JP3657917B2 - Toner for developing electrostatic image, full color toner kit, image forming method and image forming apparatus - Google Patents

Description

【００５１】
（分子量）
ＧＰＣ（ゲルパーミエーションクロマトグラフィー）による数平均分子量（Ｍｎ）、重量平均分子量（Ｍｗ）およびピーク分子量Ｍｐの測定は、以下のように行った。試料８０ｍｇをＴＨＦ１０ｍｌに溶解して試料液を調製し、５μｍのフィルターで濾過して、この試料液１００μｌをカラムに注入し、下記の条件で保持時間の測定を行う。また、平均分子量既知のポリスチレンを標準物質として用いて、保持時間を測定して、あらかじめ作成しておいた検量線から試料の数平均分子量をポリスチレン換算で求めた。

【００５２】
（針入度、耐熱保存性）
トナーを１０ｇずつ計量し、２０ｃｃのガラス容器に入れ、５０℃にセットした恒温槽に５時間放置した後、針入度計で針入度を測定した。
【００５３】
（バインダー樹脂）
本発明で用いるトナーのバインダー樹脂としては、ポリスチレン、ポリｐ−クロロスチレン、ポリビニルトルエンなどのスチレンおよびその置換体の重合体；スチレン−ｐ−クロロスチレン共重合体、スチレン−プロピレン共重合体、スチレン−ビニルトルエン共重合体、スチレン−ビニルナフタリン共重合体、スチレン−アクリル酸メチル共重合体、スチレン−アクリル酸エチル共重合体、スチレン−アクリル酸ブチル共重合体、スチレン−アクリル酸オクチル共重合体、スチレン−メタクリル酸メチル共重合体、スチレン−メタクリル酸エチル共重合体、スチレン−メタクリル酸ブチル共重合体、スチレン−α−クロルメタクリル酸メチル共重合体、スチレン−アクリロニトリル共重合体、スチレン−ビニルメチルケトン共重合体、スチレン−ブタジエン共重合体、スチレン−イソプレン共重合体、スチレン−アクリロニトリル−インデン共重合体、スチレン−マレイン酸共重合体、スチレン−マレイン酸エステル共重合体などのスチレン系共重合体；ポリメチルメタクリレート、ポリブチルメタクリレート、ポリ塩化ビニル、ポリ酢酸ビニル、ポリエチレン、ポリプロピレン、ポリエステル、エポキシ樹脂、ポリオール樹脂、ポリウレタン、ポリアミド、ポリビニルブチラール、ポリアクリル酸樹脂、ロジン、変性ロジン、テルペン樹脂、脂肪族叉は脂環族炭化水素樹脂、芳香族系石油樹脂、塩素化パラフィン、パラフィンワックスなどが挙げられ、単独あるいは混合して使用できる。特に、ポリオール樹脂、ポリエステル樹脂がより好ましい。
【００５４】
また、バインダー樹脂のポリオール樹脂末端が不活性であると環境安定性、有害性の少ないトナーとすることができる。
本発明に用いられるポリオール樹脂（エポキシ樹脂）としては、ビスフェノールＡやビスフェノールＦ等のビスフェノールとエピクロロヒドリンを結合して得られたものを用いるのが好ましい。エポキシ樹脂は、安定した定着特性や光沢を得るために、数平均分子量の相違する少なくとも２種以上のビスフェノールＡ型エポキシ樹脂で、低分子量成分の数平均分子量が３６０〜２０００であり、高分子量成分の数平均分子量が３０００〜１００００であることを好ましい。更に低分子量成分が２０〜５０ｗｔ％、高分子量成分が５〜４０ｗｔ％であることが好ましい。低分子量成分が多すぎたり分子量３６０よりさらに低分子の場合は、光沢が出すぎたり、さらには保存性の悪化の可能性がある。また、高分子量成分が多すぎたり分子量１００００よりさらに高分子の場合は、光沢が不足したり、さらには定着性の悪化の可能性がある。
【００５５】
本発明で用いられる樹脂化合物として、２価フェノールのアルキレンオキサイド付加物としては以下のものが例示される。エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド及びこれらの混合物とビスフェノールＡやビスフェノールＦ等のビスフェノールとの反応生成物が挙げられる。得られた付加物をエピクロロヒドリンやβ−メチルエピクロロヒドリンでグリシジル化して用いてもよい。特に下記一般式（１）で表わされるビスフェノールＡのアルキレンオキサイド付加物のジグリシジルエーテルが好ましい。
【化１】

【００５６】
また、２価フェノールのアルキレンオキサイド付加物もしくはそのグリシジルエーテルが、ポリオール樹脂に対して１０〜４０ｗｔ％含まれていることが好ましい。ここで量が少ないとカールが増すなどの不具合が生じ、またｎ＋ｍが７以上であったり量が多すぎると光沢が出すぎたり、さらには保存性の悪化の可能性がある。本発明で用いられるエポキシ基と反応する活性水素を分子中に一個有する化合物としては、１価フェノール類、２級アミン類、カルボン酸類がある。１価フェノール類としては以下のものが例示される。フェノール、クレゾール、イソプロピルフェノール、アミノフェノール、ノニルフェノール、ドデシルフェノール、キシレノール、ｐ−クミルフェノール等が挙げられる。２級アミン類としては、ジエチルアミン、ジプロピルアミン、ジブチルアミン、Ｎ−メチル（エチル）ピペラジン、ピペリジンなどが挙げられる。また、カルボン酸類としては、プロピオン酸、カプロン酸などが挙げられる。
【００５７】
本発明で用いられるエポキシ基と反応する活性水素を分子中に２個以上有する化合物としては、２価フェノール類、多価フェノール類、多価カルボン酸類が挙げられる。２価フェノールとしてはビスフェノールＡやビスフェノールＦ等のビスフェノールが挙げられる。また、多価フェノール類としてはオルソクレゾールノボラック類、フェノールノボラック類、トリス（４−ヒドロキシフェニル）メタン、１−〔α−メチル−α−（４−ヒドロキシフェニル）エチル〕ベンゼンが例示される。多価カルボン酸類としては、マロン酸、コハク酸、グルタル酸、アジピン酸、マレイン酸、フマル酸、フタル酸、テレフタル酸、トリメリット酸、無水トリメリット酸が例示される。
【００５８】
また、該バインダー樹脂のエポキシ当量を、２００００以上に制御することで、樹脂の熱特性を制御できるとともに、反応残留物である低分子のエピクロロヒドリン等の量を低減することができ、安全性、樹脂特性ともに優れたトナーとすることができる。
【００５９】
ポリオール樹脂あるいは少なくとも主鎖にエポキシ樹脂部とポリオキシアルキレン部を有するポリオール樹脂を少なくとも含むことで、十分な耐圧縮強度、引張破断強度、環境安定性、安定した定着特性、コピー定着画像面の塩化ビニル系樹脂へのシートに密着時のシートへのトナー画像の転移防止を図ることができ、特にカラートナーに使用した場合カラー再現性、安定した光沢、コピー定着画像のカール防止等に効果をもたらしより好ましい。さらに少なくともポリオール樹脂部とポリエステル樹脂部を含むことで、耐圧縮強度とともに伸縮性と付着性のバランスのとれたトナーとなり、さらに安定した転写性、現像性、定着特性が得られたより好ましい。
【００６０】
樹脂としては、ポリエステル樹脂も好ましく使用することができ、各種のタイプのポリエステル樹脂が使用できるが、特に、以下に示す▲１▼〜▲３▼を反応させて形成したポリエステル樹脂であることが好ましい。
▲１▼ ２価のカルボン酸ならびにその低級アルキルエステル及び酸無水物のいずれかから選ばれる少なくとも一種、
▲２▼ 下記一般式（２）で示されるジオール成分
【化２】

（式中、Ｒ¹及びＲ²は、同一でも異なっていてもよく、炭素数２〜４のアルキレン基であり、またｘ、ｙは繰り返し単位の数であり、各々１以上であって、ｘ＋ｙ＝２〜１６である）
▲３▼ ３価以上の多価カルボン酸ならびにその低級アルキルエステル及び酸無水物、及び、３価以上の多価アルコールのいずれかから選ばれる少なくとも一種
ここで、▲１▼の２価カルボン酸ならびにその低級アルキルエステル及び酸無水物の一例としては、テレフタル酸、イソフタル酸、セバシン酸、イソデシルコハク酸、マレイン酸、フマル酸及びこれらのモノメチル、モノエチル、ジメチル及びジエチルエステル、及び無水フタル酸、無水マレイン酸等があり、特にテレフタル酸、イソフタル酸及びこれらのジメチルエステルが耐ブロッキング性及びコストの点で好ましい。これらの２価カルボン酸ならびにその低級アルキルエステル及び酸無水物はトナーの定着性や耐ブロッキング性に大きく影響する。すなわち、縮合度にもよるが、芳香族系のテレフタル酸、イソフタル酸等を多く用いると耐ブロッキング性は向上するが、定着性が低下する。逆に、セバシン酸、イソデシルコハク酸、マレイン酸、フマル酸等を多く用いると定着性は向上するが、耐ブロッキング性が低下する。従って、他のモノマー組成や比率、縮合度に合わせてこれらの２価カルボン酸類が適宜選定され、単独又は組合わせて使用される。
【００６１】
▲２▼の前記一般式（Ｉ）で示されるジオール成分の一例としては、ポリオキシプロピレン−（ｎ）−ポリオキシエチレン−（ｎ’）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシプロピレン−（ｎ）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシエチレン−（ｎ）−２，２−ビス（４−ヒドロキシフェニル）プロパン等が挙げられるが、特に、２．１≦ｎ≦２．５であるポリオキシプロピレン−（ｎ）−２，２−ビス（４−ヒドロキシフェニル）プロパン及び２．０≦ｎ≦２．５であるポリオキシエチレン−（ｎ）−２，２−ビス（４−ヒドロキシフェニル）プロパンが好ましい。このようなジオール成分は、ガラス転移温度を向上させ、反応を制御し易くするという利点がある。なお、ジオール成分として、エチレングリコール、ジエチレングリコール、１，２−ブタンジオール、１、３−ブタンジオール、１，４−ブタンジオール、ネオペンチルグリコール、プロピレングリコール等の脂肪族ジオールを使用することも可能である。
【００６２】
▲３▼の３価以上の多価カルボン酸ならびにその低級アルキルエステル及び酸無水物の一例としては、１，２，４−ベンゼントリカルボン酸（トリメリット酸）、１，３，５−ベンゼントリカルボン酸、１，２，４−シクロヘキサントリカルボン酸、２，５，７−ナフトレントリカルボン酸、１，２，４−ナフタレントリカルボン酸、１，２，４−ブタントリカルボン酸、１，２，５−ヘキサトリカルボン酸、１，３−ジカルボキシル−２−メチル−２−メチレンカルボキシプロパン、テトラ（メチレンカルボキシ）メタン、１，２，７，８−オクタンテトラカルボン酸、エンポール三量体酸及びこれらのモノメチル、モノエチル、ジメチルおよびジエチルエステル等が挙げられる。
【００６３】
また、▲３▼の３価以上の多価アルコールの一例としては、ソルビトール、１，２，３，６−ヘキサンテトロール、１，４−ソルビタン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、ショ糖、１，２，４−ブタントリオール、１，２，５−ペンタトリオール、グリセロール、ジグリセロール、２−メチルプロパントリオール、２−メチル−１，２，４−ブタントリオール、トリメチロールエタン、トリメチロールプロパン、１，３，５−トリヒドロキシメチルベンゼン等が挙げられる。
【００６４】
ここで、３価以上の多価単量体の配合割合は、単量体組成物全体の１〜３０モル％程度が適当である。１モル％以下の時には、トナーの耐オフセット性が低下し、また、耐久性も悪化しやすい。一方、３０モル％以上の時には、トナーの定着性が悪化しやすい。
【００６５】
これらの３価以上の多価単量体のうち、特にベンゼントリカルボン酸、これらの酸の無水物又はエステル等のベンゼントリカルボン酸類が好ましい。すなわち、ベンゼントリカルボン酸類を用いることにより、定着性と耐オフセット性の両立を図ることができる。
また、これらのポリエステル樹脂やポリオール樹脂は、高い架橋密度を持たせると、透明性や光沢度が得られにくくなるため、好ましくは、非架橋もしくは弱い架橋（ＴＨＦ不溶分が５％以下）であることが好ましい。
また、これらの結着樹脂の製造法は、特に限定されるものではなく、塊状重合、溶液重合、乳化重合、懸濁重合等のいずれも用いることができる。
【００６６】
（帯電制御剤）
本発明のトナーは、必要に応じて帯電制御剤を含有してもよい。帯電制御剤としては公知のものが全て使用でき、例えばニグロシン系染料、トリフェニルメタン系染料、クロム含有金属錯体染料、モリブデン酸キレート顔料、ローダミン系染料、アルコキシ系アミン、４級アンモニウム塩（フッ素変性４級アンモニウム塩を含む）、アルキルアミド、燐の単体または化合物、タングステンの単体または化合物、フッ素系活性剤、サリチル酸金属塩および、サリチル酸誘導体の金属塩等である。具体的にはニグロシン系染料のボントロン０３、第四級アンモニウム塩のボントロンＰ−５１、含金属アゾ染料のボントロンＳ−３４、オキシナフトエ酸系金属錯体のＥ−８２、サリチル酸系金属錯体のＥ−８４、フェノール系縮合物のＥ−８９（以上、オリエント化学工業社製）、第四級アンモニウム塩モリブデン錯体のＴＰ−３０２、ＴＰ−４１５（以上、保土谷化学工業社製）、第四級アンモニウム塩のコピーチャージＰＳＹ ＶＰ２０３８、トリフェニルメタン誘導体のコピーブルーＰＲ、第四級アンモニウム塩のコピーチャージ ＮＥＧＶＰ２０３６、コピーチャージ ＮＸ ＶＰ４３４（以上、ヘキスト社製）、ＬＲＡ−９０１、ホウ素錯体であるＬＲ−１４７（日本カーリット社製）、銅フタロシアニン、ペリレン、キナクリドン、アゾ系顔料、その他スルホン酸基、カルボキシル基、四級アンモニウム塩等の官能基を有する高分子系の化合物が挙げられる。本発明において帯電制御剤の使用量は、バインダー樹脂の種類、必要に応じて使用される添加剤の有無、分散方法を含めたトナー製造方法によって決定されるもので、一義的に限定されるものではないが、好ましくはバインダー樹脂１００重量部に対して、０．１〜１０重量部の範囲で用いられる。好ましくは、１〜５重量部の範囲が良い。１０重量部を越える場合にはトナーの帯電性が大きすぎ、主帯電制御剤の効果を減退させ、現像ローラとの静止電的吸引力が増大し、現像剤の流動性低下や、画像濃度の低下を招く。また０．１重量部未満の場合、帯電制御剤の機能を十分発揮できない。
【００６７】
（キャリア）
また、本発明のトナーを２成分系現像剤に用いる場合には、磁性キャリアと混合して用いれば良く、現像剤中のキャリアとトナーの含有比は、キャリア１００重量部に対してトナー１〜１０重量部が好ましい。キャリアとしては公知のものが全て使用でき、粒子径２０〜２００μｍ程度の鉄粉、フェライト粉、マグネタイト粉、磁性樹脂キャリアなど従来から公知のものが使用できる。また、被覆材料としては、アミノ系樹脂、例えば尿素−ホルムアルデヒド樹脂、メラミン樹脂、ベンゾグアナミン樹脂、ユリア樹脂、ポリアミド樹脂、エポキシ樹脂等があげられる。またポリビニルおよびポリビニリデン系樹脂、例えばアクリル樹脂、ポリメチルメタクリレート樹脂、ポリアクリロニトリル樹脂、ポリ酢酸ビニル樹脂、ポリビニルアルコール樹脂、ポリビニルブチラール樹脂、ポリスチレン樹脂およびスチレンアクリル共重合樹脂等のポリスチレン系樹脂、ポリ塩化ビニル等のハロゲン化オレフィン樹脂、ポリエチレンテレフタレート樹脂およびポリブチレンテレフタレート樹脂等のポリエステル系樹脂、ポリカーボネート系樹脂、ポリエチレン樹脂、ポリ弗化ビニル樹脂、ポリ弗化ビニリデン樹脂、ポリトリフルオロエチレン樹脂、ポリヘキサフルオロプロピレン樹脂、弗化ビニリデンとアクリル単量体との共重合体、弗化ビニリデンと弗化ビニルとの共重合体、テトラフルオロエチレンと弗化ビニリデンと非弗化単量体とのターポリマー等のフルオロターポリマー、およびシリコーン樹脂等が使用できる。またこれら被覆材料の膜厚は０．０１〜３μｍ、より好ましくは０．１〜０．３μｍである。０．０１μｍ以下であると膜制御が困難でかつコート膜としての機能が発揮できない。さらに３μｍ以上であると導電性が得られず、好ましくない。また必要に応じて、導電粉等を被覆樹脂中に含有させてもよい。導電粉としては、金属粉、カーボンブラック、酸化チタン、酸化錫、酸化亜鉛等が使用できる。これらの導電粉は、平均粒子径１μｍ以下のものが好ましい。平均粒子径が１μｍよりも大きくなると、電気抵抗の制御が困難になる。
また、本発明のトナーはキャリアを使用しない１成分系の磁性トナー或いは、非磁性トナーとしても用いることができる。
【００６８】
（磁性材料）
更に、本発明のトナーは、磁性材料を含有させ、磁性トナーとしても使用し得る。磁性トナーとする場合には、トナー粒子に磁性体の微粒子を含有させれば良い。斯かる磁性体としては、フェライト、マグネタイトをはじめとする鉄、ニッケル、コバルトなどの強磁性を示す金属もしくは合金またはこれらの元素を含む化合物、強磁性元素を含まないが適当な熱処理を施すことによって強磁性を示すようになる合金、例えばマンガン銅アルミニウム、マンガン−銅−錫、などのマンガンと銅とを含むホイスラー合金と呼ばれる種頼の合金、二酸化クロム、その他を挙げることができる。磁性体は、平均粒径が０．１〜１μｍの微粉末の形態で均一に分散されて含有されることが好ましい。そして磁性体の含有割合は、得られるトナーの１００重量部に対して、１０〜７０重量部であることが好ましく、特に２０〜５０重量部であることが好ましい。
【００６９】
（ワックス）
トナーあるいは現像剤に定着離型性を持たせる為に、トナーあるいは現像剤の中にワックスを含有させることが好ましい。特に画像定着部にオイル塗布を行わない、オイルレス定着機を用いた場合、トナー中にワックスを含むことが好ましい。前記ワックスは、その融点が４０〜１２０℃のものであり、特に５０〜１１０℃のものであることが好ましい。ワックスの融点が過大のときには低温での定着性が不足する場合があり、一方融点が過小のときには耐オフセット性、耐久性が低下する場合がある。なお、ワックスの融点は、示差走査熱量測定法（ＤＳＣ）によって求めることができる。すなわち、数ｍｇの試料を一定の昇温速度、例えば（１０℃／ｍｉｎ）で加熟したときの融解ピーク値を融点とする。ワックスの含有量は０〜２０重量部が好ましく、特に０〜１０重量部であることがより好ましい。
【００７０】
本発明に用いることができるワックスとしては、例えば固形のパラフィンワックス、マイクロワックス、ライスワックス、脂肪酸アミド系ワックス、脂肪酸系ワックス、死亡族モノケトン類、脂肪酸金属塩系ワックス、脂肪酸エステル系ワックス、部分ケン化脂肪酸エステル系ワックス、シリコーンワニス、高級アルコール、カルナウバワックスなどを挙げることができる。また低分子量ポリエチレン、ポリプロピレン等のポリオレフィンなども用いることができる。特に、環球法による軟化点が６０〜１５０℃のポリオレフィン、エステルが好ましく、さらには当該軟化点が７０〜１２０℃のポリオレフィン、エステルが好ましい。
【００７１】
さらに好ましくは、酸価５以下の脱遊離脂肪酸型カルナウバワックス、モンタン系エステルワックス、酸価１０〜３０の酸化ライスワックス及びサゾールワックスから選ばれた少なくとも一種のワックス類を含有することが効果的であることが判明した。脱遊離脂肪酸型カルナウバワックスは、カルナウバワックスを原料にして遊離脂肪酸を脱離したものであり、このため酸価が５％以下となり、且つ従来のカルナウバワックスより微結晶となり、結着樹脂中での分散平均粒径が１μｍ以下となり、分散性が向上する。モンタン系エステルワックスは鉱物より精製されたものであり、カルナウバワックスと同様に微結晶となり、結着樹脂中での分散平均粒径が１μｍ以下となり、分散性が向上する。モンタン系エステルワックスの場合、酸価として特に５〜１４であることが好ましい。
【００７２】
なお、ワックスの分散径は３μｍ以下であることが好ましく、より好ましくは２μｍ以下、さらに好ましくは１μｍ以下である。３μｍ以上の分散径になるとワックス流出性、転写材剥離性は向上するが、トナーとしての高温高湿耐久性、帯電安定性等が低下する。
また、酸化ラスイスワックスは、米ぬかワックスを空気酸化したものである。酸価は１０〜３０であることが好ましく、１０未満では定着下限温度が上昇し低温定着性が不十分となり、３０より大きいとコールドオフセット温度が上昇しやはり低温定着性が不十分となる。サゾールワックスは、サゾール社製サゾールワックスＨ１、Ｈ２、Ａ１、Ａ２、Ａ３、Ａ４、Ａ６、Ａ７、Ａ１４、Ｃ１、Ｃ２、ＳＰＲＡＹ３０、ＳＰＲＡＹ４０等が使用できるが、中でもＨ１、Ｈ２、ＳＰＲＡＹ３０、ＳＰＲＡＹ４０が低温定着、保存安定性にすぐれ好ましい。また、上記ワックスは単独で用いても組み合わせて用いても良く、結着樹脂１００重量部に対して１〜１５重量部、好ましくは２〜１０重量部含有させることが好ましい。
【００７３】
（クリーニング性向上剤）
感光体や一次転写媒体に残存する転写後の現像剤を除去するためのクリーニング性向上剤をトナー中に含有あるいはトナー表面に添加あるいは、現像剤中に含有あるいは表面に添加することがより好ましい。クリーニング性向上剤としては、例えばステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸など脂肪酸金属塩、例えばポリメチルメタクリレート微粒子、ポリスチレン微粒子などのソープフリー乳化重合などによって製造された、ポリマー微粒子などを挙げることかできる。ポリマー微粒子は比較的粒度分布が狭く、体積平均粒径が０．０１から１μｍのものが好ましい。クリーニング性向上剤の含有量は０．００１〜５重量部が好ましく、特に０．００１〜１重量部であることがより好ましい。
【００７４】
（製造方法）
本発明のトナー製造方法は、条件があえば公知の製造方法すべてが使用できる。
少なくともバインダー剤樹脂、主帯電制御剤および顔料を含む現像剤成分を機械的に混合する工程と、溶融混練する工程と、粉砕する工程と、分級する工程とを有するトナーの製造方法が適用できる。また機械的に混合する工程や溶融混練する工程において、粉砕または分級する工程で得られる製品となる粒子以外の粉末を戻して再利用する製造方法も含まれる。
ここで言う製品となる粒子以外の粉末（副製品）とは、溶融混練する工程後、粉砕工程で得られる所望の粒径の製品となる成分以外の微粒子や粗粒子や引き続いて行われる分級工程で発生する所望の粒径の製品となる成分以外の微粒子や粗粒子を意味する。このような副製品を混合工程や溶融混練する工程で原料と好ましくは副製品１に対しその他原材料９９から副製品５０に対し、その他原材料５０の重量比率で混合するのが好ましい。
少なくともバインダー剤樹脂、主帯電制御剤および顔料、副製品を含む現像剤成分を機械的に混合する混合工程は、回転させる羽による通常の混合機などを用いて通常の条件で行えばよく、特に制限はない。より好ましくはあらかじめ樹脂と着色剤。
【００７５】
以上の混合工程が終了したら、次いで混合物を混練機に仕込んで溶融混練する。溶融混練機としては、一軸、二軸の連続混練機や、ロールミルによるバッチ式混練機を用いることができる。例えば、神戸製鋼所社製ＫＴＫ型２軸押出機、東芝機械社製ＴＥＭ型押出機、ケイ・シー・ケイ社製２軸押出機、池貝鉄工所社製ＰＣＭ型２軸押出機、ブス社製コニーダー等が好適に用いられる。
この溶融混練は、バインダー樹脂の分子鎖の切断しないような適正な条件で行うことが重要である。具体的には、溶融混練温度は、バインダー剤樹脂の軟化点を参考に行うべきであり、軟化点より低温過ぎると切断が激しく、高温過ぎると分散が進まない。またトナー中の揮発性成分量を制御する場合、溶融混練温度と時間、雰囲気は、その時の残留揮発性成分量をモニターしながら最適条件を設定することがより好ましい。
【００７６】
以上の溶融混練工程が終了したら、次いで混練物を粉砕する。この粉砕工程においては、まず粗粉砕し、次いで微粉砕することが好ましい。この際 ジェット気流中で衝突板に衝突させて粉砕する衝突式粉砕方式や、機械的に回転するローターとステーターの狭いギャップで粉砕するローター粉砕方式が好ましく用いられる。衝突式粉砕機としては、ハンマーミル、ボールミル、チューブミル、振動ミル等を挙げることができる。圧縮空気及び衝突板を主構成要素として具備してなるジェット式粉砕機としてＩタイプ及びＩＤＳタイプ衝突式粉砕機（日本ニューマチック工業社製）を好ましく使用できる。また、ローター粉砕機としては、ロールミル、ピンミル、流動層式ジェットミル等を例示できるが、特に外壁としての固定容器と該固定容器と中心軸を同一にする回転片とを主構成要素として具備するものが好ましい。この種のローター式粉砕機としてターボミル（ターボ工業社製）、クリプトロン（川崎重工業社製）、ファインミル（日本ニューマチック工業社製）等が使用できる。トナーをより球形化したい場合は、ローター粉砕機を用いることが好ましい。
【００７７】
この粉砕工程が終了した後に、粉砕物を遠心力などで気流中で分級し、もって所定の粒径例えば体積平均粒径が１〜２０μｍのトナー（母体粒子）を製造する。トナーの体積平均粒径は１〜６μｍであることが、トナー転写定着の転写チリを防止し、かつトナーとしての十分な着色性を発揮させることができる。またトナー飛散、地肌汚れの防止にも有効であった。また画像品質、製造コスト、外添剤との被覆率等からより好ましい。体積平均粒径は例えば、ＣＯＵＬＴＥＲＴＡ−II（ＣＯＵＬＴＥＲ ＥＬＥＣＴＲＯＮＩＣＳ，ＩＮＣ）等を用いて測定できる。
【００７８】
また、トナーを調製する際には、トナーの流動性や保存性、現像性、転写性を高めるために、以上のようにして製造されたトナーにさらに先に挙げた本発明の酸化物微粒子、疎水性シリカ微粉末等の無機微粒子を添加混合してもよい。外添剤の混合は一般の粉体の混合機が用いられるがジャケット等装備して、内部の温度を調節できることが好ましい。外添剤に与える負荷の履歴を変えるには、途中または漸次外添剤を加えていけばよい。もちろん混合機の回転数、転動速度、時間、温度などを変化させてもよい。はじめに強い負荷を、次に比較的弱い負荷を与えても良いし、その逆でも良い。
使用できる混合設備の例としては、Ｖ型混合機、ロッキングミキサー、レーディゲミキサー、ナウターミキサー、ヘンシェルミキサーなどが挙げられる。
また、その他の製造法として、重合法、カプセル法等を用いることも可能である。これらの製造法の概略を以下に述べる。
【００７９】
（重合法）
▲１▼ 重合性モノマー、低分子量ポリマー必要に応じて重合開始剤、着色剤等を水性分散媒中で造粒する。
▲２▼ 造粒されたモノマー組成物粒子を適当な粒子径に分級する。
▲３▼ 上記分級により得た規定内粒径のモノマー組成物粒子を重合させる。
▲４▼ 適当な処理をして分散剤を取り除いた後、上記により得た重合生成物をろ過、水洗、乾燥して母体粒子を得る。
【００８０】
（カプセル法）
▲１▼ 樹脂、必要に応じて着色剤等を混練機等で混練し、溶融状態のトナー芯材を得る。
▲２▼ トナー芯材を水中に入れて強く撹拌し、微粒子状の芯材を作成する。
▲３▼ シェル材溶液中に上記芯材微粒子を入れ、撹拌しながら、貧溶媒を滴下し、芯材表面をシェル材で覆うことによりカプセル化する。
▲４▼ 上記により得たカプセルをろ過後、乾燥して母体粒子を得る。
【００８１】
（中間転写体）
本発明において転写システムに中間転写体を用いることもできる。中間転写体の１実施形態について説明する。図１は本実施形態に係る複写機の概略構成図である。像担持体としての感光体ドラム（以下、感光体という）１０の回りには、帯電装置としての帯電ローラ２０、露光装置３０、クリーニングブレードを有するクリーニング装置６０、除電装置としての除電ランプ７０、現像装置４０、中間転写体としての中間転写体５０とが配設されている。該中間転写体５０は、複数の懸架ローラ５１によって懸架され、図示しないモータ等の駆動手段により矢印方向に無端状に走行するように構成されている。この該懸架ローラ５１の一部は、中間転写体へ転写バイアスを供給する転写バイアスローラとしての役目を兼ねており、図示しない電源から所定の転写バイアス電圧が印加される。また、該中間転写体５０のクリーニングブレードを有するクリーニング装置９０も配設されている。また、該中間転写体５０に対向し、最終転写材としての転写紙１００に現像像を転写するための転写手段として転写ローラ８０が配設され、該転写ローラ８０は図示しない電源装置により転写バイアスを供給される。そして、上記中間転写体５０の周りには、電荷付与手段としてのコロナ帯電器５２が設けられている。
【００８２】
上記現像装置４０は、現像剤担持体としての現像ベルト４１と、該現像ベルト４１の回りに併設した黒（以下、Ｂｋという）現像ユニット４５Ｋ、イエロー（以下、Ｙという）現像ユニット４５Ｙ、マゼンタ（以下、マゼンタという）現像ユニット４５Ｍ、シアン（以下、Ｃという）現像ユニット４５Ｃとから構成されている。また、該現像ベルト４１は、複数のベルトローラに張り渡され、図示しないモータ等の駆動手段により矢印方向に無端状に走行するように構成され、上記感光体１０との接触部では該感光体１０とほぼ同速で移動する。
【００８３】
各現像ユニットの構成は共通であるので、以下の説明はＢｋ現像ユニット５０Ｂｋについてのみ行ない、他の現像ユニット５０Ｙ、５０Ｍ、５０Ｃについては、図中でＢｋ現像ユニット５０Ｂｋにおけるものと対応する部分に、該ユニットにおけるものに付した番号の後にＹ、Ｍ、Ｃを付すに止め説明は省略する。現像ユニット５０Ｂｋは、トナー粒子とキャリア液成分とを含む、高粘度、高濃度の液体現像剤を収容する現像タンク４２Ｂｋと、下部を該現像タンク４２Ｂｋ内の液体現像剤に浸漬するように配設された汲み上げローラ４３Ｂｋと、該汲み上げローラ４３Ｂｋから汲み上げられた現像剤を薄層化して現像ベルト４１に塗布する塗布ローラ４４Ｂｋとから構成されている。該塗布ローラ４４Ｂｋは、導電性を有しており、図示しない電源から所定のバイアスが印加される。
【００８４】
なお、本実施形態に係る複写機の装置構成としては、図１に示すような装置構成以外にも、図２に示すような、各色の現像ユニット４５を感光体１０の回りに併設した装置構成であっても良い。
次に、本実施形態に係る複写機の動作について説明する。図１において、感光体１０を矢印方向に回転駆動しながら帯電ローラ２０により一様帯電した後、露光装置３０により図示しない光学系で原稿からの反射光を結像投影して該感光体１０上に静電潜像を形成する。この静電潜像は、現像装置４０により現像され、顕像としてのトナー像が形成される。現像ベルト４１上の現像剤薄層は、現像領域において感光体との接触により薄層の状態で該ベルト４１から剥離し、感光体１０上の潜像の形成されている部分に移行する。この現像装置４０により現像されたトナー像は、感光体１０と等速移動している中間転写体５０との当接部（一次転写領域）にて中間転写体５０の表面に転写される（一次転写）。３色あるいは４色を重ね合わせる転写を行う場合は、この行程を各色ごとに繰り返し、中間転写体５０にカラー画像を形成する。
【００８５】
上記中間転写体上の重ね合せトナー像に電荷を付与するための上記コロナ帯電器５２を、該中間転写体５０の回転方向において、上記感光体１０と該中間転写体５０との接触対向部の下流側で、かつ該中間転写体５０と転写紙１００との接触対向部の上流側の位置に設置する。そして、このコロナ帯電器５２が、該トナー像に対して、該トナー像を形成するトナー粒子の帯電極性と同極性の真電荷を付与し、転写紙１００へ良好な転写がなされるに十分な電荷をトナー像に与える。上記トナー像は、上記コロナ帯電器５２によりに帯電された後、上記転写ローラ８０からの転写バイアスにより、図示しない給紙部から矢印方向に搬送された転写紙１００上に一括転写される（二次転写）。この後、トナー像が転写された転写紙１００は、図示しない分離装置により感光体１０から分離され、図示しない定着装置で定着処理がなされた後に装置から排紙される。一方、転写後の感光体１０は、クリーニング装置６０よって未転写トナーが回収除去され、次の帯電に備えて除電ランプ７０により残留電荷が除電される。
【００８６】
該中間転写体の静止摩擦係数は、好ましくは０．１〜０．６、より好ましくは０．３〜０．５が良い。該中間転写体の体積抵抗は数Ωｃｍ以上１０³Ωｃｍ以下であることが好ましい。体積抵抗を数Ωｃｍ以上１０³Ωｃｍ以下とすることにより、中間転写体自身の帯電を防ぐとともに、電荷付与手段により付与された電荷が該中間転写体上に残留しにくくなるので、二次転写時の転写ムラを防止できる。また、二次転写時の転写バイアス印加を容易にできる。
【００８７】
中間転写体の材質は特に制限されず、公知の材料が全て使用できる。その一例を以下に示す。（１）ヤング率（引張弾性率）の高い材料を単層ベルトとして用いたものであり、ＰＣ（ポリカーボネイト）、ＰＶＤＦ（ポリフッ化ビニリデン）、ＰＡＴ（ポリアルキレンテレフタレート）、ＰＣ（ポリカーボネイト）／ＰＡＴ（ポリアルキレンテレフタレート）のブレンド材料、ＥＴＦＥ（エチレンテトラフロロエチレン共重合体）／ＰＣ、ＥＴＦＥ／ＰＡＴ、ＰＣ／ＰＡＴのブレンド材料、カーボンブラック分散の熱硬化性ポリイミドなど。これらヤング率の高い単層ベルトは画像形成時の応力に対する変形量が少なく、特にカラー画像形成時にレジズレを生じにくいとの利点を有している。（２）上記のヤング率の高いベルトを基層とし、その外周上に表面層または中間層を付与した２〜３層構成のベルトであり、これら２〜３層構成のベルトは単層ベルトの硬さに起因し発生するライン画像の中抜けを防止しうる性能を有している。（３）ゴムおよびエラストマーを用いたヤング率の比較的低いベルトであり、これらのベルトは、その柔らかさによりライン画像の中抜けが殆ど生じない利点を有している。また、ベルトの幅を駆動ロールおよび張架ロールより大きくし、ロールより突出したベルト耳部の弾力性を利用して蛇行を防止するので、リブや蛇行防止装置を必要とせず低コストを実現できる。
【００８８】
中間転写ベルトは、従来から弗素系樹脂、ポリカーボネート樹脂、ポリイミド樹脂等が使用されてきていたが、近年ベルトの全層や、ベルトの一部を弾性部材にした弾性ベルトが使用されてきている。樹脂ベルトを用いたカラー画像の転写は以下の課題がある。
カラー画像は通常４色の着色トナーで形成される。１枚のカラー画像には、１層から４層までのトナー層が形成されている。トナー層は１次転写（感光体から中間転写ベルトへの転写）や、２次転写（中間転写ベルトからシートへの転写）を通過することで圧力を受け、トナー同士の凝集力が高くなる。トナー同士の凝集力が高くなると文字の中抜けやベタ部画像のエッジ抜けの現象が発生しやすくなる。樹脂ベルトは硬度が高くトナー層に応じて変形しないため、トナー層を圧縮させやすく文字の中抜け現象が発生しやすくなる。
【００８９】
また、最近はフルカラー画像を様々な用紙、例えば和紙や意図的に凹凸を付けや用紙に画像を形成したいという要求が高くなってきている。しかし、平滑性の悪い用紙は転写時にトナーと空隙が発生しやすく、転写抜けが発生しやすくなる。密着性を高めるために２次転写部の転写圧を高めると、トナー層の凝縮力を高めることになり、上述したような文字の中抜けを発生させることになる。
弾性ベルトは次の狙いで使用される。弾性ベルトは、転写部でトナー層、平滑性の悪い用紙に対応して変形する。つまり、局部的な凹凸に追従して弾性ベルトは変形するため、過度にトナー層に対して転写圧を高めることなく、良好な密着性が得られ文字の中抜けの無い、平面性の悪い用紙に対しても均一性の優れた転写画像を得ることができる。
【００９０】
弾性ベルトの樹脂は、ポリカーボネート、フッ素系樹脂（ＥＴＦＥ、ＰＶＤＦ）、ポリスチレン、クロロポリスチレン、ポリ−α−メチルスチレン、スチレン−ブタジエン共重合体、スチレン−塩化ビニル共重合体、スチレン−酢酸ビニル共重合体、スチレン−マレイン酸共重合体、スチレン−アクリル酸エステル共重合体（スチレン−アクリル酸メチル共重合体、スチレン−アクリル酸エチル共重合体、スチレン−アクリル酸ブチル共重合体、スチレン−アクリル酸オクチル共重合体及びスチレン−アクリル酸フェニル共重合体等）、スチレン−メタクリル酸エステル共重合体（スチレン−メタクリル酸メチル共重合体、スチレン−メタクリル酸エチル共重合体、スチレン−メタクリル酸フェニル共重合体等）、スチレン−α−クロルアクリル酸メチル共重合体、スチレン−アクリロニトリル−アクリル酸エステル共重合体等のスチレン系樹脂（スチレンまたはスチレン置換体を含む単重合体または共重合体）、メタクリル酸メチル樹脂、メタクリル酸ブチル樹脂、アクリル酸エチル樹脂、アクリル酸ブチル樹脂、変性アクリル樹脂（シリコーン変性アクリル樹脂、塩化ビニル樹脂変性アクリル樹脂、アクリル・ウレタン樹脂等）、塩化ビニル樹脂、スチレン−酢酸ビニル共重合体、塩化ビニル−酢酸ビニル共重合体、ロジン変性マレイン酸樹脂、フェノール樹脂、エポキシ樹脂、ポリエステル樹脂、ポリエステルポリウレタン樹脂、ポリエチレン、ポリプロピレン、ポリブタジエン、ポリ塩化ビニリデン、アイオノマー樹脂、ポリウレタン樹脂、シリコーン樹脂、ケトン樹脂、エチレン−エチルアクリレート共重合体、キシレン樹脂及びポリビニルブチラール樹脂、ポリアミド樹脂、変性ポリフェニレンオキサイド樹脂等からなる群より選ばれる１種類あるいは２種類以上を使用することができる。ただし、上記材料に限定されるものではないことは当然である。
【００９１】
弾性材ゴム、エラストマーとしては、ブチルゴム、フッ素系ゴム、アクリルゴム、ＥＰＤＭ、ＮＢＲ、アクリロニトリル−ブタジエン−スチレンゴム天然ゴム、イソプレンゴム、スチレン−ブタジエンゴム、ブタジエンゴム、エチレン−プロピレンゴム、エチレン−プロピレンターポリマー、クロロプレンゴム、クロロスルホン化ポリエチレン、塩素化ポリエチレン、ウレタンゴム、シンジオタクチック１，２−ポリブタジエン、エピクロロヒドリン系ゴム、リコーンゴム、フッ素ゴム、多硫化ゴム、ポリノルボルネンゴム、水素化ニトリルゴム、熱可塑性エラストマー（例えばポリスチレン系、ポリオレフィン系、ポリ塩化ビニル系、ポリウレタン系、ポリアミド系、ポリウレア、ポリエステル系、フッ素樹脂系）等からなる群より選ばれる１種類あるいは２種類以上を使用することができる。ただし、上記材料に限定されるものではないことは当然である。
【００９２】
抵抗値調節用導電剤に特に制限はないが、例えば、カーボンブラック、グラファイト、アルミニウムやニッケル等の金属粉末、酸化錫、酸化チタン、酸化アンチモン、酸化インジウム、チタン酸カリウム、酸化アンチモン−酸化錫複合酸化物（ＡＴＯ）、酸化インジウム−酸化錫複合酸化物（ＩＴＯ）等の導電性金属酸化物、導電性金属酸化物は、硫酸バリウム、ケイ酸マグネシウム、炭酸カルシウム等の絶縁性微粒子を被覆したものでもよい。上記導電剤に限定されるものではないことは当然である。
【００９３】
表層材料、表層は弾性材料による感光体への汚染防止と、転写ベルト表面への表面摩擦抵抗を低減させてトナーの付着力を小さくしてクリーニング性、２次転写性を高めるものが要求される。たとえばポリウレタン、ポリエステル、エポキシ樹脂等の１種類あるいは２種類以上を使用し表面エネルギーを小さくし潤滑性を高める材料、たとえばフッ素樹脂、フッ素化合物、フッ化炭素、２酸化チタン、シリコンカーバイト等の粉体、粒子を１種類あるいは２種類以上または粒径を異ならしたものを分散させ使用することができるまたフッ素系ゴム材料のように熱処理を行うことで表面にフッ素リッチな層を形成させ表面エネルギーを小さくさせたものを使用することもできる。
【００９４】
なお、ベルトの製造方法は限定されるものではない。回転する円筒形の型に材料を流し込みベルトを形成する遠心成型法や、液体塗料を噴霧し膜を形成させるスプレイ塗工法、円筒形の型を材料の溶液の中に浸けて引き上げるディッピング法、内型、外型の中に注入する注型法、円筒形の型にコンパウンドを巻き付け、加硫研磨を行う方法等があるが、これらに限定されるものではなく、複数の製法を組み合わせてベルトを製造することが一般的である。
【００９５】
弾性ベルトとして伸びを防止する方法として、伸びの少ない芯体樹脂層にゴム層を形成する方法、芯体層に伸びを防止する材料を入れる方法等があるが、特に製法に関わるものではない。
伸びを防止する芯体層を構成する材料は、例えば、綿、絹、などの天然繊維、ポリエステル繊維、ナイロン繊維、アクリル繊維、ポリオレフィン繊維、ポリビニルアルコール繊維、ポリ塩化ビニル繊維、ポリ塩化ビニリデン繊維、ポリウレタン繊維、ポリアセタール繊維、ポリフロロエチレン繊維、フェノール繊維などの合成繊維、炭素繊維、ガラス繊維、ボロン繊維などの無機繊維、鉄繊維、銅繊維などの金属繊維からなる群より選ばれる１種あるいは２種以上を用い織布状あるいは糸状のものができる。もちろん上記材料に限定されるものではない。
糸は１本または複数のフィラメントを撚ったもの、片撚糸、諸撚糸、双糸等、どのような撚り方であってもよい。また、例えば上記材料群から選択された材質の繊維を混紡してもよい。もちろん糸に適当な導電処理を施して使用することもできる。
【００９６】
一方、織布は、メリヤス織り等どのような織り方の織布でも使用可能であり、もちろん交織した織布も使用可能であり当然導電処理を施すこともできる。
芯体層を設ける製造方法は特に限定されるものではない、例えば筒状に織った織布を金型等に被せ、その上に被覆層を設ける方法、筒状に織った織布を液状ゴム等に浸漬して芯体層の片面あるいは両面に被覆層を設ける方法、糸を金型等に任意のピッチで螺旋状に巻き付け、その上に被覆層を設ける方法等を挙げることができる。
弾性層の厚さは、弾性層の硬度にもよるが、厚すぎると表面の伸縮が大きくなり表層に亀裂の発生しやすくなる。又、伸縮量が大きくなることから画像に伸びちじみが大きくなること等から厚すぎることは好ましくない（およそ１ｍｍ以上）。
【００９７】
（タンデム型カラー画像形成装置）
本発明のタンデム型カラー画像形成装置の実施形態について説明する。タンデム型の静電荷像現像装置には、図３に示すように、各感光体１上の画像を転写装置２により、シート搬送ベルト３で搬送するシートｓに順次転写する直接転写方式のものと、図４に示すように、各感光体１上の画像を１次転写装置２によりいったん中間転写体４に順次転写して後、その中間転写体４上の画像を２次転写装置５によりシートｓに一括転写する間接転写方式のものとがある。転写装置５は転写搬送ベルトであるが、ローラ形状も方式もある。
【００９８】
直接転写方式のものと、間接転写方式のものとを比較すると、前者は、感光体１を並べたタンデム型画像形成装置Ｔの上流側に給紙装置６を、下流側に定着装置７を配置しなければならず、シート搬送方向に大型化する欠点がある。
これに対し、後者は、２次転写位置を比較的自由に設置することができる。
給紙装置６、および定着装置７をタンデム型画像形成装置Ｔと重ねて配置することができ、小型化が可能となる利点がある。
また、前者は、シート搬送方向に大型化しないためには、定着装置７をタンデム型画像形成装置Ｔに接近して配置することとなる。そのため、シートｓがたわむことができる十分な余裕をもって定着装置７を配置することができず、シートｓの先端が定着装置７に進入するときの衝撃（特に厚いシートで顕著となる）や、定着装置７を通過するときのシート搬送速度と、転写搬送ベルトによるシート搬送速度との速度差により、定着装置７が上流側の画像形成に影響を及ぼしやすい欠点がある。
これに対し、後者は、シートｓがたわむことができる十分な余裕をもって定着装置７を配置することができるから、定着装置７がほとんど画像形成に影響を及ぼさないようにすることができる。
【００９９】
以上のようなことから、最近は、タンデム型静電荷像現像装置の中の、特に間接転写方式のものが注目されてきている。
そして、この種のカラー静電荷像現像装置では、図４に示すように、１次転写後に感光体１上に残留する転写残トナーを、感光体クリーニング装置８で除去して感光体１表面をクリーニングし、再度の画像形成に備えていた。また、２次転写後に中間転写体４上に残留する転写残トナーを、中間転写体クリーニング装置９で除去して中間転写体４表面をクリーニングし、再度の画像形成に備えていた。
【０１００】
以下、図面を参照しつつ、本発明の実施の形態につき説明する。
図５は、この発明の一実施の形態を示すもので、タンデム型間接転写方式の静電荷像現像装置である。図中符号１００は複写装置本体、２００はそれを載せる給紙テーブル、３００は複写装置本体１００上に取り付けるスキャナ、４００はさらにその上に取り付ける原稿自動搬送装置（ＡＤＦ）である。複写装置本体１００には、中央に、無端ベルト状の中間転写体１０を設ける。
そして、図５に示すとおり、図示例では３つの支持ローラ１４・１５・１６に掛け回して図中時計回りに回転搬送可能とする。
この図示例では、３つのなかで第２の支持ローラ１５の左に、画像転写後に中間転写体１０上に残留する残留トナーを除去する中間転写体クリーニング装置１７を設ける。
また、３つのなかで第１の支持ローラ１４と第２の支持ローラ１５間に張り渡した中間転写体１０上には、その搬送方向に沿って、イエロー、シアン、マゼンタ、ブラックの４つの画像形成手段１８を横に並べて配置してタンデム画像形成装置２０を構成する。
【０１０１】
そのタンデム画像形成装置２０の上には、図５に示すように、さらに露光装置２１を設ける。一方、中間転写体１０を挟んでタンデム画像形成装置２０と反対の側には、２次転写装置２２を備える。２次転写装置２２は、図示例では、２つのローラ２３間に、無端ベルトである２次転写ベルト２４を掛け渡して構成し、中間転写体１０を介して第３の支持ローラ１６に押し当てて配置し、中間転写体１０上の画像をシートに転写する。
２次転写装置２２の横には、シート上の転写画像を定着する定着装置２５を設ける。定着装置２５は、無端ベルトである定着ベルト２６に加圧ローラ２７を押し当てて構成する。
上述した２次転写装置２２には、画像転写後のシートをこの定着装置２５へと搬送するシート搬送機能も備えてなる。もちろん、２次転写装置２２として、転写ローラや非接触のチャージャを配置してもよく、そのような場合は、このシート搬送機能を併せて備えることは難しくなる。
なお、図示例では、このような２次転写装置２２および定着装置２５の下に、上述したタンデム画像形成装置２０と平行に、シートの両面に画像を記録すべくシートを反転するシート反転装置２８を備える。
【０１０２】
さて、いまこのカラー静電荷像現像装置を用いてコピーをとるときは、原稿自動搬送装置４００の原稿台３０上に原稿をセットする。または、原稿自動搬送装置４００を開いてスキャナ３００のコンタクトガラス３２上に原稿をセットし、原稿自動搬送装置４００を閉じてそれで押さえる。
そして、不図示のスタートスイッチを押すと、原稿自動搬送装置４００に原稿をセットしたときは、原稿を搬送してコンタクトガラス３２上へと移動して後、他方コンタクトガラス３２上に原稿をセットしたときは、直ちにスキャナ３００を駆動し、第１走行体３３および第２走行体３４を走行する。そして、第１走行体３３で光源から光を発射するとともに原稿面からの反射光をさらに反射して第２走行体３４に向け、第２走行体３４のミラーで反射して結像レンズ３５を通して読取りセンサ３６に入れ、原稿内容を読み取る。
また、不図示のスタートスイッチを押すと、不図示の駆動モータで支持ローラ１４・１５・１６の１つを回転駆動して他の２つの支持ローラを従動回転し、中間転写体１０を回転搬送する。同時に、個々の画像形成手段１８でその感光体４０を回転して各感光体４０上にそれぞれ、ブラック・イエロー・マゼンタ・シアンの単色画像を形成する。そして、中間転写体１０の搬送とともに、それらの単色画像を順次転写して中間転写体１０上に合成カラー画像を形成する。
【０１０３】
一方、不図示のスタートスイッチを押すと、給紙テーブル２００の給紙ローラ４２の１つを選択回転し、ペーパーバンク４３に多段に備える給紙カセット４４の１つからシートを繰り出し、分離ローラ４５で１枚ずつ分離して給紙路４６に入れ、搬送ローラ４７で搬送して複写機本体１００内の給紙路４８に導き、レジストローラ４９に突き当てて止める。
または、給紙ローラ５０を回転して手差しトレイ５１上のシートを繰り出し、分離ローラ５２で１枚ずつ分離して手差し給紙路５３に入れ、同じくレジストローラ４９に突き当てて止める。
そして、中間転写体１０上の合成カラー画像にタイミングを合わせてレジストローラ４９を回転し、中間転写体１０と２次転写装置２２との間にシートを送り込み、２次転写装置２２で転写してシート上にカラー画像を記録する。
画像転写後のシートは、２次転写装置２２で搬送して定着装置２５へと送り込み、定着装置２５で熱と圧力とを加えて転写画像を定着して後、切換爪５５で切り換えて排出ローラ５６で排出し、排紙トレイ５７上にスタックする。または、切換爪５５で切り換えてシート反転装置２８に入れ、そこで反転して再び転写位置へと導き、裏面にも画像を記録して後、排出ローラ５６で排紙トレイ５７上に排出する。
【０１０４】
一方、画像転写後の中間転写体１０は、中間転写体クリーニング装置１７で、画像転写後に中間転写体１０上に残留する残留トナーを除去し、タンデム画像形成装置２０による再度の画像形成に備える。
ここで、レジストローラ４９は一般的には接地されて使用されることが多いが、シートの紙粉除去のためにバイアスを印加することも可能である。
さて、上述したタンデム画像形成装置２０において、個々の画像形成手段１８は、詳しくは、例えば図６に示すように、ドラム状の感光体４０のまわりに、帯電装置６０、現像装置６１、１次転写装置６２、感光体クリーニング装置６３、除電装置６４などを備えてなる。
【０１０５】
【実施例】
以下に実施例および比較例を挙げて本発明について具体的に説明するが、本発明は、これらの実施例のみに限定されるものではない。また、以下の例おいて、部および％は、特に断りのない限り重量基準である。用いた評価機、および得られた特性および評価結果は表１に示した。実施例において評価は以下のように行った。
【０１０６】
（評価機）
評価で用いる画像は以下の評価機Ａ、Ｂ、Ｃ、Ｄ、Ｅいずれかを用いて評価した。
【０１０７】
（評価機Ａ）
４色の非磁性２成分系の現像部と４色用の感光体を有するタンデム方式のリコー社製フルカラーレーザープリンター ＩＰＳｉＯ Ｃｏｌｏｒ ８０００の定着ユニットをオイルレス定着ユニットに改良しチューニングした評価機Ａを用いて評価した。印字速度は高速印字、フルカラーで２０枚〜５０枚／ｍｉｎ・Ａ４まで変化させて評価した。
（評価機Ｂ）
４色の非磁性２成分系の現像部と４色用の感光体を有するタンデム方式のリコー社製フルカラーレーザープリンター ＩＰＳｉＯ Ｃｏｌｏｒ ８０００を改良して、中間転写体上に一次転写し、該トナー像を転写材に二次転写する、中間転写方式に変更して、かつ定着ユニットをオイルレス定着ユニットに改良しチューニングした評価機Ｂを用いて評価した。印字速度は高速印字、フルカラーで２０枚〜５０枚／ｍｉｎ・Ａ４まで変化させて評価した。
【０１０８】
（評価機Ｃ）
４色の現像部が２成分系現像剤を１つのドラム状感光体に各色現像し、中間転写体に順次転写し、転写材に４色を一括転写する方式のリコー社製フルカラーレーザー複写機 ＩＭＡＧＩＯ Ｃｏｌｏｒ ２８００の定着ユニットをオイルレス定着ユニットに改良しチューニングした評価機Ｃを用いて評価した。印字速度はフルカラーで６枚／ｍｉｎ・Ａ４で評価した。
（評価機Ｄ）
４色の現像部が非磁性一成分系現像剤を１つのベルト感光体に各色順次現像し、中間転写体に順次転写し、転写材に４色を一括転写する方式のリコー社製フルカラーレーザープリンター ＩＰＳｉＯ Ｃｏｌｏｒ ５０００の定着ユニットをオイルレス定着ユニットに改良し、オイルレス定着ユニットに改良しチューニングした評価機Ｄを用いて評価した。印字速度はフルカラーで６枚／ｍｉｎ・Ａ４で評価した。
【０１０９】
（評価機Ｅ）
４色の非磁性２成分系の現像部と４色用の感光体を有するタンデム方式のリコー社製フルカラーレーザープリンター ＩＰＳｉＯ Ｃｏｌｏｒ ８０００をオイル塗布型定着部のままチューニングした評価機Ｅを用いて評価した。印字速度は高速印字、２０枚〜５０枚／ｍｉｎ・Ａ４まで変化させて評価した。
【０１１０】
（評価項目）
１）高温高湿環境下でのトナー飛散性
３５℃８０％の高温高湿環境下にトナーを１２時間調湿保管後、同環境に評価機を設置して、単色モードで８０％画像面積の画像チャートを３０，０００枚ランニング出力した後、現像部から飛散したトナー量を現像ユニットをオープンにして目視で判断した。×、△、○、◎の順にランクが良くなる。
２）低温低湿環境下での地肌汚れ
単色モードで７％画像面積の画像チャートを３０，０００枚ランニング出力した後、白紙画像を現像中に停止させ、現像後の感光体上の現像剤をテープ転写し、未転写のテープの画像濃度との差を９３８スペクトロデンシトメーター（Ｘ−Ｒｉｔｅ社製）により測定。画像濃度の差が少ない方が地肌汚れは良く、×、△、○、◎の順にランクが良くなる。
【０１１１】
３）画像濃度（着色度）
単色モードで５０％画像面積の画像チャートを２００，０００枚ランニング出力した後、ベタ画像をリコー社製６０００ペーパーに画像出力後、画像濃度をＸ−Ｒｉｔｅ（Ｘ−Ｒｉｔｅ社製）により測定。これを４色単独に行い平均を求めた。この値が、１．２未満の場合は×、１．２以上１．４未満の場合は△、１．４以上１．８未満の場合は○、１．８以上２．２未満の場合は◎とした。
４）透明性
単色モードで５０％画像面積の画像チャートを１００，０００枚ランニング出力した後、リコー社製タイプＤＸのＯＨＰシート上に、それぞれ単色で画像濃度；１．０ｍｇ／ｃｍ²、定着温度；１４０℃の条件で定着し、スガ試験機社製の直続ヘーズコンピューターＨＧＭ−２ＤＰ型により測定。透明性の良好な順に◎、○、△、×とした。
【０１１２】
５）色の鮮やかさ
単色モードで５０％画像面積の画像チャートを１００，０００枚ランニング出力した後、色の鮮やかさをリコー社製６０００ペーパーに出力した画像を視覚的に評価した。良好な順に◎、○、△、×とした。
６）色再現性
単色モードで５０％画像面積の画像チャートを１００，０００枚ランニング出力した後、色再現性をリコー社製６０００ペーパーに出力した画像を視覚的に評価した。良好な順に◎、○、△、×とした。
【０１１３】
７）光沢
単色モードで５０％画像面積の画像チャートを１００，０００枚ランニング出力した後、リコー社製６０００ペーパーに出力した画像を、光沢度計（ＶＧ−１Ｄ）（日本電色社製）を用い、投光角度、受光角度をそれぞれ６０°に合わせ、Ｓ、Ｓ／１０切り替えＳＷはＳに合わせ、０調製および標準板を用いた標準設定の後、測定した。光沢度が良好なものから、◎：１３以上、○：５以上１３未満、△：２以上〜５未満、×：２未満、とした。
８）耐光性
単色モードで５０％画像面積の画像チャートを１００，０００枚ランニング出力した後、リコー社製６０００ペーパーに出力した画像を、ＸＥＮＯＮＴＥＳＴＥＲ ＸＷ−１５０（島津製作所社製）により画像に１万ルックスで１５時間照射した後の画像を観察し次の基準により耐光性を評価した。
◎：ほとんど変化しない。
○：わずかに変化する。
△：やや変化する。
×：かなり変化する。
【０１１４】
９）細線再現性
単色モードで５０％画像面積の画像チャートを３０，０００枚ランニング出力した後、６００ｄｐｉの細線画像をリコー社製タイプ６０００ペーパーに出力させ、細線のにじみ度合いを段階見本と比較した。×、△、○、◎の順にランクが良くなる。これを４色重ねて行った。
１０）耐熱保存性
各色トナーを１０ｇずつ計量し、２０ｍｌのガラス容器に入れ、１００回ガラス瓶をタッピングした後、５５℃にセットした恒温槽に２４時間放置した後、針入度計で針入度を測定した。良好なものから、◎：２０ｍｍ以上、○：１５ｍｍ以上２０ｍｍ未満、△：１０ｍｍ以上〜１５ｍｍ未満、×：１０ｍｍ未満、とした。
【０１１５】
１１）高温高湿環境帯電安定性
温度４０℃、湿度９０％の環境において、単色モードで７％画像面積の画像チャートを１００，０００枚ランニング出力する間に、１０００枚ごとに現像剤を一部サンプリングしてブローオフ法により帯電量を測定して、帯電安定性を評価した。帯電上昇や帯電低下が少なく安定して良好な順に◎、○、△、×とした。
１２）低温低湿環境帯電安定性
温度１０℃、湿度１５％の環境において、単色モードで７％画像面積の画像チャートを１００，０００枚ランニング出力する間に、１０００枚ごとに現像剤を一部サンプリングしてブローオフ法により帯電量を測定して、帯電安定性を評価した。帯電上昇や帯電低下が少なく安定して良好な順に◎、○、△、×とした。
【０１１６】
１３）定着性
トナーの定着下限温度、定着上限温度が定着温度領域内で十分あり、ホットオフセット、コールドオフセットが発生せず、巻き付き、紙づまり、等、搬送トラブルも発生しにくく、定着の良好な順に◎、○、△、×として総合的な定着性を評価した。
【０１１７】
（２成分現像剤評価）
２成分系現像剤で画像評価する場合は、以下のように、シリコーン樹脂により０．３μｍの平均厚さでコーティングされた平均粒径５０μｍのフェライトキャリアを用い、キャリア１００重量部に対し各色トナー５重量部を容器が転動して攪拌される型式のターブラーミキサーを用いて均一混合し帯電させて、現像剤を作成した。
【０１１８】

上記コート材を１０分間スターラーで分散してコート液を調整し、このコート液と芯材を流動床内に回転式底板ディスクと攪拌羽根を設けた旋回流を形成させながらコートを行うコーティング装置に投入して、当該コート液を芯材上に塗布した。得られた塗布物を電気炉で２５０℃、２時間焼成し上記キャリアを得た。
【０１１９】
実施例１
（ポリオール樹脂１）
撹拌装置、温度計、Ｎ_２導入口、冷却管付セパラブルフラスコに、低分子ビスフェノールＡ型エポキシ樹脂（数平均分子量：約３６０）３７８．４ｇ、高分子ビスフェノールＡ型エポキシ樹脂（数平均分子量：約２７００）８６．０ｇ、ビスフェノールＡ型プロピレンオキサイド付加体のジグリシジル化物〔前記一般式（１）においてｎ＋ｍ：約２．１〕１９１．０ｇ、ビスフェノールＦ２７４．５ｇ、ｐ−クミルフェノール７０．１ｇ、キシレン２００ｇを加えた。Ｎ_２雰囲気下で７０〜１００℃まで昇温し、塩化リチウムを０．１８３ｇ加え、更に１６０℃まで昇温し減圧下で水を加え、水とキシレンをバブリングさせることで水、キシレン、他揮発性成分、極性溶媒可溶成分を除去し、１８０℃の反応温度で６〜９時間重合させて、Ｍｎ；３８００、Ｍｗ／Ｍｎ；３．９、Ｍｐ；５０００、軟化点１０９℃、Ｔｇ５８℃、エポキシ当量２００００以上のポリオール樹脂１０００ｇを得た（ポリオール樹脂１）。重合反応ではモノマー成分が残留しないように、反応条件を制御した。主鎖のポリオキシアルキレン部については、ＮＭＲにて確認した。
【０１２０】
（トナーの製造）
［マゼンタトナー］
水 ６００部
Ｐｉｇｍｅｎｔ Ｒｅｄ １２２ １２００部
ポリオール樹脂１ １２００部
上記原材料をヘンシェルミキサーにて混合し、顔料凝集体中に水が染み込んだ混合物を得た。これをロール表面温度１２８℃に設定した２本ロールにより４５分間混練を行ない、圧延冷却しパルペライザーで粉砕、マスターバッチ着色剤を得た。

上記材料をミキサーで混合後、２本ロールミルで５回溶融混練し、混練物を圧延冷却した。その後ジェットミルによる衝突板方式の粉砕機（Ｉ式ミル；日本ニューマチック工業社製）と旋回流による風力分級（ＤＳ分級機；日本ニューマチック工業社製）を行い、体積平均粒径５．５μｍ、個数平均粒径４．５μｍのマゼンタ色の着色粒子を得た。さらに、一次粒子径１０ｎｍの疎水性シリカ（ＨＤＫ Ｈ２０００、クラリアントジャパン）を１．０ｗｔ％、一次粒子径１５ｎｍの酸化チタン（ＭＴ−１５０Ａ、テイカ）を０．９ｗｔ％添加し、ヘンシェルミキサーで混合、目開き５０μｍの篩を通過させ凝集物を取り除くことによりマゼンタトナーを得た。ワックスのトナー中での分散径は０．２μｍであった。得られたトナー表面の着色剤分子の被覆率は１４．１（ａｔｏｍｉｃ％）であった。
【０１２１】
実施例２
実施例１において、以下のようにトナーを製造した以外は実施例１と同様にして評価した。
［シアントナー］
水 ６００部
Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３ １２００部
ポリオール樹脂１ １２００部
上記原材料をヘンシェルミキサーにて混合し、顔料凝集体中に水が染み込んだ混合物を得た。これをロール表面温度１２８℃に設定した２本ロールにより４５分間混練を行ない、圧延冷却しパルペライザーで粉砕、マスターバッチ着色剤を得た。

上記材料をミキサーで混合後、２本ロールミルで５回溶融混練し、混練物を圧延冷却した。その後ジェットミルによる衝突板方式の粉砕機（Ｉ式ミル；日本ニューマチック工業社製）と旋回流による風力分級（ＤＳ分級機；日本ニューマチック工業社製）を行い、体積平均粒径５．５μｍ、個数平均粒径４．５μｍのシアン色の着色粒子を得た。さらに、一次粒子径１０ｎｍの疎水性シリカ（ＨＤＫＨ２０００、クラリアントジャパン）を１．０ｗｔ％、一次粒子径１５ｎｍの酸化チタン（ＭＴ−１５０Ａ、テイカ）を０．９ｗｔ％添加し、ヘンシェルミキサーで混合、目開き５０μｍの篩を通過させ凝集物を取り除くことによりシアントナーを得た。ワックスのトナー中での分散径は０．２μｍであった。得られたトナー表面の着色剤分子の被覆率は４．７（ａｔｏｍｉｃ％）であった。
【０１２２】
実施例３
実施例１において、以下のようにトナーを製造した以外は実施例１と同様にして評価した。
［イエロートナー］
水 ６００部
Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １８０ １２００部
ポリオール樹脂１ １２００部
上記原材料をヘンシェルミキサーにて混合し、顔料凝集体中に水が染み込んだ混合物を得た。これをロール表面温度１２８℃に設定した２本ロールにより４５分間混練を行ない、圧延冷却しパルペライザーで粉砕、マスターバッチ着色剤を得た。

上記材料をミキサーで混合後、２本ロールミルで５回溶融混練し、混練物を圧延冷却した。その後ジェットミルによる衝突板方式の粉砕機（Ｉ式ミル；日本ニューマチック工業社製）と旋回流による風力分級（ＤＳ分級機；日本ニューマチック工業社製）を行い、体積平均粒径５．５μｍ、個数平均粒径４．５μｍのイエロー色の着色粒子を得た。さらに一次粒子径１０ｎｍの疎水性シリカ（ＨＤＫＨ２０００、クラリアントジャパン）を１．０ｗｔ％、一次粒子径１５ｎｍの酸化チタン（ＭＴ−１５０Ａ、テイカ）を０．９ｗｔ％添加し、ヘンシェルミキサーで混合、目開き５０μｍの篩を通過させ凝集物を取り除くことによりイエロートナーを得た。ワックスのトナー中での分散径は０．３μｍであった。得られたトナー表面の着色剤分子の被覆率は６．５（ａｔｏｍｉｃ％）であった。
【０１２３】
実施例４
実施例１において、以下のようにトナーを製造した以外は実施例１と同様にして評価した。
［マゼンタトナー］
水 ６００部
Ｐｉｇｍｅｎｔ Ｒｅｄ ５７：１ １２００部
ポリオール樹脂１ １２００部
上記原材料をヘンシェルミキサーにて混合し、顔料凝集体中に水が染み込んだ混合物を得た。これをロール表面温度１２８℃に設定した２本ロールにより４５分間混練を行ない、圧延冷却しパルペライザーで粉砕、マスターバッチ着色剤を得た。

上記材料をミキサーで混合後、２本ロールミルで５回溶融混練し、混練物を圧延冷却した。その後ジェットミルによる衝突板方式の粉砕機（Ｉ式ミル；日本ニューマチック工業社製）と旋回流による風力分級（ＤＳ分級機；日本ニューマチック工業社製）を行い、体積平均粒径５．５μｍ、個数平均粒径４．５μｍのマゼンタ色の着色粒子を得た。さらに、一次粒子径１０ｎｍの疎水性シリカ（ＨＤＫ Ｈ２０００、クラリアントジャパン）を１．０ｗｔ％、一次粒子径１５ｎｍの酸化チタン（ＭＴ−１５０Ａ、テイカ）を０．９ｗｔ％添加し、ヘンシェルミキサーで混合、目開き５０μｍの篩を通過させ凝集物を取り除くことによりマゼンタトナーを得た。ワックスのトナー中での分散径は０．２μｍであった。得られたトナー表面の着色剤分子の被覆率は１．６（ａｔｏｍｉｃ％）であった。
【０１２４】
実施例５
実施例１において、以下のようにトナーを製造した以外は実施例１と同様にして評価した。
［マゼンタトナー］
水 ６００部
Ｐｉｇｍｅｎｔ Ｒｅｄ １８５ １２００部
ポリオール樹脂１ １２００部
上記原材料をヘンシェルミキサーにて混合し、顔料凝集体中に水が染み込んだ混合物を得た。これをロール表面温度１２６℃に設定した２本ロールにより４５分間混練を行ない、圧延冷却しパルペライザーで粉砕後さらに、ロール表面温度１２５℃に設定した２本ロールにより４０分間混練を行ない、圧延冷却しパルペライザーで粉砕マスターバッチ着色剤を得た。

上記材料をミキサーで混合後、２本ロールミルで５回溶融混練し、混練物を圧延冷却した。その後ジェットミルによる衝突板方式の粉砕機（Ｉ式ミル；日本ニューマチック工業社製）と旋回流による風力分級（ＤＳ分級機；日本ニューマチック工業社製）を行い、体積平均粒径５．５μｍ、個数平均粒径４．５μｍのマゼンタ色の着色粒子を得た。さらに、一次粒子径１０ｎｍの疎水性シリカ（ＨＤＫ Ｈ２０００、クラリアントジャパン）を１．０ｗｔ％、一次粒子径１５ｎｍの酸化チタン（ＭＴ−１５０Ａ、テイカ）を０．９ｗｔ％添加し、ヘンシェルミキサーで混合、目開き５０μｍの篩を通過させ凝集物を取り除くことによりマゼンタトナーを得た。ワックスのトナー中での分散径は０．２μｍであった。得られたトナー表面の着色剤分子の被覆率は８．０（ａｔｏｍｉｃ％）であった。
【０１２５】
実施例６
実施例１において、以下のようにトナーを製造した以外は実施例１と同様にして評価した。
［マゼンタトナー］
水 ６００部
Ｐｉｇｍｅｎｔ Ｒｅｄ ５７：１ １２００部
ポリオール樹脂１ １２００部
上記原材料をヘンシェルミキサーにて混合し、顔料凝集体中に水が染み込んだ混合物を得た。これをロール表面温度１２８℃に設定した２本ロールにより４５分間混練を行ない、圧延冷却しパルペライザーで粉砕、マスターバッチ着色剤を得た。

上記材料をミキサーで混合後、２本ロールミルで５回溶融混練し、混練物を圧延冷却した。その後ジェットミルによる衝突板方式の粉砕機（Ｉ式ミル；日本ニューマチック工業社製）と旋回流による風力分級（ＤＳ分級機；日本ニューマチック工業社製）を行い、体積平均粒径５．５μｍ、個数平均粒径４．５μｍのマゼンタ色の着色粒子を得た。さらに、一次粒子径１０ｎｍの疎水性シリカ（ＨＤＫ Ｈ２０００、クラリアントジャパン）を１．０ｗｔ％、一次粒子径１５ｎｍの酸化チタン（ＭＴ−１５０Ａ、テイカ）を０．９ｗｔ％添加し、ヘンシェルミキサーで混合、目開き５０μｍの篩を通過させ凝集物を取り除くことによりマゼンタトナーを得た。ワックスのトナー中での分散径は０．２μｍであった。得られたトナー表面の着色剤分子の被覆率は１５．０（ａｔｏｍｉｃ％）であった。
【０１２６】
実施例７
実施例１、２、３記載のマゼンタトナー、シアントナー、イエロートナーと以下に記載するブラックトナーを含んだフルカラートナーキットを作成し、実施例１と同様にして評価した。各種評価はフルカラーモードで行った。なおここで作成したブラックトナーは着色剤に特有の元素がないため、着色剤分子の被覆率は測定しなかった。
［ブラックトナー］
水 １０００部
フタロシアニングリーン含水ケーキ（固形分３０％） ２００部
カーボンブラック（ＭＡ６０ 三菱化学社製） １０００部
ポリオール樹脂１ １０００部
上記原材料をヘンシェルミキサーにて混合し、顔料凝集体中に水が染み込んだ混合物を得た。これをロール表面温度１２８℃に設定した２本ロールにより４５分間混練を行ない、圧延冷却しパルペライザーで粉砕、マスターバッチ着色剤を得た。

上記材料をミキサーで混合後、２本ロールミルで３回以上溶融混練し、混練物を圧延冷却した。その後ジェットミルによる衝突板方式の粉砕機（Ｉ式ミル；日本ニューマチック工業社製）と旋回流による風力分級（ＤＳ分級機；日本ニューマチック工業社製）を行い、体積平均粒径５．５μｍ、個数平均粒径４．５μｍのブラック色の着色粒子を得た。さらに一次粒子径１０ｎｍの疎水性シリカ（ＨＤＫ Ｈ２０００、クラリアントジャパン）を１．０ｗｔ％、一次粒子径１５ｎｍの酸化チタン（ＭＴ−１５０Ａ、テイカ）を０．９ｗｔ％添加し、ヘンシェルミキサーで混合、目開き５０μｍの篩を通過させ凝集物を取り除くことによりブラックトナーを得た。ワックスのトナー中での分散径は０．２μｍであった。
【０１２７】
実施例８
実施例１において、樹脂をポリエステル樹脂（フマル酸、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、ポリオキシエチレン−（２．３）−２，２−ビス（４−ヒドロキシフェニル）プロパン、無水トリメリット酸から合成された樹脂、酸価；１０、水酸基価；３０、Ｍｎ；５０００、Ｍｗ／Ｍｎ；１０、Ｍｐ；９０００、Ｔｇ；６１℃、軟化点１０８℃）に変更した以外は実施例１と同様にして評価した。得られたトナーの体積平均粒径は５．５μｍ、個数平均粒径は４．５μｍであり、トナー表面の着色剤分子の被覆率は１２．８（ａｔｏｍｉｃ％）であった。
【０１２８】
実施例９
実施例１において、トナーの体積平均粒径が６．５μｍ、個数平均粒径が５．４μｍになるように分級してトナーを得た以外は実施例１と同様にしてトナー、現像剤を作成して評価した。トナー表面の着色剤分子の被覆率は１３．８（ａｔｏｍｉｃ％）であった。
【０１２９】
実施例１０
実施例１において、トナーの体積平均粒径が４．５μｍ、個数平均粒径が３．６μｍになるように分級してトナーを得た以外は実施例１と同様にしてトナー、現像剤を作成して評価した。トナー表面の着色剤分子の被覆率は１４．３（ａｔｏｍｉｃ％）であった。
【０１３０】
実施例１１
実施例１において、トナーの体積平均粒径が２μｍ、個数平均粒径が１．４μｍになるように分級してトナーを得た以外は実施例１と同様にしてトナー、現像剤を作成して評価した。トナー表面の着色剤分子の被覆率は１４．９（ａｔｏｍｉｃ％）であった。
【０１３１】
実施例１２
実施例１において、トナーをターボミル（ターボ工業社製）で粉砕し、トナー形状を球形化処理した以外は、実施例１と同様にしてトナー、現像剤を作成して評価した。トナーの円形度ＳＦ−１は１４０、ＳＦ−２は１３０であった。トナー表面の着色剤分子の被覆率は１３．５（ａｔｏｍｉｃ％）であった。
【０１３２】
実施例１３
実施例１において、トナーの製造法を以下の乳化重合法に変更した以外は、実施例１と同様にして評価した。
まず、樹脂分散液１として、

以上を混合溶解したものを非イオン性界面活性剤（三洋化成社製、ノニボール８５）９部、アニオン性界面活性剤（第一工業製薬社製、ネオゲンＳＣ）１１部をイオン交換水５８２部に溶解してフラスコ中で分散、乳化し１５分ゆっくりと混合しながら、過硫酸アンモニウム（東海電化社製）３．４ｇを溶解したイオン交換水５０ｇを投入し、窒素置換を行った。その後フラスコを攪拌しながらオイルバスで内容物が７３℃になるまで加熱し、７時間そのまま乳化重合を継続し、その後室温まで冷却し樹脂分散液を得た。得られた樹脂分散液から溶媒を８０℃のオーブン上に放置し水分を除去した。中心粒径１２０ｎｍ、ガラス転移点５５℃、Ｍｗ２２，０００の分散液を得た。
顔料Ｐｉｇｍｅｎｔ Ｒｅｄ １２２、７０部をアニオン性界面活性剤（三洋化成社製、イオネットＤ−２）２部と共にイオン交換水３００部中に添加混合し、ＩＫＡ製ウルトラタラックスＴ５０にて分散処理し、中心径１６０ｎｍの顔料分散液１を得た。
ワックス（脂肪酸エステルワックス、融点８３℃、粘度２８０ｍＰａ・ｓ（９０℃））５０部をアニオン性界面活性剤（三洋化成社製、イオネットＤ−２）２部と共にイオン交換水３００部中に添加混合し、ＩＫＡ製ウルトラタラックスＴ５０にて分散処理し、ワックス分散液１を得た。
【０１３３】
次に、上記の樹脂分散液１、顔料分散液１、ワックス分散液１を以下の割合、

で丸形ステンレス製フラスコ中にウルトラタラックスＴ５０で混合分散した後、加熱用オイルバスでフラスコを攪拌しながら４８℃まで加熱した。４８℃で４時間保持した後、光学顕微鏡にて観察すると約５．５μｍの凝集粒子が生成していることが確認された。その後、ネオゲンＳＣを６部を追添加した後、攪拌を継続しながら９３℃まで加熱し、９時間保持した。この後フラスコを１０℃／分で室温まで冷却し、更に濾過した後、イオン交換水で充分洗浄後、真空乾燥機内で５０℃、１２時間保持し、体積平均粒径は５．５μｍ、個数平均粒径は４．７μｍ、分子量Ｍｗは２２，０００のマゼンタ色の着色粒子を得た。さらに、一次粒子径１０ｎｍの疎水性シリカ（ＨＤＫ Ｈ２０００、クラリアントジャパン）を１．０ｗｔ％、一次粒子径１５ｎｍの酸化チタン（ＭＴ−１５０Ａ、テイカ）を０．９ｗｔ％添加し、ヘンシェルミキサーで混合、目開き５０μｍの篩を通過させ凝集物を取り除くことによりマゼンタトナーを得た。トナーの円形度ＳＦ−１は１０８、ＳＦ−２は１０５であった。トナー表面の着色剤分子の被覆率は１４．８（原子％）であった。
【０１３４】
実施例１４
実施例１において、評価機Ｂを用いた以外は同様にして評価した。
【０１３５】
実施例１５
実施例１において、評価機Ｃを用いた以外は同様にして評価した。
【０１３６】
実施例１６
実施例１において、評価機Ｄを用いた以外は同様にして評価した。
【０１３７】
実施例１７
実施例１において、ワックスを加えずにトナーを製造して、かつ評価機Ｅを用いた以外は実施例１と同様に製造、評価した。得られたトナーの体積平均粒径は５．５μｍ、個数平均粒径は４．６μｍ、トナー表面の着色剤分子の被覆率は１２．８（原子％）であった。
【０１３８】
比較例１
実施例１において、マスターバッチ着色剤の製造条件を変更した以外は実施例１と同様にしてトナー、現像剤を作成して評価した。マスターバッチ着色剤はロール表面温度１１５℃に設定した２本ロールにより４０分間混練して得た。得られたトナー表面の着色剤分子の被覆率は１６．１（原子％）であった。
【０１３９】
比較例２
実施例４において、トナーの製造条件を変更した以外は実施例４と同様にしてトナー、現像剤を作成して評価した。トナーの混練りをブス社製コニーダーに変更して作成し、混練物を圧延冷却した。そして粗粉砕して再度コニーダーで混練りして最終的な混練物を得た。その後、実施例４と同様にトナーを作成して評価した。得られたトナー表面の着色剤分子の被覆率は１．３（原子％）であった。
【０１４０】
比較例３
実施例１において、トナー中の着色剤が１．３重量％になるようにマスターバッチ着色剤とバインダー樹脂の処方量比を変更した以外は実施例１と同様にしてトナーを作成して評価した。得られたトナー表面の着色剤分子の被覆率は１．８（原子％）であった。
【０１４１】
比較例４
実施例４において、トナー中の着色剤が１６重量％になるようにマスターバッチ着色剤とバインダー樹脂の処方量比を変更した以外は実施例１と同様にしてトナーを作成して評価した。得られたトナー表面の着色剤分子の被覆率は１４．２（原子％）であった。
【０１４２】
【表１】

【０１４３】
【発明の効果】
上記に記載した少なくともバインダー樹脂と着色剤とを含有するトナーにおいて、ＸＰＳ測定による該トナー表面の着色剤分子の被覆率が１．５〜１５原子％であり、かつ、着色剤が含有量がトナーに対して２〜１５重量％である静電荷像現像用トナーを用いることで、トナーを高温高湿環境で長時間保管後に高温高湿環境下で数万枚画像を出力した後においても帯電安定性に優れた弱帯電、逆帯電トナーの少なく、トナー飛散が発生しない、トナー、現像剤、画像形成方法、画像形成装置を提供でき、かつ、常温常湿環境だけでなく、低温低湿環境下において数万枚画像を出力した後でも帯電安定性に優れた弱帯電、逆帯電トナーの少なく、地肌汚れ（かぶり）が発生しないトナー、現像剤、画像形成方法、画像形成装置を提供でき、かつ、数万枚画像を出力した後でも、十分な着色性、耐光性、透明性、発色性、鮮明性、色再現性、彩度、光沢を有するトナー、現像剤、画像形成方法、画像形成装置を提供できる。
【図面の簡単な説明】
【図１】本発明の実施形態の一例を示す概略構成図である。
【図２】本発明の実施形態の他の一例を示す概略構成図である。
【図３】本発明の実施形態の他の一例を示す概略構成図である。
【図４】本発明の実施形態の他の一例を示す概略構成図である。
【図５】本発明の実施形態の他の一例を示す概略構成図である。
【図６】本発明の実施形態の他の一例を示す概略構成図である。
【符号の説明】
１０ 感光体
２０ 帯電ローラ
３０ 露光装置
４０ 現像装置
４１ 現像ベルト
４２ 現像タンク
４３ 汲み上げローラ
４４ 塗布ローラ
４５ 現像ユニット
５０ 中間転写体
５１ 懸架ローラ
５２ コロナ帯電器
５３ 定電流源
６０ クリーニング装置
７０ 除電ランプ
８０ 転写ローラ
９０ クリーニング装置
１００ 転写紙[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrostatic image developing toner, an electrostatic image developing developer, a full color toner kit, an image forming method, and an image forming apparatus.
[0002]
[Prior art]
In a typical image forming process using an electrostatic charge image developing method or an electrostatic printing method, a photoconductive insulating layer is uniformly charged, the insulating layer is exposed, and then the charge on the exposed portion is dissipated. A development process for forming an electrical latent image and making the latent image visible by attaching a finely charged toner to the latent image, and transferring the resulting visible image to a transfer material such as transfer paper It consists of a fixing step for fixing by a process, heating or pressurization (usually using a heat roller). As a developer for developing an electrostatic image formed on a latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer that does not require a carrier (magnetic toner, non-magnetic toner) )It has been known. As a full-color image forming apparatus, a system is well known in which toner images of respective colors formed on a photosensitive member are sequentially transferred to an intermediate transfer member, temporarily held, and then collectively transferred again onto a sheet.
[0003]
The toner used in such an electrostatic charge image developing method or electrostatic printing method has a binder resin and a colorant as main components, and if necessary, an additive such as a charge control agent or an offset preventive agent. Various performances are required in each of the above steps. For example, in the development process, in order to attach toner to an electrical latent image, the toner and the binder resin for toner are charged appropriately for a copier or printer without being affected by the surrounding environment such as temperature and humidity. You must keep the amount. Further, in the fixing step by the heat roller fixing method, the non-offset property that does not adhere to the heat roller that is usually heated to a temperature of about 100 to 230 ° C. and the fixing property to paper must be good. Furthermore, blocking resistance that prevents toner from blocking during storage in a copier is also required.
In recent years, in the field of electrostatic charge image development, high image quality has been studied from various angles, and among them, the recognition that toner diameter reduction and spheroidization are extremely effective is increasing. However, as the diameter of the toner is reduced and the spheroidization is progressed, environmental charging stability and the like are lowered, and the phenomenon that the toner is scattered and adhered from the developing unit to the inner wall of the apparatus (toner scattering) has become a problem. In particular, this phenomenon occurs remarkably in a high temperature and high humidity environment.
[0004]
Under such circumstances, further speeding up of image formation is desired in the field of color copiers and color printers. The “tandem method” is effective for speeding up (for example, Japanese Patent Laid-Open No. 5-341617). The “tandem method” is a method in which an image formed by an image forming unit is transferred onto a transfer sheet (transfer material) by sequentially superimposing and transferring it onto a single transfer sheet (transfer material) conveyed to a transfer belt. This is a method for obtaining a full-color image. The tandem color image forming apparatus has a wide variety of usable transfer papers (transfer materials), has high quality of full color images, and can obtain full color images at high speed. In particular, obtaining a full-color image at a high speed is a unique property not found in other types of color image forming apparatuses. On the other hand, attempts have been made to achieve high speed while improving image quality using spherical toner. However, since it is necessary to shorten the time required for the toner to pass through the developing portion if an attempt is made to achieve high speed in an apparatus that employs the above-described method, it is necessary to reduce the developer when attempting to obtain the same developing ability as in the past. It is necessary to stir at high speed and with high torque for charge development. As a result, weakly charged toner and reversely charged toner are likely to be generated, and toner scattering from the developing portion is a problem.
[0005]
On the other hand, a method of mixing toner particles and inorganic powders such as various metal oxides for the purpose of improving the flow characteristics and charging characteristics of the toner has been proposed and is called an external additive. If necessary, the surface of the inorganic powder may be treated with a specific silane coupling agent, titanate coupling agent, silicone oil, organic acid, etc., or a specific resin may be coated to improve the hydrophobicity or charging characteristics of the surface of the inorganic powder. A method to do this has also been proposed. As the inorganic powder, for example, silicon dioxide (silica), titanium dioxide (titania), aluminum oxide, zinc oxide, magnesium oxide, cerium oxide, iron oxide, copper oxide, tin oxide and the like are known.
[0006]
In particular, silica particles in which silica or titanium oxide fine particles are reacted with organosilicon compounds such as dimethyldichlorosilane, hexamethyldisilazane, silicone oil, etc. to replace the silanol groups on the surface of the silica fine particles with organic groups are used to make them hydrophobic. .
Of these, silicone oil is known as a hydrophobizing agent that exhibits sufficient hydrophobicity and exhibits excellent transferability due to its low surface energy when contained in the toner. Japanese Patent Publication No. 7-3600 and Japanese Patent No. 2568244 define the degree of hydrophobicity of silica treated with silicone oil. JP-A-7-271087 and JP-A-8-29598 define the amount of silicone oil added and the carbon content in the additive. In order to ensure the stability of developer chargeability under high humidity by hydrophobizing inorganic fine particles that are the base material of external additives, the silicone oil content and hydrophobization degree described in the above publication are satisfactory. did it. However, a member that comes into contact with the developer using low surface energy, which is an important specificity of silicone oil, such as a contact charging device, a developer carrier (sleeve), a doctor blade, a carrier, an electrostatic latent image carrier ( No aggressive attempts have been made to reduce adhesion to photoconductors) and intermediate transfer members. Silicone oil is especially used for background stains due to strong developer adhesion to the photoconductor, and for post-transfer on the character and line portions of the image, the edge portion and the center portion of the dot portion (portions where the developer is not transferred). It could not be improved only by adjusting the amount of addition and the degree of hydrophobicity. Further, the white spots due to the inability to transfer to the recesses during transfer to a transfer member with severe irregularities have not been improved as well. Japanese Unexamined Patent Publication No. 11-212299 discloses inorganic fine particles containing a specific amount of silicone oil as a liquid component. However, such a definition of the amount cannot satisfy the above-mentioned characteristics.
[0007]
Further, the toner for developing an electrostatic image is required to be charged uniformly and stably, and when these are insufficient, the image quality is deteriorated due to the occurrence of background stains, density unevenness and the like. Further, since the developing mechanism has been miniaturized with the miniaturization of the image forming apparatus, the toner charge rising has become an even more important item in order to obtain high image quality. In order to improve these, various proposals have been made so far. Among these, as an example of proposed improvement in chargeability by using an additive for developing an electrostatic charge image toner, JP-A-3-294864 discloses a non-magnetic one-component development containing inorganic powder treated with silicone oil. JP-A-4-204665 discloses a one-component magnetic developer having an additive coverage of 3 to 30% with respect to toner, and JP-A-4-335357 discloses a BET non-surface area of 5 to 100 m. ² An electrostatic charge developer containing particles having a specific surface area of 1.2 times or more of the fine particles fixed to the toner and externally added to the toner. Kaihei 7-43930 discloses a developer using a non-magnetic one-component toner containing a hydrophobic silica fine powder and a specific hydrophobic titanium oxide, and JP-A-8-202071 discloses an organic polymer skeleton and a polysiloxane. Developers containing toner additives composed of organic-inorganic composite particles containing a skeleton are disclosed.
[0008]
However, even with the above method, sufficient charge uniformity cannot be obtained, the toner charge amount does not rise sufficiently, and the environmental stability of the toner charge amount, particularly the stability against humidity, is not necessarily sufficient. There was no. In particular, the use of additives that have been improved in hydrophobicity by surface treatment of general oxide particles, as seen in many of the proposals, shows initially desired charge stability, but the additives are used over time such as running. There is a problem that the toner is deteriorated due to the composition change. Further, for example, in composite particles synthesized using a liquid phase method as described in JP-A-8-202071, sufficient hydrophobicity cannot be obtained due to the influence of a liquid substance remaining inside the particles. In some cases, the hydrophobicity may change.
[0009]
On the other hand, as a binder resin, polystyrene, styrene are required in terms of properties required for toner, that is, transparency, insulation, water resistance, fluidity (as powder), mechanical strength, gloss, thermoplasticity, grindability, etc. -Acrylic copolymers, polyester resins, epoxy resins and the like are generally used, and among them, styrene resins are widely used because they are excellent in grindability, water resistance and fluidity. However, in order to store a copy obtained with a styrene resin-containing toner, if placed in a vinyl chloride resin sheet document holder, the image surface of the copy is left in close contact with the sheet. That is, the plasticizer contained in the vinyl chloride resin is transferred and plasticized to the fixed toner image and welded to the sheet side. As a result, when the copy is released from the sheet, the toner image is partially or completely peeled from the copy. The sheet also had the disadvantage of getting dirty. Such a defect is also seen in the polyester resin-containing toner.
As a measure for preventing the transition to the vinyl chloride resin sheet as described above, JP-A-60-263951 and 61-24025 disclose an epoxy which is not plasticized with a vinyl chloride resin plasticizer to a styrene resin or a polyester resin. Proposals for blending resins have been made.
[0010]
However, when such a blend resin is used particularly for color toners, the incompatibility between different types of resins causes offset properties, fixed image curl, and glossiness (in the case of color toner images, poor images without gloss). Colorability, transparency, and color developability become problems. These problems cannot be solved by conventional epoxy resins or acetylated modified epoxy resins as proposed in JP-A-61-235852.
[0011]
Then, although it is possible to solve the said problem by using an epoxy resin independently, the reactivity with the amine of an epoxy resin arises as a new problem. Epoxy resins are generally used as curable resins having excellent mechanical strength and chemical resistance by reacting an epoxy group with a curing agent to form a crosslinked structure. Curing agents are roughly divided into amine-based and organic acid anhydride-based. Of course, an epoxy resin used as an electrostatic charge image developing toner is used as a thermoplastic resin. However, dyes and pigments kneaded together with the resin as a toner, some charge control agents are amine-based, A cross-linking reaction may occur during kneading and may not be used as a toner. In addition, the chemical activity of this epoxy group is considered to be biochemical, that is, toxic such as skin irritation, and its presence requires careful attention.
[0012]
In addition, since the epoxy group exhibits hydrophilicity, water absorption at a high temperature and high humidity is remarkable, which causes a decrease in charge, background contamination, poor cleaning, and the like. Furthermore, the charging stability in the epoxy resin is another problem.
Generally, the toner is composed of a binder resin, a colorant, a charge control agent, and the like. Various dyes and pigments are known as colorants, some of which have charge controllability, and some of which have two functions of a colorant and a charge control agent. Although various resins are used as binder resins to form toners with the above-described composition, there is a problem that there is dispersibility of dyes and pigments, charge control agents and the like. In general, the kneading of the binder resin, the dye / pigment, the charge control agent and the like is performed by a hot roll mill, and it is necessary to uniformly disperse the dye / pigment, the charge control agent and the like in the binder resin. However, it is difficult to sufficiently disperse, and if the dye / pigment as a colorant is poorly dispersed, color development is poor and the coloring degree is lowered. Further, when the dispersion of the charge control agent or the like is poor, the charge distribution becomes non-uniform, which causes various defects such as charging failure, background smearing, scattering, insufficient ID, blurring, and cleaning failure. Japanese Patent Laid-Open No. 61-219051 discloses a toner using an epoxy resin ester-modified with ε-caprolactone as a binder resin. There were also 15 to 90% by weight, so that the softening point was too low and the gloss was too high.
[0013]
Japanese Laid-Open Patent Publication No. 52-86334 discloses that a primary primary or secondary amine is reacted with a terminal epoxy group of a ready-made epoxy resin to have positive chargeability. As described above, there may be a case where the epoxy group and the amine cause a crosslinking reaction and cannot be used as a toner. Furthermore, Japanese Patent Application Laid-Open No. 52-156632 discloses that one or both of the terminal epoxy groups of the epoxy resin are reacted with alcohol, phenol, Grignard reagent, organic acid sodium acetylide, alkyl chloride or the like. However, when an epoxy group remains, problems such as reactivity with amine, toxicity, and hydrophilicity occur as described above. In addition, some of the reactants described above are hydrophilic, have an effect on charging, and have an effect on pulverizability when being made into toner, and are not necessarily all effective in the present invention.
[0014]
JP-A-1-267560 discloses that both terminal epoxy groups of an epoxy resin are reacted with a monovalent active hydrogen-containing compound and then esterified with a monocarboxylic acid, an ester derivative thereof, or a lactone. Although the reactivity, toxicity, and hydrophilicity of the epoxy resin have been solved, curling has not been improved much in fixing.
[0015]
Furthermore, generally, a solvent such as xylene is often used during the synthesis of the epoxy resin or polyol resin (for example, JP-A-11-189646), but these solvents or unreacted residual monomers such as bisphenol A, It was present in a large amount in the resin after production, and the remaining amount of toner using these resins was also a problem.
[0016]
On the other hand, the performance required for a color toner for developing an electrostatic image, particularly used for forming a color image, is stricter than that for obtaining a black image. In other words, in addition to mechanical and electrical stability against external factors such as impact and humidity, as a toner, appropriate color expression (coloring degree), color reproducibility when color is superimposed, color developability, and color gradation , Clarity, light transparency (transparency) when used in an overhead projector (OHP), and high light resistance in all environments.
[0017]
Examples of using a dye as the colorant include those described in JP-A Nos. 57-130043 and 57-130044. However, when a dye is used as the colorant, the resulting image has excellent transparency and good color development, and a clear color image can be formed, but on the other hand, it is inferior in light resistance and left under direct light. In this case, there is a problem of discoloration or fading.
[0018]
On the other hand, those using pigments as colorants include those described in JP-A-49-46951 and JP-A-52-17023. However, although pigment-based color toners are excellent in light resistance, there is a problem that coloring degree (coloring property) and transparency are inferior due to poor dispersibility of the pigment in the binder resin.
As a method for improving the dispersibility of the pigment with respect to the binder resin, the following has been proposed.
(1) Japanese Patent Application Laid-Open No. Sho 62-280755; a polyester resin (resin A) is used as a binder resin, and a pigment is previously coated with a polyester resin (resin B) having a higher molecular weight than the resin A. That obtains a color toner by dispersing the resin in resin A.
(2) Japanese Patent Laid-Open No. 2-66561; a processed pigment selected by melting and kneading a resin and a pigment resin is dispersed and contained in the binder resin, and the weight average molecular weight of the pigment resin is the binder. A color toner, wherein the weight average molecular weight of the resin is smaller, and the weight average molecular weight of the binder resin is 100,000 or more.
(3) JP-A-9-101632; a mixture of a binder resin and a pigment is kneaded in advance with an organic solvent at a temperature lower than the melting temperature of the binder resin, and further, the binder resin and the charge control agent To obtain color toners by adding heat and kneading in the second stage.
(4) JP-A-4-39671; a toner comprising a binder resin having a weight average molecular weight of 40,000 or less and a colorant made of a flushing pigment using the binder resin.
(5) JP-A-4-230770; a solvent, a first binder resin soluble in the solvent, and particles of a colorant insoluble in the solvent are mixed, and the temperature is 50 to 100 ° C. under pressure. The colorant particles are dispersed in the binder resin while applying a shearing force, and then the solvent is removed to obtain a colored binder resin composition in which the colorant particles are dispersed. Technology that obtains toner by adding resin and charge control agent and heat-melting and kneading the second stage.
[0019]
However, neither of the methods described in the above (1) and (2) publications can provide sufficient dispersion of the pigment, and the present situation is that the coloring degree and transparency are inferior.
In addition, although the methods described in the above (3), (4), and (5) improve the dispersion of the pigment, since any method uses a solvent, no matter how much it is removed, a very small amount in the product or toner. However, recently, the solvent remains, and this causes a problem such as a decrease in toner charge amount in a special environment of use in a high temperature environment and a problem such as toner scattering in the developing portion. It became clear by examination of those. Toner scattering not only causes a decrease in maintainability of the apparatus, but also causes a problem that the scattered toner adheres to the non-printing portion.
[0020]
In addition, there are also known examples in which the particle diameter of the colorant in the toner is defined (Japanese Patent Nos. 2992924 and 3047310), but these particle size distributions provide sufficient coloration, but color transparency. However, sufficient effects were not obtained in terms of color developability and light resistance. In particular, the effect of improving toner scattering under high-temperature and high-humidity environment and background stain under low-temperature and low-humidity could not be obtained. Similarly, in Japanese Patent Application Laid-Open No. 2001-228653, the particle size distribution is defined, but the small particle size side is not considered, and there is a problem in light resistance in particular.
[0021]
On the other hand, as represented by Japanese Patent Application Laid-Open No. 1-304467, the toner is produced by mixing all the raw materials at once and heating, melting, and dispersing them with a kneader to obtain a uniform composition. A method of producing a toner having a volume average particle diameter of about 6 to 10 μm by cooling, pulverizing and classifying the toner is generally employed. In particular, a color toner for developing an electrostatic image used for forming a color image is generally constituted by dispersing and containing various chromatic dyes or pigments in a binder resin. In this case, the performance required for the toner to be used is stricter than that for obtaining a black image. That is, as a toner, in addition to mechanical and electrical stability against external factors such as impact and humidity, appropriate color expression (coloring degree) and light transmission (transparency) when used in an overhead projector (OHP) )Is required. Examples of using a dye as the colorant include those described in JP-A Nos. 57-130043 and 57-130044. However, when a dye is used as the colorant, the resulting image has excellent transparency and good color development, and a clear color image can be formed, but on the other hand, it is inferior in light resistance and left under direct light. In this case, there is a problem of discoloration or fading.
[0022]
Also, high temperature and high humidity, low temperature and low humidity environment during storage and transportation after toner production are harsh conditions for the toner, and the toner does not aggregate even after storage in the environment, charging characteristics, fluidity, transferability, fixing However, an effective means for this has not been found so far.
[0023]
[Problems to be solved by the invention]
The problems of the present invention are as follows.
(1) After storing the toner in a high-temperature and high-humidity environment for a long time and after printing tens of thousands of sheets in a high-temperature and high-humidity environment, the charging stability is excellent and the charging property is good. To provide a toner, a developer, an image forming method, and an image forming apparatus that do not occur.
(2) Toner that does not cause background stains (fogging) with little weakly charged and reversely charged toner that has excellent charging stability even after outputting tens of thousands of images in a low temperature and low humidity environment, not only in a normal temperature and normal humidity environment. To provide a developer, an image forming method, and an image forming apparatus.
(3) Even after outputting tens of thousands of images, a toner, developer, image forming method, and image having sufficient colorability, light resistance, transparency, color development, sharpness, color reproducibility, saturation, and gloss Providing a forming device.
(4) To provide an image forming apparatus and an image forming method having high durability and low maintenance as an image forming system.
(5) To provide a toner, a developer, an image forming apparatus, and an image forming method exhibiting necessary and sufficient charge rising property and holding charge amount in both high temperature and high humidity and low temperature and low humidity environments.
(6) To provide an image forming apparatus and an image forming method excellent in the balance between fixing property and non-offset property, in which the printing speed is not inferior from a low speed to a high speed region, the image density is not lowered by continuous image output.
(7) A toner, a developer, and an image forming method in which spherical toner having a small particle size and high circularity has excellent charging stability and good chargeability, little weakly charged and reversely charged toner, and no toner scattering occurs. An image forming apparatus is provided.
(8) To provide an image forming apparatus and an image forming method in which a toner image is not transferred to a sheet even when a fixed image surface is brought into close contact with a vinyl chloride resin sheet.
(9) To provide an image forming apparatus and an image forming method in which a fixed image is not substantially curled.
[0024]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the toner containing at least a binder resin and a colorant has a colorant molecule coverage of 1.5 to 15 atom% by XPS. In addition, by using a toner for developing an electrostatic image having a colorant content of 2 to 15% by weight, the toner can be charged even after outputting tens of thousands of images after storing the toner in a high temperature and high humidity environment for a long time. Low-charge and reverse-charged toner with excellent stability, no toner scattering, and charging even after outputting tens of thousands of images not only in normal temperature and normal humidity environment but also in high temperature and high humidity environment and low temperature and low humidity environment Slightly charged with excellent stability, few reversely charged toners, no background stains (fogging), and even after outputting tens of thousands of images, sufficient colorability, light resistance, transparency, color development, sharpness , Color reproducibility, saturation, light Found that superior can form high quality images on.
[0025]
The mechanism is currently being elucidated, but the following were inferred from some analysis data. XPS (X-ray photoelectron spectroscopy) is a technique for irradiating a sample with X-rays and analyzing the energy of the generated photoelectrons. Qualitative and quantitative analysis of the elements on the extreme surface (several nm) of the sample is possible. The surface of the toner is very important in terms of generating and maintaining charge, and the control of the surface state is essential for controlling the chargeability, fixability, color characteristics, and the like. On the other hand, the colorant is literally a necessary material for forming an image by imparting a color to the toner, but it has been found that the colorant is an undesirable material particularly in terms of the chargeability of the toner. In other words, if the colorant is present on the toner surface beyond a certain amount, the chargeability of the toner is adversely affected, and the resin or charge control agent that exerts the charge of the toner is covered and consequently the charging site of the toner is lowered. found. Therefore, the present inventors have controlled the colorant molecule coverage on the toner surface measured using XPS to 1.5 to 15 atom%, preferably 2.0 to 13 atom%, and the colorant. It has been found that by containing 2 to 15% by weight, preferably 4 to 11% by weight of the toner, the above problem can be solved and a toner having sufficient charging characteristics can be obtained.
[0026]
Here, if the coverage of the colorant molecule is less than 1.5 atomic%, the toner surface amount of the colorant particles is too small, and the colorant is finely dispersed in order to reduce the color degree or reduce the surface amount. If the amount is too much, the crystallinity of the colorant is lowered, and the light resistance is particularly lowered. It has also been found that, if the dispersion is too high, the molecular chain of the binder resin is broken, and the fixing property such as the occurrence of hot offset is adversely affected. Further, in the case of a pulverized toner, the pulverization property of the toner is lowered, which is undesirable because it causes a decrease in productivity and an increase in cost. On the other hand, when the coverage of the colorant molecule exceeds 15 atomic%, the aggregate of the colorant on the toner surface is peeled off when the toner is produced, and the colorant spent or the like is likely to be caused on the carrier surface or the developing sleeve surface. The number of charging sites is reduced, and the chargeability and print quality stability are adversely affected. In addition, the colorant tends to be exposed on the toner surface, and the surface coverage of the binder resin and charge control agent that exerts an effect on the chargeability of the toner is reduced, which adversely affects the chargeability of the total toner. In addition, it produces weakly charged toner and reversely charged toner, especially in environments where the charge level tends to fluctuate, such as in high-temperature, high-humidity, low-temperature, low-humidity environments, and this effect is particularly significant, leading to the occurrence of toner scattering and background contamination. .
[0027]
Further, when the content of the colorant particles is 2 to 15% by weight with respect to the toner, the toner has a sufficient coloring degree and an effect of preventing toner scattering, background stains, and the like. That is, when the colorant particles are less than 2% by weight, the degree of coloration per weight of the toner is lowered, and it is necessary to increase the thickness of the toner layer in order to give the same degree of coloration as the image. In this case, as the toner layer becomes thicker, toner development and transfer amount increase, and toner scattering, transfer toner dust and the like are more likely to occur. Further, since the layer is thick, the color reproduction accuracy is also lowered. On the other hand, if it exceeds 15% by weight, the colorability is sufficient, but a problem occurs in terms of the chargeability of the toner. That is, the colorant covers the toner surface, the amount of the binder resin and charge control agent on the toner surface is reduced, the charging ability as the toner is reduced, and problems such as toner scattering and background contamination as described above occur.
[0028]
In the present invention, control of the toner surface amount of the colorant, that is, control of dispersibility of the colorant in the resin is important. When the binder resin of the toner contains at least a polyol resin, The dispersibility of the toner was extremely good, and sufficient environmental chargeability, tensile strength at break, environmental stability, and stable fixing characteristics were obtained. Further, since the binder resin of the toner contains at least a polyol resin having an epoxy resin part and a polyoxyalkylene part in the main chain, further stable colorant dispersibility and environmental stability, stable fixing characteristics, copy fixing The toner image can be prevented from transferring to the sheet when it is in close contact with the vinyl chloride resin on the image surface, especially when used with color toners, color reproducibility, stable gloss, curling of copy-fixed images, etc. Found to have an effect.
[0029]
In addition, when an electrostatic charge image developing toner having a small particle diameter of 1 to 6 μm is used, the toner is advantageous in terms of high image quality. Due to the particle size, the chargeability of each toner particle tends to decrease from the point of contact charging probability, and the weakly charged and reversely charged toner tends to increase. It was. As a means to make full use of this small particle size toner, by controlling the coverage of the colorant molecules on the surface of the toner toner, it is possible to maintain a sufficient degree of coloration and prevent toner scattering, dirt, etc. I found out.
[0030]
Further, when a toner having a high degree of circularity with a circularity SF-1 of 100 to 140 and a circularity SF-2 of 100 to 130 is used, the toner is also advantageous in terms of high image quality. However, due to the spherical shape, the frictional resistance between the toner and the carrier (developing sleeve) decreases, making it difficult for the toner to be held with the carrier (developing sleeve), and there is a problem with a small margin for toner scattering and dirt. It was. As a means to make full use of this high-circularity toner, it is possible to maintain sufficient coloring degree by controlling the coating ratio of colorant molecules on the toner surface, and to prevent toner scattering, background staining, etc. I found it.
[0031]
In addition, by using a two-component development system including at least a carrier composed of the toner and magnetic particles, stable charging characteristics can be maintained even when the highly colored and highly dispersed colorant toner is used. As a developer, a development property with excellent charge rising property and environmental charge stability having a sufficient bulk density with little stress fluctuation as a developer was obtained. Further, a developing system having excellent toner density controllability using a bulk density sensor or the like was obtained.
[0032]
In addition, the electrostatic image divided into multiple colors on the electrostatic charge image carrier is developed with a plurality of multi-color electrostatic charge image developing agents to form a toner image and transferred to the surface of the electrostatic charge image carrier. In the tandem type color image forming apparatus that obtains a color image on the transfer material by sequentially superposing and transferring the toner image on a single transfer material by contacting the means, the printing speed is equivalent to A4 size and 20 In the case of high-speed printing of at least 25 sheets / minute, more preferably at least 25 sheets / minute, and even more preferably at least 30 sheets / minute, it is necessary to shorten the time required for the toner to pass through the developing portion. In order to obtain the capability, it is necessary to stir the developer at a higher speed and with a higher torque to perform charging development. As a result, weakly charged toner and reversely charged toner are more likely to be generated, and toner scattering from the developing portion occurs. Question to do There was. As a countermeasure, it has been found that by controlling the coating ratio of the colorant molecules on the toner surface, it is possible to maintain a sufficient degree of coloring and to prevent toner scattering and background contamination. As a result, image formation that is compatible with high-speed printing, is less affected by the material of the transfer material such as OHP, cardboard, coated paper, etc., has few transfer defects during transfer, has few image defects, and has high image quality and excellent maintainability. A device was obtained.
[0033]
The present invention has been completed based on the above findings.
That is, according to the present invention, the following toner, full color tonerket, image forming method, and image forming apparatus are provided.
(1) In a toner containing at least a binder resin and a colorant, the coverage of the colorant molecules on the toner surface by XPS measurement is 1.5 to 15 atomic%, and the colorant content is 2 to 2%. An electrostatic charge image developing toner, wherein the toner is 15% by weight.
(2) The toner for electrophotography as described in (1) above, wherein the binder resin of the toner contains at least a polyol resin.
(3) The electrophotography according to any one of (1) to (2), wherein the binder resin of the toner includes at least a polyol resin having an epoxy resin portion and a polyoxyalkylene portion in the main chain. Toner.
(4) The toner for developing an electrostatic charge image according to any one of (1) to (3), wherein the toner has a volume average particle diameter of 1 to 6 μm.
(5) The electrostatic charge image according to any one of (1) to (4), wherein the toner has a circularity SF-1 value of 100 to 140 and a circularity SF-2 value of 100 to 130. Developing toner.
(6) In a toner containing at least a binder resin and a colorant, the coverage of the colorant molecules on the toner surface by XPS is 1.5 to 15 atomic%, and the colorant content is 2 to 15% by weight. %, A full color toner kit containing at least a magenta toner for developing an electrostatic charge image, a yellow toner, and a cyan toner.
(7) A two-component developer comprising at least a carrier comprising the toner according to any one of (1) to (6) and magnetic particles.
(8) An image forming method using the toner or full color toner kit or developer according to any one of (1) to (7).
(9) A tandem system characterized in that the toner or full color toner kit or developer described in any one of (1) to (7) above is used and the printing speed is equivalent to A4 size and is 20 sheets / minute or more. Color image forming method.
(10) An image forming apparatus comprising a container filled with the toner or full color toner kit or developer according to any one of (1) to (7).
[0034]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. Here, as long as the conditions regarding the electrostatic charge image developing toner used in the present invention, the production method and materials of the developer, and the overall system relating to the electrostatic charge image development process are satisfied, all known ones can be used.
[0035]
(Colorant molecule coverage)
The coverage of the colorant molecule in the present invention is 1.5 to 15 atomic%, preferably 2.0 to 13 atomic%. As the colorant molecule coverage in this case, the coverage C value calculated by the following equation (1) using the element quantification result obtained by XPS (X-ray photoelectron spectroscopy) measurement of the toner is used. The device type and conditions are not particularly limited as long as similar results can be obtained, but the following conditions are preferable.
C = E × T / N (1)
C: Colorant coverage (atomic%)
E: Quantitative value by XPS of elements peculiar to colorants (atomic%)
T: Total number of atoms in the colorant molecule
N: Number of atoms of specific elements in the colorant molecule
In addition, as an element peculiar to a coloring agent, a nitrogen atom can be utilized preferably, for example.
The equipment and conditions are shown below.
Apparatus: 1600S type X-ray photoelectron spectrometer manufactured by PHI
X-ray source; MgKα (400W)
Analysis area: 0.8 × 2.0mm
Pretreatment: Sample was packed in an aluminum dish, and was measured by adhering to a sample holder with a carbon sheet; calculation of surface atomic concentration; relative sensitivity factor provided by PHI was used.
[0036]
(Masterbatch colorant)
In the present invention, for the purpose of improving the affinity between the resin and the colorant, a master batch colorant in which the resin and the colorant are mixed and kneaded in advance can also be used. Any colorant can be used as long as it is a substance colored by pigments, dyes and the like. The ratio of the resin to the colorant is more preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and still more preferably 40:60 to 60:40. The resin used here is not necessarily the toner binder resin itself, and a polyol resin, a polyester resin, or the like having good affinity with the toner binder resin can be used more preferably. For these, the same resin as the binder resin described later can be used. Furthermore, dispersibility can be further improved by using dry powder pigment and using water as a method of wetting with the resin. In the first place, the primary particles of the pigment are as small as 0.001 to 0.1 μm, but in the state of the raw material dry powder, a large aggregate of several μm is formed. The ideal dispersion of the pigment is to break up the agglomerates into pieces of primary particles. However, the primary particles of about 0.001 to 0.1 μm are reduced to less than that by a normal kneading method. The reduction in size is the limit in such a normal kneading method by repeated mechanical shearing. That is, the fact that the dispersion of the pigment is bad is none other than that the aggregate cannot be crushed. The necessary condition for the aggregates to be crushed is that the surrounding resin penetrates into the voids inside the aggregates and efficiently wets all the primary particle surfaces. Accordingly, the point of pigment dispersion is whether or not the surrounding resin can enter the voids inside the aggregate. However, since the binder resin used for ordinary toner has a high melt viscosity, it requires a large amount of energy to enter the aggregate, and the pigment is not yet the primary particle desired. It is.
[0037]
Organic pigments that are generally used as colorants are hydrophobic, but in the manufacturing process, they are washed with water and dried, so if some force is applied, water is soaked into the pigment aggregate. It is possible. When a mixture of a pigment in which water is soaked into the aggregate and a resin is kneaded at a set temperature of 100 ° C. or higher with an open type kneader, the water inside the aggregate instantaneously reaches the boiling point and expands in volume. Therefore, a force is applied to break up the aggregate from the inside of the aggregate. The force from the inside of the aggregate can disintegrate the aggregate very efficiently compared to the force applied from the outside. Furthermore, at this time, since the resin is heated to a temperature higher than the softening point, the viscosity is lowered and the aggregate is efficiently wetted. By substituting with the effect, a master batch colorant in which the pigment is dispersed in a state close to primary particles can be obtained. Furthermore, in the process of evaporating water, the heat of vaporization accompanying water evaporation is taken away from the kneaded product, so the temperature of the kneaded product is kept at a relatively low temperature and high viscosity of 100 ° C. or less, so the shearing force is effective. In addition, it has the effect of being added to the pigment aggregate. As an open type kneader for producing a masterbatch colorant, a method of using a Banbury mixer as an open type, a continuous two roll kneader manufactured by Mitsui Mining Co., Ltd., etc. is used in addition to the usual two rolls and three rolls. be able to. As a means for better dispersing the colorant in the resin, it is also effective to coarsely pulverize the master batch colorant once kneaded with a pulverizer or the like and then knead it again twice or three times.
[0038]
(Coloring agent)
As the colorant of the toner of the present invention, all known dyes and pigments can be used. Of these, organic pigments having particularly high lipophilicity are more preferable. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, oil yellow, Hansa yellow, (GR , A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Pyrazolone Orange, Benzidine Orange G, Permanent Red 4R, Watching Red Calcium Salt, Brilliant Carmine 38, Fast Bio Red B, Methyl Bio Red Lake, Indanthrene Blue BC, Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anslagen Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Zhu, Cado New Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fire Red, Parachlor Ortho Nitroaniline Red, Rissor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scalate VD, Belcan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Naphthol Carmine, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, -Damin Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigolet B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultraviolet, Bituminous, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, manganese purple, dioxazine violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridiane Emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof.
[0039]
In the present invention, high light resistance of polycondensed azo pigments, insoluble azo pigments, quinacridone pigments, carmine pigments, naphthol carmine pigments, isoindolinone pigments, perylene pigments, anthraquinone pigments, copper phthalocyanine pigments, etc. And highly dispersible pigments are preferred.
[0040]
Examples of the color pigment for magenta include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209, 211; C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.
[0041]
Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45, copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, green 7 and green 36, and the like.
[0042]
Examples of the color pigment for yellow include C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. I. Bat yellow 1, 3, 20, orange 36 and the like.
The content of the colorant is 2 to 15% by weight, more preferably 4 to 11% by weight, based on the toner.
Various dispersion improvers can also be contained for the purpose of improving the dispersibility of the colorant in the resin.
[0043]
(External additive)
Any known external additive can be used. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate), metal oxides (such as titania, alumina, tin oxide, and antimony oxide), fluoropolymers, and the like may be contained.
Particularly suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H1303 (above Hoechst), and R972, R974, RX200, RY200, R202, R805, and R812 (above Nippon Aerosil). Further, as titania fine particles, P-25 (Nippon Aerosil), STT-30, STT-65C-S (above Titanium Industry), TAF-140 (Fuji Titanium Industry), MT-150W, MT-500B, MT-600B MT-150A (taker above). Particularly, the hydrophobized titanium oxide fine particles include T-805 (Nippon Aerosil), STT-30A, STT-65S-S (above Titanium Industry), TAF-500T, TAF-1500T (above Fuji Titanium Industry), MT -100S, MT-100T (above Taka), IT-S (Ishihara Sangyo), etc.
[0044]
In order to obtain hydrophobized oxide fine particles, silica fine particles, titania fine particles, and alumina fine particles, hydrophilic fine particles are treated with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Can be obtained. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, amino modified silicone. Oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, and the like can be used. Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, quartz sand, clay, mica, and silica ash. Examples thereof include stone, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Of these, silica and titanium dioxide are particularly preferred.
[0045]
The addition amount can be 0.1 to 5% by weight, preferably 0.3 to 3% by weight, based on the toner. The average particle size of the primary particles of the inorganic fine particles is 100 nm or less, preferably 3 nm or more and 70 nm or less. If it is smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exhibited effectively. On the other hand, if it is larger than this range, the surface of the photoreceptor is undesirably damaged.
As the external additive, inorganic fine particles and hydrophobized inorganic particles can be used in combination, but at least 2 inorganic fine particles having an average particle size of 1 to 100 nm, more preferably 5 to 70 nm, of the primary particles subjected to the hydrophobizing treatment can be used. It is more desirable to include more than one type. Further, it is more preferable that at least two kinds of inorganic fine particles having an average particle diameter of 20 nm or less of the primary particles subjected to the hydrophobization treatment and at least one kind of inorganic fine particles of 30 nm or more are contained. The specific surface area according to the BET method is 20 to 500 m. ² / G is preferable.
[0046]
(Surface treatment agent)
Examples of surface treatment agents for external additives containing fine oxide particles include silane coupling agents such as dialkyl dihalogenated silanes, trialkyl halogenated silanes, alkyl trihalogenated silanes, and hexaalkyldisilazanes, silylating agents, and fluorinating agents. Examples thereof include silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and silicone varnishes. More preferred are organosilicon compound surface treatment agents and hydrophobic treatment agents.
[0047]
(Resin fine particles)
As the external additive, resin fine particles can also be used. For example, polystyrene particles obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization, methacrylic acid ester or acrylic acid ester copolymer, polycondensation systems such as silicone, benzoguanamine, and nylon, and polymer particles by thermosetting resin can be mentioned. . By using in combination with such resin fine particles, the chargeability of the developer can be enhanced, the reversely charged toner particles can be reduced, and the background stain can be reduced. The addition amount may be 0.01 to 5% by weight, preferably 0.1 to 2% by weight, based on the toner.
[0048]
(Roundness)
The shape factors SF-1 and SF-2, which are the circularity used in the present invention, are obtained by randomly sampling 300 SEM images of toner obtained by measurement with a FE-SEM (S-4200) manufactured by Hitachi, Ltd. The image information was introduced into an image analysis apparatus (Luzex AP) manufactured by Nireco through an interface and analyzed, and the values obtained from the following equations were defined as SF-1 and SF-2. The values of SF-1 and SF-2 are preferably values obtained by Luzex, but are not particularly limited to the FE-SEM device and the image analysis device as long as similar analysis results can be obtained.
SF-1 = (L ² / A) × (π / 4) × 100
SF-2 = (P ² / A) × (1 / 4π) × 100
here,
The absolute maximum length of toner is L
The projected area of the toner is A
The maximum toner circumference is P
And In the case of a true sphere, all become 100, and from a spherical shape to an indefinite shape as the value becomes larger than 100. In particular, SF-1 represents the shape of the entire toner (ellipse, sphere, etc.), and SF-2 is a shape factor indicating the degree of surface irregularities.
[0049]
(Softening point, outflow start temperature)
The softening point of the toner of the present invention was measured using a softening point measuring device (FP90, manufactured by Mettler Co., Ltd.) at a heating rate of 1 ° C./min.
[0050]
(Glass transition temperature (Tg))
The Tg of the toner of the present invention was measured under the following conditions using the following differential scanning calorimeter.

[0051]
(Molecular weight)
The number average molecular weight (Mn), weight average molecular weight (Mw), and peak molecular weight Mp were measured by GPC (gel permeation chromatography) as follows. A sample solution is prepared by dissolving 80 mg of a sample in 10 ml of THF, filtered through a 5 μm filter, 100 μl of this sample solution is injected into the column, and the retention time is measured under the following conditions. Moreover, the retention time was measured using polystyrene having a known average molecular weight as a standard substance, and the number average molecular weight of the sample was determined in terms of polystyrene from a calibration curve prepared in advance.

[0052]
(Penetration, heat-resistant storage stability)
The toner was weighed 10 g at a time, placed in a 20 cc glass container and left in a thermostatic bath set at 50 ° C. for 5 hours, and the penetration was measured with a penetration meter.
[0053]
(Binder resin)
As the binder resin of the toner used in the present invention, polymers of styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene -Vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl Methyl ketone copolymer, steel -Styrene copolymer such as styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate , Polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or fat Examples thereof include cyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes, which can be used alone or in combination. In particular, a polyol resin and a polyester resin are more preferable.
[0054]
Further, when the terminal of the polyol resin of the binder resin is inactive, a toner having less environmental stability and harmfulness can be obtained.
As the polyol resin (epoxy resin) used in the present invention, it is preferable to use a resin obtained by binding bisphenol such as bisphenol A or bisphenol F and epichlorohydrin. The epoxy resin is at least two or more bisphenol A type epoxy resins having different number average molecular weights in order to obtain stable fixing characteristics and gloss, and the number average molecular weight of the low molecular weight component is 360 to 2000, and the high molecular weight component The number average molecular weight is preferably 3000 to 10,000. Further, it is preferable that the low molecular weight component is 20 to 50 wt% and the high molecular weight component is 5 to 40 wt%. When the amount of the low molecular weight component is too large or the molecular weight is lower than the molecular weight 360, there is a possibility that the gloss is too high or the storage stability is deteriorated. Further, when the amount of the high molecular weight component is too large or the molecular weight is higher than 10,000, the gloss may be insufficient or the fixing property may be deteriorated.
[0055]
Examples of the resin compound used in the present invention include the followings as alkylene oxide adducts of dihydric phenols. Examples include reaction products of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof with bisphenols such as bisphenol A and bisphenol F. The resulting adduct may be used after glycidylation with epichlorohydrin or β-methylepichlorohydrin. In particular, diglycidyl ether of an alkylene oxide adduct of bisphenol A represented by the following general formula (1) is preferable.
[Chemical 1]

[0056]
Moreover, it is preferable that 10-40 wt% of the alkylene oxide adduct of dihydric phenol or its glycidyl ether is contained with respect to polyol resin. If the amount is small, problems such as an increase in curl occur, and if n + m is 7 or more, or if the amount is too large, the gloss may be excessively increased, and the storage stability may be deteriorated. Examples of the compound having one active hydrogen in the molecule that reacts with the epoxy group used in the present invention include monohydric phenols, secondary amines, and carboxylic acids. The following are illustrated as monohydric phenols. Examples include phenol, cresol, isopropylphenol, aminophenol, nonylphenol, dodecylphenol, xylenol, and p-cumylphenol. Secondary amines include diethylamine, dipropylamine, dibutylamine, N-methyl (ethyl) piperazine, piperidine and the like. Examples of carboxylic acids include propionic acid and caproic acid.
[0057]
Examples of the compound having two or more active hydrogens in the molecule that react with the epoxy group used in the present invention include dihydric phenols, polyhydric phenols, and polycarboxylic acids. Examples of the dihydric phenol include bisphenols such as bisphenol A and bisphenol F. Examples of polyhydric phenols include orthocresol novolaks, phenol novolacs, tris (4-hydroxyphenyl) methane, and 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] benzene. Examples of the polyvalent carboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, trimellitic acid, and trimellitic anhydride.
[0058]
In addition, by controlling the epoxy equivalent of the binder resin to 20000 or more, the thermal characteristics of the resin can be controlled, and the amount of low-molecular epichlorohydrin that is a reaction residue can be reduced. Toner having excellent properties and resin characteristics.
[0059]
By containing at least a polyol resin or at least a polyol resin having an epoxy resin part and a polyoxyalkylene part in the main chain, sufficient compression resistance, tensile strength at break, environmental stability, stable fixing characteristics, and chlorination of the copy fixing image surface The toner image can be prevented from transferring to the sheet when it is in close contact with the vinyl resin, especially when used for color toners, and it is effective for color reproducibility, stable gloss, curling of copy-fixed images, etc. More preferred. Further, by including at least a polyol resin portion and a polyester resin portion, a toner having a good balance between stretch resistance and adhesion as well as compression strength is obtained, and more stable transferability, developability, and fixing characteristics are obtained.
[0060]
As the resin, a polyester resin can also be preferably used, and various types of polyester resins can be used. Particularly, a polyester resin formed by reacting the following (1) to (3) is preferable. .
(1) At least one selected from any of divalent carboxylic acids and lower alkyl esters and acid anhydrides thereof,
(2) Diol component represented by the following general formula (2)
[Chemical formula 2]

(Wherein R ¹ And R ² And may be the same or different, and is an alkylene group having 2 to 4 carbon atoms, and x and y are the number of repeating units, each being 1 or more, and x + y = 2 to 16)
(3) At least one selected from trivalent or higher polyvalent carboxylic acids and their lower alkyl esters and acid anhydrides, and trivalent or higher polyhydric alcohols
Here, examples of the divalent carboxylic acid of (1) and its lower alkyl ester and acid anhydride include terephthalic acid, isophthalic acid, sebacic acid, isodecyl succinic acid, maleic acid, fumaric acid and monomethyl, monoethyl thereof. , Dimethyl and diethyl esters, phthalic anhydride, maleic anhydride and the like, and terephthalic acid, isophthalic acid and these dimethyl esters are particularly preferred in terms of blocking resistance and cost. These divalent carboxylic acids and their lower alkyl esters and acid anhydrides greatly affect the fixing properties and blocking resistance of the toner. That is, although depending on the degree of condensation, if a large amount of aromatic terephthalic acid, isophthalic acid or the like is used, the blocking resistance is improved, but the fixing property is lowered. Conversely, if a large amount of sebacic acid, isodecyl succinic acid, maleic acid, fumaric acid or the like is used, the fixing property is improved, but the blocking resistance is lowered. Accordingly, these divalent carboxylic acids are appropriately selected according to the other monomer composition, ratio and degree of condensation, and used alone or in combination.
[0061]
As an example of the diol component represented by the general formula (I) of (2), polyoxypropylene- (n) -polyoxyethylene- (n ′)-2,2-bis (4-hydroxyphenyl) propane, Examples include polyoxypropylene- (n) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (n) -2,2-bis (4-hydroxyphenyl) propane, and the like. .Ltoreq.n.ltoreq.2.5 polyoxypropylene- (n) -2,2-bis (4-hydroxyphenyl) propane and 2.0.ltoreq.n.ltoreq.2.5 polyoxyethylene- (n)- 2,2-bis (4-hydroxyphenyl) propane is preferred. Such a diol component has the advantage of improving the glass transition temperature and making it easier to control the reaction. In addition, it is also possible to use aliphatic diols such as ethylene glycol, diethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, propylene glycol as the diol component. is there.
[0062]
Examples of (3) trivalent or higher polyvalent carboxylic acids and lower alkyl esters and anhydrides thereof include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,3,5-benzenetricarboxylic acid 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthylenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexatricarboxylic acid Acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empor trimer acid and their monomethyl, monoethyl , Dimethyl and diethyl ester and the like.
[0063]
Examples of the trihydric or higher polyhydric alcohol (3) include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, Sugar, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, diglycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylol Examples include propane and 1,3,5-trihydroxymethylbenzene.
[0064]
Here, the blending ratio of the trivalent or higher polyvalent monomer is suitably about 1 to 30 mol% of the whole monomer composition. When it is 1 mol% or less, the offset resistance of the toner is lowered, and the durability is likely to deteriorate. On the other hand, when the amount is 30 mol% or more, toner fixability tends to deteriorate.
[0065]
Of these trivalent or higher polyvalent monomers, benzenetricarboxylic acids such as benzenetricarboxylic acid and anhydrides or esters of these acids are particularly preferable. That is, by using benzenetricarboxylic acids, both fixability and offset resistance can be achieved.
Further, these polyester resins and polyol resins are preferably non-crosslinked or weakly crosslinked (THF insoluble content is 5% or less) because it is difficult to obtain transparency and gloss when having a high crosslinking density. It is preferable.
Moreover, the manufacturing method of these binder resin is not specifically limited, Any of block polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc. can be used.
[0066]
(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEGVP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex ( Nippon Carlit), copper phthalocyanine, perylene, quinacridone, Examples thereof include azo pigments and other polymer compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt. In the present invention, the amount of charge control agent used is determined uniquely by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 1 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. On the other hand, when the amount is less than 0.1 part by weight, the function of the charge control agent cannot be exhibited sufficiently.
[0067]
(Career)
In addition, when the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier and the toner in the developer is 1 to 100 parts by weight of the carrier. 10 parts by weight is preferred. Any known carrier can be used, and conventionally known carriers such as iron powder, ferrite powder, magnetite powder, and magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, the film thickness of these coating materials is 0.01-3 micrometers, More preferably, it is 0.1-0.3 micrometers. When the thickness is 0.01 μm or less, film control is difficult and the function as a coat film cannot be exhibited. Further, if it is 3 μm or more, conductivity cannot be obtained, which is not preferable. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.
[0068]
(Magnetic material)
Furthermore, the toner of the present invention contains a magnetic material and can be used as a magnetic toner. When the magnetic toner is used, the toner particles may contain magnetic fine particles. Such magnetic materials include metals, alloys such as ferrite, magnetite and other irons, nickel, cobalt, etc., or compounds containing these elements, and those containing no ferromagnetic elements, but by applying an appropriate heat treatment. An alloy that exhibits ferromagnetism, for example, a seed alloy called Heusler alloy containing manganese and copper such as manganese copper aluminum and manganese-copper-tin, chromium dioxide, and the like. It is preferable that the magnetic material is contained in a uniformly dispersed form in the form of fine powder having an average particle size of 0.1 to 1 μm. The content of the magnetic material is preferably 10 to 70 parts by weight, particularly preferably 20 to 50 parts by weight, with respect to 100 parts by weight of the obtained toner.
[0069]
(wax)
In order to give the toner or developer a fixing releasability, it is preferable to include a wax in the toner or developer. In particular, when an oilless fixing machine that does not apply oil to the image fixing unit is used, it is preferable that the toner contains wax. The wax has a melting point of 40 to 120 ° C., and preferably 50 to 110 ° C. When the melting point of the wax is excessive, the fixing property at a low temperature may be insufficient. On the other hand, when the melting point is excessively low, the offset resistance and durability may be decreased. The melting point of the wax can be obtained by differential scanning calorimetry (DSC). That is, the melting peak value when a sample of several mg is ripened at a constant temperature increase rate, for example, (10 ° C./min) is defined as the melting point. The content of the wax is preferably 0 to 20 parts by weight, and more preferably 0 to 10 parts by weight.
[0070]
Examples of the wax that can be used in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide wax, fatty acid wax, dead monoketone, fatty acid metal salt wax, fatty acid ester wax, and partial kenne. And fatty acid ester wax, silicone varnish, higher alcohol, carnauba wax and the like. Also, polyolefins such as low molecular weight polyethylene and polypropylene can be used. In particular, polyolefins and esters having a softening point by the ring-and-ball method of 60 to 150 ° C are preferable, and polyolefins and esters having a softening point of 70 to 120 ° C are more preferable.
[0071]
More preferably, it contains at least one kind of wax selected from de-free fatty acid type carnauba wax having an acid value of 5 or less, montan ester wax, oxidized rice wax having an acid value of 10 to 30 and sazol wax. Turned out to be. The de-free fatty acid type carnauba wax is obtained by removing free fatty acid from carnauba wax as a raw material. Therefore, the acid value is 5% or less, and it becomes finer than conventional carnauba wax, resulting in a binder resin. The dispersion average particle diameter becomes 1 μm or less, and dispersibility is improved. The montan-based ester wax is refined from a mineral, becomes microcrystalline like the carnauba wax, has a dispersion average particle size of 1 μm or less in the binder resin, and improves dispersibility. In the case of montan ester wax, the acid value is particularly preferably 5 to 14.
[0072]
The dispersion diameter of the wax is preferably 3 μm or less, more preferably 2 μm or less, and still more preferably 1 μm or less. When the dispersion diameter is 3 μm or more, the wax outflow property and the transfer material peelability are improved, but the high-temperature and high-humidity durability as a toner, the charging stability and the like are lowered.
Oxidized russian wax is air-oxidized rice bran wax. The acid value is preferably 10 to 30, and if it is less than 10, the minimum fixing temperature increases and the low temperature fixability becomes insufficient. If it exceeds 30, the cold offset temperature increases and the low temperature fixability becomes insufficient. As the sazol wax, Sazol wax H1, H2, A1, A2, A3, A4, A6, A7, A14, C1, C2, SPRAY30, SPRAY40, etc. can be used, among which H1, H2, SPRAY30, SPRAY40. Is preferable because of low temperature fixing and storage stability. The wax may be used alone or in combination, and is preferably contained in an amount of 1 to 15 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the binder resin.
[0073]
(Cleaning improver)
It is more preferable that a cleaning property improving agent for removing the transferred developer remaining on the photoreceptor or the primary transfer medium is contained in the toner or added to the toner surface, or contained in the developer or added to the surface. Examples of the cleaning improver include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. . The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm. The content of the cleaning improver is preferably 0.001 to 5 parts by weight, and more preferably 0.001 to 1 part by weight.
[0074]
(Production method)
As the toner production method of the present invention, all known production methods can be used if there are conditions.
A toner production method including a step of mechanically mixing developer components including at least a binder resin, a main charge control agent, and a pigment, a melt-kneading step, a pulverizing step, and a classification step can be applied. In addition, in the mechanical mixing step and the melt-kneading step, a production method is also included in which powder other than the particles obtained as a product obtained in the pulverization or classification step is returned and reused.
The powders (sub-products) other than the particles used as the product referred to here are fine particles and coarse particles other than the components used as the product having a desired particle size obtained in the pulverization step after the melt-kneading step, and the subsequent classification step. It means fine particles and coarse particles other than the components that become products of a desired particle size generated in (1). It is preferable that such a by-product is mixed in the weight ratio of the other raw material 50 to the sub-product 50 from the other raw material 99 to the sub-product 1 in the mixing step and the melt-kneading step.
The mixing step of mechanically mixing at least the binder resin, the main charge control agent and the pigment, and the developer component including the by-product may be performed under normal conditions using a normal mixer using a rotating wing. There is no limit. More preferably a resin and a colorant in advance.
[0075]
When the above mixing process is completed, the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Kay Sea Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikegai Iron Works Co., Ltd. A kneader is preferably used.
It is important that this melt-kneading is performed under appropriate conditions so as not to break the molecular chain of the binder resin. Specifically, the melt-kneading temperature should be performed with reference to the softening point of the binder resin. If the temperature is too low than the softening point, cutting is severe, and if the temperature is too high, dispersion does not proceed. When controlling the amount of volatile components in the toner, it is more preferable to set optimum conditions for the melt-kneading temperature, time, and atmosphere while monitoring the amount of residual volatile components at that time.
[0076]
When the above melt-kneading process is completed, the kneaded product is then pulverized. In this pulverization step, it is preferable to first coarsely pulverize and then finely pulverize. At this time, a collision pulverization method in which the pulverization is performed by colliding with a collision plate in a jet stream, or a rotor pulverization method in which pulverization is performed with a narrow gap between a mechanically rotating rotor and a stator is preferably used. Examples of the collision pulverizer include a hammer mill, a ball mill, a tube mill, and a vibration mill. I-type and IDS type collision type crushers (manufactured by Nippon Pneumatic Industrial Co., Ltd.) can be preferably used as jet type crushers comprising compressed air and a collision plate as main components. Examples of the rotor pulverizer include a roll mill, a pin mill, and a fluidized bed jet mill. In particular, the rotor pulverizer includes a fixed container as an outer wall and a rotating piece having the same central axis as the fixed container as main components. Those are preferred. A turbo mill (manufactured by Turbo Industry Co., Ltd.), a kryptron (manufactured by Kawasaki Heavy Industries, Ltd.), a fine mill (manufactured by Nippon Pneumatic Industrial Co., Ltd.), etc. can be used as this type of rotor type pulverizer. In order to make the toner more spherical, it is preferable to use a rotor grinder.
[0077]
After the pulverization step is completed, the pulverized product is classified in an air stream by centrifugal force or the like, thereby producing a toner (matrix particle) having a predetermined particle diameter, for example, a volume average particle diameter of 1 to 20 μm. When the toner has a volume average particle diameter of 1 to 6 μm, it is possible to prevent transfer dust in toner transfer and fixing and to exhibit sufficient colorability as a toner. It was also effective in preventing toner scattering and background contamination. Further, it is more preferable from the viewpoint of image quality, production cost, coverage with external additives, and the like. The volume average particle diameter can be measured using, for example, COULTERTA-II (COULTER ELECTRONICS, INC).
[0078]
Further, when preparing the toner, in order to improve the fluidity, storage stability, developability, and transferability of the toner, the oxide fine particles of the present invention listed above in addition to the toner produced as described above, Inorganic fine particles such as hydrophobic silica fine powder may be added and mixed. For mixing external additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, then a relatively weak load, and vice versa.
Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, and the like.
As other production methods, a polymerization method, a capsule method, or the like can be used. An outline of these production methods is described below.
[0079]
(Polymerization method)
(1) Polymerizable monomer, low molecular weight polymer If necessary, a polymerization initiator, a colorant and the like are granulated in an aqueous dispersion medium.
(2) The granulated monomer composition particles are classified to an appropriate particle size.
(3) The monomer composition particles having a prescribed inner particle diameter obtained by the above classification are polymerized.
{Circle around (4)} After removing the dispersant by appropriate treatment, the polymerized product obtained above is filtered, washed with water and dried to obtain base particles.
[0080]
(Capsule method)
{Circle around (1)} A resin and, if necessary, a colorant are kneaded with a kneader or the like to obtain a molten toner core material.
(2) Put the toner core material in water and stir vigorously to prepare a fine particle core material.
{Circle around (3)} The above core material fine particles are put in a shell material solution, and a poor solvent is added dropwise with stirring to encapsulate the surface of the core material with a shell material.
(4) Capsules obtained above are filtered and dried to obtain base particles.
[0081]
(Intermediate transfer member)
In the present invention, an intermediate transfer member can also be used in the transfer system. One embodiment of the intermediate transfer member will be described. FIG. 1 is a schematic configuration diagram of a copying machine according to the present embodiment. Around a photosensitive drum (hereinafter referred to as a photosensitive member) 10 as an image carrier, a charging roller 20 as a charging device, an exposure device 30, a cleaning device 60 having a cleaning blade, a static elimination lamp 70 as a static elimination device, and development. An apparatus 40 and an intermediate transfer member 50 as an intermediate transfer member are provided. The intermediate transfer member 50 is suspended by a plurality of suspension rollers 51 and is configured to run endlessly in the direction of the arrow by a driving unit such as a motor (not shown). A part of the suspension roller 51 also serves as a transfer bias roller for supplying a transfer bias to the intermediate transfer member, and a predetermined transfer bias voltage is applied from a power source (not shown). A cleaning device 90 having a cleaning blade for the intermediate transfer member 50 is also provided. Further, a transfer roller 80 is provided as a transfer means for transferring the developed image onto the transfer paper 100 as the final transfer material, facing the intermediate transfer member 50, and the transfer roller 80 is transferred by a power supply device (not shown). Supplied. Around the intermediate transfer member 50, a corona charger 52 as a charge applying unit is provided.
[0082]
The developing device 40 includes a developing belt 41 as a developer carrier, a black (hereinafter referred to as “Bk”) developing unit 45K, a yellow (hereinafter referred to as “Y”) developing unit 45Y, The developing unit 45M is hereinafter referred to as magenta and the cyan (hereinafter referred to as C) developing unit 45C. Further, the developing belt 41 is stretched between a plurality of belt rollers, and is configured to run endlessly in a direction indicated by an arrow by a driving unit such as a motor (not shown). Moves at approximately the same speed as 10.
[0083]
Since the configuration of each developing unit is common, the following description will be given only for the Bk developing unit 50Bk, and for the other developing units 50Y, 50M, and 50C, the portions corresponding to those in the Bk developing unit 50Bk in the figure are as follows. Y, M, and C are appended to the numbers given to those in the unit, and the description is omitted. The developing unit 50Bk is disposed so that a developing tank 42Bk containing a high-viscosity, high-concentration liquid developer containing toner particles and a carrier liquid component, and a lower part is immersed in the liquid developer in the developing tank 42Bk. And a coating roller 44Bk that thins the developer pumped from the pumping roller 43Bk and applies it to the developing belt 41. The application roller 44Bk has conductivity, and a predetermined bias is applied from a power source (not shown).
[0084]
In addition to the apparatus configuration as shown in FIG. 1, the apparatus configuration of the copying machine according to the present embodiment is an apparatus configuration in which development units 45 for each color are provided around the photoconductor 10 as shown in FIG. It may be.
Next, the operation of the copying machine according to the present embodiment will be described. In FIG. 1, the photosensitive member 10 is uniformly charged by the charging roller 20 while being driven to rotate in the direction of the arrow, and then the reflected light from the original is imaged and projected by an optical system (not shown) by the exposure device 30 on the photosensitive member 10. An electrostatic latent image is formed on the surface. This electrostatic latent image is developed by the developing device 40 to form a toner image as a visible image. The developer thin layer on the developing belt 41 is peeled off from the belt 41 in a thin layer state by contact with the photosensitive member in the developing region, and moves to a portion where a latent image is formed on the photosensitive member 10. The toner image developed by the developing device 40 is transferred to the surface of the intermediate transfer member 50 at the contact portion (primary transfer region) between the photosensitive member 10 and the intermediate transfer member 50 moving at a constant speed (primary transfer). Transcription). When transferring three or four colors to be superimposed, this process is repeated for each color to form a color image on the intermediate transfer member 50.
[0085]
The corona charger 52 for applying an electric charge to the superimposed toner image on the intermediate transfer member is provided at a contact facing portion between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is installed on the downstream side and on the upstream side of the contact facing portion between the intermediate transfer member 50 and the transfer paper 100. The corona charger 52 gives the toner image a true charge having the same polarity as the charge polarity of the toner particles forming the toner image, and is sufficient for good transfer to the transfer paper 100. Charge is applied to the toner image. The toner image is charged by the corona charger 52, and then transferred to the transfer paper 100 conveyed in the direction of the arrow from a paper supply unit (not shown) by a transfer bias from the transfer roller 80 (two). Next transfer). Thereafter, the transfer paper 100 onto which the toner image has been transferred is separated from the photoconductor 10 by a separation device (not shown), and after a fixing process is performed by a fixing device (not shown), the transfer paper 100 is discharged from the device. On the other hand, after the transfer, the untransferred toner is collected and removed by the cleaning device 60, and the residual charge is discharged by the discharging lamp 70 in preparation for the next charging.
[0086]
The static friction coefficient of the intermediate transfer member is preferably 0.1 to 0.6, more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is several Ωcm or more and 10 ^Three It is preferable that it is below Ωcm. Volume resistance is several Ωcm or more 10 ^Three By setting the resistance to Ωcm or less, the intermediate transfer member itself can be prevented from being charged, and the charge imparted by the charge imparting means hardly remains on the intermediate transfer member, so that transfer unevenness during secondary transfer can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.
[0087]
The material of the intermediate transfer member is not particularly limited, and all known materials can be used. An example is shown below. (1) A material having a high Young's modulus (tensile modulus) is used as a single-layer belt. PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) / PAT ( Polyalkylene terephthalate) blend material, ETFE (ethylene tetrafluoroethylene copolymer) / PC, ETFE / PAT, PC / PAT blend material, carbon black dispersed thermosetting polyimide, and the like. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and registration is not likely to occur particularly during color image formation. (2) A belt having a two- or three-layer structure in which a belt having a high Young's modulus is used as a base layer and a surface layer or an intermediate layer is provided on the outer periphery thereof. Therefore, the line image has a performance capable of preventing the line image from being lost. (3) Belts having a relatively low Young's modulus using rubber and elastomer, and these belts have an advantage that line images are hardly lost due to their softness. In addition, the width of the belt is made larger than that of the drive roll and the tension roll, and the elasticity of the belt ear protruding from the roll is used to prevent meandering, so that a low cost can be realized without the need for ribs or meandering prevention devices. .
[0088]
Conventionally, a fluorine-based resin, a polycarbonate resin, a polyimide resin, or the like has been used for the intermediate transfer belt, but in recent years, an elastic belt in which the entire belt layer or a part of the belt is used as an elastic member has been used. The transfer of a color image using a resin belt has the following problems.
A color image is usually formed with four colored toners. On one color image, toner layers of 1 to 4 layers are formed. The toner layer receives pressure by passing through the primary transfer (transfer from the photoreceptor to the intermediate transfer belt) and the secondary transfer (transfer from the intermediate transfer belt to the sheet), and the cohesive force between the toners increases. When the cohesive force between the toners increases, the phenomenon of missing characters in the characters and missing edges in the solid portion image tends to occur. Since the resin belt has a high hardness and does not deform according to the toner layer, the toner layer is easily compressed, and the character dropout phenomenon is likely to occur.
[0089]
Recently, there is an increasing demand for forming full-color images on various papers, for example, Japanese paper, intentionally irregularities, and forming images on paper. However, a paper with poor smoothness is liable to generate toner and voids at the time of transfer, and transfer loss is likely to occur. When the transfer pressure at the secondary transfer portion is increased to improve the adhesion, the condensing power of the toner layer is increased, and the above-described character void is generated.
The elastic belt is used for the following purposes. The elastic belt is deformed corresponding to the toner layer and the paper having poor smoothness at the transfer portion. In other words, since the elastic belt deforms following local irregularities, it is possible to obtain a good adhesion without excessively increasing the transfer pressure with respect to the toner layer, and a paper with poor flatness that has no void in characters. In contrast, a transfer image with excellent uniformity can be obtained.
[0090]
The elastic belt resin is polycarbonate, fluorine resin (ETFE, PVDF), polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer. Polymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylic acid Octyl copolymer and styrene-phenyl acrylate copolymer), styrene-methacrylic acid ester copolymer (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-phenyl methacrylate copolymer) Coalesce etc.), styrene-α-chloroacryl Styrenic resin (monopolymer or copolymer containing styrene or styrene-substituted product), methyl methacrylate resin, butyl methacrylate resin, acrylic resin, such as methyl phosphate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer Ethyl acid resin, butyl acrylate resin, modified acrylic resin (silicone modified acrylic resin, vinyl chloride resin modified acrylic resin, acrylic / urethane resin, etc.), vinyl chloride resin, styrene-vinyl acetate copolymer, vinyl chloride-vinyl acetate Polymer, rosin-modified maleic resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene, polyvinylidene chloride, ionomer resin, polyurethane resin, silicone resin, ketone resin, Len - ethyl acrylate copolymer, it may be used xylene resin and polyvinyl butyral resin, polyamide resin, one kind or two kinds or more selected from the group consisting of modified polyphenylene oxide resin. However, it is a matter of course that the material is not limited to the above materials.
[0091]
Elastic rubber and elastomer include butyl rubber, fluorine rubber, acrylic rubber, EPDM, NBR, acrylonitrile-butadiene-styrene rubber natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene ter Polymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, ricone rubber, fluororubber, polysulfide rubber, polynorbornene rubber, hydrogenated nitrile rubber , Selected from the group consisting of thermoplastic elastomers (eg, polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide, polyurea, polyester, fluororesin) It is possible to use one kind or two or more kinds. However, it is a matter of course that the material is not limited to the above materials.
[0092]
There are no particular restrictions on the conductive agent for adjusting the resistance value. For example, carbon black, graphite, metal powder such as aluminum and nickel, tin oxide, titanium oxide, antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite Conductive metal oxides such as oxides (ATO) and indium oxide-tin oxide composite oxides (ITO), and conductive metal oxides are coated with insulating fine particles such as barium sulfate, magnesium silicate and calcium carbonate But you can. Of course, the conductive agent is not limited thereto.
[0093]
The surface layer material and the surface layer are required to prevent contamination of the photoconductor by the elastic material, reduce the surface friction resistance to the transfer belt surface, reduce the adhesion of the toner, and improve the cleaning property and the secondary transfer property. . For example, materials that use one or more of polyurethane, polyester, epoxy resin, etc. to reduce surface energy and increase lubricity, such as powders of fluororesins, fluorine compounds, fluorocarbons, titanium dioxide, silicon carbide, etc. Can be used by dispersing one or more kinds of particles, particles or particles having different particle sizes, and by forming a fluorine-rich layer on the surface by heat treatment like a fluorine-based rubber material, the surface energy can be increased. It is also possible to use a smaller one.
[0094]
In addition, the manufacturing method of a belt is not limited. Centrifugal molding method in which material is poured into a rotating cylindrical mold to form a belt, spray coating method in which liquid paint is sprayed to form a film, dipping method in which a cylindrical mold is dipped in a solution of the material, There are methods such as casting methods that are poured into a mold and an outer mold, and a method in which a compound is wound around a cylindrical mold and vulcanized and polished, but is not limited to these. It is common to manufacture.
[0095]
As a method for preventing elongation as an elastic belt, there are a method of forming a rubber layer in a core resin layer with little elongation, a method of putting a material for preventing elongation into the core layer, and the like, but it is not particularly related to the production method.
Materials constituting the core layer for preventing elongation include, for example, natural fibers such as cotton and silk, polyester fibers, nylon fibers, acrylic fibers, polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, One or two selected from the group consisting of synthetic fibers such as polyurethane fibers, polyacetal fibers, polyfluoroethylene fibers and phenol fibers, inorganic fibers such as carbon fibers, glass fibers and boron fibers, and metal fibers such as iron fibers and copper fibers A woven or thread-like material can be formed using more than one seed. Of course, the material is not limited to the above.
The yarn may be twisted in any manner, such as one or a plurality of filaments twisted, a single twisted yarn, various twisted yarns, a double yarn or the like. Further, for example, fibers of a material selected from the above material group may be blended. Of course, the yarn can be used after being subjected to an appropriate conductive treatment.
[0096]
On the other hand, the woven fabric can be any woven fabric such as knitted weave. Of course, a woven fabric that has been woven can also be used, and naturally conductive treatment can be applied.
The production method for providing the core layer is not particularly limited, for example, a method of providing a woven fabric woven in a cylindrical shape on a mold and the like, and providing a coating layer thereon, the woven fabric woven in a cylindrical shape is a liquid rubber And a method of providing a coating layer on one side or both sides of the core layer, and a method of winding a thread spirally around a mold at an arbitrary pitch and providing a coating layer thereon.
The thickness of the elastic layer depends on the hardness of the elastic layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur in the surface layer. Also, it is not preferable that the thickness is too large (approximately 1 mm or more) because the amount of expansion and contraction becomes large and the spread of the image increases.
[0097]
(Tandem type color image forming device)
An embodiment of a tandem color image forming apparatus of the present invention will be described. As shown in FIG. 3, the tandem electrostatic image developing device includes a direct transfer system in which an image on each photoreceptor 1 is sequentially transferred onto a sheet s conveyed by a sheet conveying belt 3 by a transfer device 2. As shown in FIG. 4, the image on each photoconductor 1 is once transferred sequentially to the intermediate transfer member 4 by the primary transfer device 2, and then the image on the intermediate transfer member 4 is sheeted by the secondary transfer device 5. There is an indirect transfer system that performs batch transfer to s. The transfer device 5 is a transfer conveyance belt, but there are also roller shapes and methods.
[0098]
Comparing the direct transfer type and the indirect transfer type, the former arranges the sheet feeding device 6 on the upstream side of the tandem image forming apparatus T on which the photoconductors 1 are arranged, and the fixing device 7 on the downstream side. There is a drawback in that the size increases in the sheet conveying direction.
On the other hand, the latter can set the secondary transfer position relatively freely.
The sheet feeding device 6 and the fixing device 7 can be arranged so as to overlap with the tandem image forming apparatus T, and there is an advantage that downsizing is possible.
In the former, in order not to increase the size in the sheet conveying direction, the fixing device 7 is disposed close to the tandem type image forming apparatus T. For this reason, the fixing device 7 cannot be disposed with a sufficient margin that allows the sheet s to bend, and an impact when the leading edge of the sheet s enters the fixing device 7 (particularly with a thick sheet) or fixing. There is a drawback that the fixing device 7 tends to affect image formation on the upstream side due to the difference in speed between the sheet conveyance speed when passing through the apparatus 7 and the sheet conveyance speed by the transfer conveyance belt.
On the other hand, in the latter case, the fixing device 7 can be disposed with a sufficient margin that the sheet s can be bent, so that the fixing device 7 can hardly affect the image formation.
[0099]
For these reasons, recently, indirect tandem type electrostatic image developing devices, particularly those of the indirect transfer type, have attracted attention.
In this type of color electrostatic image developing device, as shown in FIG. 4, the transfer residual toner remaining on the photoreceptor 1 after the primary transfer is removed by the photoreceptor cleaning device 8 to remove the surface of the photoreceptor 1. It was cleaned and prepared for another image formation. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.
[0100]
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 5 shows an embodiment of the present invention, which is a tandem indirect transfer type electrostatic charge image developing apparatus. In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which the copying apparatus is placed, 300 is a scanner mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) mounted thereon. The copying machine main body 100 is provided with an endless belt-shaped intermediate transfer member 10 at the center.
Then, as shown in FIG. 5, in the illustrated example, it is wound around three support rollers 14, 15, and 16 so that it can be rotated and conveyed clockwise in the figure.
In this illustrated example, an intermediate transfer body cleaning device 17 for removing residual toner remaining on the intermediate transfer body 10 after image transfer is provided on the left of the second support roller 15 among the three.
Further, among the three images, four images of yellow, cyan, magenta, and black are arranged on the intermediate transfer member 10 stretched between the first support roller 14 and the second support roller 15 along the conveyance direction. The tandem image forming apparatus 20 is configured by arranging the forming units 18 side by side.
[0101]
An exposure device 21 is further provided on the tandem image forming apparatus 20 as shown in FIG. On the other hand, a secondary transfer device 22 is provided on the side opposite to the tandem image forming apparatus 20 with the intermediate transfer body 10 interposed therebetween. In the illustrated example, the secondary transfer device 22 is configured by spanning a secondary transfer belt 24, which is an endless belt, between two rollers 23, and is pressed against the third support roller 16 via the intermediate transfer body 10. The image on the intermediate transfer body 10 is transferred to a sheet.
A fixing device 25 for fixing the transfer image on the sheet is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt.
The secondary transfer device 22 described above is also provided with a sheet transport function for transporting the image-transferred sheet to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveying function together.
In the illustrated example, under such a secondary transfer device 22 and a fixing device 25, a sheet reversing device 28 for reversing the sheet so as to record images on both sides of the sheet in parallel with the tandem image forming device 20 described above. Is provided.
[0102]
Now, when making a copy using this color electrostatic image developing device, the document is set on the document table 30 of the automatic document feeder 400. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed and pressed by it.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the other contact glass 32. At that time, the scanner 300 is immediately driven to travel the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34, and is reflected by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.
When a start switch (not shown) is pressed, one of the support rollers 14, 15, and 16 is driven to rotate by a drive motor (not shown), and the other two support rollers are driven to rotate to convey the intermediate transfer member 10. To do. At the same time, the individual image forming means 18 rotates the photoconductor 40 to form black, yellow, magenta, and cyan monochrome images on each photoconductor 40. Then, along with the conveyance of the intermediate transfer member 10, the single color images are sequentially transferred to form a composite color image on the intermediate transfer member 10.
[0103]
On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, and the sheet is fed out from one of the paper feed cassettes 44 provided in multiple stages in the paper bank 43, and the separation roller 45. Then, the sheets are separated one by one into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying machine main body 100, and abutted against the registration roller 49 and stopped.
Alternatively, the sheet feed roller 50 is rotated to feed out the sheets on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped.
Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer member 10, the sheet is fed between the intermediate transfer member 10 and the secondary transfer device 22, and transferred by the secondary transfer device 22. A color image is recorded on the sheet.
The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching roller 55 is used to switch the discharge roller. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.
[0104]
On the other hand, the intermediate transfer body 10 after the image transfer is removed by the intermediate transfer body cleaning device 17 to remove residual toner remaining on the intermediate transfer body 10 after the image transfer, so that the tandem image forming apparatus 20 can prepare for another image formation.
Here, the registration roller 49 is generally used while being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.
Now, in the tandem image forming apparatus 20 described above, the individual image forming means 18 includes, for example, a charging device 60, a developing device 61, and a primary device around a drum-shaped photoconductor 40 as shown in FIG. The image forming apparatus includes a transfer device 62, a photoconductor cleaning device 63, a charge removal device 64, and the like.
[0105]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited only to these examples. In the following examples, parts and% are based on weight unless otherwise specified. Table 1 shows the evaluation machines used and the characteristics and evaluation results obtained. In the examples, evaluation was performed as follows.
[0106]
(Evaluation machine)
Images used in the evaluation were evaluated using any of the following evaluation machines A, B, C, D, and E.
[0107]
(Evaluation machine A)
Using a tandem Ricoh full color laser printer IPSiO Color 8000 fixing unit, which has a four-color non-magnetic two-component developing unit and a four-color photoreceptor, an oil-less fixing unit, and tuned. And evaluated. The printing speed was evaluated by changing the printing speed from 20 to 50 sheets / min · A4 in high-speed printing and full color.
(Evaluation machine B)
Tandem Ricoh's full-color laser printer IPSiO Color 8000, which has a four-color non-magnetic two-component developing unit and a four-color photoconductor, was modified to perform primary transfer onto an intermediate transfer member, and the toner image Evaluation was carried out using an evaluation machine B which was tuned by changing to an intermediate transfer system in which secondary transfer was performed on a transfer material and the fixing unit was improved to an oilless fixing unit. The printing speed was evaluated by changing the printing speed from 20 to 50 sheets / min · A4 in high-speed printing and full color.
[0108]
(Evaluation machine C)
RICOH's full-color laser copier with four-color developing unit that develops each component of two-component developer on a drum-shaped photoconductor, sequentially transfers it to an intermediate transfer member, and transfers all four colors onto a transfer material. The Color 2800 fixing unit was evaluated as an evaluation machine C, which was improved to an oil-less fixing unit and tuned. The printing speed was evaluated at 6 sheets / min · A4 in full color.
(Evaluation machine D)
Ricoh's full-color laser printer with a four-color developing unit that develops each non-magnetic one-component developer on a belt photoreceptor in sequence, transfers it onto an intermediate transfer member, and transfers all four colors onto a transfer material. The IPSiO Color 5000 fixing unit was improved to an oilless fixing unit, and evaluation was performed using an evaluation machine D that was improved and tuned to an oilless fixing unit. The printing speed was evaluated at 6 sheets / min · A4 in full color.
[0109]
(Evaluation machine E)
Evaluation was performed using an evaluation machine E that was tuned with a tandem Ricoh full color laser printer IPSiO Color 8000 having a four-color non-magnetic two-component developing section and a four-color photoconductor as an oil-coated fixing section. . Evaluation was made by changing the printing speed from high-speed printing to 20 to 50 sheets / min · A4.
[0110]
(Evaluation item)
1) Toner scattering property under high temperature and high humidity environment
After the toner is conditioned and stored for 12 hours in a high-temperature and high-humidity environment at 35 ° C. and 80%, an evaluation machine is installed in the same environment, and after running 30,000 image charts of 80% image area in a monochrome mode, The amount of toner scattered from the developing unit was judged visually by opening the developing unit. The rank improves in the order of ×, Δ, ○, ◎.
2) Background dirt in a low temperature and low humidity environment
After running 30,000 image charts of 7% image area in monochrome mode, the blank image is stopped during development, the developer on the photoconductor after development is tape transferred, and the image density of the untransferred tape The difference is measured with a 938 spectrodensitometer (manufactured by X-Rite). The smaller the difference in image density, the better the background dirt, and the rank improves in the order of x, Δ, ○, ◎.
[0111]
3) Image density (coloring degree)
After running 200,000 image charts with a 50% image area in monochromatic mode, the solid image was output to 6000 paper manufactured by Ricoh, and the image density was measured by X-Rite (manufactured by X-Rite). This was performed for four colors alone, and an average was obtained. If this value is less than 1.2, x, if it is 1.2 or more and less than 1.4, Δ, if it is 1.4 or more and less than 1.8, ○, if it is 1.8 or more and less than 2.2 ◎.
4) Transparency
After running 100,000 image charts with 50% image area in monochrome mode, each image density is 1.0 mg / cm on a Ricoh type DX OHP sheet. ² Fixing temperature: Fixing was performed under the condition of 140 ° C., and measured with a continuous haze computer model HGM-2DP manufactured by Suga Test Instruments. ◎, ○, Δ, and × in order of good transparency.
[0112]
5) Color vividness
After running 100,000 image charts of 50% image area in the single color mode, the image output on 6000 paper manufactured by Ricoh was visually evaluated for color vividness. ◎, ○, Δ, and × in the order of goodness.
6) Color reproducibility
After 100,000 sheets of a 50% image area running chart were output in monochromatic mode, the color reproducibility was visually evaluated on images output to 6000 paper manufactured by Ricoh. ◎, ○, Δ, and × in the order of goodness.
[0113]
7) Gloss
After running 100,000 sheets of an image chart with a 50% image area in the single color mode, the image output to 6000 paper manufactured by Ricoh was used to cast the image using a gloss meter (VG-1D) (manufactured by Nippon Denshoku). The light angle and the light receiving angle were adjusted to 60 °, and the S and S / 10 switch SWs were adjusted to S, and measurement was performed after 0 preparation and standard setting using a standard plate. From those having good glossiness, ◎: 13 or more, ◯: 5 or more and less than 13, Δ: 2 or more to less than 5, and x: less than 2.
8) Light resistance
After running 100,000 sheets of 50% image area image chart in monochrome mode, the image output on 6000 paper manufactured by Ricoh Co., Ltd. is applied to XENONTESTER XW-150 (manufactured by Shimadzu Corporation) for 15 hours at 10,000 lux. The image after irradiation was observed and light resistance was evaluated according to the following criteria.
A: Almost no change.
○: Slightly changes.
Δ: Slightly changes.
X: It changes considerably.
[0114]
9) Fine line reproducibility
After running 30,000 image charts with a 50% image area in monochromatic mode, a 600 dpi fine line image was output to Ricoh type 6000 paper, and the degree of fine line bleeding was compared with a step sample. The rank improves in the order of ×, Δ, ○, ◎. This was performed by overlapping four colors.
10) Heat resistant storage stability
10 g of each color toner was weighed, put into a 20 ml glass container, tapped with a glass bottle 100 times, allowed to stand in a thermostatic bath set at 55 ° C. for 24 hours, and the penetration was measured with a penetration meter. From the good one, ◎: 20 mm or more, ◯: 15 mm or more and less than 20 mm, Δ: 10 mm or more to less than 15 mm, x: less than 10 mm.
[0115]
11) High-temperature and high-humidity charging stability
In an environment with a temperature of 40 ° C and a humidity of 90%, while running a 100,000 sheets image chart with a 7% image area in the monochrome mode, a part of the developer is sampled every 1000 sheets and the charge amount is determined by the blow-off method. Measurement was made to evaluate the charging stability. ◎, ○, Δ, and × were given in the order of stable and favorable charge increase and charge decrease.
12) Low-temperature and low-humidity charging stability
In an environment with a temperature of 10 ° C and a humidity of 15%, while running an output chart of 7% image area in a monochrome mode with 100,000 sheets running, a part of the developer is sampled every 1000 sheets and the charge amount is determined by the blow-off method. Measurement was made to evaluate the charging stability. ◎, ○, Δ, and × were given in the order of stable and favorable charge increase and charge decrease.
[0116]
13) Fixability
The minimum fixing temperature and the maximum fixing temperature of the toner are sufficient within the fixing temperature range, hot offset and cold offset do not occur, and troubles such as winding and paper jam do not occur easily. The overall fixability was evaluated as, Δ, and X.
[0117]
(Evaluation of two-component developer)
When evaluating an image with a two-component developer, a ferrite carrier having an average particle diameter of 50 μm coated with a silicone resin with an average thickness of 0.3 μm is used as follows, and toner of each color 5 is used with respect to 100 parts by weight of the carrier. The developer was prepared by uniformly mixing and charging the parts by weight using a tumbler mixer of the type in which the container rolls and stirs.
[0118]

The coating material is dispersed with a stirrer for 10 minutes to prepare a coating solution, and the coating solution and the core material are coated in a fluidized bed while forming a swirling flow with a rotating bottom plate disk and stirring blades. The coating solution was applied on the core material. The obtained coated material was baked in an electric furnace at 250 ° C. for 2 hours to obtain the carrier.
[0119]
Example 1
(Polyol resin 1)
Stirrer, thermometer, N ₂ In a separable flask with an inlet and a cooling tube, 378.4 g of a low molecular weight bisphenol A type epoxy resin (number average molecular weight: about 360), 86.0 g of a high molecular weight bisphenol A type epoxy resin (number average molecular weight: about 2700), bisphenol 191.0 g of a diglycidylation product of an A-type propylene oxide adduct [n + m: about 2.1 in the general formula (1)], 274.5 g of bisphenol F, 70.1 g of p-cumylphenol, and 200 g of xylene were added. N ₂ The temperature is raised to 70 to 100 ° C. under an atmosphere, 0.183 g of lithium chloride is added, the temperature is further raised to 160 ° C., water is added under reduced pressure, and water and xylene are bubbled to cause water, xylene, and other volatile components. , Removing polar solvent soluble components, polymerizing at a reaction temperature of 180 ° C. for 6-9 hours, Mn: 3800, Mw / Mn; 3.9, Mp: 5000, softening point 109 ° C., Tg 58 ° C., epoxy equivalent 1000 g of polyol resin of 20000 or more was obtained (polyol resin 1). The reaction conditions were controlled so that no monomer component remained in the polymerization reaction. The polyoxyalkylene part of the main chain was confirmed by NMR.
[0120]
(Manufacture of toner)
[Magenta toner]
600 parts of water
Pigment Red 122 1200 parts
Polyol resin 1 1200 parts
The raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 128 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch colorant.

The above materials were mixed with a mixer, melt-kneaded five times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed, and the volume average particle size is 5.5 μm. Thus, magenta colored particles having a number average particle diameter of 4.5 μm were obtained. Furthermore, 1.0 wt% of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9 wt% of titanium oxide (MT-150A, Teica) having a primary particle diameter of 15 nm are added and mixed with a Henschel mixer. A magenta toner was obtained by passing through a sieve having an opening of 50 μm to remove aggregates. The dispersion diameter of the wax in the toner was 0.2 μm. The coverage of the colorant molecules on the obtained toner surface was 14.1 (atomic%).
[0121]
Example 2
In Example 1, evaluation was performed in the same manner as in Example 1 except that the toner was produced as follows.
[Cyan toner]
600 parts of water
Pigment Blue 15: 3 1200 parts
Polyol resin 1 1200 parts
The raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 128 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch colorant.

The above materials were mixed with a mixer, melt-kneaded five times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed, and the volume average particle size is 5.5 μm. Cyan colored particles having a number average particle diameter of 4.5 μm were obtained. Further, 1.0 wt% of hydrophobic silica (HDKH2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9 wt% of titanium oxide (MT-150A, Teica) having a primary particle diameter of 15 nm are added and mixed with a Henschel mixer. A cyan toner was obtained by passing through a sieve having an opening of 50 μm to remove aggregates. The dispersion diameter of the wax in the toner was 0.2 μm. The coverage of colorant molecules on the obtained toner surface was 4.7 (atomic%).
[0122]
Example 3
In Example 1, evaluation was performed in the same manner as in Example 1 except that the toner was produced as follows.
[Yellow Toner]
600 parts of water
Pigment Yellow 180 1200 parts
Polyol resin 1 1200 parts
The raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 128 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch colorant.

The above materials were mixed with a mixer, melt-kneaded five times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I-type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed to obtain a volume average particle size of 5.5 μm. As a result, yellow colored particles having a number average particle diameter of 4.5 μm were obtained. Furthermore, 1.0 wt% of hydrophobic silica (HDKH2000, Clariant Japan) with a primary particle diameter of 10 nm and 0.9 wt% of titanium oxide (MT-150A, Teica) with a primary particle diameter of 15 nm are added, mixed with a Henschel mixer, and opened Yellow toner was obtained by passing through a 50 μm sieve to remove aggregates. The dispersion diameter of the wax in the toner was 0.3 μm. The colorant molecule coverage on the obtained toner surface was 6.5 (atomic%).
[0123]
Example 4
In Example 1, evaluation was performed in the same manner as in Example 1 except that the toner was produced as follows.
[Magenta toner]
600 parts of water
Pigment Red 57: 1 1200 parts
Polyol resin 1 1200 parts
The raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 128 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch colorant.

The above materials were mixed with a mixer, melt-kneaded five times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed, and the volume average particle size is 5.5 μm. Thus, magenta colored particles having a number average particle diameter of 4.5 μm were obtained. Furthermore, 1.0 wt% of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9 wt% of titanium oxide (MT-150A, Teica) having a primary particle diameter of 15 nm are added and mixed with a Henschel mixer. A magenta toner was obtained by passing through a sieve having an opening of 50 μm to remove aggregates. The dispersion diameter of the wax in the toner was 0.2 μm. The coverage of colorant molecules on the obtained toner surface was 1.6 (atomic%).
[0124]
Example 5
In Example 1, evaluation was performed in the same manner as in Example 1 except that the toner was produced as follows.
[Magenta toner]
600 parts of water
Pigment Red 185 1200 parts
Polyol resin 1 1200 parts
The raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This is kneaded for 45 minutes with two rolls set at a roll surface temperature of 126 ° C., rolled and cooled, pulverized with a pulverizer, and further kneaded for 40 minutes with two rolls set at a roll surface temperature of 125 ° C. A pulverized masterbatch colorant was obtained with a pulverizer.

The above materials were mixed with a mixer, melt-kneaded five times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I-type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed to obtain a volume average particle size of 5.5 μm. Thus, magenta colored particles having a number average particle diameter of 4.5 μm were obtained. Furthermore, 1.0 wt% of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9 wt% of titanium oxide (MT-150A, Teica) having a primary particle diameter of 15 nm are added and mixed with a Henschel mixer. A magenta toner was obtained by passing through a sieve having an opening of 50 μm to remove aggregates. The dispersion diameter of the wax in the toner was 0.2 μm. The coverage of the colorant molecules on the obtained toner surface was 8.0 (atomic%).
[0125]
Example 6
In Example 1, evaluation was performed in the same manner as in Example 1 except that the toner was produced as follows.
[Magenta toner]
600 parts of water
Pigment Red 57: 1 1200 parts
Polyol resin 1 1200 parts
The raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 128 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch colorant.

The above materials were mixed with a mixer, melt-kneaded five times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I-type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed to obtain a volume average particle size of 5.5 μm. Thus, magenta colored particles having a number average particle diameter of 4.5 μm were obtained. Furthermore, 1.0 wt% of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9 wt% of titanium oxide (MT-150A, Teica) having a primary particle diameter of 15 nm are added and mixed with a Henschel mixer. A magenta toner was obtained by passing through a sieve having an opening of 50 μm to remove aggregates. The dispersion diameter of the wax in the toner was 0.2 μm. The coverage of the colorant molecules on the obtained toner surface was 15.0 (atomic%).
[0126]
Example 7
A full color toner kit containing magenta toner, cyan toner, yellow toner described in Examples 1, 2, and 3 and black toner described below was prepared and evaluated in the same manner as in Example 1. Various evaluations were performed in full color mode. Note that the black toner prepared here does not have any element specific to the colorant, and thus the coverage of the colorant molecule was not measured.
[Black Toner]
1000 parts of water
200 parts phthalocyanine green water cake (solid content 30%)
1000 parts of carbon black (MA60 manufactured by Mitsubishi Chemical Corporation)
Polyol resin 1 1000 parts
The raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 128 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch colorant.

After mixing the said material with a mixer, it melt-kneaded 3 times or more with a 2 roll mill, and the kneaded material was rolling-cooled. Thereafter, a collision plate type pulverizer (I-type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed to obtain a volume average particle size of 5.5 μm. Black colored particles having a number average particle diameter of 4.5 μm were obtained. Furthermore, 1.0 wt% of hydrophobic silica (HDK H2000, Clariant Japan) with a primary particle size of 10 nm and 0.9 wt% of titanium oxide (MT-150A, Teica) with a primary particle size of 15 nm are added and mixed with a Henschel mixer. A black toner was obtained by passing through a 50 μm sieve and removing aggregates. The dispersion diameter of the wax in the toner was 0.2 μm.
[0127]
Example 8
In Example 1, the resin was a polyester resin (fumaric acid, polyoxypropylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (2.3) -2,2- Resin synthesized from bis (4-hydroxyphenyl) propane and trimellitic anhydride, acid value; 10, hydroxyl value; 30, Mn; 5000, Mw / Mn; 10, Mp; 9000, Tg; 61 ° C., softening point Evaluation was conducted in the same manner as in Example 1 except that the temperature was changed to 108 ° C. The obtained toner had a volume average particle size of 5.5 μm and a number average particle size of 4.5 μm, and the colorant molecule coverage on the toner surface was 12.8 (atomic%).
[0128]
Example 9
In Example 1, toner and developer were prepared in the same manner as in Example 1 except that the toner was obtained by classification so that the volume average particle diameter of the toner was 6.5 μm and the number average particle diameter was 5.4 μm. And evaluated. The coverage of the colorant molecules on the toner surface was 13.8 (atomic%).
[0129]
Example 10
In Example 1, a toner and a developer are prepared in the same manner as in Example 1 except that the toner is obtained by classification so that the volume average particle diameter of the toner is 4.5 μm and the number average particle diameter is 3.6 μm. And evaluated. The coverage of the colorant molecules on the toner surface was 14.3 (atomic%).
[0130]
Example 11
In Example 1, a toner and a developer were prepared in the same manner as in Example 1 except that the toner was obtained by classification so that the volume average particle diameter of the toner was 2 μm and the number average particle diameter was 1.4 μm. evaluated. The coverage of the colorant molecules on the toner surface was 14.9 (atomic%).
[0131]
Example 12
In Example 1, toner and developer were prepared and evaluated in the same manner as in Example 1 except that the toner was pulverized with a turbo mill (manufactured by Turbo Kogyo Co., Ltd.) and the toner shape was spheroidized. The circularity SF-1 of the toner was 140, and SF-2 was 130. The coverage of the colorant molecules on the toner surface was 13.5 (atomic%).
[0132]
Example 13
In Example 1, evaluation was performed in the same manner as in Example 1 except that the toner production method was changed to the following emulsion polymerization method.
First, as the resin dispersion 1,

9 parts of a nonionic surfactant (Sanyo Kasei Co., Ltd., Nonibol 85) and 11 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC) are mixed with 582 parts of ion-exchanged water. Dissolving, dispersing and emulsifying in the flask, and slowly mixing for 15 minutes, 50 g of ion-exchanged water in which 3.4 g of ammonium persulfate (manufactured by Tokai Denka Co., Ltd.) was dissolved was added to perform nitrogen substitution. Thereafter, the flask was heated with an oil bath while stirring the flask until the content reached 73 ° C., and emulsion polymerization was continued for 7 hours, and then cooled to room temperature to obtain a resin dispersion. The solvent was left in an oven at 80 ° C. to remove moisture from the obtained resin dispersion. A dispersion having a center particle size of 120 nm, a glass transition point of 55 ° C., and a Mw of 22,000 was obtained.
Pigment Pigment Red 122, 70 parts are added and mixed in 300 parts of ion-exchanged water together with 2 parts of an anionic surfactant (Sanyo Kasei Co., Ltd., Ionette D-2), and dispersed with IKA Ultra Turrax T50. A pigment dispersion 1 having a center diameter of 160 nm was obtained.
50 parts of wax (fatty acid ester wax, melting point 83 ° C., viscosity 280 mPa · s (90 ° C.)) and 2 parts of anionic surfactant (Sanyo Kasei Co., Ltd., Ionette D-2) are added and mixed in 300 parts of ion-exchanged water. Then, a dispersion treatment was performed using an Ultra-Turrax T50 manufactured by IKA to obtain a wax dispersion 1.
[0133]
Next, the resin dispersion 1, the pigment dispersion 1, and the wax dispersion 1 are mixed in the following proportions:

After mixing and dispersing in a round stainless steel flask with Ultra Turrax T50, the flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 4 hours, observation with an optical microscope confirmed that aggregated particles of about 5.5 μm were formed. Then, after adding 6 parts of neogen SC further, it heated to 93 degreeC, continuing stirring, and hold | maintained for 9 hours. Thereafter, the flask was cooled to room temperature at 10 ° C./min, further filtered, thoroughly washed with ion-exchanged water, and kept in a vacuum dryer at 50 ° C. for 12 hours. The volume average particle diameter was 5.5 μm, the number average Magenta colored particles having a particle diameter of 4.7 μm and a molecular weight Mw of 22,000 were obtained. Furthermore, 1.0 wt% of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm and 0.9 wt% of titanium oxide (MT-150A, Teica) having a primary particle diameter of 15 nm are added and mixed with a Henschel mixer. A magenta toner was obtained by passing through a sieve having an opening of 50 μm to remove aggregates. The toner circularity SF-1 was 108, and SF-2 was 105. The coverage of the colorant molecules on the toner surface was 14.8 (atomic%).
[0134]
Example 14
In Example 1, it evaluated similarly except having used the evaluation machine B.
[0135]
Example 15
In Example 1, it evaluated similarly except having used the evaluation machine C.
[0136]
Example 16
In Example 1, it evaluated similarly except having used the evaluation machine D.
[0137]
Example 17
In Example 1, toner was manufactured without adding wax, and evaluation and production were performed in the same manner as in Example 1 except that the evaluation machine E was used. The obtained toner had a volume average particle size of 5.5 μm, a number average particle size of 4.6 μm, and a coverage of colorant molecules on the toner surface of 12.8 (atomic%).
[0138]
Comparative Example 1
In Example 1, a toner and a developer were prepared and evaluated in the same manner as in Example 1 except that the production conditions of the master batch colorant were changed. The master batch colorant was obtained by kneading for 40 minutes with two rolls set at a roll surface temperature of 115 ° C. The obtained toner surface had a colorant molecule coverage of 16.1 (atomic%).
[0139]
Comparative Example 2
In Example 4, a toner and a developer were prepared and evaluated in the same manner as in Example 4 except that the toner production conditions were changed. The toner kneading was changed to a KONDER made by Buss, and the kneaded product was rolled and cooled. Then, coarsely pulverized and kneaded again with a kneader to obtain a final kneaded product. Thereafter, a toner was prepared and evaluated in the same manner as in Example 4. The coverage of the colorant molecules on the obtained toner surface was 1.3 (atomic%).
[0140]
Comparative Example 3
In Example 1, a toner was prepared and evaluated in the same manner as in Example 1 except that the prescription amount ratio of the master batch colorant and the binder resin was changed so that the colorant in the toner was 1.3% by weight. . The coverage of colorant molecules on the obtained toner surface was 1.8 (atomic%).
[0141]
Comparative Example 4
In Example 4, a toner was prepared and evaluated in the same manner as in Example 1 except that the prescription amount ratio of the master batch colorant and the binder resin was changed so that the colorant in the toner was 16% by weight. The resulting toner surface had a colorant molecule coverage of 14.2 (atomic%).
[0142]
[Table 1]

[0143]
【The invention's effect】
In the toner containing at least the binder resin and the colorant described above, the coverage of the colorant molecules on the toner surface by XPS measurement is 1.5 to 15 atomic%, and the content of the colorant is the toner. By using 2 to 15% by weight of the toner for developing electrostatic images, the toner is stable even after the toner is stored for a long time in a high temperature and high humidity environment and after tens of thousands of images are output in the high temperature and high humidity environment. Can provide toner, developer, image forming method, and image forming apparatus that are less susceptible to weakly charged and reversely charged toner and that do not cause toner scattering, and can be provided not only in a normal temperature and normal humidity environment but also in a low temperature and low humidity environment. It is possible to provide a toner, a developer, an image forming method, and an image forming apparatus that are weakly charged with excellent charging stability even after outputting tens of thousands of images, have less reversely charged toner, and do not cause background stains (fogging), and Even after outputting tens of thousands of images, a toner, developer, image forming method, and image forming apparatus having sufficient colorability, light resistance, transparency, color development, sharpness, color reproducibility, saturation, and gloss Can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram showing an example of an embodiment of the present invention.
FIG. 2 is a schematic configuration diagram illustrating another example of the embodiment of the present invention.
FIG. 3 is a schematic configuration diagram showing another example of the embodiment of the present invention.
FIG. 4 is a schematic configuration diagram showing another example of the embodiment of the present invention.
FIG. 5 is a schematic configuration diagram showing another example of the embodiment of the present invention.
FIG. 6 is a schematic configuration diagram showing another example of the embodiment of the present invention.
[Explanation of symbols]
10 photoconductor
20 Charging roller
30 exposure equipment
40 Developer
41 Development belt
42 Development tank
43 Pumping roller
44 Application roller
45 Development unit
50 Intermediate transfer member
51 Suspended roller
52 Corona charger
53 Constant current source
60 Cleaning device
70 Static elimination lamp
80 Transfer roller
90 Cleaning device
100 transfer paper

Claims (9)

In a toner containing at least a binder resin and a colorant, the coverage of the colorant molecules on the toner surface by XPS measurement is 1.5 to 15 atomic%, and the colorant content is 2 to 15 % by weight . the toner for developing an electrostatic image, comprising free.   2. The electrophotographic toner according to claim 1, wherein the binder resin of the toner contains at least a polyol resin.   3. The toner for electrophotography according to claim 1, wherein the binder resin of the toner contains at least a polyol resin having an epoxy resin part and a polyoxyalkylene part in the main chain.   The toner for developing an electrostatic charge image according to claim 1, wherein the toner has a volume average particle diameter of 1 to 6 μm.   5. The electrostatic image developing toner according to claim 1, wherein the toner has a circularity SF-1 value of 100 to 140 and a circularity SF-2 value of 100 to 130.   In a toner containing at least a binder resin and a colorant, the coverage of the colorant molecules on the toner surface by XPS is 1.5 to 15 atomic%, and the colorant content is 2 to 15% by weight. A full-color toner kit comprising at least magenta toner for developing an electrostatic charge image, yellow toner, and cyan toner.   A two-component developer comprising at least a carrier comprising the toner according to claim 1 and magnetic particles.   An image forming method using the toner according to claim 1, a full color toner kit, or a developer.   A tandem color image forming method using the toner or full color toner kit or developer according to any one of claims 1 to 7 and having a printing speed of 20 sheets / minute or more corresponding to A4 size.

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