JP3943878B2 - toner - Google Patents

Description

【００４１】
本発明のトナーに含有される結着樹脂において、「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。
【００４２】
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。
【００４３】
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。
【００４４】
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。
【００４５】
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。
【００４６】
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。
【００４７】
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。
【００４８】
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。
【００４９】
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。
【００５０】
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。
【００５１】
（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。
【００５２】
（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。
【００５３】
（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。
【００５４】
（４）ビニル系重合体ユニット及びポリエステルユニット製造後に、これらの重合体ユニット存在下にビニル系モノマー及び／またはポリエステルモノマー（アルコール、カルボン酸）を添加することによりハイブリッド樹脂成分を製造される。この場合も適宜、有機溶剤を使用することができる。
【００５５】
（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。
【００５６】
（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。
【００５７】
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。
【００５８】
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を使用しても良い。
【００５９】
本発明のトナーに含有される結着樹脂は、上記ハイブリッド樹脂とビニル系共重合体との混合物を使用しても良い。
【００６０】
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。
【００６１】
本発明で使用される着色剤として、黒色着色剤としては、カーボンブラック、磁性体、イエロー／マゼンタ／シアン着色剤を用い黒色に調色されたものが利用される。
【００６２】
黒色着色剤として磁性体を用いた場合には、他の着色剤と異なり、樹脂１００質量部に対し３０〜２００質量部添加して用いられる。
【００６３】
磁性体としては、鉄，コバルト，ニッケル，銅，マグネシウム，マンガン，アルミニウム，珪素などの元素を含む金属酸化物などがある。中でも四三酸化鉄，γ−酸化鉄等、酸化鉄を主成分とするものが好ましい。また、トナー帯電性コントロールの観点から硅素元素またはアルミニウム元素等、他の金属元素を含有していてもよい。これら磁性粒子は、窒素吸着法によるＢＥＴ比表面積が２〜３０ｍ²／ｇ、特に３〜２８ｍ²／ｇが好ましく、更にモース硬度が５〜７の磁性粉が好ましい。
【００６４】
磁性体量は結着樹脂１００質量部に対し３０〜２００質量部、好ましくは４０〜２００質量部、さらには５０〜１５０質量部が好ましい。３０質量部未満では、着色力が不足したりトナー搬送に磁気力を用いる現像器においては、搬送性が不十分で現像剤担持体上の現像剤層にムラが生じ画像ムラが発生する傾向があり、さらに現像剤トリボの上昇に起因する画像濃度の低下が生じ易い傾向がある。一方、２００質量部を超えると定着性に問題が生ずる傾向がある。
【００６５】
本発明のトナーをカラートナーとして用いた場合の着色剤としては、公知の染料または／及び顔料が使用される。
【００６６】
マゼンタトナー用着色顔料としてはＣ．Ｉ．ピグメントレッド１，２，３，４，５，６，７，８，９，１０，１１，１２，１３，１４，１５，１６，１７，１８，１９，２１，２２，２３，３０，３１，３２，３７，３８，３９，４０，４１，４８，４９，５０，５１，５２，５３，５４，５５，５７，５８，６０，６３，６４，６８，８１，８３，８７，８８，８９，９０，１１２，１１４，１２２，１２３，１６３，２０２，２０６，２０７．２０９；Ｃ．Ｉ．ピグメントバイオレット１９；Ｃ．Ｉ．バットレッド１，２，１０，１３，１５，２３，２９，３５などが挙げられる。
【００６７】
顔料単独使用でもかまわないが、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。
【００６８】
マゼンタトナー用染料としては、Ｃ．Ｉソルベントレッド１，３，８，２３，２４，２５，２７，３０，４９，８１，８２，８３，８４，１００，１０９，１２１；Ｃ．Ｉ．ディスパースレッド９；Ｃ．Ｉ．ソルベントバイオレット８，１３，１４，２１，２７；Ｃ．Ｉ．ディスパーバイオレット１の如き油溶染料、Ｃ．Ｉ．ベーシックレッド１，２，９，１２，１３，１４，１５，１７，１８，２２，２３，２４，２７，２９，３２，３４，３５，３６，３７，３８，３９，４０；Ｃ．Ｉ．ベーシックバイオレット１，３，７，１０，１４，１５，２１，２５，２６，２７，２８などの塩基性染料が挙げられる。
【００６９】
シアントナー用着色顔料としては、Ｃ．Ｉ．ピグメントブルー２，３，１５，１６，１７；Ｃ．Ｉ．バットブルー６；Ｃ．Ｉ．アシッドブルー４５または下記式で示される構造を有するフタロシアニン骨格にフタルイミドメチル基を１〜５個置換した銅フタロシアニン顔料などが挙げられる。
【００７０】
【化２】

〔式中、ｎは１〜５の整数を示す〕
【００７１】
イエロー用着色顔料としてはＣ．Ｉ．ピグメントイエロー１，２，３，４，５，６，７，１０，１１，１２，１３，１４，１５，１６，１７，２３，６５，７３，８３，９７，１８０；Ｃ．Ｉ．バットイエロー１，３，２０などが挙げられる。
【００７２】
着色剤の使用量は、結着樹脂１００質量部に対して好ましくは０．１〜１５質量部、より好ましくは０．５〜１２質量部、最も好ましくは３〜１０質量部が良い。
【００７３】
本発明のトナーは示差熱分析（ＤＳＣ）測定における吸熱曲線において、温度３０〜２００℃の範囲における最大吸熱ピークのピーク温度が６０〜９０℃の範囲にあることが定着性、耐ブロッキング性の点でより好ましい。
【００７４】
本発明のトナーは、トナーに電荷を保有せしめるために有機金属化合物を用いても良いが、例えば下記に示す芳香族オキシカルボン酸誘導体の金属化合物が挙げられる。
【００７５】
【化３】

【００７６】
式中のＭ₂は２価の金属原子であり、Ｍｇ²⁺，Ｃａ²⁺，Ｓｒ²⁺，Ｐｂ²⁺，Ｆｅ²⁺，Ｃｏ²⁺，Ｎｉ²⁺，Ｚｎ²⁺，Ｃｕ²⁺が挙げられる。Ｍ₃は３価の金属原子であり、Ａｌ³⁺，Ｃｒ³⁺，Ｆｅ³⁺，Ｎｉ³⁺が挙げられる。Ｍ₄は４価の金属原子であり、Ｚｒ⁴⁺，Ｈｆ⁴⁺，Ｍｎ⁴⁺，Ｃｏ⁴⁺が挙げられる。これらの金属原子の中で好ましいのはＡｌ³⁺，Ｆｅ³⁺，Ｃｒ³⁺，Ｚｒ⁴⁺，Ｈｆ⁴⁺，Ｚｎ²⁺である。
【００７７】
また、式中Ｒ₁乃至Ｒ₄は同一又は異なる基を示し、水素原子、炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基、−ＯＨ，−ＮＨ₂，−ＮＨ（ＣＨ₃），−Ｎ（ＣＨ₃）₂，−ＯＣＨ₃，−Ｏ（Ｃ₂Ｈ₅），−ＣＯＯＨ又は−ＣＯＮＨ₂を示す。好ましいＲ₁としては、ヒドロキシル基、アミノ基及びメトキシ基が挙げられるが、中でもヒドロキシル基が好ましい。
【００７８】
本発明のトナー粒子には、流動性向上剤が外添されていることが画質向上のために好ましい。流動性向上剤としては、ケイ酸微粉体，酸化チタン，酸化アルミニウム等の無機微粉体が好ましい。該無機微粉体は、シランカップリング剤，シリコーンオイル又はそれらの混合物の如き疎水化剤で疎水化されていることが好ましい。トナー粒子がフルカラー画像形成用の非磁性のカラートナー粒子である場合は、外添剤として、酸化チタン微粒子を使用することが好ましい。
【００７９】
流動性向上剤は通常、トナー粒子１００質量部に対して０．１〜５質量部使用される。
【００８０】
トナー粒子と外添剤との混合は、ヘンシェルミキサーの如き混合機を用いるのが良い。
【００８１】
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。
【００８２】
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。
【００８３】
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。
【００８４】
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。
【００８５】
酸価の測定方法
試料２〜１０ｇを２００〜３００ｍｌの三角フラスコに秤量し、メタノール：トルエン＝３０：７０の混合溶媒約５０ｍｌ加えて樹脂を溶解する。溶解性が悪いようであれば少量のアセトンを加えても良い。０．１％のブロムチモールブルーとフェノールレッドの混合指示薬を用い、あらかじめ標定されたＮ／１０水酸化カリウム〜アルコール溶液で滴定し、アルコールカリウム液の消費量から次の計算式（ＩＩＩ）で酸価を求める。
酸価＝ＫＯＨ（ｍｌ数）×ｆ×５６．１／試料質量 ……（ＩＩＩ）
（ただしｆはＮ／１０ ＫＯＨのファクター）
【００８６】
トナー中に磁性粉が含有する場合には、磁性体を酸で溶出させた残分を試料として測定する。
【００８７】
示差走査熱量計（ＤＳＣ測定装置），ＤＳＣ−７（パーキンエルマー社製）を用いて以下のようにして測定する。
【００８８】
測定試料は２〜１０ｍｇ、好ましくは５ｍｇを精密に秤量する。
【００８９】
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。
【００９０】
この昇温過程で、温度３０〜２００℃の範囲におけるＤＳＣ曲線のメインピークの吸熱ピークが得られる。
【００９１】
ＧＰＣ測定
ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるクロマトグラムの分子量は次の条件で測定される。
【００９２】
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。
【００９３】
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。
【００９４】
【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。
【００９５】
（変性パラフィンワックスの製造法）
スチレンモノマー６００ｇに反応開始剤としてジクミルパーオキサイド５０ｇを添加した後、加熱溶融したパラフィンワックスＡ３０００ｇ中に撹拌しながら滴下し、４時間反応させ、スチレン変性パラフィンワックス１を得た。
【００９６】
パラフィンワックスの種類、スチレンモノマーの比率を変え、同様に変性パラフィンワックスを得た。比率及び特性を表１、表２に示す。
【００９７】
【表１】

【００９８】
【表２】

【００９９】
（混合ワックスの製造法）
溶液重合によりあらかじめ作製しておいたポリスチレン重合体にパラフィンワックスＡを質量比３０：７０で１００℃で加熱混合したものを冷却、粉砕し、混合ワックスとした。
【０１００】
（トナー製造法）
表３、表４に示すトナー材料をヘンシェルミキサーにより十分予備混合を行った後、二軸式押出機で溶融混練し、冷却後ハンマーミルを用いて粒径約１〜２ｍｍ程度に粗粉砕した。次いでエアージェット方式による微粉砕機で微粉砕した。さらに、得られた微粉砕物を多分割分級装置で分級して、重量平均粒径８．０μｍのトナー樹脂粒子を得た。
【０１０１】
上記トナー樹脂粒子１００質量部に対して、ｎ−Ｃ₄Ｈ₉Ｓｉ（ＯＣＨ₃）₃で処理した疎水性酸化チタン（ＢＥＴ１１０ｍ²／ｇ）１．０質量部を合せてトナー１とした。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５０μｍ）とを、トナー濃度が６質量％になるように混合し、二成分系現像剤１とした。同様にしてトナー１〜２０及び、現像剤１〜２０を得た。
【０１０２】
【表３】

【０１０３】
【表４】

【０１０４】
＜実施例１＞
以下のようにしてトナー１及び現像剤１の評価を行った。
【０１０５】
市販の普通紙フルカラー複写機（ＣＬＣ９００）を用い、低湿環境下（２３℃／５％）及び高湿環境下（３０℃／９０％）で、画像面積比率２５％のオリジナル原稿を用いて、連続複写２万枚の耐久試験を行った。
【０１０６】
現像性は耐久初期と２万枚耐久後の画像濃度の変化を評価の基準とした。画像濃度は、マクベス社製のマクベス濃度計にてオリジナル画像のベタ部（初期画像濃度＝１．５）を５回平均し、画像濃度の変化値を見た。
【０１０７】
転写性は、耐久前後の画像を現像，転写し、感光体上の転写前のトナー量（単位面積あたり）と、転写材上のトナー量（単位面積あたり）をそれぞれ測定し、下式により求めた。
転写率（％）＝（転写材上のトナー量）／（感光体上の転写前のトナー量）×１００
【０１０８】
クリーニング性は、クリーニング不良が若干でも発生した時点の耐久枚数を表示する。
【０１０９】
定着温度領域はカラー複写機ＣＬＣ９００（キヤノン製）のオイル塗布機構を取り外し、さらに定着温度を自由に設定できるように改造して定着試験をおこなった。このときの画像面積比率は２５％であり、単位面積当たりの、トナー載り量は、０．７ｍｇ／ｃｍ²に設定した。定着開始温度とオフセット開始温度の測定は、定着器の設定温度を１１０〜２５０℃迄の温度範囲で５℃おきに温度調節して、各々の温度で定着画像を出力し、得られた定着画像を４．９ｋＰａ（５０ｇ／ｃｍ²）の荷重をかけたシルボン紙で摺擦し、摺擦前後の濃度低下率が１０％以下となる定着温度を定着開始温度とした。また定着開始温度から更に設定温度を上げて行き、目視で高温オフセットの発生した温度をオフセット開始温度とした。
【０１１０】
トナーの保存性（耐ブロッキング性）に関しては、５０℃のオーブン内にて１週間放置することにより評価した。該評価としては目視による凝集性のレベルを判定した。トナー凝集性評価基準を以下に示す。
Ａ：凝集体が全く見られなく流動性が非常に良い
Ｂ：凝集体が全く見られない
Ｃ：若干の凝集体は見られるがすぐにほぐれる
Ｄ：現像剤撹拌装置で凝集体がほぐれる（普通）
Ｅ：現像剤撹拌装置では凝集体が十分にほぐれない（やや悪い）
【０１１１】
評価の結果、転写性、クリーニング性が良く、２００００枚後の耐久性も非常に良好な性能を示した。また、低湿環境下、高湿環境下においても、きわめて安定した現像性を示した。
【０１１２】
また、広い定着温度幅をとることができた。結果を表５、６に示す。
【０１１３】
＜実施例２〜６＞
実施例１と同様にしてトナー２〜６及び現像剤２〜６の評価を行った。
【０１１４】
実施例２〜６も実施例１と同様に、転写性、クリーニング性が良く、２００００枚後の耐久性も非常に良好な性能を示した。また、低湿環境下、高湿環境下においても、きわめて安定した現像性を示した。結果を表５、６に示す。
【０１１５】
＜実施例７＞
実施例１と同様にしてトナー７及び現像剤７の評価を行った。
【０１１６】
実施例７では耐久後において、若干の画像濃度の低下が見られたが、問題無かった。また、保存性が若干不利であったが、問題ないレベルであった。結果を表５、６に示す。
【０１１７】
＜実施例８＞
実施例１と同様にしてトナー８及び現像剤８の評価を行った。
【０１１８】
実施例８では定着開始温度が若干高くなったが、使用上問題無かった。結果を表５、６に示す。
【０１１９】
＜実施例９＞
実施例１と同様にしてトナー９及び現像剤９の評価を行った。
【０１２０】
実施例９では定着温度幅が狭くなったが問題無かった。結果を表５、６に示す。
【０１２１】
＜実施例１０＞
実施例１と同様にしてトナー１０及び現像剤１０の評価を行った。
【０１２２】
実施例１０では耐久後において、画像濃度の低下が見られ、保存性が若干不利であったが、使用上問題無かった。結果を表５、６に示す。
【０１２３】
＜参考例１＞
実施例１と同様にしてトナー１１及び現像剤１１の評価を行った。
【０１２４】
参考例１では耐久後において、若干の画像濃度の低下が見られた。また、クリーニング性が若干不利であるが使用上問題無かった。結果を表５、６に示す。
【０１２５】
＜参考例２＞
実施例１と同様にしてトナー１２及び現像剤１２の評価を行った。
【０１２６】
参考例２ではワックスの分散性が良く、現像性や耐久性は優れているが、定着温度幅が小さくなった。結果を表５、６に示す。
【０１２７】
＜実施例１１＞
マゼンタ現像剤、イエロー現像剤、シアン現像剤、及び現像剤１を用いてカラー複写機ＣＬＣ−９００にてフルカラーモードで低湿環境下（２３℃／５％）及び高湿環境下（３０℃／９０％）で、画像面積比率２５％のオリジナル原稿を用いて、連続複写２万枚の耐久試験を行った。フルカラーモードにおいても画像濃度の低下が無く、転写性、クリーニング性にも優れたトナーを得ることができた。
【０１２８】
また、ＣＬＣ−９００のオイル塗布機構を取り外し、さらに定着温度を１６０℃設定してフルカラーの画像を出力した。色再現性の優れた画像を出力することができた。
【０１２９】
＜比較例１＞
実施例１と同様にしてトナー１６及び現像剤１６の評価を行った。
【０１３０】
比較例１ではトナー中のワックス量が少ないためか、定着温度幅がほとんど無く、オイルレス定着は不可能であった。結果を表５、６に示す。
【０１３１】
＜比較例２＞
実施例１と同様にしてトナー１７及び現像剤１７の評価を行った。
【０１３２】
比較例２ではトナー中のワックス量が多すぎるためか、ワックスのドラム融着、キャリア汚染などが起こり、画像濃度や転写効率の低下、クリーニング不良が発生した。また、保存性も若干不利になっていた。結果を表５、６に示す。
【０１３３】
＜比較例３＞
実施例１と同様にしてトナー１８及び現像剤１８の評価を行った。
【０１３４】
比較例３ではワックスがトナー中に完全に分散されてないためか、耐久性、クリーニング性、転写性において良くなかった。結果を表５、６に示す。
【０１３５】
＜比較例４＞
実施例１と同様にしてトナー１９及び現像剤１９の評価を行った。
【０１３６】
比較例４ではトナー中のワックスが脱離しているためか、耐久後、画像濃度の低下が見られた。また、脱離ワックスがキャリアも汚染しているためか、特に高湿環境下で十分な帯電が得られず、かぶりが発生した。また、クリーニング不良の発生も早く、転写性も悪化した。結果を表５、６に示す。
【０１３７】
＜比較例５＞
実施例１と同様にしてトナー２０及び現像剤２０の評価を行った。
【０１３８】
比較例５ではトナー中のワックスが脱離しているためか、耐久後、画像濃度の低下が見られた。また、脱離ワックスがキャリアも汚染しているためか、特に高湿環境下で十分な帯電が得られず、かぶりが発生した。また、クリーニング不良の発生も早く、転写性も悪化した。更にこのトナーは保存性も悪かった。結果を表５、６に示す。
【０１３９】
【表５】

【０１４０】
【表６】

【０１４１】
【発明の効果】
本発明によれば、トナーの原材料である離型剤の改良によって、低温定着が可能で、耐オフセット性に優れ、さまざまな環境に対して、長期にわたり使用しても高い画像品質の安定性、耐久性に優れるとともに転写性、クリーニング性に優れたトナーを提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a toner used for developing an electrostatic image formed in an image forming method such as an electrophotographic method, an electrostatic recording method, or an electrostatic printing method.
[0002]
[Prior art]
Conventionally, as an electrophotographic method, many methods are known as described in US Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. 43-24748, and the like. In general, a photoconductive substance is used to form an electrical latent image on the photosensitive member by various means, and then the latent image is developed with toner to form a visible image. After the toner image is transferred to the transfer material, the toner image is fixed on the transfer material by heat and pressure to obtain a copy. Further, the toner particles remaining on the photosensitive member without being transferred onto the transfer material are removed from the photosensitive member by the cleaning step, and the above-described steps are repeated.
[0003]
For example, fixing performance is the most important performance required for toners in digital printers and high-definition image copying. Various methods and apparatuses have been developed for the fixing process, but the most common method at present is a pressure heating method using a heat roller. This pressure heating method using a heating roller performs fixing by allowing the toner image surface of a fixing sheet to pass through the surface of a heat roller formed with a material having releasability with respect to the toner while being in contact with pressure. It is. In this method, since the surface of the heat roller and the toner image of the fixing sheet are brought into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image on the fixing sheet is extremely good, and the fixing can be performed quickly. This is very effective in a high-speed electrophotographic copying machine.
[0004]
It is known to contain a wax as a release agent in a toner. For example, techniques such as JP-A-52-3304, JP-A-52-3305, and JP-A-57-52574 are disclosed.
[0005]
These waxes are used to improve the offset resistance of toner at low and high temperatures. However, while these performances are improved, blocking resistance is deteriorated or developability is deteriorated.
[0006]
Further, in recent years, it has been demanded to prevent the offset phenomenon, and at the same time, it is required to realize a fixing method with a shorter wait time and lower power consumption in fixing. On the other hand, a design capable of realizing fixing at a lower temperature is demanded. For example, JP-A-51-14333, JP-A-57-14852, JP-A-58-97056, JP-A-60-247250, JP-A-4-362953, JP-A-6-6- No. 230600 and JP-A-8-030036 use a solid silicone varnish, a higher fatty acid wax, a higher alcohol wax, a plant natural wax (carnauba, rice), or a montan ester wax as a release agent. Proposed.
[0007]
However, when such a wax, which is such a low softening point release agent, is contained in the toner as a release agent, it tends to adversely affect the development characteristics, chargeability, durability, and storage stability of the toner. Further, these waxes are difficult to uniformly disperse in the toner, and the wax that is free or unevenly distributed in the toner tends to adversely affect the developability and durability.
[0008]
JP-A-8-278657, JP-A-8-334919, and JP-A-8-334920 disclose two types of wax components in order to obtain a toner having excellent low-temperature fixability and offset resistance. Proposed to be included in toner. In JP-A-7-281478, a polypropylene resin and an acid-modified polyethylene resin are used as a release agent for toner in order to lower the minimum fixing temperature and increase the hot offset temperature. Proposed.
[0009]
However, even if any of these release agents is used, the range of low-temperature fixability and high-temperature offset resistance will surely expand, but toner deterioration will occur due to high durability, and it will be stable over a long period of time. Therefore, further improvement of the toner has been desired in order to exhibit excellent fixability and maintain high durability and excellent developability.
[0010]
[Problems to be solved by the invention]
The object of the present invention is that low temperature fixing is possible, excellent offset resistance, high image quality stability and durability even in long-term use in various environments, transferability and cleaning properties. The object is to provide an excellent toner.
[0011]
[Means for Solving the Problems]
  The object of the present invention is achieved by the following. That is, the present invention relates to a toner containing at least a binder resin, a colorant, and a release agent.
  The release agent is a modified paraffin wax modified with a styrene monomer, and the modified paraffin wax is contained in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the resin component in the toner.And
  The toner further contains unmodified paraffin, and (1) the content of paraffin modified with styrene monomer and (2) unmodified paraffin is expressed by the following formula:
    0.05 ≦ (2) / ((1) + (2)) ≦ 0.90              (Formula 1)
SatisfyThe toner is characterized by that.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments of the present invention.
[0013]
The present inventors have found that the above-mentioned problems can be achieved by using a modified paraffin wax modified with a styrene monomer as a release agent that is a raw material of toner. Usually, paraffin wax has a lower molecular weight and a lower melt viscosity than low molecular weight polyolefins such as polyethylene and polypropylene, or graft polyolefins. Therefore, it exhibits excellent releasability. However, since it is very soft, the interfacial adhesive force between the toner resin and paraffin is weak, and the paraffin is easily detached from the toner. The detached paraffin was fused to the cleaning blade and the photosensitive member, and the developing property and cleaning property were deteriorated. In addition, self-aggregation and adhesion are high, and the fluidity of the toner deteriorates. For this reason, problems such as a decrease in the rising speed of charging, sleeve contamination of the developing device, and carrier contamination in the two-component development have occurred.
[0014]
Therefore, the present inventors considered to improve the interfacial adhesion and prevent the detachment by modifying the paraffin so as to be easily compatible with the toner resin component. As a result of intensive studies, the styrene monomer modified with paraffin is the most effective in terms of ease of modification, dispersibility when incorporated in toner, fluidity, developability and fixability. I found it to be a method. The details of this effect are not clear, but it is probably because of the following reasons.
[0015]
The modified paraffin wax of the present invention uses a styrene-based monomer. However, the compatibility of the aromatic part of the modified product and the aromatic of the toner resin component increases, so that the wax is not easily detached. It is thought that it has become. As a result, the wax was not fused to the cleaning blade or the photoconductor, and excellent developability and cleanability could be maintained.
[0016]
In particular, in the present study, the toner resin component is a hybrid resin in which the toner resin component is a copolymer having a vinyl unit rather than a single polyester, a mixture of a polyester and a hybrid resin component, a polyester and vinyl copolymer, and the like. In particular, the use of a styrene monomer was very effective in terms of wax dispersibility and developability.
[0017]
In the toner of the present invention, since the amount of wax deposited on the toner surface is small, self-aggregation and adhesion of the toner can be suppressed and the fluidity can be improved. Therefore, the rising speed of the charge is increased, and the sleeve contamination of the developing device and the carrier contamination are eliminated in the two-component development.
[0018]
The modified paraffin wax used in the present invention may be 1 to 20 parts by mass, more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the resin component in the toner. If the amount is less than 1 part by mass, the effect of the modified paraffin wax as a release agent is lost, and the fixing temperature range is reduced. If it exceeds 20 parts by mass, the toner itself is softened and the durability becomes very poor.
[0019]
Next, the modified paraffin wax used in the present invention will be described.
[0020]
As the modified paraffin wax used in the present invention, one obtained by modifying paraffin wax with a styrenic monomer can be used without limitation. The modified paraffin wax functions as a release agent in the toner.
[0021]
As the paraffin wax before modification, natural paraffin wax, synthetic paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc. can be used. Examples of the styrene monomer include styrene, α-methyl styrene, vinyl toluene, isopropenyl toluene, p-methyl styrene, p-methoxy styrene, m-methyl styrene and the like.
[0022]
Using the above paraffin wax and styrenic monomer, a modified paraffin wax can be obtained according to ordinary methods and conditions. Specifically, for example, a method using radiation or a method using a radical catalyst can be used, but a method using a radical catalyst is preferable.
[0023]
As radical catalysts, organic peroxides, organic peroxides such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxidebenzoate) hexyne-3 1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl -2,5-di (tert-butylperoxy) hexane, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octate, ter - butyl perpivalate, cumyl perpivalate and tert- butyl hydroperoxide diethyl acetate; other azo compounds such as azobisisobutyronitrile, and the like dimethyl azoisobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert- Dialkyl peroxides such as butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.
[0024]
The modified paraffin wax used in the present invention contains a styrene monomer-modified paraffin modified with a styrene monomer, but also contains an unmodified paraffin. Although it is preferable that unmodified paraffin exists from the viewpoint of fixing property, when the content of the styrenic monomer-modified paraffin is (1) and the content of the unmodified paraffin is (2), the following formula
0.05 ≦ ▲ 2 ▼ / (▲ 1 ▼ + ▲ 2 ▼) ≦ 0.90
It is preferable that More preferably
0.15 ≦ ▲ 2 ▼ / (▲ 1 ▼ + ▲ 2 ▼) ≦ 0.80
It is.
[0025]
If (2) / ((1) + (2)) is greater than 0.90, the dispersion of the wax in the toner becomes poor, which is disadvantageous in terms of developability and durability. If (2) / ((1) + (2)) is smaller than 0.05, the exudation of wax during fixing becomes disadvantageous, and the fixing temperature width becomes small.
[0026]
The modified paraffin wax used in the present invention contains a polymer of a styrene monomer in addition to a styrene monomer modified paraffin modified with a styrene monomer and an unmodified paraffin, but this quantitative ratio is not limited at all. There is no place to do it.
[0027]
The composition ratio of the unmodified paraffin in the modified paraffin wax was determined and classified as follows.
[0028]
The unmodified paraffin and the modified paraffin wax were subjected to GPC measurement under the same conditions, and the amount reduced from the GPC peak area of the unmodified paraffin wax was defined as the amount of styrene-modified paraffin and the rest as the amount of unmodified paraffin.
[0029]
The modified paraffin wax used in the present invention is preferably charged in an amount of 5 to 200 parts by mass of a styrene monomer with respect to 100 parts by mass of the paraffin wax. If the styrene monomer is less than 5 parts by mass, the effect as a modified paraffin wax cannot be obtained, which is disadvantageous for the wax fusion of the cleaning blade and the photoreceptor, the decrease in the rising speed of charging, the sleeve, carrier contamination, and the like. become. When the amount of the styrene monomer exceeds 200 parts by mass, the speed of exudation of wax during fixing of the modified paraffin wax decreases, and the fixing property becomes disadvantageous.
[0030]
The modified paraffin wax used in the present invention has a main peak value (hereinafter referred to as “melting point”) of 60 to 90 ° C. in the DSC endothermic curve. This is preferable.
[0031]
For DSC measurement, for example, DSC-7 manufactured by PerkinElmer is used. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
[0032]
The measurement sample is precisely weighed in an amount of 2 to 10 mg, preferably 5 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 the main peak of the DSC curve in the temperature range of 30 to 200 ° C. is obtained.
[0033]
The toner of the present invention has a molecular weight distribution measured by gel permeation chromatography (GPC) of a THF soluble component (resin component) having a main peak in a molecular weight region of 3,000 to 40,000. It is preferable that Mw / Mn is 100 or more. When the main peak is in a region having a molecular weight of less than 3,000, the hot offset resistance of the toner may be deteriorated. When the main peak is in a region having a molecular weight of more than 40,000, the toner has low temperature fixability. It may be damaged, and when used with a color toner, it is not preferable from the viewpoint of poor glossiness. Further, when Mw / Mn is less than 100, it is disadvantageous to obtain a wide fixing temperature range.
[0034]
The acid value of the toner is preferably 5 to 45 mgKOH / g. If it is less than 5 mg KOH / g, it may be difficult to disperse the pigment or the like. When it exceeds 45 mgKOH / g, the hygroscopicity of the binder resin is increased, so that the charge relaxation of the toner becomes strong, and the toner scattering and transferability are deteriorated.
[0035]
Next, the binder resin used in the present invention will be described.
[0036]
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.
[0037]
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.
[0038]
Acidic components include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or their anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides; 6-12 carbon atoms 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;
[0039]
Among these, in particular, a bisphenol derivative represented by the following general formula (7-1) as a diol component, a carboxylic acid component (for example, a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof) , Fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.), and the polyester resin obtained by condensation polymerization of these has good charging characteristics as a color toner. preferable.
[0040]
[Chemical 1]

[0041]
In the binder resin contained in the toner of the present invention, the “hybrid resin component” 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.
[0042]
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 and 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.
[0043]
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.
[0044]
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.
[0045]
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 acrylates of the above compounds replaced by methacrylate; linked by an alkyl chain containing an ether bond. As diacrylate compounds For example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate Examples of diacrylate compounds connected by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene ( 4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate.
[0046]
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.
[0047]
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.
[0048]
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.
[0049]
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, siku Ketone peroxides such as hexanone 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 Oxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate Di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide , T-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate, t-butyl Peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl peroxy F Sa Hydro terephthalate, di -t- butyl peroxy azelate and the like.
[0050]
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).
[0051]
(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.
[0052]
(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.
[0053]
(3) A method for producing a vinyl polymer unit and a hybrid resin component in the presence of the polyester unit after the production. The hybrid resin component is produced by a reaction between a polyester unit (a polyester monomer can be added if necessary) and a vinyl monomer and / or vinyl polymer unit.
[0054]
(4) After the production of the vinyl polymer unit and the polyester unit, the hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. Also in this case, an organic solvent can be appropriately used.
[0055]
(5) After producing the hybrid resin component, vinyl polymer units and / or polyester units (alcohol, carboxylic acid) are added to carry out addition polymerization and / or polycondensation reaction to produce vinyl polymer units and polyester units. Is done. In this case, as the hybrid resin component, those produced by the production methods (2) to (4) can be used, and those produced by a known production method can be used as necessary. Furthermore, an organic solvent can be used as appropriate.
[0056]
(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.
[0057]
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.
[0058]
As the binder resin contained in the toner of the present invention, a mixture of the polyester and the vinyl copolymer may be used.
[0059]
As the binder resin contained in the toner of the present invention, a mixture of the above hybrid resin and vinyl copolymer may be used.
[0060]
As the binder resin contained in the toner of the present invention, a mixture of a vinyl copolymer may be used in addition to the polyester resin and the hybrid resin.
[0061]
As the colorant used in the present invention, as the black colorant, a carbon black, a magnetic material, and a color adjusted to black using a yellow / magenta / cyan colorant are used.
[0062]
When a magnetic material is used as the black colorant, it is used by adding 30 to 200 parts by mass with respect to 100 parts by mass of the resin, unlike other colorants.
[0063]
Examples of the magnetic material include metal oxides containing elements such as iron, cobalt, nickel, copper, magnesium, manganese, aluminum, and silicon. Among them, those containing iron oxide as a main component, such as triiron tetroxide and γ-iron oxide, are preferable. Further, from the viewpoint of toner chargeability control, other metal elements such as silicon element or aluminum element may be contained. These magnetic particles have a BET specific surface area of 2 to 30 m by the nitrogen adsorption method.²/ G, especially 3 to 28m²/ G is preferable, and magnetic powder having a Mohs hardness of 5 to 7 is more preferable.
[0064]
The amount of magnetic material is 30 to 200 parts by mass, preferably 40 to 200 parts by mass, and more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the binder resin. If the amount is less than 30 parts by mass, in a developing device that has insufficient coloring power or uses magnetic force for toner transport, the transportability is insufficient, and the developer layer on the developer carrier tends to be uneven and image unevenness tends to occur. In addition, the image density tends to decrease due to the increase in developer tribo. On the other hand, if it exceeds 200 parts by mass, there is a tendency that a problem arises in the fixing property.
[0065]
As the colorant when the toner of the present invention is used as a color toner, a known dye or / and pigment is used.
[0066]
As a coloring pigment for magenta toner, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207.209; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.
[0067]
Although the pigment alone may be used, it is more preferable from the viewpoint of the image quality of the full-color image that the combination of the dye and the pigment improves the sharpness.
[0068]
Examples of the magenta toner dye include C.I. I solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disperse thread 9; C.I. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic violet 1,3,7,10,14,15,21,25,26,27,28 etc. are mentioned.
[0069]
Examples of the color pigment for cyan toner include C.I. I. Pigment blue 2, 3, 15, 16, 17; 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 a phthalocyanine skeleton having a structure represented by the following formula.
[0070]
[Chemical 2]

[Wherein n represents an integer of 1 to 5]
[0071]
As a coloring pigment for yellow, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 83, 97, 180; I. Examples include bat yellow 1, 3, 20 and the like.
[0072]
The amount of the colorant used is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 12 parts by mass, and most preferably 3 to 10 parts by mass with respect to 100 parts by mass of the binder resin.
[0073]
In the endothermic curve in the differential thermal analysis (DSC) measurement of the toner of the present invention, the peak temperature of the maximum endothermic peak in the temperature range of 30 to 200 ° C. is in the range of 60 to 90 ° C. And more preferable.
[0074]
In the toner of the present invention, an organometallic compound may be used in order to retain the charge in the toner, and examples thereof include the following metal compounds of aromatic oxycarboxylic acid derivatives.
[0075]
[Chemical 3]

[0076]
M in the formula₂Is a divalent metal atom, Mg²⁺, Ca²⁺, Sr²⁺, Pb²⁺, Fe²⁺, Co²⁺, Ni²⁺, Zn²⁺, Cu²⁺Is mentioned. M_ThreeIs a trivalent metal atom, Al³⁺, Cr³⁺, Fe³⁺, Ni³⁺Is mentioned. M_FourIs a tetravalent metal atom, Zr⁴⁺, Hf⁴⁺, Mn⁴⁺, Co⁴⁺Is mentioned. Among these metal atoms, Al is preferable.³⁺, Fe³⁺, Cr³⁺, Zr⁴⁺, Hf⁴⁺, Zn²⁺It is.
[0077]
In the formula, R₁To R_FourAre the same or different groups, and are a hydrogen atom, a C1-C12 alkyl group, a C2-C12 alkenyl group, -OH, -NH.₂, -NH (CH_Three), -N (CH_Three)₂, -OCH_Three, -O (C₂H_Five), -COOH or -CONH₂Indicates. Preferred R₁Examples thereof include a hydroxyl group, an amino group, and a methoxy group, and among them, a hydroxyl group is preferable.
[0078]
In order to improve the image quality, it is preferable that a fluidity improver is externally added to the toner particles of the present invention. As the fluidity improver, inorganic fine powders such as silicate fine powder, titanium oxide, and aluminum oxide are preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane coupling agent, silicone oil or a mixture thereof. When the toner particles are non-magnetic color toner particles for forming a full color image, it is preferable to use titanium oxide fine particles as an external additive.
[0079]
Usually, the fluidity improver is used in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the toner particles.
[0080]
For mixing the toner particles and the external additive, it is preferable to use a mixer such as a Henschel mixer.
[0081]
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.
[0082]
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.
[0083]
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.
[0084]
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.
[0085]
Method for measuring acid value
Samples 2 to 10 g are weighed into a 200 to 300 ml Erlenmeyer flask, and about 50 ml of a mixed solvent of methanol: toluene = 30: 70 is added to dissolve the resin. A small amount of acetone may be added if the solubility is poor. Using a mixed indicator of 0.1% bromthymol blue and phenol red, titration with a pre-standardized N / 10 potassium hydroxide-alcohol solution, and using the following formula (III) to calculate the acid from the consumption of alcohol potassium solution Find the price.
Acid value = KOH (ml) × f × 56.1 / Sample mass (III)
(Where f is a factor of N / 10 KOH)
[0086]
When the magnetic powder is contained in the toner, the residue obtained by eluting the magnetic substance with an acid is measured as a sample.
[0087]
It measures as follows using a differential scanning calorimeter (DSC measuring apparatus) and DSC-7 (made by Perkin Elmer).
[0088]
The measurement sample is precisely weighed in an amount of 2 to 10 mg, preferably 5 mg.
[0089]
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.
[0090]
In this temperature raising process, an endothermic peak of the main peak of the DSC curve in the temperature range of 30 to 200 ° C. is obtained.
[0091]
GPC measurement
The molecular weight of the chromatogram by gel permeation chromatography (GPC) is measured under the following conditions.
[0092]
The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. About 50 to 200 μl of THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts (retention time). Examples of standard polystyrene samples for preparing a calibration curve include those manufactured by Tosoh Corporation or Pressure Chemical Co. Made molecular weight 6 × 10²2.1 × 10^Three4 × 10^Three1.75 × 10^Four5.1 × 10^Four1.1 × 10^Five3.9 × 10^Five8.6 × 10^Five2 × 10⁶4.48 × 10⁶It is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
[0093]
As column, 10^Three~ 2x10⁶In order to accurately measure the molecular weight region, it is preferable to combine a plurality of commercially available polystyrene gel columns, such as the combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807 manufactured by Showa Denko KK [Mu] -styragel 500, 10 manufactured by Waters^Three10^Four10^FiveCan be mentioned.
[0094]
【Example】
Specific examples of the present invention will be described below, but the present invention is not limited to these examples.
[0095]
(Method for producing modified paraffin wax)
After adding 50 g of dicumyl peroxide as a reaction initiator to 600 g of styrene monomer, it was added dropwise to 3000 g of heated and melted paraffin wax with stirring and reacted for 4 hours to obtain styrene-modified paraffin wax 1.
[0096]
Modified paraffin wax was obtained in the same manner by changing the type of paraffin wax and the ratio of styrene monomer. The ratios and characteristics are shown in Tables 1 and 2.
[0097]
[Table 1]

[0098]
[Table 2]

[0099]
(Mixed wax production method)
A polystyrene polymer prepared in advance by solution polymerization and paraffin wax A heated and mixed at a mass ratio of 30:70 at 100 ° C. was cooled and pulverized to obtain a mixed wax.
[0100]
(Toner production method)
The toner materials shown in Tables 3 and 4 were sufficiently premixed with a Henschel mixer, melted and kneaded with a twin screw extruder, and after cooling, coarsely pulverized to a particle size of about 1 to 2 mm using a hammer mill. Subsequently, it was finely pulverized by an air jet type fine pulverizer. Further, the obtained finely pulverized product was classified with a multi-division classifier to obtain toner resin particles having a weight average particle size of 8.0 μm.
[0101]
N-C with respect to 100 parts by mass of the toner resin particles._FourH₉Si (OCH_Three)_ThreeTreated with hydrophobic titanium oxide (BET110m²/ G) Toner 1 was combined with 1.0 part by mass. Further, the toner 1 and magnetic ferrite carrier particles (average particle diameter 50 μm) coated with a silicone resin were mixed so that the toner concentration was 6% by mass to obtain a two-component developer 1. Similarly, toners 1 to 20 and developers 1 to 20 were obtained.
[0102]
[Table 3]

[0103]
[Table 4]

[0104]
<Example 1>
The toner 1 and the developer 1 were evaluated as follows.
[0105]
Using a commercially available plain paper full-color copier (CLC900), using an original document with an image area ratio of 25% in a low humidity environment (23 ° C / 5%) and a high humidity environment (30 ° C / 90%) Durability tests were conducted on 20,000 copies.
[0106]
The developability was evaluated based on the change in image density after the end of durability and after the end of 20,000 sheets. The image density was determined by averaging the solid portion (initial image density = 1.5) of the original image five times with a Macbeth densitometer manufactured by Macbeth Co., Ltd., and observing the change value of the image density.
[0107]
Transferability is determined by developing and transferring the pre- and post-endurance images, measuring the amount of toner before transfer on the photoconductor (per unit area), and the amount of toner on the transfer material (per unit area). It was.
Transfer rate (%) = (toner amount on transfer material) / (toner amount before transfer on photoconductor) × 100
[0108]
The cleaning property indicates the number of durable sheets when a slight cleaning failure occurs.
[0109]
In the fixing temperature range, the oil application mechanism of the color copier CLC900 (manufactured by Canon) was removed, and the fixing test was performed by remodeling so that the fixing temperature could be freely set. The image area ratio at this time is 25%, and the applied toner amount per unit area is 0.7 mg / cm.²Set to. The fixing start temperature and offset start temperature are measured by adjusting the set temperature of the fixing device every 5 ° C. within a temperature range of 110 to 250 ° C., and outputting a fixed image at each temperature. 4.9 kPa (50 g / cm²The fixing temperature at which the density reduction rate before and after the rubbing was 10% or less was determined as the fixing start temperature. Further, the set temperature was further raised from the fixing start temperature, and the temperature at which the high temperature offset occurred was determined as the offset start temperature.
[0110]
The storage stability (blocking resistance) of the toner was evaluated by leaving it in an oven at 50 ° C. for 1 week. As the evaluation, the level of cohesiveness by visual observation was determined. Toner cohesion evaluation criteria are shown below.
A: No agglomerates are seen and fluidity is very good
B: No aggregates are seen
C: Some agglomerates are seen but loosen immediately
D: Aggregates are loosened by the developer stirring device (normal)
E: Aggregates are not sufficiently loosened with the developer stirring device (somewhat bad)
[0111]
As a result of the evaluation, the transferability and cleaning properties were good, and the durability after 20,000 sheets was very good. In addition, extremely stable developability was exhibited even in a low and high humidity environment.
[0112]
Moreover, a wide fixing temperature range could be taken. The results are shown in Tables 5 and 6.
[0113]
<Examples 2 to 6>
In the same manner as in Example 1, toners 2 to 6 and developers 2 to 6 were evaluated.
[0114]
In Examples 2 to 6, as in Example 1, the transferability and cleaning properties were good, and the durability after 20,000 sheets was very good. In addition, extremely stable developability was exhibited even in a low and high humidity environment. The results are shown in Tables 5 and 6.
[0115]
<Example 7>
In the same manner as in Example 1, the toner 7 and the developer 7 were evaluated.
[0116]
In Example 7, a slight decrease in image density was observed after the endurance, but there was no problem. Moreover, although the storage stability was slightly disadvantageous, it was at a level with no problem. The results are shown in Tables 5 and 6.
[0117]
<Example 8>
In the same manner as in Example 1, toner 8 and developer 8 were evaluated.
[0118]
In Example 8, the fixing start temperature was slightly higher, but there was no problem in use. The results are shown in Tables 5 and 6.
[0119]
<Example 9>
In the same manner as in Example 1, toner 9 and developer 9 were evaluated.
[0120]
In Example 9, there was no problem although the fixing temperature range was narrowed. The results are shown in Tables 5 and 6.
[0121]
<Example 10>
In the same manner as in Example 1, the toner 10 and the developer 10 were evaluated.
[0122]
In Example 10, the image density decreased after the endurance and the storage stability was slightly disadvantageous, but there was no problem in use. The results are shown in Tables 5 and 6.
[0123]
  <Reference example 1>
  In the same manner as in Example 1, the toner 11 and the developer 11 were evaluated.
[0124]
  Reference example 1Then, after the endurance, a slight decrease in image density was observed. In addition, although the cleaning property was slightly disadvantageous, there was no problem in use. The results are shown in Tables 5 and 6.
[0125]
  <Reference example 2>
  In the same manner as in Example 1, the toner 12 and the developer 12 were evaluated.
[0126]
  Reference example 2However, the dispersibility of the wax was good and the developability and durability were excellent, but the fixing temperature range was small. The results are shown in Tables 5 and 6.
[0127]
  <Example11>
  Using a magenta developer, yellow developer, cyan developer, and developer 1, the color copier CLC-900 is in full color mode in a low humidity environment (23 ° C./5%) and a high humidity environment (30 ° C./90 %), An endurance test of 20,000 continuous copies was performed using an original document with an image area ratio of 25%. Even in the full color mode, there was no decrease in image density, and a toner excellent in transferability and cleaning property could be obtained.
[0128]
Further, the oil application mechanism of CLC-900 was removed, and the fixing temperature was set to 160 ° C. to output a full color image. An image with excellent color reproducibility could be output.
[0129]
<Comparative Example 1>
In the same manner as in Example 1, the toner 16 and the developer 16 were evaluated.
[0130]
In Comparative Example 1, there was almost no fixing temperature range because the amount of wax in the toner was small, and oilless fixing was impossible. The results are shown in Tables 5 and 6.
[0131]
<Comparative example 2>
In the same manner as in Example 1, toner 17 and developer 17 were evaluated.
[0132]
In Comparative Example 2, because the amount of wax in the toner is too large, wax drum fusing, carrier contamination, and the like occurred, resulting in a decrease in image density and transfer efficiency and poor cleaning. In addition, storage stability was slightly disadvantageous. The results are shown in Tables 5 and 6.
[0133]
<Comparative Example 3>
In the same manner as in Example 1, the toner 18 and the developer 18 were evaluated.
[0134]
In Comparative Example 3, the durability, cleaning property, and transferability were not good because the wax was not completely dispersed in the toner. The results are shown in Tables 5 and 6.
[0135]
<Comparative example 4>
In the same manner as in Example 1, the toner 19 and the developer 19 were evaluated.
[0136]
In Comparative Example 4, the image density decreased after the endurance because the wax in the toner was detached. In addition, due to the desorbed wax contaminating the carrier, sufficient charging was not obtained particularly in a high humidity environment, and fogging occurred. In addition, the occurrence of poor cleaning was quick and the transferability deteriorated. The results are shown in Tables 5 and 6.
[0137]
<Comparative Example 5>
In the same manner as in Example 1, the toner 20 and the developer 20 were evaluated.
[0138]
In Comparative Example 5, a decrease in image density was observed after the endurance because the wax in the toner was detached. In addition, due to the desorbed wax contaminating the carrier, sufficient charging was not obtained particularly in a high humidity environment, and fogging occurred. In addition, the occurrence of poor cleaning was quick and the transferability deteriorated. Furthermore, this toner also had poor storage stability. The results are shown in Tables 5 and 6.
[0139]
[Table 5]

[0140]
[Table 6]

[0141]
【The invention's effect】
According to the present invention, by improving the release agent that is a raw material of the toner, low-temperature fixing is possible, the offset resistance is excellent, and the stability of the image quality is high even when used for a long time in various environments. It is possible to provide a toner that is excellent in durability and excellent in transferability and cleaning properties.

Claims (8)

In a toner containing at least a binder resin, a colorant and a release agent,
The release agent is a modified paraffin wax modified with a styrenic monomer, and the modified paraffin wax is contained in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the resin component in the toner .
The toner further contains unmodified paraffin, and (1) the content of paraffin modified with styrene monomer and (2) unmodified paraffin is expressed by the following formula:
0.05 ≦ (2) / ((1) + (2)) ≦ 0.90 (Formula 1)
Toner which is characterized that you satisfy. The toner according to claim 1 , wherein the toner further contains a polymer of a styrene monomer. 2. The modified paraffin wax has an endothermic curve in a differential scanning calorimeter (DSC) measurement, wherein a peak temperature of a maximum endothermic peak in a temperature range of 30 to 200 ° C. is in a range of 60 to 90 ° C. Or the toner according to 2 . Toner the modified paraffin wax according to any one of claims 1 to 3, characterized in that it is modified with 5 to 200 parts by weight of a styrene-based monomer relative to 100 parts by weight of paraffin wax. The toner has an acid value of 5 to 45 mgKOH / g, and the molecular weight distribution by gel permeation chromatography (GPC) of the soluble portion of tetrahydrofuran (THF) of the toner is in the region of molecular weight 3,000 to 40,000. the main peak is present, the toner according to any one of claims 1 to 4 ratio of the weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn) is equal to or 100 or more. The binder resin is any one of claims 1 to 5, characterized in that a mixture of a hybrid resin component, or a hybrid resin and a polyester resin component and a polyester unit and a vinyl copolymer unit The toner described in 1. The toner according to any one of claims 1 to 5 , wherein the binder resin is a mixture of a polyester resin and a vinyl copolymer, or a mixture of a hybrid resin component and a vinyl copolymer. The binder resin is a polyester resin, the toner according to any one of claims 1 to 5, characterized in that a mixture of the hybrid resin component, and a vinyl copolymer.