JP4536945B2 - Image forming method - Google Patents

Description

【００４３】
次に、前記結着樹脂において、「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。
【００４４】
該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。
【００４５】
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。
【００４６】
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。
【００４７】
本発明でいう結着樹脂のビニル系重合体ユニットは、ビニル基を２個以上有する架橋剤で架橋された架橋構造を有していてもよい。この場合に用いられる架橋剤としては、以下のものが挙げられる。
【００４８】
芳香族ジビニル化合物として例えば、ジビニルベンゼン、ジビニルナフタレンが挙げられ、アルキル鎖で結ばれたジアクリレート化合物類として例えば、エチレングリコールジアクリレート、１，３−ブチレングリコールジアクリレート、１，４−ブタンジオールジアクリレート、１，５−ペンタンジオールジアクリレート、１，６ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられ、エーテル結合を含むアルキル鎖で結ばれたジアクリレート化合物類としては、例えば、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコール＃４００ジアクリレート、ポリエチレングリコール＃６００ジアクリレート、ジプロピレングリコールジアクリレート及び以上の化合物のアクリレートをメタアクリレートに代えたものが挙げられ、芳香族基及びエーテル結合を含む鎖で結ばれたジアクリレート化合物類として例えば、ポリオキシエチレン（２）−２，２−ビス（４−ヒドロキシフェニル）プロパンジアクリレート、ポリオキシエチレン（４）−２，２−ビス（４−ヒドロキシフェニル）プロパンジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられる。
【００４９】
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。
【００５０】
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。
【００５１】
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。
【００５２】
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。
【００５３】
次に、本発明の結着樹脂に用いられるハイブリッド樹脂の製造方法を説明する。以下の（１）〜（６）に示す製造方法等で本発明のハイブリッド樹脂が製造できる。
【００５４】
（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。
【００５５】
（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。
【００５６】
（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。
【００５７】
（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。
【００５８】
（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。
【００５９】
（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。
【００６０】
上記（１）〜（５）の製造方法において、ビニル系重合体ユニット及び／またはポリエステルユニットは複数の異なる分子量、架橋度を有する重合体ユニットを使用することができる。
【００６１】
次に、本発明のカラートナーが有する一種または二種以上のワックスについて説明する。
【００６２】
本発明に用いられるワックスとしては、例えば、次のものが挙げられる。低分子量ポリエチレン、低分子量ポリプロピレン、マイクロクリスタリンワックス、パラフィンワックスなどの脂肪族炭化水素系ワックス、また酸化ポリエチレンワックスなどの脂肪族炭化水素系ワックスの酸化物、またはそれらのブロック共重合物；カルナバワックス、サゾールワックス、モンタン酸エステルワックスなどの脂肪酸エステルを主成分とするワックス類、及び脱酸カルナバワックスなどの脂肪酸エステル類を一部または全部を脱酸化したものなどが挙げられる。
【００６３】
さらに、パルミチン酸、ステアリン酸、モンタン酸などの飽和直鎖脂肪酸類；ブランジン酸、エレオステアリン酸、バリナリン酸などの不飽和脂肪酸類；ステアリルアルコール、アラルキルアルコール、ベヘニルアルコール、カルナウビルアルコール、セリルアルコール、メリシルアルコールなどの飽和アルコール類；ソルビトールなどの多価アルコール類；リノール酸アミド、オレイン酸アミド、ラウリン酸アミドなどの脂肪酸アミド類；メチレンビスステアリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、ヘキサメチレンビスステアリン酸アミドなどの飽和脂肪酸ビスアミド類；エチレンビスオレイン酸アミド、ヘキサメチレンビスオレイン酸アミド、Ｎ，Ｎ'ジオレイルアジピン酸アミド、Ｎ，Ｎ'ジオレイルセバシン酸アミドなどの不飽和脂肪酸アミド類；ｍ−キシレンビスステアリン酸アミド、Ｎ，Ｎ'ジステアリルイソフタル酸アミドなどの芳香族系ビスアミド類；ステアリン酸カルシウム、ラウリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸マグネシウムなどの脂肪族金属塩（一般に金属石けんといわれているもの）；脂肪族炭化水素系ワックスにスチレンやアクリル酸などのビニル系モノマーを用いてグラフト化させたワックス類；ベヘニン酸モノグリセリドなどの脂肪酸と多価アルコールの部分エステル化物；植物性油脂の水素添加などによって得られるヒドロキシル基を有するメチルエステル化合物などが挙げられる。
【００６４】
本発明において特に好ましく用いられるワックスとしては、脂肪族炭化水素系ワックスが挙げられる。例えば、アルキレンを高圧下でラジカル重合あるいは低圧下でチーグラー触媒で重合した低分子量のアルキレンポリマー；高分子量のアルキレンポリマーを熱分解して得られるアルキレンポリマー；一酸化炭素及び水素を含む合成ガスからアーゲ法により得られる炭化水素の蒸留残分から、あるいはこれらを水素添加して得られる合成炭化水素ワックスがよい。
【００６５】
さらにプレス発汗法、溶剤法、真空蒸留の利用や分別結晶方式により炭化水素ワックスの分別を行なったものが、より好ましく用いられる。
【００６６】
母体としての炭化水素は、金属酸化物系触媒（多くは２種以上の多元系）を使用した一酸化炭素と水素の反応によって合成されるもの［例えばジントール法、ヒドロコール法（流動触媒床を使用）によって合成された炭化水素化合物］；ワックス状炭化水素が多く得られるアーゲ法（同定触媒床を使用）により得られる炭素数が数百ぐらいまでの炭化水素；エチレンなどのアルキレンをチーグラー触媒により重合した炭化水素が、分岐が少なくて小さく、飽和の長い直鎖状炭化水素であるので好ましい。特にアルキレンの重合によらない方法により合成されたワックスがその分子量分布からも好ましいものである。
【００６７】
ワックスの分子量分布では、メインピークが分子量４００〜２４００の領域にあることが好ましく、４3０〜２０００の領域にあることがより好ましい。このような分子量分布をもたせると、トナーに好ましい熱特性を付与することができる。
【００６８】
また、トナーの定着時により有効に機能させるために、上記ワックスの融点は、６０〜１００℃にあることが好ましく、６５〜９０℃にあることがより好ましい。ワックスは結着樹脂１００質量部あたり０．１〜２０質量部、好ましくは０．５〜１０質量部使用するのが良い。
【００６９】
ワックスは通常、樹脂を溶剤に溶解し樹脂溶液温度を上げ、撹拌しながら添加混合する方法や、混練時に混合する方法で結着樹脂に含有させる。
【００７０】
次に、本発明のカラートナーが有する着色剤について説明する。本発明に用いられる着色剤としては、顔料及び／又は染料を用いることができる。
【００７１】
例えば染料としては、Ｃ．Ｉ．ダイレクトレッド１、Ｃ．Ｉ．ダイレクトレッド４、Ｃ．Ｉ．アシッドレッド１、Ｃ．Ｉ．ベーシックレッド１、Ｃ．Ｉ．モーダントレッド３０、Ｃ．Ｉ．ダイレクトブルー１、Ｃ．Ｉ．ダイレクトブルー２、Ｃ．Ｉ．アシッドブルー９、Ｃ．Ｉ．アシッドブルー１５、Ｃ．Ｉ．ベーシックブルー３、Ｃ．Ｉ．ベーシックブルー５、Ｃ．Ｉ．モーダントブルー７、Ｃ．Ｉ．ダイレクトグリーン６、Ｃ．Ｉ．ベーシックグリーン４、Ｃ．Ｉ．ベーシックグリーン６等が挙げられる。
【００７２】
また、顔料としては、ミネラルファストイエロー、ネーブルイエロー、ナフトールイエローＳ、ハンザイエローＧ、パーマネントイエローＮＣＧ、タートラジンレーキ、モリブデンオレンジ、パーマネントオレンジＧＴＲ、ピラゾロンオレンジ、ベンジジンオレンジＧ、パーマネントレッド４Ｒ、ウオッチングレッドカルシウム塩、エオシンレーキ、ブリリアントカーミン３Ｂ、マンガン紫、ファストバイオレットＢ、メチルバイオレットレーキ、コバルトブルー、アルカリブルーレーキ、ビクトリアブルーレーキ、フタロシアニンブルー、ファーストスカイブルー、インダンスレンブルーＢＣ、クロムグリーン、ピグメントグリーンＢ、マラカイトグリーンレーキ、ファイナルイエローグリーンＧ等が挙げられる。
【００７３】
また、マゼンタ用着色顔料としては、Ｃ．Ｉ．ピグメントレッド１，２，３，４，５，６，７，８，９，１０，１１，１２，１３，１４，１５，１６，１７，１８，１９，２１，２２，２３，３０，３１，３２，３７，３８，３９，４０，４１，４８，４９，５０，５１，５２，５３，５４，５５，５７，５８，６０，６３，６４，６８，８１，８３，８７，８８，８９，９０，１１２，１１４，１２２，１２３，１６３，２０２，２０６，２０７，２０９，２３８，Ｃ．Ｉ．ピグメントバイオレット１９、Ｃ．Ｉ．バットレッド１，２，１０，１３，１５，２３，２９，３５等が挙げられる。
【００７４】
上述の顔料は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。使用し得る種々の染料、顔料をさらに例示する。
【００７５】
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の如き塩基性染料が挙げられる。
【００７６】
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．アシッドブルー６；Ｃ．Ｉ．アシッドブルー４５又はフタロシアニン骨格にフタルイミドメチル基を１〜５個置換した銅フタロシアニン顔料等が挙げられる。
【００７７】
イエロー用着色顔料としては、Ｃ．Ｉ．ピグメントイエロー１，２，３，４，５，６，７，１０，１１，１２，１３，１４，１５，１６，１７，２３，６５，７３，８３，９３，９７，１８０、Ｃ．Ｉ．バットイエロー１，３，２０等が挙げられる。
【００７８】
着色剤の使用量は、結着樹脂１００質量部に対して、１〜１５質量部、好ましくは３〜１２質量部、より好ましくは４〜１０質量部含有していることが良い。着色剤の含有量が１５質量部より多い場合には、透明性が低下し、加えて人間の肌色に代表される様な中間色の再現性も低下し易くなり、更にはトナーの帯電性の安定性が低下し、目的とする帯電量が得られにくくなる。一方、着色剤の含有量が１質量部より少ない場合には、目的とする着色力が得られ難く、高い画像濃度の高品位画像が得られ難い。
【００７９】
尚、本発明のカラートナーは、さらに有機金属化合物を含有させてもよい。該有機金属化合物を含有させると、帯電レベルを調整でき、帯電の立ち上がりを良くし、トナーの熱溶融特性を改良することが出来るなどの点で、より好ましい態様となる。
【００８０】
使用する有機金属化合物としては、芳香族オキシカルボン酸及び芳香族アルコキシカルボン酸から選択される芳香族カルボン酸誘導体、該芳香族カルボン酸誘導体の金属化合物であることが好ましく、その金属としては、２価以上の金属原子が好ましい。
【００８１】
２価の金属としてＭｇ²⁺，Ｃａ²⁺，Ｓｒ²⁺，Ｐｂ²⁺，Ｆｅ²⁺，Ｃｏ²⁺，Ｎｉ²⁺，Ｚｎ²⁺，Ｃｕ²⁺，が挙げられる。２価の金属としては、Ｚｎ²⁺，Ｃａ²⁺，Ｍｇ²⁺，Ｓｒ²⁺が好ましい。３価以上の金属としてはＡｌ³⁺，Ｃｒ³⁺，Ｆｅ³⁺，Ｎｉ³⁺，があげられる。これら３価以上の金属の中で好ましいのはＡｌ³⁺， Ｃｒ³⁺であり、特に好ましいのはＡｌ³⁺である。
【００８２】
本発明においては、有機金属化合物として、ジ−ｔｅｒｔ−ブチルサリチル酸のアルミニウム化合物が特に好ましい。
【００８３】
芳香族オキシカルボン酸及び芳香族アルコキシカルボン酸から選択される芳香族カルボン酸誘導体、該芳香族カルボン酸誘導体の金属化合物は、例えば、オキシカルボン酸及びアルコキシカルボン酸を水酸化ナトリウム水溶液に溶解させ、２価以上の金属原子を溶融している水溶液を水酸化ナトリウム水溶液に滴下し、加熱撹拌し、次に水溶液のｐＨを調整し、室温まで冷却した後、ろ過水洗することにより芳香族オキシカルボン酸及び芳香族アルコキシカルボン酸の金属化合物を合成し得る。ただし、上記の合成方法だけに限定されるものではない。
【００８４】
該有機金属化合物は、カラートナーの質量を基準として0.1〜10質量％含有させると、好ましい。該含有量とすると、トナーの帯電量の初期変動が少なく、現像時に必要な絶対帯電量が得られやすく、結果的に「カブリ」や画像濃度ダウンの如き画像品質の低下をおさえることが出来る。
【００８５】
＜本発明の黒用磁性トナーについて＞
本発明に用いられる黒用磁性トナーについて説明する。
【００８６】
磁性トナーは、磁性体を含む。その場合、磁性体は着色剤としての機能も有する。磁性材料としては、マグネタイト、マグヘマイト、フェライト等の酸化鉄、及び他の金属酸化物を含む酸化鉄；Ｆｅ，Ｃｏ，Ｎｉのような金属、あるいは、これらの金属とＡｌ，Ｃｏ，Ｃｕ，Ｐｂ，Ｍｇ，Ｎｉ，Ｓｎ，Ｚｎ，Ｓｂ，Ｂｅ，Ｂｉ，Ｃｄ，Ｃａ，Ｍｎ，Ｓｅ，Ｔｉ，Ｗ，Ｖのような金属との合金、およびこれらの混合物等が挙げられる。
【００８７】
例えば、磁性材料としては、四三酸化鉄（Ｆｅ₃Ｏ₄）、三二酸化鉄（γ−Ｆｅ₂Ｏ₃）、酸化鉄亜鉛（ＺｎＦｅ₂Ｏ₄）、酸化鉄イットリウム（Ｙ₃Ｆｅ₅Ｏ₁₂），酸化鉄カドミウム（ＣｄＦｅ₂Ｏ₄）、酸化鉄ガドリニウム（Ｇｄ₃Ｆｅ₅−Ｏ₁₂）、酸化鉄銅（ＣｕＦｅ₂Ｏ₄）、酸化鉄鉛（ＰｂＦｅ₁₂−Ｏ₁₉）、酸化鉄ニッケル（ＮｉＦｅ₂Ｏ₄）、酸化鉄ネオジム（ＮｄＦｅ₂Ｏ₃）、酸化鉄バリウム（ＢａＦｅ₁₂Ｏ₁₉）、酸化鉄マグネシウム（ＭｇＦｅ₂Ｏ₄）、酸化鉄マンガン（ＭｎＦｅ₂Ｏ₄）、酸化鉄ランタン（ＬａＦｅＯ₃）、鉄粉（Ｆｅ）、コバルト粉（Ｃｏ）、ニッケル粉（Ｎｉ）等が挙げられる。好適な磁性材料は四三酸化鉄，磁性フェライト又はγ−三二酸化鉄の微粉末である。磁性体の含有率は、トナーの重量基準で1５〜８５質量％であることが好ましい。
【００８８】
黒用磁性トナーにおいては、他の色トナーに比べて抵抗値が低くなりやすいことから、帯電を安定させるのがより困難である。本発明においては、この点を改善するべく、鋭意検討を行った。
【００８９】
その結果、黒用磁性トナーには、磁性酸化鉄を含有させることが好ましく、特に磁性体表面の僅かなSiもしくはAl元素量の影響で現像性が向上し、他のカラートナーとの混合性が向上することが見出された。
【００９０】
具体的には、磁性酸化鉄は、鉄元素を基準として、アルミニウム元素又はケイ素元素を０．３〜１．４重量％含有させることが効果的であることが見い出された。このことによって他のカラートナーとの帯電安定性ひいては現像性の差を少なくし、原稿に忠実でばらつきのない画像を得ることが可能となる。
【００９１】
また、該磁性酸化鉄は、該磁性酸化鉄の鉄元素溶解率が２０重量％までに存在するケイ素元素の含有量ＢSiと該磁性酸化鉄中に存在する全ケイ素元素の含有量ＡSiとの比（ＢSi／ＡSi）×１００が3５〜８５％であることがより好ましく、4０〜８０％であることがさらに好ましい。
【００９２】
（ＢＳｉ／ＡＳｉ）×１００が３５％より小さい場合には、トナー中における磁性体分散が悪化し、現像性、特に画像均一性が不安定なトナーとなる場合がある。また、文字画像の解像度が劣る傾向が見られる。（ＢＳｉ／ＡＳｉ）×１００が８５％より大きい場合には、磁性酸化鉄の表層部にケイ素元素が多く存在し、トナーの帯電量の分布が広がりやすいことから、カラートナーとの混合性に弊害が発生し易い。
【００９３】
本発明において、磁性酸化鉄は、以下に記載する測定方法に基づく個数平均粒径が、好ましくは、０．０５〜１．００μｍ、より好ましくは、０．１０〜０．４０μｍであると、磁性トナーの結着樹脂中での分散性及び帯電の均一性の点から良い。
【００９４】
磁性酸化鉄の個数平均粒径が１．００μｍよりも大きい場合には、トナー中に含まれる磁性酸化鉄粒子の個数が減るために、結着樹脂中への磁性酸化鉄の分散に偏りが生じ易く帯電の均一性が損なわれる。磁性酸化鉄の個数平均粒径が０．０５μｍよりも小さい場合には、磁性酸化鉄粒子間の付着力が強まり、結着樹脂中への分散性が悪化する。
【００９５】
上記条件を満たした磁性体を用いることによって、黒トナーの他の色トナーに対する混合性が向上し、より均一な色再現が行われるようになる。また、定着性に悪影響を及ぼすことがない。
【００９６】
本発明において、黒用トナーに用いる磁性体に関する測定法は、以下のようにして行った。尚、後述の実施例においても同様に測定した。
【００９７】
（４）金属元素に関する測定
本発明において、磁性酸化鉄中の鉄以外の金属元素の含有率（鉄元素を基準とする）および鉄元素の溶解率及び鉄元素溶解率に対する鉄以外の金属元素の含有量は、次のような方法によって求めることができる。
【００９８】
例えば、５リットルのビーカーに約３リットルの脱イオン水を入れ４５〜５０℃になるようにウォーターバスで加温する。約４００ｍｌの脱イオン水でスラリーとした磁性酸化鉄約２５ｇを約３００ｍｌの脱イオン水で水洗いしながら、該脱イオン水とともに５リットルビーカー中に加える。
【００９９】
次いで、温度を約５０℃、撹拌スピードを約２００ｒｐｍに保ちながら、特級塩酸または塩酸とフッ化水素酸との混酸を加え、溶解を開始する。このとき、塩酸水溶液は約３規定となっている。溶解開始から、すべて溶解して透明になるまでの間に数回約２０ｍｌサンプリングし、０．１μメンブランフィルターでろ過し、ろ液を採取する。ろ液をプラズマ発光分光（ＩＣＰ）によって、鉄元素及び鉄元素以外の金属元素の定量を行う。各サンプルごとの鉄元素溶解率は次式によって、計算する。
【０１００】
【数１】

【０１０１】
各試料ごとの鉄元素以外の金属元素の含有量は次式によって計算される。
【０１０２】
【数２】

【０１０３】
そして、磁性酸化鉄の鉄元素以外の金属元素の全含有量Ａは、全て溶解した後の磁性酸化鉄の単位重量当たりの金属元素濃度（ｍｇ／ｌ）とする。また、磁性酸化鉄の鉄元素以外の金属元素の含有量Ｂは、磁性酸化鉄の溶解率が２０％の場合に、検出される磁性酸化鉄の単位重量当たりの鉄元素以外の金属元素濃度（ｍｇ／ｌ）とする。
【０１０４】
（５）磁性酸化鉄の個数平均粒径の測定
透過電子顕微鏡写真（倍率３００００倍）より写真上の粒子を無作為に１００個選び、その粒子径を計測し、その平均値をもって、個数平均粒径とした。
【０１０５】
＜黒用磁性トナー及びカラー用非磁性トナーについて＞
黒用磁性トナー及びカラー用非磁性トナーには、流動性向上剤が外添されていてもよい。ここで、流動性向上剤とは、トナー粒子に外添することにより、流動性が増加し得る機能を有するものであり、画質向上の観点から添加される。
【０１０６】
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の如きフッ素系樹脂粉末；湿式製法によるシリカ微粉末、乾式製法によるシリカ微粉末の如きシリカ微粉末、それらシリカ微粉末をシランカップリング剤、チタンカップリング剤、シリコンオイルの如き処理剤により表面処理を施した処理シリカ微粉末；酸化チタン微粉末；アルミナ微粉末、処理酸化チタン微粉末、処理酸化アルミナ微粉末が用いられる。
【０１０７】
該流動性向上剤は、ＢＥＴ法で測定した窒素吸着により比表面積が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。トナー粒子１００質量部に対して流動性向上剤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。
【０１０８】
上述のＢＥＴ法の測定は、次のようにして行った。
（６）ＢＥＴ比表面積は、湯浅アイオニクス（株）製、全自動ガス吸着量測定装置：オートソーブ１を使用し、吸着ガスに窒素ガスを用い、ＢＥＴ多点法により求める。なお、サンプルの前処理として、温度５０℃で１０時間の脱気を行う。
【０１０９】
本発明のトナー粒子（磁性タイプも非磁性タイプも含む）は、以下で述べる方法により得ることができる。つまり、結着樹脂、着色剤、ワックス、有機金属化合物、磁性体及びその他の任意成分の添加剤の中から必要な構成成分を選択し、該構成成分をヘンシェルミキサー、ボールミルの如き混合機により充分混合し、ニーダー、エクストルーダーの如き熱混練機を用いて溶融、捏和及び練肉し、溶融混練物を冷却固化後に固化物を粉砕し、粉砕物を分級することにより、所定の平均粒径のトナー粒子を得ることができる。尚、トナー粒子表面に流動性向上剤を有したトナーを得る場合には、さらに、流動性向上剤とトナー粒子をヘンシェルミキサーの如き混合機で混合させればよい。
【０１１０】
＜本発明のカラー現像を行うための磁性キャリアについて＞
本発明の二成分系現像剤に用いるキャリアとしては、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、希土類等の金属及びそれらの合金または酸化物及びフェライトなどが使用できる。
【０１１１】
特に、マンガン、マグネシウム及び鉄成分を主成分として形成されるＭｎ−Ｍｇ−Ｆｅの３元素の磁性フェライト粒子がキャリア粒子として好ましく、さらに、Ｍｎ−Ｍｇ−Ｆｅの３元素の磁性フェライト粒子は、ケイ素元素を０．００１〜１質量％（より好ましくは、０．００５〜０．５質量％）有していることが磁性フェライト粒子の被覆樹脂としてシリコーン樹脂を使用する場合に特に好ましい。
【０１１２】
磁性キャリア粒子は、樹脂で被覆されていることが好ましく、樹脂としてはシリコーン樹脂が好ましい。特に、含窒素シリコーン樹脂または、含窒素シランカップリング剤とシリコーン樹脂とが反応することにより生成した変性シリコーン樹脂が、本発明のカラートナーへのマイナスの摩擦電荷の付与性、環境安定性、キャリアの表面の汚染に対する抑制の点で好ましい。磁性キャリアは、平均粒径が１５〜７０μｍ（より好ましくは、２５〜６０μｍ）がカラートナーの重量平均粒径との関係で好ましい。
【０１１３】
【実施例】
以下、実施例により本発明を更に具体的に説明する。
【０１１４】
本発明の具体的トナーの製造例について説明するが、本発明はこれらのトナーの製造例に限定されるものではない。
【０１１５】
（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１．８ｍｏｌ、２−エチルヘキシルアクリレート０．２１ｍｏｌ、フマル酸０．１５ｍｏｌ、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６．９ｍｏｌ、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、コハク酸３．０ｍｏｌ、無水トリメリット酸２．０ｍｏｌ、フマル酸４．９ｍｏｌ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。本製造例においては、ポリエステル樹脂の、スチレン−アクリル系樹脂とのハイブリッド樹脂の製造条件を適正化することで、本発明の粘弾性特性を得た。ＧＰＣによる分子量測定の結果を表１に示す。
【０１１６】
【表１】

【０１１７】
（ハイブリッド樹脂製造例２）
スチレン３．９ｍｏｌ、α−メチルスチレンの２量体０．０７ｍｏｌ、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。
【０１１８】
（ハイブリッド樹脂製造例３）
フマル酸４．９ｍｏｌに代えてマレイン酸３．９ｍｏｌとイタコン酸３．６ｍｏｌ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。
【０１１９】
（ハイブリッド樹脂製造例４）
テレフタル酸３．０ｍｏｌ、無水トリメリット酸２．０ｍｏｌ、の替わりに無水トリメリット酸５．２ｍｏｌにして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（４）を得た。ＧＰＣによる分子量測定の結果を表１に示す。
【０１２０】
（ポリエステル樹脂製造例１）
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１．１ｍｏｌ、フマル酸２．４ｍｏｌ及び酸化ジブチル錫０．１ｇ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。
【０１２１】
（ポリエステル樹脂製造例２）
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１．６ｍｏｌ、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３．３ｍｏｌ、テレフタル酸１．６ｍｏｌ、無水トリメリット酸０．３ｍｏｌ、フマル酸３．２ｍｏｌのモノマー構成で上記と同様に反応させ、ポリエステル樹脂（２）を得た。ＧＰＣによる分子量測定の結果を表１に示す。
【０１２２】
（ビニル系樹脂の製造例１）
トルエン溶媒1000mlとビニル系共重合体として、スチレン２．３mol、ｎ-ブチルアクリレート０．２５mol、モノブチルマレート０．０７mol、ジ-ｔ-ブチルパーオキサイド０.１１molを温度計、ステンレス製攪拌棒、流下式コンデンサー及び窒素導入管を装備した３リットルの４口フラスコに入れ、マントルヒーター中で、窒素雰囲気にて120℃の温度で攪拌しつつトルエンを還流させながら反応させ、ビニル系樹脂（１）を得た。ＧＰＣによる分子量測定の結果を表１に示す。
【０１２３】
次に、本発明に用いたワックスを表２に示す。
【０１２４】
【表２】

【０１２５】
＜カラートナー製造例1＞
以下の方法により、非磁性カラートナーの一例としてシアントナー１を調製した。
ハイブリッド樹脂（１） １００質量部
ワックス（Ａ） ５質量部
Ｃ．Ｉ．ピグメントブルー１５：３ ５質量部
ジ−ｔｅｒｔ−ブチルサリチル酸アルミニウム錯体 ６質量部
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７．６μｍのシアン系トナー粒子を得た。
【０１２６】
上記シアン系トナー粒子１００質量部に対して、ｉ−Ｃ₄Ｈ₉Ｓｉ（ＯＣＨ₃）₃：２５質量部で処理した疎水性酸化アルミニウム（ＢＥＴ法での測定結果１７０ｍ²／ｇ）１．１質量部を合せてシアントナー１とした。カラートナーの貯蔵弾性率及び吸熱ピークの測定結果を表１に示す。
【０１２７】
＜カラートナー製造例2＞
ハイブリッド樹脂（１）に替えてハイブリッド樹脂（２）を使用したこと以外はカラートナー製造例１と同様にしてシアントナー２を得た。カラートナーの測定結果を表１に示す。
【０１２８】
＜参考カラートナー製造例３＞
ハイブリッド樹脂（１）に替えて、５０質量部のポリエステル樹脂（１）と５０質量部のハイブリッド樹脂（１）との混合物を使用したこと、ジ−ｔｅｒｔ−ブチルサリチル酸アルミニウム錯体を８質量部使用したこと以外はカラートナー製造例１と同様にしてシアントナー３を得た。カラートナーの測定結果を表１に示す。
【０１２９】
＜参考カラートナー製造例４＞
ハイブリッド樹脂（１）に替えてハイブリッド樹脂（３）を使用したこと、ジ−ｔｅｒｔ−ブチルサリチル酸アルミニウム錯体を9.5質量部使用したこと以外はカラートナー製造例１と同様にしてシアントナー４を得た。カラートナーの測定結果を表１に示す。
【０１３０】
＜カラートナー製造例５＞
ワックス（Ａ）に替えてワックス（Ｂ）を使用した以外はカラートナー製造例１と同様にしてシアントナー５を得た。カラートナーの測定結果を表１に示す。
【０１３１】
＜参考カラートナー製造例６＞
ジ−ｔｅｒｔ−ブチルサリチル酸アルミニウム錯体を２質量部使用したこと以外はカラートナー製造例１と同様にしてシアントナーを得た。カラートナーの測定結果を表１に示す。
【０１３２】
＜参考カラートナー製造例７＞
ジ−ｔｅｒｔ−ブチルサリチル酸アルミニウム錯体を３質量部使用したこと、ワックス（Ａ）に替えてワックス（Ｄ）を使用したこと以外はカラートナー製造例１と同様にしてシアントナー７を得た。カラートナーの測定結果を表１に示す。
【０１３３】
＜カラートナー製造例８＞
ジ−ｔｅｒｔ−ブチルサリチル酸アルミニウム錯体を使用しないこと以外はカラートナー製造例１と同様にしてシアントナー８を得た。カラートナーの測定結果を表１に示す。
【０１３４】
＜カラートナー製造例９＞
Ｃ．Ｉ．ピグメントブルー１５：３に替えてＣ．Ｉ．ピグメントレッド２０２を６質量部使用したこと以外はカラートナー製造例１と同様にしてマゼンタトナー１を得た。カラートナーの測定結果を表１に示す。
【０１３５】
＜カラートナー製造例１０＞
Ｃ．Ｉ．ピグメントブルー１５：３に替えてＣ．Ｉ．ピグメントイエロー１７を４質量部使用したこと以外はカラートナー製造例１と同様にしてイエロートナー１を得た。カラートナーの測定結果を表１に示す。
【０１３６】
＜カラートナー製造例11＞
ジ−ｔｅｒｔ−ブチルサリチル酸亜鉛錯体を６質量部使用したこと以外はカラートナー製造例１と同様にしてシアントナー9を得た。カラートナーの測定結果を表１に示す。
【０１３７】
＜比較トナー製造例１＞
ハイブリッド樹脂（１）に替えてハイブリッド樹脂（４）を使用したこと、ジ−ｔｅｒｔ−ブチルサリチル酸アルミニウム錯体を７．５質量部使用したこと以外はカラートナー製造例１と同様にしてシアントナー10を得た。カラートナーの測定結果を表１に示す。
【０１３８】
＜比較トナー製造例２＞
ハイブリッド樹脂（１）に替えてポリエステル樹脂（２）を使用したこと、ジ−ｔｅｒｔ−ブチルサリチル酸アルミニウム錯体を４質量部使用したこと以外はカラートナー製造例１と同様にしてシアントナー11を得た。カラートナーの測定結果を表１に示す。
【０１３９】
＜比較トナー製造例３＞
ハイブリッド樹脂（１）に替えてビニル系樹脂（１）を使用したこと、ジ−ｔｅｒｔ−ブチルサリチル酸アルミニウム錯体を７．５質量部使用したこと以外はカラートナー製造例１と同様にしてシアントナー12を得た。カラートナーの測定結果を表１に示す。
【０１４０】
＜比較トナー製造例４＞
ハイブリッド樹脂（１）に替えてポリエステル樹脂（１）を使用したこと、ジ−ｔｅｒｔ−ブチルサリチル酸アルミニウム錯体を１２質量部使用したこと以外はカラートナー製造例１と同様にしてシアントナー13を得た。カラートナーの測定結果を表１に示す。
【０１４１】
比較トナー製造例５＞
、ワックス（Ａ）に替えてワックス（Ｅ）を使用したこと以外はカラートナー製造例１と同様にしてシアントナー14を得た。カラートナーの測定結果を表１に示す。
【０１４２】
＜比較トナー製造例６＞
カラートナー製造例１において，精製ノルマルパラフィンワックス（A）に替えて，低融点のパラフィンワックス（C）を用いたことを除いてあとは同様にしてシアントナー15を得た。カラートナーの測定結果を表１に示す。
【０１４３】
＜黒色トナー製造例1＞
以下の方法により、磁性黒トナーの一例として黒トナー１を調製した。
ハイブリッド樹脂（１） １００質量部
ワックス（Ａ） ７質量部
磁性酸化鉄1 ９０質量部
ジ−ｔｅｒｔ−ブチルサリチル酸アルミニウム錯体 ９質量部
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８.２μｍの黒トナー1を得た。尚、使用した磁性酸化鉄の特性は表３に示すとおりである。
【０１４４】
【表３】

【０１４５】
＜黒色トナー製造例２＞
磁性酸化鉄２を４５質量部使用する以外は、黒色トナー製造例１と同様にして重量平均粒径８.３μｍの黒トナー２を得た。黒トナー２の測定結果を表３に示す。
【０１４６】
＜黒色トナー製造例３＞
磁性酸化鉄３を４５質量部使用する以外は、黒色トナー製造例１と同様にして重量平均粒径８.４μｍの黒トナー３を得た。黒トナー３の測定結果を表３に示す。
【０１４７】
［実施例1］
カラートナー製造例1で得られたシアントナー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、二成分系シアン現像剤１とした。
【０１４８】
評価機としては、カラー用現像器を非磁性1成分トナー用から非磁性2成分現像剤用に改造したカラー複写機ＣＰ−６６０（キヤノン製）を用いた。
【０１４９】
この評価機のカラーステーションにシアン現像剤１を装填し、単色モードで高温高湿環境下（３０℃，８０％）、常温低湿環境下（２３℃，５％）で画像面積比率２０％のオリジナル原稿を用いて、単位面積当たりのトナー載り量は0.7ｍｇ/ｃｍ²に設定し、１万枚の未定着画像出力による耐刷試験を行った。
【０１５０】
なお、出力した未定着画像の定着可能領域の評価については、カラー複写機ＣＰ−６６０（キヤノン製）の定着ユニット（定着オイルレス）を手動で定着温度が設定できるように改造して評価した。
【０１５１】
ＯＨＰ透明性の測定は、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。評価法として、Ａ：８５％以上、Ｂ：７５〜８５％、Ｃ：６５〜７５％、Ｄ：６５％未満で表示する。
【０１５２】
転写性は、カラー複写機ＣＰ−６６０（キヤノン製）の改造機を用いて常温低湿環境下（２３℃，５％）で１０，０００枚の耐久試験を行い、耐久前後のベタ画像を現像，転写し、感光体上の転写前のトナー量（単位面積あたり）と、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。
【０１５３】
【数３】

【０１５４】
カラー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。該評価としては目視による凝集性のレベルを判定した。
【０１５５】
カラー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）
シアン現像剤1は、転写性に優れるとともに、光沢性、ＯＨＴ透明性ともに良く、優れた定着性と耐ブロッキング性を示した。また、環境安定性も良好であった。結果を表４に示す。尚、表４中、各環境下での画像濃度（マクベス）は、初期／耐久後の値を示す。
【０１５６】
【表４】

【０１５７】
［実施例2］
シアントナー2を用い、実施例1と同様にしてシアン現像剤2を調製し、各項目を評価した。その結果、シアン現像剤2は転写性に優れるとともに、光沢性、ＯＨＴ透過性ともに良く、優れた定着性、耐ブロッキング性、環境安定性を示した。結果を表４に示す。
【０１５８】
［参考例3］
シアントナー3を用い、実施例1と同様にしてシアン現像剤3を調製し、各項目を評価した。その結果、得られた画像は転写性に優れるとともに、光沢性、ＯＨＴ透過性ともに良く、優れた定着性、耐ブロッキング性、環境安定性を示した。結果を表４に示す。
【０１５９】
［参考例4］
シアントナー4を用い、実施例1と同様にしてシアン現像剤4を調製し、各項目を評価した。その結果、得られた画像は低湿環境下での転写性が若干低く、やや光沢性に欠け、ＯＨＴ透過性やや低めではあるものの、優れた定着性と耐ブロッキング性を示した。結果を表４に示す。
【０１６０】
［実施例5］
シアントナー5を用い、実施例1と同様にしてシアン現像剤5を調製し、各項目を評価した。その結果、得られた画像は転写性に優れるとともに、光沢性、ＯＨＴ透過性ともに良く、優れた定着性、耐ブロッキング性、環境安定性を示した。結果を表４に示す。
【０１６１】
［参考例6］
シアントナー6を用い、実施例1と同様にしてシアン現像剤6を調製し、各項目を評価した。その結果、得られた画像は転写性に優れるとともに、光沢性、ＯＨＴ透過性ともに良く、優れた定着性と環境安定性を示した。耐ブロッキング性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。結果を表４に示す。
【０１６２】
［参考例7］
シアントナー7を用い、実施例1と同様にしてシアン現像剤7を調製し、各項目を評価した。その結果、得られた画像はワックスの高結晶性が影響してややＯＨＰの透過性が悪く、また高融点であるためにワックスが定着時にトナー表面に出にくくなり、低温定着性をやや悪化させたものの、比較的良好な結果を得た。また、得られた画像の転写性は良好であり、耐ブロッキング性と環境安定性も良好であった。結果を表４に示す。
【０１６３】
［実施例8］
シアントナー8を用い、実施例1と同様にしてシアン現像剤8を調製し、各項目を評価した。その結果、ジ−ｔｅｒｔ−ブチルサリチル酸アルミニウム錯体を含有していないために、トナーの帯電量がやや低くなったことおよび定着温度領域の高温側がやや狭くなったこと以外は、特に問題を生じなかった。結果を表４に示す。
【０１６４】
［実施例9］
マゼンタトナー1を用い、実施例1と同様にしてマゼンタ現像剤1を調製し、各項目を評価した。その結果、光沢性、ＯＨＴ透過性ともに良く、高精細なフルカラー画像を得ることができた。結果を表４に示す。
【０１６５】
［実施例10］
イエロートナー1を用い、実施例1と同様にしてイエロー現像剤1を調製し、各項目を評価した。その結果、光沢性、ＯＨＴ透過性ともに良く、高精細なフルカラー画像を得ることができた。結果を表４に示す。
【０１６６】
［実施例11］
シアントナー9を用い、実施例1と同様にしてシアン現像剤9を調製し、各項目を評価した。その結果、得られた画像は、耐久後にやや画像濃度や転写率が低下し、耐ブロッキング性がやや悪化するものの、比較的良好な結果を示した。結果を表４に示す。
【０１６７】
［実施例12］
黒トナー1、シアントナー1、イエロートナー1、マゼンダトナー1を組み合わせて用い、カラートナーは実施例1と同様にして、黒トナーは一成分現像剤として各現像剤を調製し、各項目を評価した。その結果、得られた画像は、色再現性が優れており文字画像も鮮明であって高解像度が得られ、良好な結果を示した。結果を表４に示す。カラー画質再現性は、写真原稿と黒文字原稿を用い、◎：ほぼ全ての色および文字が忠実に再現された、○：写真画像部分の黒味がかった部分が若干不明瞭である、△：写真画像部分の黒味がかった部分が若干不明瞭であり、文字画像の解像度がやや劣っていた ことを示す。尚、画像濃度、転写率、耐ブロッキング性は黒トナー単独の結果を示す。
【０１６８】
［実施例13］
黒トナー２、シアントナー1、イエロートナー1、マゼンダトナー1を組み合わせて用い、実施例12と同様にして各現像剤を調製し、各項目を評価した。その結果、得られた画像は、濃色部分の色再現性がやや劣っていたものの、文字画像は鮮明であって高解像度が得られ、良好な結果を示した。結果を表４に示す。尚、画像濃度、転写率、耐ブロッキング性は黒トナー単独の結果を示す。
【０１６９】
［実施例14］
黒トナー３、シアントナー1、イエロートナー1、マゼンダトナー1を組み合わせて用い、実施例12と同様にして各現像剤を調製し、各項目を評価した。その結果、得られた画像は、濃色部分の色再現性と文字画像の解像度がやや劣っていたものの、良好な結果を示した。結果を表４に示す。尚、画像濃度、転写率、耐ブロッキング性は黒トナー単独の結果を示す。
【０１７０】
［比較例1］
シアントナー10を用い、実施例1と同様にしてシアン現像剤10を調製し、各項目を評価した。その結果、シアントナー10は非常に硬いトナーとなり、貯蔵弾性率（Ｇ'₈₀）が大きいために、光沢性とＯＨＴの透過性が悪く、またワックスが定着時にトナー表面に出にくくなり、低温定着性を悪化させた。また、高温高湿環境下ではドラムへの融着が若干発生すると伴に低湿環境下で帯電量が著しく上がり、十分な画像濃度を得ることができなかった。結果を表４に示す。
【０１７１】
［比較例2］
シアントナー11を用い、実施例1と同様にしてシアン現像剤11を調製し、各項目を評価した。その結果、シアントナー11は非常に軟らかいトナーとなり、耐ブロッキング性が悪くなり、耐高温オフセット性を悪化させた。また、高温高湿環境においては、顕著なドラム融着とフィルミングが発生した。さらに、有機金属化合物の含有量が多いため、低湿環境下で帯電量が著しく上がり、十分な画像濃度を得ることができなかった。結果を表４に示す。
【０１７２】
［比較例3］
シアントナー12を用い、実施例1と同様にしてシアン現像剤12を調製し、各項目を評価した。その結果、シアントナー12は光沢性とＯＨＴの透過性が悪く、定着温度領域も狭くなった。また、高温高湿環境下ではドラムへの融着が若干発生した。結果を表４に示す。
【０１７３】
［比較例4］
シアントナー13を用い、実施例1と同様にしてシアン現像剤13を調製し、各項目を評価した。その結果、シアントナー13は光沢性とＯＨＴの透過性が悪くなった。また、高温高湿環境下ではドラムへの融着が若干発生した。結果を表４に示す。
【０１７４】
［比較例5］
シアントナー14を用い、実施例1と同様にしてシアン現像剤14を調製し、各項目を評価した。その結果、高融点であるためにワックスが定着時にトナー表面に出にくくなり、低温定着性を悪化させ、ＯＨＴの透過性が悪くなった。トナーの帯電結果を表４に示す。
【０１７５】
［比較例6］
シアントナー15を用い、実施例1と同様にしてシアン現像剤15を調製し、各項目を評価した。その結果、耐久１０００枚を過ぎたあたりから，かぶり，飛散が悪化し耐久を中断した。 またトナーの流動性が悪く，転写性が初期から悪かった。シアントナー15.は、低融点のワックスを含有しているため、定着性が不十分である上に、特に高温環境下でワックスがトナー表面に出てきて、帯電性、耐熱性、耐ブロッキング性を悪化させたものと考えられる。また、高温高湿環境においては、顕著なドラム融着とフィルミングが発生した。結果を表４に示す。
【０１７６】
【発明の効果】
本発明により、ＯＰＣ（有機光導電体）感光体をフルカラー機に搭載する場合において、耐久安定性に優れ、高精彩性を満足した画像を形成できるカラートナー、該カラートナーを有する画像形成方法及び画像形成装置を提供することができる。具体的には、トナーが感光体表面へ融着せず、フィルミングが削減でき、ＯＨＰでの透明度を高め、定着時の低温定着に支障なく耐高温オフセットの問題も解消し、色の混色度も優れたカラートナー、該カラートナーを有する画像形成方法及び画像形成装置を提供することができる。
【図面の簡単な説明】
【図１】本発明の画像形成装置の一実施例図。
【図２】現像手段の概略図。
（ａ）一成分現像剤を使用した現像手段の一例を示す図。
（ｂ）二成分現像剤を使用した現像手段の一例を示す図。[0001]
BACKGROUND OF THE INVENTION
  The present invention uses an OPC (organic photoconductor) photoreceptor as an image carrier used in a color printer, a color copier, etc., and uses a one-component magnetic toner for black development and a two-component non-magnetic toner for color development. Image formation using andTo the lawRelated.
[0002]
[Prior art]
2. Description of the Related Art An apparatus using an electrophotographic process is widely used in addition to a so-called copying machine for copying a conventional manuscript, in addition to a computer whose output has been increasing rapidly in recent years and a printer as an output means of a word processor. In such printers, it is important to provide not only conventional monochrome image output but also color image output.
[0003]
In such an environment, a plurality of developing units each containing a developer of different colors are provided, and toners of a plurality of colors are formed on a photosensitive drum which is an image carrier using electrophotography in one or a plurality of recording cycles. There has been proposed a multicolor (color) image forming apparatus that forms an image and transfers and fixes the toner images of a plurality of colors onto a recording material to obtain a desired multicolor image.
[0004]
At that time, it is necessary for the color development that each toner is sufficiently mixed in the heat and pressure fixing step without impairing the color reproducibility and the transparency of the overhead projector (OHP) image. Compared with black toner for general black-and-white copying machines and printers, the full-color image toner is preferably a binder resin having a sharp melt property and a low molecular weight and a low softening point. This is because, when a toner having a high softening point is used, the color mixing property in the fixing device falls and a problem occurs in color reproducibility. However, when such a low softening point toner is used in a high-speed full-color copying machine, the mechanical share increases at the contact portion between the cleaner portion and the transfer portion roller with the photosensitive member. Since the amount of generated heat becomes large, a phenomenon occurs in which the toner is softened on the photoreceptor. This leads to a problem that toner adheres (fuses) to the photoconductor and a filming problem that toner resin accumulates on the surface of the photoconductor. For this reason, the photoconductor cannot obtain a sufficient life.
[0005]
Therefore, when the OPC photosensitive member is mounted on a color machine that requires a high-definition image, fusion to the photosensitive member is prevented, filming is reduced, and color reproducibility is not affected during fixing. It has been desired to develop a toner that satisfies all the requirements.
[0006]
Conventionally, various proposals have been made on toners having a specific storage elastic modulus in order to solve the offset problem in the fixing process without impairing the transparency of the OHP image. For example, there are JP-A-11-84716 and JP-A-11-7151.
[0007]
However, these are not sufficient in terms of color reproducibility in the fixing process, that is, transparency in OHP, constant temperature fixing during heating and pressure fixing, and high-temperature offset resistance. There is room for improvement in order to achieve sufficient color mixing and to obtain ideal fixing characteristics, storage stability, and OHP transparency as a color toner.
[0008]
[Problems to be solved by the invention]
An object of the present invention is to provide a color toner, an image forming method, and an image forming apparatus that solve the above-described problems. That is, an object of the present invention is to provide a color toner that can form an image having excellent durability stability and satisfying high definition when an OPC (organic photoconductor) photoreceptor is mounted on a full-color machine, and the color toner. An image forming method and an image forming apparatus are provided. Specifically, the toner does not fuse to the surface of the photoconductor, filming can be reduced, transparency in OHP is improved, the problem of high temperature offset resistance is solved without hindering the low temperature fixing during fixing, and the color mixing degree is also improved. An excellent color toner, an image forming method and an image forming apparatus having the color toner are provided.
[0009]
[Means for Solving the Problems]
  Thus, as a result of intensive studies, the present inventors have found that the above-described problems can be solved by using the following color toner, and have completed the present invention.
(1) An electrostatic latent image forming step for forming an electrostatic latent image on an image carrier using an organic photoconductor, and transferring toner to the electrostatic latent image formed on the image carrier. A developing process for forming and developing a toner image corresponding to the latent image, a transfer process for electrostatically transferring the toner image formed on the image carrier onto a transfer material, and a fixing member for the electrostatically transferred toner image A two-component developer comprising a one-component developer composed of a magnetic toner for performing black development, a magnetic carrier for performing color development, and a non-magnetic toner. The non-magnetic toner has at least a binder resin, a colorant, and a wax, and is produced by a melt-kneading pulverization method. Toner,The binder resin is a hybrid resin having a polyester unit and a vinyl copolymer unit,In the viscoelastic properties, the storage elastic modulus at a temperature of 80 ° C. (G ′₈₀) Is 1 × 10⁶~ 1x10⁸[DN / m²], And the storage elastic modulus (G ′ at a temperature of 120 to 180 ° C._120-180) Is 1 × 10⁴~ 5x10⁵[DN / m²In the endothermic curve in the differential scanning calorimetry (DSC) measurement, the maximum endothermic peak in the temperature range of 30 to 200 ° C. is a color toner having a peak temperature in the range of 50 to 110 ° C. Image forming method.
(2) The color toner has an endothermic curve in differential scanning calorimetry (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 55 to 100 ° C. ( The image forming method according to 1).
(3) The color toner is characterized in that 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. in the endothermic curve in differential scanning calorimetry (DSC) measurement ( The image forming method according to 1).
(4) In the molecular weight distribution by gel permeation chromatography (GPC), the binder resin has a main peak in the molecular weight region of 6000 to 8000, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) ( (Mw / Mn) is 300 or more (1) to (3The image forming method according to any one of the above.
(5) In the molecular weight distribution by gel permeation chromatography (GPC), the binder resin has a main peak in the molecular weight region of 6000 to 8000, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) ( (Mw / Mn) is 500 or more (1) to (1)3The image forming method according to any one of the above.
(6The color toner has an organometallic compound (1) to (1)5The image forming method according to any one of the above.
(7) The organometallic compound is a metal compound of an aromatic carboxylic acid derivative (6) Image forming method.
(8) The metal compound of the aromatic carboxylic acid derivative is an aluminum compound of an aromatic carboxylic acid derivative (7) Image forming method.
(9The organometallic compound is contained in the color toner in an amount of 0.1 to 10% by mass based on the mass of the color toner (6) ~ (8The image forming method according to any one of the above.
(10The magnetic toner for black development contains at least magnetic iron oxide, and the magnetic iron oxide contains 0.3 to 1.4% of Si element or Al element (1) ) ~ (9The image forming method according to any one of the above.
(11) The magnetic toner for black development contains at least magnetic iron oxide, and the magnetic iron oxide has a silicon element content BSi that is present up to 20% by weight of the iron element dissolution rate of the magnetic iron oxide. The ratio (BSi / ASi) × 100 of the total silicon element content ASi present in the magnetic iron oxide is 35 to 85% (1) to (10The image forming method according to any one of the above.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an image carrier using OPC (organic photoconductor),
A developing step of transferring the toner to the electrostatic latent image formed on the image bearing member to form a toner image corresponding to the latent image and developing the toner image;
A transfer step of electrostatically transferring a toner image formed on the image carrier onto a transfer material;
A fixing step of fixing the electrostatically transferred toner image by a fixing member. One embodiment of an image forming apparatus for carrying out this image forming method is shown in FIG. The image forming apparatus includes a plurality of developing units each containing a developer of a different color, and forms a plurality of color toner images on one photosensitive drum by one or a plurality of recording cycles. This is a digital full-color multicolor image forming apparatus that obtains a desired multicolor image by transferring and fixing a toner image onto a transfer material.
[0011]
The apparatus has a photosensitive drum 202 which is an image carrier. The image carrier is a drum-type electrophotographic photosensitive member that is rotationally driven in a clockwise direction indicated by an arrow A at a predetermined peripheral speed (process speed). Reference numeral 201 denotes a charging means for uniformly charging the photosensitive member 202. The photosensitive member 202 is uniformly charged by the charging unit 201 and then supplied to the electrostatic latent image forming unit. A latent image is formed by the image signal applying unit 203, and a developed image (toner image) corresponding to the latent image is formed by the next developing unit 204. The developing means 204 includes a first developing device 204 (a) for developing a first color developer, a second developing device 204 (b) for developing a second color developer, and a third developing device. 204 (c) and a fourth developing device 204 (d) (each of which contains toner of different colors).
[0012]
The toner image is electrostatically transferred to a transfer material by a transfer unit. That is, the intermediate transfer material 222 is driven by the drive system 221 that also serves as a transfer unit, and the toner image is transferred to the intermediate transfer material 222. Thereafter, the intermediate transfer material 222 is further transferred to a final transfer material P made of paper or the like. After the toner image is transferred to the final transfer material P, the intermediate transfer material 222 is cleaned by an intermediate transfer material cleaning unit 223 including a cleaning blade 224 and the like, and used for the next transfer process. The transfer process may be configured to be transferred directly to the final transfer material P. In that case, the final transfer material P is configured to circulate in the apparatus a plurality of times. The configuration is slightly different.
[0013]
On the other hand, the surface of the photoreceptor 202 is cleaned by a cleaning unit (cleaner) 207 after being separated from the transfer material (222 or P) onto which the toner image has been transferred. Thereafter, the electrostatic latent image remaining on the surface of the photoconductor is neutralized by the neutralizing unit 208 and then supplied again to the charging step.
[0014]
On the other hand, after the transfer material P made of paper or the like passes through the paper feed path 219 of the paper feed system 205, the timing is controlled by the register roller 220 or the like and is supplied to the photoconductor side. Further, the visible image on the surface of the intermediate transfer material 222 (or the photoreceptor 202) is transferred to the transfer material P by the transfer means 206 (a), and the transfer material P is separated from the photoreceptor side by the separation means 206 (b). After the transfer material P is separated, the toner image is fixed by a fixing unit 211 including a roller -212 and the like via a conveyance system 210 and discharged outside the apparatus.
[0015]
The image signal providing means reflects the irradiation light from the light source 215 on the document 213 placed on the document table 214 and stores it in the scanner 216 or directly stores a signal from an external computer or the like instead of from the document. . In response to the stored signal, a latent image light source 217 made of a laser or the like is scanned and intensity-modulated, and is supplied to the image signal applying unit 203 through a polarizing unit such as a mirror 218. When forming a multicolor (two or more colors) image of the present invention, the above process is repeated as many times as necessary in accordance with the color of the toner to form an image.
[0016]
Next, the developing process of the present invention will be described. In the development step, a one-component developer made of magnetic toner for black development, a magnetic carrier for color development, and a two-component developer made of non-magnetic toner are used. In this way, by changing the developing method between black and color and using them properly, black development is frequently used, but maintenance such as carrier replacement can be suppressed.
[0017]
Further, in many cases, since the frequency of using black toner such as a character document is high in a color copying machine, a tendency that a large amount of black toner is consumed is seen. Therefore, it is desired to supply a large amount of black toner, and the magnetic toner increases the specific gravity of the toner, which is advantageous for increasing the fluidity of the toner, and the development position and toner hopper shape are designed. The result was a greater degree of freedom.
[0018]
On the other hand, development for color (other than black) has been able to widen the range of toners that can be used to achieve the purpose of sharpening colors.
[0019]
Here, the developing means using the developer of the present invention will be described with reference to FIG. FIG. 2 shows a schematic view of the inside of the developing means and the vicinity of the area facing the photoconductor. FIG. 2A shows a case where a one-component developer is used in the case of black development, and FIG. 2B shows a case where a two-component developer is used in the case of color development. The developing unit 50 includes at least a developer 51, a sleeve 52, a blade 53, a developer reservoir 54, and a peeling member 55. FIG. 2A depicts the case of a magnetic one-component developer, and a magnetic body 56 is installed in the sleeve 52. Further, the developing means 50 may have a stirring screw (not shown) or the like. The sleeve 52 has a predetermined DC voltage or an AC voltage applied to the DC voltage, and is driven to rotate at a predetermined speed. The developer 51 is conveyed from the developer reservoir 54 while adhering onto the sleeve 52. Further, the developer 51 passes between the sleeve 52 and the blade 53, is controlled to have a predetermined coat thickness, is given a predetermined charge, and is conveyed to an area facing the photoconductor. In the region, the developer 51 is developed on the surface of the photoconductor by the potential difference between the photoconductor and the sleeve 52 and the applied voltage. The developer 51 remaining on the surface of the sleeve 52 is collected in the developing means 50 by the sleeve 52 and peeled and removed from the sleeve by the peeling member 55.
[0020]
In the one-component development system, the developer 51 is composed of toner 511, and in the two-component development system, the developer 51 is composed of toner 511 and a carrier 512. Furthermore, both one component and two components have an external additive (not shown). In the magnetic one-component developer, as shown in FIG. 2A, the blade 53 is made of a magnetic member, and is installed with a predetermined distance from the sleeve 52. On the other hand, in the non-magnetic two-component development, as shown in FIG. 2B, the toner blade 53 is made of an elastic member and is in contact with the sleeve 52 with a predetermined contact pressure. Here, the carrier 512 and the toner 511 are coated on the developing sleeve 52 with a predetermined thickness, and come into contact with the photoconductor 1002 in a state where so-called “ears” are formed. At the contact portion, the toner adheres to the photoconductor 1002 with an electrostatic force according to the latent image to form a toner image.
[0021]
<About the color toner of the present invention>
The color toner of the present invention has at least a binder resin, a colorant and a wax, and has a viscoelastic property and a storage elastic modulus (G ′ at a temperature of 80 ° C.).₈₀) Is 1 × 10⁶~ 1x10^Ten[DN / m²], And the storage elastic modulus (G ′ at a temperature of 120 to 180 ° C._120-180) Is 5 × 10^Three~ 1x10⁶[DN / m²] Is satisfied,Differential scanning calorimetryIn the endothermic curve in the (DSC) measurement, the color toner has a peak temperature of a maximum endothermic peak in the range of 30 to 200 ° C. in the range of 50 to 110 ° C.
[0022]
In the present invention, measurement of viscoelasticity andDifferential scanning calorimetryThe measurement of was performed as follows. The same measurement was performed in the examples described later.
[0023]
(1)Measurement of toner viscoelasticity
The toner is pressure-molded into a disk-shaped sample having a diameter of 25 mm and a thickness of about 2 to 3 mm. Next, set it on a parallel plate, gradually raise the temperature within the temperature range of 50 to 200 ° C, and measure the temperature dispersion. The heating rate is 2 ° C / min, the angular frequency (ω) is fixed at 6.28 rad / sec, and the distortion is automatic. The horizontal axis is temperature, and the vertical axis is storage modulus (G ') And read the value at each temperature. For the measurement, RDA-II (manufactured by Rheometrics) is used.
[0024]
(2) Differential scanning calorimetry measurement
It measures according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device) and DSC-7 (manufactured by Perkin Elmer). 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 normal humidity within a measurement temperature range of 30 to 200 ° C. In the temperature raising process and the temperature lowering process, the endothermic and exothermic peaks of the main peak of the DSC curve in the temperature range of 30 to 200 ° C. are obtained.
[0025]
In the above viscoelastic characteristics, the storage elastic modulus (G′80) of the nonmagnetic color toner at a temperature of 80 ° C. is 1 × 10.⁶~ 1x10^Ten[DN / m²] Is preferable. More preferably, 1 × 10⁶~ 1x10⁸[DN / m²]. Thereby, the storage stability, heat resistance, and blocking resistance of the toner in a high temperature environment can be improved. The value of the viscoelastic modulus can be adjusted by appropriately considering various factors such as the type and molecular weight of the binder resin itself, the amount of the crosslinking component, and the structure of the molecular chain.
[0026]
Storage modulus (G '₈₀) Is 1 × 10⁶[DN / m²Smaller than], storage stability, heat resistance, and blocking resistance under high temperature environment are poor, and toner particles coalesce to form a large toner aggregate, resulting in fusion and filming on the drum surface. Problem arises. On the other hand, storage elastic modulus (G ′₈₀) Is 1 × 10^Ten[DN / m²], The storage stability, heat resistance, and blocking resistance are sufficient, but there is a problem that sufficient fixability at a low temperature cannot be obtained.
[0027]
Next, the storage elastic modulus (G ′) of the nonmagnetic color toner at a temperature of 120 to 180 ° C._120-180) Is 5 × 10^Three~ 1x10⁶[DN / m²] Is preferable. More preferably, 1 × 10^Four~ 5x10^Five[DN / m²]. Thereby, sufficient low-temperature fixability and high-temperature offset resistance can be made compatible.
[0028]
Storage modulus (G '_120-180) Is 5 × 10^Three[DN / m²] Is not preferable because sufficient high temperature offset resistance of the toner cannot be obtained, and storage modulus (G ′_120-180) Is 1 × 10⁶[DN / m²] Is not preferable because sufficient low-temperature fixability of the toner cannot be obtained.
[0029]
Next, the non-magnetic color tonerDifferential scanning calorimetryIn the endothermic curve in (DSC) measurement, the peak temperature of the maximum endothermic peak in the temperature range of 30 to 200 ° C is preferably in the range of 50 to 110 ° C. More preferably, it is the range of 55-100 degreeC, More preferably, it is the range of 60-90 degreeC. The value of the endothermic peak can be adjusted by appropriately considering the type of wax. Thus, good results are shown in terms of low-temperature fixability, blocking resistance, and prevention of filming on the surface of the OPC photoreceptor.
[0030]
When the maximum peak of the endothermic curve exceeds 110 ° C., the low-temperature fixability of the toner deteriorates, and at the same time, a saturation failure due to insufficient melting of the toner in the fixed image occurs. On the other hand, when the maximum peak of the endothermic curve is less than 50 ° C., the toner has poor blocking resistance, and at the same time, fusion and filming to the surface of the OPC photoreceptor occur.
[0031]
Next, the binder resin contained in the color toner of the present invention will be described.
[0032]
The binder resin contained in the color toner of the present invention includes (a) a hybrid resin having a polyester unit and a vinyl copolymer unit, or (b) a mixture of a hybrid resin and a polyester resin, (c) Any of a mixture of a hybrid resin and a vinyl copolymer, (d) a polyester resin, and (e) a mixture of a polyester resin and a vinyl copolymer can be used. A hybrid resin having a polyester unit and a vinyl copolymer unit or a mixture of a polyester resin and a vinyl copolymer is used because sufficient high-temperature offset resistance, heat resistance, and blocking resistance can be obtained. It is preferable.
[0033]
The binder resin has a peak molecular weight (MP) of 6000 to 8000 in a molecular weight distribution measured by gel permeation chromatography (GPC), and a ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn). (Mw / Mn) is preferably 300 or more, and preferably 500 or more.
[0034]
When the peak molecular weight (MP) of the binder resin is less than 6000, the fixability at a low temperature is good, but the hot offset temperature is lowered, and as a result, the non-offset temperature region is narrowed. Fusing and filming problems occur. On the other hand, when the peak molecular weight (MP) exceeds 8000, the hot offset temperature becomes high, and as a result, the non-offset temperature region becomes wide, but the gloss of the image becomes low and the OHP permeability is adversely affected. . Further, when the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin is less than 300, there arises a problem that high temperature offset is likely to occur.
[0035]
In the present invention, measurement of molecular weight distribution by GPC measurement was performed as follows. The same measurement was performed in the examples described later.
[0036]
(3)Measurement of molecular weight distribution by GPC measurement
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. 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 , Waters μ-styragel 500, 10^Three10^Four10^FiveCan be mentioned.
[0037]
Next, the material of the binder resin will be described. When a polyester-based resin is used as the binder resin, alcohol and carboxylic acid, carboxylic acid anhydride, or carboxylic acid ester can be used as raw material monomers.
[0038]
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.
[0039]
Examples of trihydric or higher alcohol components 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.
[0040]
The carboxylic acid content includes 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 12 alkyl groups or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof;
[0041]
Among the above, in particular, a bisphenol derivative represented by the following general formula (1) as a diol component, a carboxylic acid component comprising a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof (for example, , Fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as an acid component, and polyester resins obtained by condensation polymerization of these are particularly preferable. The polyester resin having this composition has good charging characteristics as a color toner.
[0042]
[Chemical 1]

[0043]
Next, in the binder resin, 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.
[0044]
Examples of the vinyl monomer for producing the vinyl resin include the following. 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.
[0045]
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.
[0046]
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.
[0047]
The vinyl polymer unit of the binder resin referred to in the present invention may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. The following are mentioned as a crosslinking agent used in this case.
[0048]
Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene, and examples of the diacrylate compound linked with an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butanediol diester. Examples include acrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing the acrylate of the above compound with methacrylate, which are linked by an alkyl chain containing an ether bond. Examples of diacrylate compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 , Polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing the acrylate of the above compounds with methacrylate, and diacrylate compounds linked by a chain containing an aromatic group and an ether bond For example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and the above compounds The thing which replaced the acrylate with the methacrylate is mentioned.
[0049]
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.
[0050]
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.
[0051]
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.
[0052]
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-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide , Lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n- Propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-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.
[0053]
Next, the manufacturing method of the hybrid resin used for the binder resin of this invention is demonstrated. The hybrid resin of the present invention can be produced by the production methods shown in the following (1) to (6).
[0054]
(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.
[0055]
(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.
[0056]
(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.
[0057]
(4) After producing 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.
[0058]
(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.
[0059]
(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.
[0060]
In the production methods of (1) to (5) above, a polymer unit having a plurality of different molecular weights and crosslinking degrees can be used as the vinyl polymer unit and / or the polyester unit.
[0061]
Next, one or more kinds of waxes that the color toner of the present invention has will be described.
[0062]
Examples of the wax used in the present invention include the following. Low molecular weight polyethylene, low molecular weight polypropylene, aliphatic hydrocarbon waxes such as microcrystalline wax, paraffin wax, and the like, or oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; carnauba wax; Examples thereof include waxes mainly composed of fatty acid esters such as sasol wax and montanic acid ester wax, and those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax.
[0063]
In addition, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brandic acid, eleostearic acid, and valinal acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, and seryl alcohol , Saturated alcohols such as melyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis laurin Saturated fatty acid bisamides such as acid amides and hexamethylene bis stearic acid amides; ethylene bis oleic acid amides, hexamethylene bis oleic acid amides, N, N′dioleyl adipic acid amides, N, N ′ geos Unsaturated fatty acid amides such as irsebacic acid amide; Aromatic bisamides such as m-xylene bis-stearic acid amide and N, N ′ distearyl isophthalic acid amide; Calcium stearate, calcium laurate, zinc stearate, magnesium stearate, etc. Aliphatic metal salts (generally referred to as metal soaps); waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides and many others Examples include partially esterified products of monohydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like.
[0064]
Examples of waxes that are particularly preferably used in the present invention include aliphatic hydrocarbon waxes. For example, a low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or a Ziegler catalyst under low pressure; an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer; from a synthesis gas containing carbon monoxide and hydrogen A synthetic hydrocarbon wax obtained from the distillation residue of hydrocarbons obtained by the method or by hydrogenation of these is preferred.
[0065]
Furthermore, the thing which fractionated hydrocarbon wax by the use of the press perspiration method, the solvent method, vacuum distillation, or a fractional crystallization system is used more preferably.
[0066]
The hydrocarbon as a base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (mostly two or more multi-component systems) [for example, the Jintol method, the Hydrocol method (the fluidized catalyst bed Hydrocarbon compounds synthesized by use); hydrocarbons with up to several hundred carbon atoms obtained by the age method (using the identified catalyst bed) from which a large amount of wax-like hydrocarbons can be obtained; alkylene such as ethylene by Ziegler catalyst Polymerized hydrocarbons are preferred because they are linear hydrocarbons with little branching, small and long saturation. In particular, a wax synthesized by a method that does not rely on polymerization of alkylene is also preferred from its molecular weight distribution.
[0067]
In the molecular weight distribution of the wax, the main peak is preferably in the region of molecular weight 400-2400, more preferably in the region of 430-2000. By providing such a molecular weight distribution, preferable thermal characteristics can be imparted to the toner.
[0068]
In order to function more effectively during toner fixing, the melting point of the wax is preferably 60 to 100 ° C., more preferably 65 to 90 ° C. The wax is used in an amount of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin.
[0069]
The wax is usually contained in the binder resin by a method in which the resin is dissolved in a solvent, the temperature of the resin solution is increased, and the mixture is added and mixed while stirring or by mixing during kneading.
[0070]
Next, the colorant that the color toner of the present invention has will be described. As the colorant used in the present invention, pigments and / or dyes can be used.
[0071]
For example, as the dye, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modern Tread 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modern Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Basic green 6 etc. are mentioned.
[0072]
The pigments include mineral fast yellow, navel yellow, naphthol yellow S, hansa yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G, permanent red 4R, and watch red. Calcium salt, Eosin lake, Brilliant carmine 3B, Manganese purple, Fast violet B, Methyl violet lake, Cobalt blue, Alkaline blue lake, Victoria blue lake, Phthalocyanine blue, Fast sky blue, Indanthrene blue BC, Chrome green, Pigment green B, Malachite Green Lake, Final Yellow Green G and the like.
[0073]
Examples of the magenta color pigment 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, 238, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.
[0074]
Although the above-mentioned pigments 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. Further examples of various dyes and pigments that can be used.
[0075]
Examples of the magenta dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1; 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 can be mentioned.
[0076]
Examples of the color pigment for cyan include C.I. I. Pigment blue 2, 3, 15, 16, 17; I. Acid Blue 6; I. Examples thereof include Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
[0077]
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, 93, 97, 180, C.I. I. Vat yellow 1, 3, 20 etc. are mentioned.
[0078]
The amount of the colorant used is 1 to 15 parts by mass, preferably 3 to 12 parts by mass, and more preferably 4 to 10 parts by mass with respect to 100 parts by mass of the binder resin. When the content of the colorant is more than 15 parts by mass, the transparency is lowered, and in addition, the reproducibility of intermediate colors as typified by human skin color is likely to be lowered, and further, the charging property of the toner is stabilized. And the target charge amount is difficult to obtain. On the other hand, when the content of the colorant is less than 1 part by mass, it is difficult to obtain the desired coloring power and it is difficult to obtain a high-quality image with a high image density.
[0079]
The color toner of the present invention may further contain an organometallic compound. The inclusion of the organometallic compound is a more preferable aspect in that the charge level can be adjusted, the rising of the charge can be improved, and the thermal melting characteristics of the toner can be improved.
[0080]
The organometallic compound to be used is preferably an aromatic carboxylic acid derivative selected from aromatic oxycarboxylic acids and aromatic alkoxycarboxylic acids, and a metal compound of the aromatic carboxylic acid derivative. A valence or higher metal atom is preferred.
[0081]
Mg as a divalent metal²⁺, Ca²⁺, Sr²⁺, Pb²⁺, Fe²⁺, Co²⁺, Ni²⁺, Zn²⁺, Cu²⁺, Are mentioned. As a divalent metal, Zn²⁺, Ca²⁺, Mg²⁺, Sr²⁺Is preferred. Al for trivalent or higher metals³⁺, Cr³⁺, Fe³⁺, Ni³⁺, Is given. Among these trivalent or higher metals, Al is preferable.³⁺, Cr³⁺And particularly preferred is Al.³⁺It is.
[0082]
In the present invention, the organometallic compound is particularly preferably an aluminum compound of di-tert-butylsalicylic acid.
[0083]
An aromatic carboxylic acid derivative selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid, and a metal compound of the aromatic carboxylic acid derivative, for example, dissolve oxycarboxylic acid and alkoxycarboxylic acid in an aqueous sodium hydroxide solution, An aqueous solution in which a metal atom having a valence of 2 or more is melted is dropped into an aqueous sodium hydroxide solution, heated and stirred, then adjusted to the pH of the aqueous solution, cooled to room temperature, and then washed with filtered water to obtain an aromatic oxycarboxylic acid. And metal compounds of aromatic alkoxycarboxylic acids can be synthesized. However, it is not limited only to the above synthesis method.
[0084]
The organometallic compound is preferably contained in an amount of 0.1 to 10% by mass based on the mass of the color toner. With this content, the initial fluctuation of the charge amount of the toner is small, and an absolute charge amount necessary for development can be easily obtained. As a result, it is possible to suppress image quality deterioration such as “fogging” and image density reduction.
[0085]
<About the magnetic toner for black of the present invention>
The black magnetic toner used in the present invention will be described.
[0086]
The magnetic toner contains a magnetic material. In that case, the magnetic material also has a function as a colorant. Examples of magnetic materials include iron oxides such as magnetite, maghemite, and ferrite, and iron oxides including other metal oxides; metals such as Fe, Co, and Ni, or these metals and Al, Co, Cu, Pb, Examples thereof include alloys with metals such as Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, and V, and mixtures thereof.
[0087]
For example, as a magnetic material, triiron tetroxide (Fe_ThreeO_Four), Iron sesquioxide (γ-Fe₂O_Three), Zinc iron oxide (ZnFe₂O_Four), Iron yttrium oxide (Y_ThreeFe_FiveO₁₂), Iron cadmium oxide (CdFe₂O_Four), Gadolinium oxide (Gd)_ThreeFe_Five-O₁₂), Copper iron oxide (CuFe₂O_Four), Lead iron oxide (PbFe₁₂-O₁₉), Nickel iron oxide (NiFe)₂O_Four), Neodymium iron oxide (NdFe₂O_Three), Iron barium oxide (BaFe)₁₂O₁₉), Magnesium iron oxide (MgFe₂O_Four), Iron manganese oxide (MnFe₂O_Four), Iron lanthanum oxide (LaFeO)_Three), Iron powder (Fe), cobalt powder (Co), nickel powder (Ni) and the like. The preferred magnetic material is triiron tetroxide, magnetic ferrite or gamma-iron sesquioxide fine powder. The content of the magnetic material is preferably 15 to 85% by mass based on the weight of the toner.
[0088]
In the magnetic toner for black, since the resistance value tends to be lower than that of other color toners, it is more difficult to stabilize the charging. In the present invention, in order to improve this point, intensive studies were conducted.
[0089]
As a result, it is preferable that the magnetic toner for black contains magnetic iron oxide. In particular, the developability is improved by the influence of a slight amount of Si or Al element on the surface of the magnetic material, and the miscibility with other color toners is improved. It has been found to improve.
[0090]
Specifically, it has been found that the magnetic iron oxide is effective to contain 0.3 to 1.4% by weight of an aluminum element or a silicon element based on the iron element. As a result, it is possible to reduce the difference in charging stability and developability with other color toners, and to obtain an image that is faithful to the original and has no variation.
[0091]
The magnetic iron oxide is a ratio of the content BSi of silicon element present in the iron oxide dissolution rate of the magnetic iron oxide up to 20% by weight and the content ASi of total silicon element present in the magnetic iron oxide. (BSi / ASi) × 100 is more preferably 35 to 85%, and further preferably 40 to 80%.
[0092]
When (BSi / ASi) × 100 is smaller than 35%, the dispersion of the magnetic substance in the toner is deteriorated, and the developing property, particularly the image uniformity may be unstable. Moreover, the tendency for the resolution of a character image to be inferior is seen. When (BSi / ASi) × 100 is larger than 85%, a large amount of silicon element is present in the surface layer portion of magnetic iron oxide, and the toner charge amount distribution is likely to be widened. Is likely to occur.
[0093]
In the present invention, the magnetic iron oxide has a number average particle diameter based on the measurement method described below, preferably 0.05 to 1.00 μm, more preferably 0.10 to 0.40 μm. From the viewpoint of dispersibility of the toner in the binder resin and uniformity of charging.
[0094]
When the number average particle diameter of the magnetic iron oxide is larger than 1.00 μm, the number of magnetic iron oxide particles contained in the toner is reduced, so that the distribution of the magnetic iron oxide in the binder resin is biased. The charge uniformity is easily lost. When the number average particle size of the magnetic iron oxide is smaller than 0.05 μm, the adhesion between the magnetic iron oxide particles is increased, and the dispersibility in the binder resin is deteriorated.
[0095]
By using a magnetic material that satisfies the above conditions, the black toner can be mixed with other color toners, and more uniform color reproduction can be performed. Further, the fixing property is not adversely affected.
[0096]
In the present invention, the measurement method related to the magnetic material used for the black toner was performed as follows. In addition, it measured similarly also in the below-mentioned Example.
[0097]
(4)Measurement of metallic elements
In the present invention, the content of metal elements other than iron in magnetic iron oxide (based on iron elements), the dissolution rate of iron elements, and the content of metal elements other than iron with respect to the iron element dissolution rate are as follows: Can be obtained by various methods.
[0098]
For example, about 3 liters of deionized water is put into a 5 liter beaker and heated in a water bath so that the temperature is 45 to 50 ° C. About 25 g of magnetic iron oxide slurried with about 400 ml of deionized water is added to a 5-liter beaker along with the deionized water while being washed with about 300 ml of deionized water.
[0099]
Next, while maintaining the temperature at about 50 ° C. and the stirring speed at about 200 rpm, a special grade hydrochloric acid or a mixed acid of hydrochloric acid and hydrofluoric acid is added to start dissolution. At this time, the aqueous hydrochloric acid solution is about 3N. About 20 ml is sampled several times during the period from the start of dissolution until all are dissolved and transparent, and filtered through a 0.1 μ membrane filter, and the filtrate is collected. The filtrate is subjected to plasma emission spectroscopy (ICP) to quantify iron elements and metal elements other than iron elements. The iron element dissolution rate for each sample is calculated by the following formula.
[0100]
[Expression 1]

[0101]
The content of metal elements other than iron elements for each sample is calculated by the following equation.
[0102]
[Expression 2]

[0103]
The total content A of the metal elements other than the iron element of the magnetic iron oxide is defined as the metal element concentration (mg / l) per unit weight of the magnetic iron oxide after all are dissolved. Further, the content B of the metal element other than the iron element of the magnetic iron oxide is the concentration of the metal element other than the iron element per unit weight of the magnetic iron oxide detected when the dissolution rate of the magnetic iron oxide is 20% ( mg / l).
[0104]
(5)Measurement of number average particle size of magnetic iron oxide
100 particles on the photograph were randomly selected from a transmission electron micrograph (magnification 30000 times), the particle diameter was measured, and the average value was taken as the number average particle diameter.
[0105]
<About magnetic toner for black and non-magnetic toner for color>
A fluidity improver may be externally added to the magnetic toner for black and the non-magnetic toner for color. Here, the fluidity improver has a function of increasing fluidity by being externally added to the toner particles, and is added from the viewpoint of improving the image quality.
[0106]
For example, fluororesin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder; silica fine powder by wet production method, silica fine powder such as silica fine powder by dry production method, these silica fine powders as silane coupling agent, A treated silica fine powder subjected to a surface treatment with a treating agent such as a titanium coupling agent or silicon oil; a titanium oxide fine powder; an alumina fine powder, a treated titanium oxide fine powder, or a treated alumina oxide fine powder is used.
[0107]
The fluidity improver has a specific surface area of 30 m due to nitrogen adsorption measured by the BET method.²/ G or more, preferably 50 m²/ G or more gives good results. The fluidity improver 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 particles.
[0108]
The measurement by the BET method described above was performed as follows.
(6)The BET specific surface area is determined by the BET multipoint method using a fully automatic gas adsorption amount measuring device: Autosorb 1 manufactured by Yuasa Ionics Co., Ltd., using nitrogen gas as the adsorption gas. As sample pretreatment, deaeration is performed at a temperature of 50 ° C. for 10 hours.
[0109]
The toner particles (including magnetic type and nonmagnetic type) of the present invention can be obtained by the method described below. In other words, the necessary constituents are selected from binder resin, colorant, wax, organometallic compound, magnetic substance and other optional additives, and these constituents are sufficiently mixed with a mixer such as a Henschel mixer or a ball mill. Mix, melt, knead, and knead using a kneader, extruder, etc. Toner particles can be obtained. When obtaining a toner having a fluidity improver on the surface of the toner particles, the fluidity improver and the toner particles may be further mixed with a mixer such as a Henschel mixer.
[0110]
<Magnetic Carrier for Performing Color Development of the Present Invention>
Examples of the carrier used for the two-component developer of the present invention include surface oxidized or unoxidized iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earth and the like, and alloys or oxides and ferrite thereof. Can be used.
[0111]
In particular, Mn—Mg—Fe three-element magnetic ferrite particles formed mainly of manganese, magnesium and iron components are preferred as carrier particles, and Mn—Mg—Fe three-element magnetic ferrite particles are preferably silicon. It is particularly preferable to use 0.001 to 1% by mass (more preferably 0.005 to 0.5% by mass) of an element when a silicone resin is used as a coating resin for magnetic ferrite particles.
[0112]
The magnetic carrier particles are preferably coated with a resin, and the resin is preferably a silicone resin. In particular, the nitrogen-containing silicone resin or the modified silicone resin produced by the reaction of the nitrogen-containing silane coupling agent and the silicone resin is capable of imparting a negative triboelectric charge to the color toner of the present invention, environmental stability, carrier This is preferable in terms of suppression of surface contamination. The magnetic carrier preferably has an average particle diameter of 15 to 70 μm (more preferably 25 to 60 μm) in relation to the weight average particle diameter of the color toner.
[0113]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples.
[0114]
Specific production examples of the toner of the present invention will be described, but the present invention is not limited to these toner production examples.
[0115]
(Hybrid resin production example 1)
As a vinyl copolymer, 1.8 mol of styrene, 0.21 mol of 2-ethylhexyl acrylate, 0.15 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, 6.9 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 3. 0 mol, 3.0 mol of succinic acid, 2.0 mol of trimellitic anhydride, 4.9 mol of fumaric acid and 0.2 g of dibutyltin oxide are placed in a 4-liter 4-neck flask made of glass, a thermometer, a stir bar, 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. Subsequently, the temperature was raised to 200 ° C. and reacted for 4 hours to obtain a hybrid resin (1). In this production example, the viscoelastic properties of the present invention were obtained by optimizing the production conditions of the polyester resin and the hybrid resin with the styrene-acrylic resin. The results of molecular weight measurement by GPC are shown in Table 1.
[0116]
[Table 1]

[0117]
(Hybrid resin production example 2)
A hybrid resin (2) was obtained by reacting in the same manner as in the hybrid resin production example 1 except that 3.9 mol of styrene, 0.07 mol of α-methylstyrene dimer, and 0.1 mol of dicumyl peroxide were used. . The results of molecular weight measurement by GPC are shown in Table 1.
[0118]
(Hybrid resin production example 3)
Hybrid resin production except that 3.9 mol of maleic acid and 3.6 mol of itaconic acid are used instead of 4.9 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.
[0119]
(Hybrid resin production example 4)
Instead of terephthalic acid 3.0 mol and trimellitic anhydride 2.0 mol, trimellitic anhydride 5.2 mol was reacted in the same manner as in hybrid resin production example 1 to obtain hybrid resin (4). The results of molecular weight measurement by GPC are shown in Table 1.
[0120]
(Polyester resin production example 1)
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, 1.1 mol of trimellitic anhydride, 2.4 mol of fumaric acid and 0.1 g of dibutyltin oxide are placed in a 4-liter 4-neck flask made of glass, a thermometer, a stir bar, a condenser and a nitrogen inlet tube Was installed in a mantle heater. Under a nitrogen atmosphere, reaction was performed at 215 ° C. for 5 hours to obtain a polyester resin (1). The results of molecular weight measurement by GPC are shown in Table 1.
[0121]
(Polyester resin production example 2)
1.6 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 3.3 mol of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, A polyester resin (2) was obtained by reacting in the same manner as above with a monomer structure of 1.6 mol of terephthalic acid, 0.3 mol of trimellitic anhydride, and 3.2 mol of fumaric acid. The results of molecular weight measurement by GPC are shown in Table 1.
[0122]
(Production example 1 of vinyl resin)
1000 ml of toluene solvent and vinyl copolymer, 2.3 mol of styrene, 0.25 mol of n-butyl acrylate, 0.07 mol of monobutyl malate, 0.11 mol of di-t-butyl peroxide, thermometer, stainless steel stirring rod Into a 3 liter four-necked flask equipped with a flow-down condenser and a nitrogen introduction tube, the reaction was carried out in a mantle heater while stirring at 120 ° C. in a nitrogen atmosphere while refluxing toluene, and a vinyl resin (1 ) The results of molecular weight measurement by GPC are shown in Table 1.
[0123]
Next, Table 2 shows the waxes used in the present invention.
[0124]
[Table 2]

[0125]
<Color toner production example 1>
Cyan toner 1 was prepared as an example of a non-magnetic color toner by the following method.
Hybrid resin (1) 100 parts by mass
5 parts by weight of wax (A)
C. I. Pigment Blue 15: 3 5 parts by mass
Di-tert-butylsalicylic acid aluminum complex 6 parts by mass
Was sufficiently premixed with a Henschel mixer, melt-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 by a multi-division classifier to obtain cyan toner particles having a weight average particle size of 7.6 μm.
[0126]
For 100 parts by mass of the cyan toner particles, i-C_FourH₉Si (OCH_Three)_Three: Hydrophobic aluminum oxide treated with 25 parts by mass (measurement result by BET method 170 m²/ G) Cyan toner 1 was prepared by combining 1.1 parts by mass. Table 1 shows the measurement results of the storage elastic modulus and endothermic peak of the color toner.
[0127]
<Color toner production example 2>
Cyan toner 2 was obtained in the same manner as in color toner production example 1 except that hybrid resin (2) was used instead of hybrid resin (1). Table 1 shows the measurement results of the color toner.
[0128]
<referenceColor toner production example 3>
  Instead of the hybrid resin (1), a mixture of 50 parts by mass of the polyester resin (1) and 50 parts by mass of the hybrid resin (1) was used, and 8 parts by mass of an aluminum di-tert-butylsalicylate complex was used. Except for this, cyan toner 3 was obtained in the same manner as in color toner production example 1. Table 1 shows the measurement results of the color toner.
[0129]
<referenceColor toner production example 4>
  Cyan toner 4 was obtained in the same manner as in color toner production example 1 except that hybrid resin (3) was used instead of hybrid resin (1) and that 9.5 parts by mass of di-tert-butylsalicylic acid aluminum complex was used. . Table 1 shows the measurement results of the color toner.
[0130]
<Color toner production example 5>
Cyan toner 5 was obtained in the same manner as in color toner production example 1 except that wax (B) was used instead of wax (A). Table 1 shows the measurement results of the color toner.
[0131]
<referenceColor toner production example 6>
  A cyan toner was obtained in the same manner as in Color Toner Production Example 1 except that 2 parts by mass of aluminum di-tert-butylsalicylate was used. Table 1 shows the measurement results of the color toner.
[0132]
<referenceColor toner production example 7>
  Cyan toner 7 was obtained in the same manner as in Color toner production example 1 except that 3 parts by mass of di-tert-butylsalicylic acid aluminum complex was used and that wax (D) was used instead of wax (A). Table 1 shows the measurement results of the color toner.
[0133]
<Example 8 of color toner production>
Cyan toner 8 was obtained in the same manner as in color toner production example 1 except that the di-tert-butylsalicylate aluminum complex was not used. Table 1 shows the measurement results of the color toner.
[0134]
<Color toner production example 9>
C. I. Pigment Blue 15: 3 instead of C.I. I. A magenta toner 1 was obtained in the same manner as in Color Toner Production Example 1 except that 6 parts by mass of Pigment Red 202 was used. Table 1 shows the measurement results of the color toner.
[0135]
<Example 10 of color toner production>
  C. I. Pigment Blue 15: 3 instead of C.I. I. 4 parts by weight of Pigment Yellow 17AndOtherwise, yellow toner 1 was obtained in the same manner as in color toner production example 1. Table 1 shows the measurement results of the color toner.
[0136]
<Color toner production example 11>
Cyan toner 9 was obtained in the same manner as in Color toner production example 1 except that 6 parts by mass of the zinc di-tert-butylsalicylate complex was used. Table 1 shows the measurement results of the color toner.
[0137]
<Comparative Toner Production Example 1>
The cyan toner 10 was prepared in the same manner as in the color toner production example 1 except that the hybrid resin (4) was used instead of the hybrid resin (1), and 7.5 parts by mass of di-tert-butylsalicylic acid aluminum complex was used. Obtained. Table 1 shows the measurement results of the color toner.
[0138]
<Comparative Toner Production Example 2>
Cyan toner 11 was obtained in the same manner as in color toner production example 1 except that polyester resin (2) was used instead of hybrid resin (1) and that 4 parts by mass of di-tert-butylsalicylic acid aluminum complex was used. . Table 1 shows the measurement results of the color toner.
[0139]
<Comparative Toner Production Example 3>
Cyan toner 12 in the same manner as in color toner production example 1 except that vinyl resin (1) was used instead of hybrid resin (1) and 7.5 parts by mass of aluminum di-tert-butylsalicylate complex was used. Got. Table 1 shows the measurement results of the color toner.
[0140]
<Comparative Toner Production Example 4>
Cyan toner 13 was obtained in the same manner as in color toner production example 1 except that polyester resin (1) was used instead of hybrid resin (1), and 12 parts by mass of di-tert-butylsalicylic acid aluminum complex was used. . Table 1 shows the measurement results of the color toner.
[0141]
Comparative Toner Production Example 5>
Cyan toner 14 was obtained in the same manner as in color toner production example 1 except that wax (E) was used instead of wax (A). Table 1 shows the measurement results of the color toner.
[0142]
<Comparative Toner Production Example 6>
In the color toner production example 1, cyan toner 15 was obtained in the same manner except that a low melting point paraffin wax (C) was used instead of the purified normal paraffin wax (A). Table 1 shows the measurement results of the color toner.
[0143]
<Black toner production example 1>
Black toner 1 was prepared as an example of magnetic black toner by the following method.
Hybrid resin (1) 100 parts by mass
7 parts by weight of wax (A)
90 parts by mass of magnetic iron oxide 1
9 parts by mass of di-tert-butylsalicylate aluminum complex
Was sufficiently premixed with a Henschel mixer, melt-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 black toner 1 having a weight average particle diameter of 8.2 μm. The characteristics of the magnetic iron oxide used are as shown in Table 3.
[0144]
[Table 3]

[0145]
<Black toner production example 2>
Black toner 2 having a weight average particle diameter of 8.3 μm was obtained in the same manner as in black toner production example 1 except that 45 parts by mass of magnetic iron oxide 2 was used. Table 3 shows the measurement results of the black toner 2.
[0146]
<Black toner production example 3>
A black toner 3 having a weight average particle diameter of 8.4 μm was obtained in the same manner as in black toner production example 1 except that 45 parts by mass of magnetic iron oxide 3 was used. The measurement results of the black toner 3 are shown in Table 3.
[0147]
[Example 1]
  Cyan toner 1 obtained in Color Toner Production Example 1 and a magnetic surface coated with silicone resin
Ferrite ferrite carrier particles (average particle size 50 μm) were mixed so that the toner concentration was 6% by mass to obtain a two-component cyan developer 1.
[0148]
As an evaluation machine, a color copying machine CP-660 (manufactured by Canon) in which a color developer was modified from a non-magnetic one-component toner to a non-magnetic two-component developer was used.
[0149]
Cyan developer 1 is loaded in the color station of this evaluation machine, and the original image with an image area ratio of 20% is obtained in a high-temperature and high-humidity environment (30 ° C, 80%) and a normal temperature and low-humidity environment (23 ° C, 5%). Using a manuscript, the applied toner amount per unit area is 0.7mg / cm²The printing durability test was performed by outputting 10,000 unfixed images.
[0150]
The fixable region of the output unfixed image was evaluated by modifying the fixing unit (fixing oil-less) of the color copying machine CP-660 (manufactured by Canon) so that the fixing temperature can be manually set.
[0151]
The OHP transparency is measured using a Shimadzu spectrophotometer UV2200 (manufactured by Shimadzu Corporation), the transmittance of the OHP film alone is 100%, magenta toner: 650 nm, cyan toner: 500 nm, yellow toner In the case of: Measure the transmittance at the maximum absorption wavelength at 600 nm. As an evaluation method, A: 85% or more, B: 75 to 85%, C: 65 to 75%, and D: less than 65% are displayed.
[0152]
For transferability, a color copier CP-660 (manufactured by Canon) was used to perform a durability test on 10,000 sheets in a normal temperature and low humidity environment (23 ° C, 5%) to develop a solid image before and after durability. After transferring, the amount of toner before transfer on the photoreceptor (per unit area) and the amount of toner on the transfer material (per unit area) were measured, respectively, and determined by the following equations.
[0153]
[Equation 3]

[0154]
The blocking resistance of the color toner was evaluated by leaving it in an oven at 50 ° C. for 2 weeks. As the evaluation, the level of cohesiveness by visual observation was determined.
[0155]
The color toner aggregation 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)
Cyan developer 1 had excellent transferability, good glossiness and OHT transparency, and showed excellent fixing properties and blocking resistance. Moreover, environmental stability was also favorable. The results are shown in Table 4. In Table 4, the image density (Macbeth) under each environment indicates a value after initial / endurance.
[0156]
[Table 4]

[0157]
[Example 2]
  Using cyan toner 2, cyan developer 2 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the cyan developer 2 was excellent in transferability, good in glossiness and OHT permeability, and exhibited excellent fixing properties, blocking resistance, and environmental stability. The results are shown in Table 4.
[0158]
[Reference Example 3]
  Using cyan toner 3, cyan developer 3 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the obtained image was excellent in transferability, good in glossiness and OHT permeability, and exhibited excellent fixing properties, blocking resistance, and environmental stability. The results are shown in Table 4.
[0159]
[Reference Example 4]
  Using cyan toner 4, cyan developer 4 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the obtained image had slightly low transferability in a low-humidity environment, slightly lacked glossiness, and showed excellent fixing properties and blocking resistance although it had a slightly lower OHT permeability. The results are shown in Table 4.
[0160]
[Example 5]
  Using cyan toner 5, cyan developer 5 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the obtained image was excellent in transferability, good in glossiness and OHT permeability, and exhibited excellent fixing properties, blocking resistance, and environmental stability. The results are shown in Table 4.
[0161]
[Reference Example 6]
  Using cyan toner 6, cyan developer 6 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the obtained image was excellent in transferability, good in glossiness and OHT transparency, and exhibited excellent fixing properties and environmental stability. Although the blocking resistance was somewhat deteriorated, it was not at a level causing a practical problem. The results are shown in Table 4.
[0162]
[Reference Example 7]
  Using cyan toner 7, cyan developer 7 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the obtained image has a slightly poor OHP permeability due to the high crystallinity of the wax, and since it has a high melting point, it is difficult for the wax to come out on the toner surface at the time of fixing, and the low temperature fixability is slightly deteriorated. However, relatively good results were obtained. Further, the transferability of the obtained image was good, and the blocking resistance and environmental stability were also good. The results are shown in Table 4.
[0163]
[Example 8]
  Using cyan toner 8, cyan developer 8 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, since no di-tert-butylsalicylate complex was contained, no problem was caused except that the charge amount of the toner was slightly lowered and the high temperature side of the fixing temperature region was slightly narrowed. . The results are shown in Table 4.
[0164]
[Example 9]
  Using magenta toner 1, magenta developer 1 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, it was possible to obtain a high-definition full-color image with good glossiness and OHT transparency. The results are shown in Table 4.
[0165]
[Example 10]
  Using yellow toner 1, yellow developer 1 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, it was possible to obtain a high-definition full-color image with good gloss and OHT transparency.. ResultThe results are shown in Table 4.
[0166]
[Example 11]
  Using cyan toner 9, cyan developer 9 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the obtained image showed a relatively good result although the image density and the transfer rate were slightly lowered after the endurance and the blocking resistance was slightly deteriorated. The results are shown in Table 4.
[0167]
[Example 12]
  Using black toner 1, cyan toner 1, yellow toner 1, and magenta toner 1 in combination, color toner is the same as in Example 1, black toner is prepared as a single component developer, and each item is evaluated. did. As a result, the obtained image was excellent in color reproducibility, the character image was clear and high resolution was obtained, and a good result was shown. The results are shown in Table 4. For color image quality reproducibility, photo manuscript and black manuscript manuscript were used, ◎: almost all colors and characters were faithfully reproduced, ○: blackish part of photo image part was slightly unclear, △: photograph The blackish part of the image part is slightly unclear, indicating that the resolution of the character image is slightly inferior. The image density, transfer rate, and anti-blocking property are the results of the black toner alone.
[0168]
[Example 13]
  Each developer was prepared in the same manner as in Example 12 using a combination of black toner 2, cyan toner 1, yellow toner 1, and magenta toner 1, and each item was evaluated. As a result, although the obtained image was slightly inferior in color reproducibility in the dark color portion, the character image was clear and high resolution was obtained, indicating a good result. The results are shown in Table 4. The image density, transfer rate, and anti-blocking property are the results of the black toner alone.
[0169]
[Example 14]
  Each developer was prepared in the same manner as in Example 12 using a combination of black toner 3, cyan toner 1, yellow toner 1, and magenta toner 1, and each item was evaluated. As a result, the obtained image showed good results although the color reproducibility of the dark color portion and the resolution of the character image were slightly inferior. The results are shown in Table 4. The image density, transfer rate, and anti-blocking property are the results of the black toner alone.
[0170]
[Comparative Example 1]
  Using cyan toner 10, cyan developer 10 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the cyan toner 10 becomes a very hard toner, and the storage elastic modulus (G ′₈₀) Is large, the glossiness and OHT permeability are poor, and it becomes difficult for the wax to come out on the toner surface during fixing, which deteriorates the low-temperature fixability. Further, in the high temperature and high humidity environment, a slight amount of fusion to the drum occurred, and the charge amount increased remarkably in the low humidity environment, and a sufficient image density could not be obtained. The results are shown in Table 4.
[0171]
[Comparative Example 2]
  Using cyan toner 11, cyan developer 11 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the cyan toner 11 became a very soft toner, the blocking resistance deteriorated, and the high temperature offset resistance deteriorated. In a high temperature and high humidity environment, remarkable drum fusion and filming occurred. Further, since the content of the organometallic compound is large, the charge amount is remarkably increased in a low humidity environment, and a sufficient image density cannot be obtained. The results are shown in Table 4.
[0172]
[Comparative Example 3]
  Using cyan toner 12, cyan developer 12 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the cyan toner 12 was poor in glossiness and OHT transparency, and the fixing temperature range was narrowed. Further, some fusion to the drum occurred in a high temperature and high humidity environment. The results are shown in Table 4.
[0173]
[Comparative Example 4]
  Using cyan toner 13, cyan developer 13 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the cyan toner 13 deteriorated in glossiness and OHT transparency. Further, some fusion to the drum occurred in a high temperature and high humidity environment. The results are shown in Table 4.
[0174]
[Comparative Example 5]
  Using cyan toner 14, cyan developer 14 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the high melting point makes it difficult for the wax to come out on the toner surface during fixing, which deteriorates the low-temperature fixability and the OHT permeability. Table 4 shows the charging results of the toner.
[0175]
[Comparative Example 6]
  Using cyan toner 15, cyan developer 15 was prepared in the same manner as in Example 1, and each item was evaluated. As a result, the fogging and scattering deteriorated and the durability was interrupted after the durability of 1,000 sheets passed. In addition, toner fluidity was poor and transferability was poor from the beginning. Cyan Toner 15. contains a low melting point wax, so the fixability is insufficient, and the wax comes out on the surface of the toner, especially in a high temperature environment. It is thought that deteriorated. In a high temperature and high humidity environment, remarkable drum fusion and filming occurred. The results are shown in Table 4.
[0176]
【The invention's effect】
According to the present invention, when an OPC (organic photoconductor) photoconductor is mounted on a full-color machine, a color toner that can form an image excellent in durability and stability and satisfying high definition, an image forming method having the color toner, and An image forming apparatus can be provided. Specifically, the toner does not fuse to the surface of the photoconductor, filming can be reduced, transparency in OHP is improved, the problem of high temperature offset resistance is solved without hindering the low temperature fixing during fixing, and the color mixing degree is also improved. An excellent color toner, an image forming method and an image forming apparatus having the color toner can be provided.
[Brief description of the drawings]
FIG. 1 is a diagram illustrating an image forming apparatus according to an embodiment of the present invention.
FIG. 2 is a schematic view of developing means.
(A) The figure which shows an example of the image development means using a one-component developer.
FIG. 4B is a diagram illustrating an example of a developing unit that uses a two-component developer.

Claims (11)

An electrostatic latent image forming step for forming an electrostatic latent image on an image carrier using an organic photoconductor, and transferring toner to the electrostatic latent image formed on the image carrier to form the latent image A developing process for forming and developing a corresponding toner image, a transfer process for electrostatically transferring the toner image formed on the image carrier onto a transfer material, and fixing the electrostatically transferred toner image by a fixing member A one-component developer composed of magnetic toner for performing black development, a magnetic carrier for performing color development, and a two-component developer composed of non-magnetic toner. The non-magnetic toner is a toner produced by a melt-kneading and pulverizing method, wherein the non-magnetic toner includes at least a binder resin, a colorant, and a wax. there are, the binder resin A hybrid resin having a polyester unit and a vinyl copolymer unit, the viscoelastic properties, storage elastic modulus at a temperature of ₈₀ ℃ (G '80) is ^{1 × 10 6 ~1 × 10 8} [dN / m ² ], the storage elastic modulus (G ′ _120-180 ) at a temperature of _{120 to 180} ° C. is in the range of 1 × 10 ^{4 to} 5 × 10 ⁵ [dN / m ² ], and differential scanning calorimetry ( An image forming method comprising: a color toner having a peak temperature of a maximum endothermic peak in a temperature range of 30 to 200 ° C. in a temperature range of 50 to 110 ° C. in an endothermic curve in DSC) measurement.   2. The color toner has a peak temperature of a maximum endothermic peak in a range of 30 to 200 ° C. in an endothermic curve in differential scanning calorimetry (DSC) measurement in a range of 55 to 100 ° C. 3. The image forming method described.   2. The color toner has a peak temperature of a maximum endothermic peak in a temperature range of 30 to 200 ° C. in a range of 60 to 90 ° C. in an endothermic curve in differential scanning calorimetry (DSC) measurement. The image forming method described. The binder resin has a main peak in the molecular weight region of 6000 to 8000 in the molecular weight distribution by gel permeation chromatography (GPC), and the ratio (Mw) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). / Mn) of the image forming method according to any one of claims 1 to 3, characterized in that 300 or more. In the molecular weight distribution by gel permeation chromatography (GPC), the binder resin has a main peak in the molecular weight region of 6000 to 8000, and the ratio (Mw) between the weight average molecular weight (Mw) and the number average molecular weight (Mn). / Mn) is 500 or more, The image forming method of any one of Claims 1-3 characterized by the above-mentioned. The color toner image forming method according to any one of claims 1 to 5, characterized in that an organic metal compound. The image forming method according to claim 6 , wherein the organometallic compound is a metal compound of an aromatic carboxylic acid derivative. The image forming method according to claim 7 , wherein the metal compound of the aromatic carboxylic acid derivative is an aluminum compound of an aromatic carboxylic acid derivative. The image forming method according to claim 6 , wherein the organometallic compound is contained in the color toner in an amount of 0.1 to 10% by mass based on the mass of the color toner. 2. The magnetic toner for performing black development contains at least magnetic iron oxide, and the magnetic iron oxide contains 0.3 to 1.4% of Si element or Al element. 10. The image forming method according to any one of items 9 to 9 . The magnetic toner for black development contains at least magnetic iron oxide, and the magnetic iron oxide has a silicon element content BSi that is present up to 20 wt% of the iron element dissolution rate of the magnetic iron oxide. 11. The ratio (BSi / ASi) × 100 of the total silicon element content ASi present in the magnetic iron oxide is 35 to 85%, according to any one of claims 1 to 10 . Image forming method.

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