfied.
[0030]
Accordingly, the present inventors have sought to improve the dispersion of colorants and release agents and their balance, and found that the above problems can be achieved by focusing on the degree of hydrophobicity, particularly the degree of methanol hydrophobicity, which is the surface physical property of the toner. I found it.
[0031]
The degree of methanol hydrophobization greatly depends on the binder resin, the release agent, the colorant, and the like, which are most of the components of the toner.
[0032]
When the lowering point of the hydrophobization degree of methanol is smaller than 35 (volume%), a binder resin and a hydrophilic colorant such as a dye or C.I. Since B and the like are biased, it is considered that the difference in charging environment is large. This makes it impossible to obtain a sufficient contrast of the photosensitive drum, so that the image density fluctuation is likely to be large and the gradation is poor. Therefore, in a full-color image, color reproducibility is very poor. .
[0033]
On the contrary, when the start point of the decrease in the degree of hydrophobization of methanol is greater than 60 (volume%), there are many release agents such as organic pigments and waxes on the toner surface. However, it is thought that the charging ability of the toner is broadened because the charging ability is quite different. This is because there is little transfer of charge between toners during continuous copying, so the difference in charge level opens, and eventually fogging and toner scattering occur.
[0034]
As described above, various materials are present on the toner surface in a well-balanced manner, so that the environmental stability of charging is excellent, the durability stability having sufficient frictional charging properties is excellent, the colorant dispersion and transparency are excellent, and the separation is good. The mold effect was high and the fixing roller could be filled simultaneously with toner that did not require silicone oil application.
[0035]
In the present invention, the toner particle releasing agent preferably has a maximum endothermic peak temperature Tsc measured by DSC of 70 ° C. <Tsc <100 ° C., more preferably 70 ° C. <Tsc <90 ° C. The above-mentioned low melting point release agent has a relatively small molecular chain, so it has excellent molecular mobility, easily adsorbs even minute irregularities and porous parts on the surface of the colorant, enters the interface of aggregation of the colorants, This is because aggregation of the colorant can be reduced.
[0036]
Although the release agent of 70 ° C. ≧ Tsc has a great effect on dispersion, it is oozed out of the toner when left at a high temperature and melts out on the toner surface, and the anti-blocking performance is greatly deteriorated. On the other hand, since the release agent with Tsc ≧ 100 ° C. has a large molecular chain, it cannot be sufficiently adsorbed and penetrated to minute irregularities and porous parts, so it seems that only low dispersibility was obtained.
[0037]
Examples of the release agent used in the present invention include the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; block copolymers of aliphatic hydrocarbon waxes; Examples thereof include waxes mainly composed of fatty acid esters such as carnauba wax, sazol wax and montanic acid ester wax; and those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax.
[0038]
Examples thereof include a partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and the like. A particularly preferably used wax is an aliphatic hydrocarbon wax such as paraffin wax having a short molecular chain and less steric hindrance and excellent mobility.
[0039]
In the molecular weight distribution of the wax, the main peak is preferably in the region of molecular weight 400 to 2400, and more preferably in the region of 430 to 2000. By giving such a molecular weight distribution, preferable thermal characteristics can be imparted to the toner.
[0040]
The addition amount of the release agent used in the present invention is 2.5 to 10 parts by mass, preferably 3 to 8 parts by mass with respect to 100 parts by mass of the binder resin. If the amount is less than 2.5 parts by mass, the surface of the colorant cannot be covered, and the dispersibility of the colorant is inferior. If the amount exceeds 10 parts by mass, the amount of the release agent in the toner is too large. This is because it is inferior.
[0041]
In the present invention, the binder resin of the toner particles is preferably Tsc + 10 ° C. <Tm <Tsc + 40 ° C., more preferably Tsc + 20 ° C. <Tm <Tsc + 40 ° C., with respect to the elution start temperature Tm of the toner flow tester. .
[0042]
The first reason is that the temperature at which the binder resin is further added and melt-mixed with respect to at least the molten mixture of the colorant and the release agent is greatly involved in the dispersion of the colorant and the release agent. I think. In other words, when Tm ≧ Tsc + 40 ° C., the temperature for melting the binder resin at the time of manufacture is considerably higher than Tsc, so even if it is a mold release agent that has been selectively adsorbed to the colorant, This is because the release agent that has been physically adsorbed is separated, and the release agent oozes out from the colored material and is liberated. As a result, the colorant also reaggregates.
[0043]
The second reason is that when Tsc + 10 ° C. ≧ Tm, the effect of the release agent becomes difficult at fixing, and it becomes difficult to fix without applying a large amount of oil or without applying any oil. I think it is because of this. The reason is not clear, but if Tsc and Tm, which are temperature factors of the release agent and the binder resin, are too close, this is remarkable in high-speed fixing, but before the release agent moves to the toner surface, The viscosity of the resin molecules increases and adheres to the fixing roller during fixing, resulting in an offset phenomenon. Therefore, before the viscosity of the binder resin molecules increases, the difference in viscosity with respect to temperature is necessary so that the release agent can move away from the colorant and move to the toner surface. That is, it does not work effectively as a release agent unless Tsc + 10 ° C. <Tm is satisfied. When a low melting point release agent that is indispensable for high-speed fixing is used, if Tsc and Tm, which are temperature factors of the release agent and the binder resin, are too close to each other, the blocking performance is deteriorated and the temperature is increased in high-speed continuous copying. Image density fluctuations due to toner charging changes due to the injection of the additive and image roughness due to deterioration of fluidity are likely to occur. Therefore, it is necessary to satisfy Tsc + 10 ° C. <Tm.
[0044]
(1): a first step of melt-mixing at least a release agent and a colorant, and (2): melt-mixing the molten mixture manufactured in (1) and a binder resin, which are manufacturing steps of the toner. A full-color toner manufacturing method comprising the second step and the third step of (3): a third step of melt-mixing the molten mixture produced in (2) and at least a binder resin, This is an important factor for causing various materials to exist on the toner surface in a well-balanced manner, and is performed by the following method.
[0045]
In the first step, at least the release agent and the colorant are sufficiently mixed by a mixer such as a Henschel mixer, a ball mill, or a kneader, or without mixing, a Banbury mixer, a kneader, a roll, a screw type extrusion continuous kneader, etc. Melt and mix with a heat kneader such as At this time, it is important that the temperature (T1) of the kneaded material is Tsc-10 ° C <T1 <Tsc + 50 ° C. When Tsc-10 ° C ≧ T1, the mobility of the release agent is not sufficiently utilized, so that the dispersion of the colorant is deteriorated. When T1 ≧ Tsc + 50 ° C., the viscosity of the release agent is too low, so the share in kneading is Resulting in poor colorant dispersion.
[0046]
Moreover, it is also an effective means for dispersibility that the ratio of the release agent to the colorant in the total amount of the first step accounts for 70% by mass or more. That is, it is important to selectively adsorb the release agent to the colorant, and for this purpose, it is necessary to increase the contact ratio of the release agent with the colorant as much as possible.
[0047]
In the second step, the colored product obtained in the first step is pulverized by a crusher such as a hammer mill or a power mill, and then mixed to melt mixed together with the binder resin in the same manner as in the first step. Alternatively, without performing pulverization, the binder resin may be directly added to the melt-kneaded material to perform melt-kneading. At this time, it is also important that the temperature (T2) of the kneaded material is Tsc + 10 ° C. <T2 <T3 <Tm + 60 ° C.
[0048]
It is considered that the release agent once physically adsorbed on the surface of the colorant is effectively released or not reaggregated. That is, by gradually raising the temperature, the colored material obtained in the previous step is not greatly broken. In the first step, at least a colorant having a release agent present around the colorant, and in the second step, a colorant having a binder resin present around the colorant, and in the third step described later, the binder resin and the charge are charged. We believe that the presence of a control agent has led to a colored product that can control various physical properties such as charging. Therefore, it is not only necessary to raise the temperature in the order of the process, and the upper limit temperature needs to be managed. That is, when T3 ≧ Tm + 60 ° C., the viscosity of the binder resin increases and the release agent is largely released. What is important is the temperature relationship in the first to third steps, which is an indispensable element for allowing various materials to exist on the toner surface in a balanced manner. That is, although it is not clear, by performing Tsc + 10 ° C. <T2 <T3, it is considered that the release agent and the colored material are gradually extruded onto the surface layer of the binder resin, so that the optimum existence balance as the toner can be achieved.
[0049]
In addition, the binder resin in the second step is added in an amount of 25 to 200 parts by mass, preferably 25 to 150 parts by mass, with respect to 100 parts by mass of the colored product obtained in the first step. If it is less than 25 parts by mass, it cannot be incorporated because it is less than the colored product obtained in the first step. Moreover, when it exceeds 200 parts by mass, the binder resin in the third step is reduced, and the charge control agent and the like are less likely to exist uniformly.
[0050]
The binder resin used in the toner of the present invention includes (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl copolymer unit, or (c) a hybrid resin and a vinyl copolymer. Preference is given to a resin selected from a mixture with a coalescence, (d) a mixture of a polyester resin and a vinyl copolymer, or (e) a mixture of a hybrid resin and a polyester resin. Further, the molecular weight distribution measured by gel permeation chromatography (GPC) of the resin component has a main peak in the region of molecular weight 3,500 to 30,000, preferably molecular weight 5,000 to 20,000. It is preferable that Mw / Mn is 5.0 or more.
[0051]
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.
[0052]
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. 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.
[0053]
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.
[0054]
Acidic components include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; Succinic acid substituted with an alkyl group or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof;
[0055]
Among these, in particular, a bisphenol derivative represented by the following general formula (1) as a diol component, a carboxylic acid component (for example, fumaric acid) composed of a divalent or higher carboxylic acid or its acid anhydride, or a lower alkyl ester thereof. Acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as an acid component, and a polyester resin obtained by condensation polymerization of these as a black toner for full color image formation has good charging characteristics This is preferable.
[0056]
[Chemical 1]

[0057]
Further, when a hybrid resin having a polyester unit and a vinyl copolymer unit is used as the binder resin, further improved wax dispersibility, low-temperature fixability, and offset resistance can be expected. The “hybrid resin component” used in the present invention means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are formed by a transesterification reaction, preferably a vinyl polymer. Is used to form a graft copolymer (or block copolymer) having a backbone polymer and a polyester unit as a branch polymer.
[0058]
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.
[0059]
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.
[0060]
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.
[0061]
In the toner of the present invention, the vinyl polymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. In this case, the crosslinking agent used is Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butanediol di Examples include acrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and the above compounds in which acrylate is replaced by methacrylate; linked by an alkyl chain containing an ether bond. As diacrylate compounds For example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and those obtained by replacing acrylates of the above compounds with methacrylate Examples of diacrylate compounds linked by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4 ) -2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate.
[0062]
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.
[0063]
In the present invention, it is preferable that the vinyl copolymer component and / or the polyester resin component contain a monomer component that can react with both resin components. Examples of the monomer constituting the polyester resin component that can react with the vinyl copolymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl copolymer 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.
[0064]
As a method for obtaining a reaction product of a vinyl resin and a polyester resin, a polymer containing a monomer component capable of reacting with each of the vinyl resin and the polyester resin listed above is present. A method obtained by polymerizing a resin is preferred.
[0065]
Examples of the polymerization initiator used for producing the vinyl copolymer of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 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, cyclohexano Ketone peroxides such as peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, Di-t-butyl peroxide, t-butyl cumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide , Lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n- Propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxide Oxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butylperoxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butylperoxyallyl carbonate, t-amylperoxy 2-ethylhexanoate, di-t-butylperoxyhexahydro Terephthalate, di -t- butyl peroxy azelate and the like.
[0066]
Examples of the production method capable of preparing the hybrid resin used in the toner of the present invention include the following production methods (1) to (6).
[0067]
(1) A method in which a vinyl resin, 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.
[0068]
(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.
[0069]
(3) A method for producing a vinyl polymer unit and a hybrid resin component in the presence of the polyester unit after the production thereof. 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.
[0070]
(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.
[0071]
(5) After producing the hybrid resin component, vinyl polymer units and / or polyester units are produced by adding vinyl monomers and / or polyester monomers (alcohols, carboxylic acids) and performing addition polymerization and / or condensation polymerization reactions. 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.
[0072]
(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.
[0073]
In the production methods (1) to (5), the vinyl polymer unit and / or the polyester unit can use a plurality of polymer units having different molecular weights and crosslinking degrees.
[0074]
The binder resin contained in the toner of the present invention includes a mixture of the polyester and vinyl copolymer, a mixture of the hybrid resin and vinyl copolymer, the polyester resin and the hybrid resin. A mixture of vinyl copolymers may be used.
[0075]
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 resin is preferably 1 to 40 mgKOH / g.
[0076]
In the toner of the present invention, a charge control agent can be used as necessary in order to further stabilize the chargeability. The charge control agent is used in an amount of 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of the binder resin. The charge control agents known in the art today include the following: For example, organometallic complexes and chelate compounds are effective. Examples include monoazo metal complexes, aromatic hydroxycarboxylic acids, metal complexes, and aromatic dicarboxylic acid metal complexes. Others include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives of bisphenol. Particularly suitable are metal compounds of aromatic carboxylic acid derivatives.
[0077]
Further, as a colorant for the full-color toner used in the present invention, BET is important because the wax is supported on the surface and uniformly dispersed together with the wax. Pigment BET is 30m ² If it is less than / g, the surface area on which the wax is carried is small, so that there is free or agglomerated wax. The pigment BET is 200m. ² If it is larger than / g, the factor on the surface of the pigment becomes strong, and the chargeability of the pigment itself appears so as to cause charging inhibition.
[0078]
Examples of the types of pigments include the following. 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.
[0079]
Although such a pigment may be used alone, 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. Such magenta dyes 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.
[0080]
As other coloring pigments, cyan pigments include C.I. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45, or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
[0081]
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, 83, C.I. I. Vat yellow 1, 3, 20 etc. are mentioned.
[0082]
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 0.5-50 mass parts.
[0083]
As the black colorant used in the present invention, carbon black, a magnetic material, and a color toned to black using the yellow / magenta / cyan colorant shown above can be used.
[0084]
The toner of the present invention can be used by improving the fluidity of the toner by pulverizing and classifying and mixing a fluidizing agent and the like with a mixer such as a Henschel mixer.
[0085]
Any negatively chargeable fluidizing agent can be used as long as the fluidity can be increased by adding the colorant-containing resin particles before and after the addition. For example, fluororesin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder, titanium oxide fine powder, alumina fine powder, wet process silica, fine powder silica such as dry process silica, silane coupling agent, There exist the process silica etc. which surface-treated with the titanium coupling agent, silicone oil, etc.
[0086]
For example, the dry process silica is a fine powder produced by vapor phase oxidation of a silicon halogen compound, which is 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 + 2H ₂ + O ₂ → SiO ₂ + 4HCl
[0087]
In this production process, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. To do. 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. .
[0088]
Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds used in the present invention include those commercially available under the following trade names.

[0089]
Further, it is more preferable to use a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of the silicon halide compound. Among the treated silica fine powders, those obtained by treating the silica fine powder so that the degree of methanol hydrophobicity is in the range of 30 to 80 are particularly preferred.
[0090]
As a hydrophobizing method, it is applied by chemically treating with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound.
[0091]
Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane. , Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyl Dimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane 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. These are used alone or in a mixture of two or more.
[0092]
As the fluidizing agent used in the present invention, the above-mentioned dry process silica treated with a coupling agent having an amino group or silicone oil may be used as necessary to achieve the object of the present invention. Absent. 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 m ² / G or more gives good results. The fluidizing agent is used 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.
[0093]
When the toner of the present invention is used for a two-component developer, the toner is used by mixing with a magnetic carrier. As the magnetic carrier, for example, surface-oxidized or unoxidized iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, alloy particles thereof, oxide particles, ferrite and the like can be used.
[0094]
The coated carrier obtained by coating the surface of the magnetic carrier particles with a resin is particularly preferable in a developing method in which an AC bias is applied to the developing sleeve. As a coating method, a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the magnetic carrier core particle, and a method in which the magnetic carrier core particle and the coating material are mixed with powder. A conventionally known method can be applied.
[0095]
Examples of the coating material on the surface of the magnetic carrier core particle include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These are used alone or in plural.
[0096]
The treatment amount of the coating material is preferably 0.1 to 30% by mass (preferably 0.5 to 20% by mass) with respect to the carrier core particles. These carriers have an average particle diameter of 10 to 100 μm, preferably 20 to 70 μm.
[0097]
When a two-component developer is prepared by mixing the toner of the present invention and a magnetic carrier, the mixing ratio is usually 2 to 15% by mass, preferably 4 to 13% by mass, as the toner concentration in the developer. Good results are obtained. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.
[0098]
The measurement method in the present invention will be described below.
[0099]
1) About transparency
0.7-0.75 mg / cm of toner on the OHT sheet ² The transparency was evaluated using numerical values obtained by fixing in a state adjusted to be. The transmittance measurement method will be described below.
[0100]
The transmittance is measured using a Shimadzu spectrophotometer UV2200 (manufactured by Shimadzu Corporation), and the transmittance of the OHP film alone is 100%.
For magenta toner: 650 nm
For cyan toner: 500 nm
For yellow toner: 600 nm
The transmittance at the maximum absorption wavelength at is measured.
○: No color unevenness and transmittance of 50% or more
Δ: There is almost no color unevenness, and the transmittance is within 40 to 50%.
X: There is uneven color and the transmittance is 40% or less
[0101]
2) Measuring method of toner triboelectric charge
FIG. 1 is an explanatory diagram of an apparatus for measuring the triboelectric charge amount. 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 mass of the entire 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). Further, the mass of the entire 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.
[0102]
Sample triboelectric charge (mC / kg) = C × V / (W1-W2)
(However, the measurement conditions are 23 ° C. and 60% RH)
[0103]
3) Measurement of maximum endothermic peak of release agent and toner
It measures using a differential thermal analysis measuring device (DSC measuring device) and DSC-7 (made by Perkin Elmer). The sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg. This 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 temperature range of 30 to 200 ° C. In this temperature raising process, an endothermic peak of a main peak in the temperature range of 30 to 160 ° C. is obtained. Needless to say, the endothermic peak is a temperature showing a maximum value in the endothermic peak.
[0104]
4) 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.
[0105]
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.
[0106]
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 × 10 ² 2.1 × 10 ^Three 4 × 10 ^Three 1.75 × 10 ^Four 5.1 × 10 ^Four 1.1 × 10 ^Five 3.9 × 10 ^Five 8.6 × 10 ^Five 2 × 10 ⁶ 4.48 × 10 ⁶ It is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
[0107]
As column, 10 ^Three ~ 2x10 ⁶ In 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 ^Three 10 ^Four 10 ^Five Can be mentioned.
[0108]
5) Measurement of toner particle size distribution
In the present invention, the average particle size and particle size distribution of the toner are measured using a Coulter Counter TA-II type (manufactured by Coulter), but a Coulter Multisizer (manufactured by Coulter) can also be used. 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. Distribution and number distribution were calculated. Then, a weight-based weight average particle diameter (D4) obtained from the volume distribution according to the present invention (the median value of each channel is a representative value for each channel) was obtained.
[0109]
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.
[0110]
6) Methanol hydrophobicity measurement
The starting point of descent in the degree of hydrophobicity (methanol wettability) of the toner can be measured using a powder wettability tester (WET-100P, manufactured by Reska Co.). In a 100 ml beaker, 42 ml of pure water (ion-exchanged water or commercially available purified water) and 18 ml of methanol are put, covered and uniformly dispersed using an ultrasonic disperser or the like. 0.5 g of toner is precisely weighed and added, stirred while the stirrer is 250 rpm, and methanol is added at 1.3 ml / min. When the toner starts to settle and disperse in the aqueous solution, the permeability of the solution decreases, and the ratio (%) of methanol / (methanol + water) at this time is set as the starting point for decreasing the hydrophobicity of the toner.
[0111]
【Example】
Specific examples of the present invention will be described below, but the present invention is not limited to these examples.
[0112]
(Hybrid resin production example 1)
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, 1.9 mol of trimellitic anhydride, 5.0 mol of fumaric acid and 0.2 g of dibutyltin oxide are put into a 4-liter 4-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 (1). The results of molecular weight measurement by GPC are shown in Table 1.
[0113]
(Hybrid resin production example 2)
Hybrid resin production except that 4.5 mol of maleic acid and 3.0 mol of itaconic acid are used instead of 5.0 mol of fumaric acid, and 0.1 mol of isobutyl peroxide is used instead of 0.05 mol of dicumyl peroxide Reaction was carried out in the same manner as in Example 1 to obtain a hybrid resin (3). The results of molecular weight measurement by GPC are shown in Table 1.
[0114]
(Hybrid resin production example 3)
A hybrid resin (2) was obtained by reacting in the same manner as in the hybrid resin production example 1 except that 3.8 mol of styrene, 0.08 mol of a dimer of α-methylstyrene, and 0.1 mol of dicumyl peroxide were used. . The results of molecular weight measurement by GPC are shown in Table 1.
[0115]
(Hybrid resin production example 4)
Hybrid resin production except that 3.0 mol of maleic acid and 3.8 mol of itaconic acid are used instead of 5.0 mol of fumaric acid, and 0.13 mol of isobutyl peroxide is used instead of 0.05 mol of dicumyl peroxide Reaction was carried out in the same manner as in Example 1 to obtain a hybrid resin (3). The results of molecular weight measurement by GPC are shown in Table 1.
[0116]
(Hybrid resin production example 5)
A hybrid resin (2) was obtained by reacting in the same manner as in the hybrid resin production example 1 except that 3.5 mol of styrene, 0.13 mol of a dimer of α-methylstyrene, and 0.14 mol of dicumyl peroxide were used. . The results of molecular weight measurement by GPC are shown in Table 1.
[0117]
(Polyester resin production example 6)
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, 1.4 mol of trimellitic anhydride, 2.4 mol of fumaric acid and 0.12 g of dibutyltin oxide are put into a glass 4-liter four-necked flask, and a thermometer, a stirring rod, a condenser and nitrogen are introduced. A tube was installed and placed in a mantle heater. Under a nitrogen atmosphere, reaction was performed at 215 ° C. for 5 hours to obtain a polyester resin (1). The results of molecular weight measurement by GPC are shown in Table 1.
[0118]
[Table 1]

[0119]
The waxes used in this example are listed in Table 2.
[0120]
[Table 2]

[0121]
<Example 1>
As shown in Table 3, Toner 1 was prepared by the following method.
[0122]
(First step)
・ Wax (A) 50 parts by mass
・ Cyan pigment 50 parts by weight
(Pigment Blue 15: 3 BET = 72m ² / G)
First, the above raw materials are charged into a kneader-type mixer, and the temperature is raised under non-pressurization while mixing. The temperature of the material itself was melted and kneaded for 30 minutes at 100 ° C. After the first step was completed, the mixture was cooled and pulverized easily to obtain a kneaded product.
[0123]
(Second kneading step)
・ 100 parts by mass of the kneaded material in the first step
・ Hybrid resin (1) 100 parts by mass
First, the above raw materials are charged into a kneader-type mixer, and the temperature is raised under non-pressurization while mixing. The temperature of the material itself was heated and melted and kneaded at 110 ° C. for 15 minutes, and after the second step, the mixture was cooled and pulverized to obtain a kneaded product.
[0124]

Preliminarily mixed with a Henschel mixer with the above formulation, melt kneaded at a material temperature of 130 ° C. with a twin-screw extruder kneader, cooled and roughly crushed to about 1 to 2 mm using a hammer mill, then air jet The powder was finely pulverized to a particle size of 20 μm or less with a fine pulverizer. Further, the obtained finely pulverized product was classified and selected so that the weight average diameter in the particle size distribution was 7.0 μm to obtain cyan particles (classified product).
[0125]
For the purpose of improving fluidity and imparting charging characteristics, i-C _Four H ₉ Si (OCH _Three ) _Three : Hydrophobic aluminum oxide treated with 23 parts by mass (BET 170 m ² / G) was combined with 1.0 part by mass with respect to 100 parts by mass of the cyan particles to obtain toner 1. The weight average diameter of the toner 1 was 7.0 μm.
[0126]
Further, the toner 1 and magnetic ferrite carrier particles (average particle size 45 μm) coated with a silicone resin were mixed so that the toner concentration would be 7% by mass to obtain a two-component developer 1. Table 4 shows the measurement results of the toner.
[0127]
Using this developer 1, a modified machine (process speed 200 mm / sec) from which the oil application mechanism of the fixing unit of the color copier CLC-1130 (manufactured by Canon) has been removed is used in a single color mode under a low temperature and low humidity environment (15 ° C./10 %), Printing test of 10,000 sheets using an original with an image area ratio of 7%, charge measurement under a high temperature and high humidity environment (30 ° C./80%), and a normal temperature and normal humidity environment (23 ° C. / 60%). Furthermore, for the evaluation of the fixable area, the fixing unit was modified so that the fixing temperature can be set manually.
[0128]
Even after the endurance of 10,000 sheets, the initial image density fluctuation was small and a cyan image that faithfully reproduced the original without fogging was obtained. Conveyance in the copying machine and detection of developer density were good and stable image density was obtained. Even when 10,000 copies were repeatedly copied at a fixing temperature setting of 170 ° C., no offset to the fixing roller occurred. The occurrence of offset on the fixing roller was performed by visually observing the surface of the fixing roller after repeated copying.
[0129]
As shown in Table 3, the toner 1 has excellent transparency as shown in Table 3, and the environmental stability in a low temperature and low humidity environment and in a high temperature and high humidity environment was examined. Met.
[0130]
As a result of examining the storage stability of Toner 1, good data was shown. That is, the blocking resistance of the sample toner was evaluated by leaving it in an oven at 50 ° C. for 2 weeks. As evaluation, it judged from the level of cohesion by visual observation.
[0131]
(Evaluation criteria for blocking resistance)
○: Aggregate is not seen at all and fluidity is very good
Δ: Some agglomerates are seen but loosen immediately
X: Aggregates are not sufficiently loosened by the developer stirring device.
[0132]
<Example 2>
In Example 1, a toner 2 is prepared in substantially the same manner as in Example 1 except that the ratio of the release agent to the colorant in the total amount of the first step is 70% by mass. 2 was obtained. Table 4 shows the measurement results of the toner. Toner 2 was slightly inferior in transparency, and fogging and endurance density fluctuations were observed, but were within practical levels.
[0133]
<Examples 3 to 6>
In Example 1, toners 3 to 6 were obtained in substantially the same manner except that resins 2 and 3 or waxes B and C were used as shown in Table 3. When an endurance test was performed in the same manner as in Example 1, as shown in Table 4, in terms of environmental differences in charging, transparency, blocking characteristics, density fluctuation range, fogging, and fixing offset, inferior points to Example 1 were also observed. However, it was within a practical level.
[0134]
<Example 7>
A toner 7 was obtained in substantially the same manner except that the resin 6 was used as the resin 1 in Example 1. Although the difference in charging environment and the fluctuation in the durable density are somewhat worse, they were not at a level that would cause a practical problem. When the durability test was conducted in the same manner as in Example 1, almost the same result was obtained.
[0135]
<Example 8>
Toner 8 was obtained in substantially the same manner as in Example 7 except that 4.0 parts by mass of azo-based chromium complex (Orient S-34) was used. Although the environmental difference of charging and the fluctuation of the durable density are slightly deteriorated, they were not at a level causing a practical problem. When the durability test was conducted in the same manner as in Example 1, almost the same result was obtained.
[0136]
<Example 9>
In Example 7, Pigment Red 57: 1 (BET = 32 m) was used as the colorant. ² The toner 9 was obtained in substantially the same manner except that / g) was used. Although the difference in charging environment and the fluctuation in the durable density are a little worse, they are not at a level that causes a problem in practical use. When the durability test was conducted in the same manner as in Example 1, almost the same result was obtained.
[0137]
<Example 10>
Except that wax D was used in Example 1, toner 10 was obtained in substantially the same manner. Toner 10 was slightly inferior in transparency, and fogging and endurance density fluctuations were observed, but were within a practical level.
[0138]
<Examples 11 to 12>
As shown in Table 3, in Example 1, toners 11 to 12 were obtained in substantially the same manner except that the temperature in step 1 was changed. As shown in Table 4, the transparency, blocking characteristics, density fluctuation range, and fog were inferior to those of Example 1, but were within practical levels.
[0139]
<Example 13>
As shown in Table 3, in Example 1, toner 13 was obtained in substantially the same manner except that the temperature in step 2 was changed. As shown in Table 4, the charging environment difference, blocking characteristics, density fluctuation range, and fixing offset were inferior to those of Example 1, but were within practical levels.
[0140]
<Example 14>
As shown in Table 3, in Example 1, toner 14 was obtained in substantially the same manner except that the temperature in step 3 was changed. As shown in Table 4, the transparency, blocking characteristics, density fluctuation range, and fog were inferior to those of Example 1, but were within practical levels.
[0141]
<Comparative Example 1>
As shown in Table 3, in Example 1, 50 parts by mass of the resin 1 instead of the wax A was added to the process 1 and charged in a kneader mixer, and the temperature was raised under no pressure while mixing. The material itself was melted and kneaded for 30 minutes at a temperature of 100 ° C., then cooled and crushed easily to obtain a kneaded product. The kneaded product was further melted and kneaded with three rolls at 100 ° C. for 30 minutes to complete the first step, and then cooled and easily pulverized to obtain a kneaded product.
[0142]
There was no second step, and toner 15 was obtained by the following formulation in the third step.

[0143]
As shown in Table 4, although the blocking characteristics were in the practical range, the transparency, density fluctuation range, and fog were significantly inferior to those of Example 1, and were not practically usable.
[0144]
<Comparative example 2>
As shown in Table 3, in Example 1, in Step 1,
・ Hybrid resin (5) 100.0 parts by mass
・ Wax A 50.0 parts by mass
Cyan pigment (Pigment Blue 15: 3) 50.0 parts by mass
Is heated in a non-pressurized state while mixing. The material itself was melted and kneaded for 30 minutes at a temperature of 100 ° C., then cooled and crushed easily to obtain a kneaded product.
[0145]
There was no second step, and toner 16 was obtained by the following formulation in the third step.

[0146]
As shown in Table 4, the transparency, blocking characteristics, density fluctuation range, fog, and fixing offset were considerably inferior to those of Example 1, and were not practically usable.
[0147]
<Comparative Example 3>
As shown in Table 3, a toner 17 was obtained in substantially the same manner as in Example 1 except that the binder resin was changed. As shown in Table 4, the fixing offset was poor and was not practically usable.
[0148]
<Comparative Examples 4-5>
As shown in Table 3, in Example 1, toners 18 and 19 were obtained in substantially the same manner except that the temperature in step 2 was changed. As shown in Table 4, the density fluctuation range and fog were considerably inferior to those of Example 1, and were not practically usable.
[0149]
<Comparative Example 6>
As shown in Table 3, a toner 20 was obtained in substantially the same manner as in Example 1 except that the temperature in Step 3 was changed. As shown in Table 4, the transparency, blocking, density fluctuation range and fog were considerably inferior to those of Example 1, and were not practically usable.
[0150]
<Comparative Example 7>
As shown in Table 3, a toner 21 was obtained in substantially the same manner as in Example 1 except that the BET of the pigment was changed. As shown in Table 4, the density fluctuation range and fog were considerably inferior to those of Example 1, and were not practically usable.
[0151]
<Comparative Example 8>
As shown in Table 3, a toner 22 was obtained in substantially the same manner as in Example 1 except that the BET of the pigment was changed. As shown in Table 4, the charging environment difference, density fluctuation range, and fogging were considerably inferior to those of Example 1, and were not practically usable.
[0152]
<Comparative Example 9>
As shown in Table 3, a toner 23 was obtained in substantially the same manner as in Example 1 except that the wax E was used. As shown in Table 4, especially in blocking, a point inferior to Example 1 was seen, and it was not practically usable.
[0153]
<Comparative Example 10>
As shown in Table 3, a toner 24 was obtained in substantially the same manner as in Example 1 except that the resin 2 and the wax F were changed. As shown in Table 4, the fixing offset was considerably inferior to that of Example 1, and was not practically usable.
[0154]
<Comparative Example 11>
As shown in Table 3, toner 25 was obtained in substantially the same manner as in Example 1 except that the number of added parts of wax A was changed to 2.3 parts. As shown in Table 4, the fixing offset was considerably inferior to that of Example 1, and was not practically usable.
[0155]
<Comparative Example 12>
As shown in Table 3, toner 25 was obtained in substantially the same manner as in Example 1, except that the number of added parts of wax A was changed to 10.5 parts. As shown in Table 4, the fixing offset was considerably inferior to that of Example 1, and was not practically usable.
[0156]
<Example 15>
In Example 7, Pigment Yellow 155 (BET = 80 m) was used as the colorant. ² The toner 27 was obtained in substantially the same manner except that / g) was used. When full-color image evaluation was performed using toner 1, toner 9 and toner 27, the density fluctuation and fogging after 10,000 sheets were good, and the transparency was also good.
[0157]
[Table 3]

[0158]
[Table 4]

[0159]
【The invention's effect】
The full-color toner of the present invention and the method for producing the same can improve the dispersibility of the colorant and the release agent, and can provide a full-color toner excellent in low-temperature fixing and charging stability in high-speed copying and excellent in blocking resistance. is there.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram of an apparatus for measuring the triboelectric charge amount of toner.

Claims (11)

In a full-color toner having at least a binder resin, a colorant, and a release agent,
(I) The content of the release agent with respect to 100 parts by mass of the binder resin is 2.5 to 10 parts by mass,
(Ii) The descent start point in the methanol hydrophobization degree of the toner is in the range of 35 ≦ methanol / (methanol + water) ≦ 60 (volume%), (iii) the resin has at least a polyester resin, maximum endothermic peak temperature Tsc as determined by DSC of iv) releasing agent is the 70 ℃ <Tsc <100 ℃, (v) BET is 30 to 200 m ² / g der of colorant Ri, (vi) full-color toner coloring agent is characterized that you have been surface treated with a release agent. The full-color toner according to claim 1 , wherein at least the release agent and the colorant are melt-mixed in advance. The binder resin is (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl copolymer unit, or (c) a mixture of a hybrid resin and a vinyl copolymer, or The resin according to claim 1 or 2 , wherein the resin is selected from (d) a mixture of a polyester resin and a vinyl copolymer, or (e) a mixture of a hybrid resin and a polyester resin. Full color toner. Full color toner according to any one of claims 1 to 3 release agent is characterized in that it is a hydrocarbon wax. Full color toner according to any one of claims 1 to 4, characterized by containing a metal compound of an aromatic carboxylic acid derivative. In the method for producing a full-color toner having at least a binder resin, a colorant, and a release agent,
The toner has (i) a content of the release agent of 2.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin, and (ii) a start point of decrease in the degree of methanol hydrophobization of the toner is 35 ≦ Methanol / (methanol + water) ≦ 60 (volume%), (iii) the resin has at least a polyester resin, and (iv) the maximum endothermic peak temperature Tsc measured by DSC of the release agent is 70 ° C. <Tsc <100 ° C. (v) the BET of the colorant is 30 to 200 m ² / g,
The toner production process includes 1): a first process in which at least a release agent and a colorant are melt-mixed, and 2) a second process in which the melt mixture produced in 1) and a binder resin are melt-mixed. And 3): a full-color toner manufacturing method comprising the third step of melting and mixing the molten mixture manufactured in 2) and at least the binder resin. The melting temperature in the manufacturing process satisfies the following relationship when the melting temperature of the first process is T1, the melting temperature of the second process is T2, and the melting temperature of the third process is T3. 6. A method for producing a full-color toner according to 6 .
Tsc-10 ° C <T1 <Tsc + 50 ° C
Tsc + 10 ° C. <T2 <T3 <Tm + 60 ° C.
(Tm is the elution start temperature of the toner flow tester) The method for producing a full-color toner according to claim 7 , wherein the toner has a relationship of Tsc + 10 ° C. <Tm <Tsc + 40 ° C. and 70 ° C. <Tsc <100 ° C. with respect to the elution start temperature Tm of the toner flow tester. . The binder resin is (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl copolymer unit, or (c) a mixture of a hybrid resin and a vinyl copolymer, or The resin according to any one of claims 6 to 8 , wherein the resin is selected from (d) a mixture of a polyester resin and a vinyl copolymer, or (e) a mixture of a hybrid resin and a polyester resin. A method for producing a full-color toner as described in 1 above. Full-color method for producing a toner according to any one of claims 6 to 9, wherein the release agent is a hydrocarbon wax. The method for producing a full-color toner according to any one of claims 6 to 10 , comprising a metal compound of an aromatic carboxylic acid derivative.

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