JP2004102236A - External additive for electrophotographic toner, electrophotographic toner, electrophotographic developer and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an external additive which is not buried in a toner even in electrostatic charge by agitation after storage in an environment at high temperature and high humidity, fulfills its functions as a fluidizing agent and an auxiliary electrostatic charging agent and suppresses abnormal rise of electrostatic chargeability even after storage in an environment at low temperature and low humidity to achieve stable image quality. <P>SOLUTION: The external additive for an electrophotographic toner comprises fine oxide particles containing at least elementary silicon. The primary particle diameter R (number average) of the fine oxide particles is 30-300 nm, standard deviation σ of the particle size distribution of R has a distribution of R/4≤σ≤R and the fine oxide particles are substantially spherical with a circularity SF1 of 100-130 and a circularity SF2 of 100-125. <P>COPYRIGHT: (C)2004,JPO

Description

【００８９】
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。
【００９０】
本発明の主鎖にエポキシ樹脂部とアルキレンオキサイド部を有するポリオール樹脂を得るためには、種々の原材料組合せが可能ではある。例えば、両末端グリシジル基のエポキシ樹脂と両末端グリシジル基の２価フェノールのアルキレンオキサイド付加物をジハライドやジイソシアネート、ジアミン、ジチオール、多価フェノール、ジカルボン酸と反応させることにより得ることができる。このうち、２価のフェノールを反応させるのが反応安定性の点で最も好ましい。また、ゲル化しない範囲で多価フェノール類や多価カルボン酸類を２価フェノールと併用するのも好ましい。ここで、多価フェノール類、多価カルボン酸類の量は全量に対し１５％以下、好ましくは１０％以下である。
【００９１】
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。
【００９２】
また本発明に用いる樹脂中の主鎖にエポキシ樹脂部とポリオキシアルキレン部およびポリエステル部を有するポリオール樹脂とすることで、特に該ポリエステル成分により樹脂の粘弾性、硬性が変化し、よりソフトな樹脂物性となり画像のカール発生を押さえることができより好ましい。
【００９３】
また該バインダー樹脂のエポキシ当量を、１００００以上、好ましくは３００００以上、より好ましくは５００００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。
【００９４】
ここで、ポリエステル樹脂としては、各種のタイプのものが使用できるが、特に、
▲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
【００９５】
【化２】

（式中、Ｒ^１及びＲ^２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。）
【００９６】
▲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上記▲１▼▲２▼▲３▼とを反応させてなるポリエステル樹脂であることが好ましい。
【００９７】
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。
【００９８】
▲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。
【００９９】
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。
【０１００】
▲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。
【０１０１】
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。
【０１０２】
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。
【０１０３】
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。
【０１０４】
また、本発明のトナーに使用するバインダ樹脂として変性ポリエステル（ｉ）も好ましいものである。変性ポリエステル（ｉ）としては、ポリエステル樹脂中にエステル結合以外の結合基が存在したり、またポリエステル樹脂中に構成の異なる樹脂成分が共有結合、イオン結合などで結合した状態をさす。具体的には、ポリエステル末端に、カルボン酸基、水酸基と反応するイソシアネート基などの官能基を導入し、さらに活性水素含有化合物と反応させ、ポリエステル末端を変性したものを指す。
【０１０５】
変性ポリエステル（ｉ）としては、イソシアネート基を有するポリエステルプレポリマー（Ａ）とアミン類（Ｂ）との反応により得られるウレア変性ポリエステルなどが挙げられる。イソシアネート基を有するポリエステルプレポリマー（Ａ）としては、多価アルコール（ＰＯ）と多価カルボン酸（ＰＣ）の重縮合物で、かつ活性水素基を有するポリエステルを、さらに多価イソシアネート化合物（ＰＩＣ）と反応させたものなどが挙げられる。上記ポリエステルの有する活性水素基としては、水酸基（アルコール性水酸基及びフェノール性水酸基）、アミノ基、カルボキシル基、メルカプト基などが挙げられ、これらのうち好ましいものはアルコール性水酸基である。
【０１０６】
ウレア変性ポリエステルは、以下のようにして生成される。
多価アルコール化合物（ＰＯ）としては、２価アルコール（ＤＩＯ）および３価以上の多価アルコール（ＴＯ）が挙げられ、（ＤＩＯ）単独、または（ＤＩＯ）と少量の（ＴＯ）との混合物が好ましい。２価アルコール（ＤＩＯ）としては、アルキレングリコール（エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオールなど）；アルキレンエーテルグリコール（ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコールなど）；脂環式ジオール（１，４−シクロヘキサンジメタノール、水素添加ビスフェノールＡなど）；ビスフェノール類（ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳなど）；上記脂環式ジオールのアルキレンオキサイド（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など）付加物；上記ビスフェノール類のアルキレンオキサイド（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など）付加物などが挙げられる。これらのうち好ましいものは、炭素数２〜１２のアルキレングリコールおよびビスフェノール類のアルキレンオキサイド付加物であり、特に好ましいものはビスフェノール類のアルキレンオキサイド付加物、およびこれと炭素数２〜１２のアルキレングリコールとの併用である。３価以上の多価アルコール（ＴＯ）としては、３〜８価またはそれ以上の多価脂肪族アルコール（グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、ソルビトールなど）；３価以上のフェノール類（トリスフェノールＰＡ、フェノールノボラック、クレゾールノボラックなど）；上記３価以上のポリフェノール類のアルキレンオキサイド付加物などが挙げられる。
【０１０７】
多価カルボン酸（ＰＣ）としては、２価カルボン酸（ＤＩＣ）および３価以上の多価カルボン酸（ＴＣ）が挙げられ、（ＤＩＣ）単独、および（ＤＩＣ）と少量の（ＴＣ）との混合物が好ましい。２価カルボン酸（ＤＩＣ）としては、アルキレンジカルボン酸（コハク酸、アジピン酸、セバシン酸など）；アルケニレンジカルボン酸（マレイン酸、フマール酸など）；芳香族ジカルボン酸（フタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸など）などが挙げられる。これらのうち好ましいものは、炭素数４〜２０のアルケニレンジカルボン酸および炭素数８〜２０の芳香族ジカルボン酸である。３価以上の多価カルボン酸（ＴＣ）としては、炭素数９〜２０の芳香族多価カルボン酸（トリメリット酸、ピロメリット酸など）などが挙げられる。なお、多価カルボン酸（ＰＣ）としては、上述のものの酸無水物または低級アルキルエステル（メチルエステル、エチルエステル、イソプロピルエステルなど）を用いて多価アルコール（ＰＯ）と反応させてもよい。
【０１０８】
多価アルコール（ＰＯ）と多価カルボン酸（ＰＣ）の比率は、水酸基［ＯＨ］とカルボキシル基［ＣＯＯＨ］の当量比［ＯＨ］／［ＣＯＯＨ］として、通常２／１〜１／１、好ましくは１．５／１〜１／１、さらに好ましくは１．３／１〜１．０２／１である。
【０１０９】
多価イソシアネート化合物（ＰＩＣ）としては、脂肪族多価イソシアネート（テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、２，６−ジイソシアナトメチルカプロエートなど）；脂環式ポリイソシアネート（イソホロンジイソシアネート、シクロヘキシルメタンジイソシアネートなど）；芳香族ジイソシアネート（トリレンジイソシアネート、ジフェニルメタンジイソシアネートなど）；芳香脂肪族ジイソシアネート（α，α，α’，α’−テトラメチルキシリレンジイソシアネートなど）；イソシアネート類；前記ポリイソシアネートをフェノール誘導体、オキシム、カプロラクタムなどでブロックしたもの；およびこれら２種以上の併用が挙げられる。
【０１１０】
多価イソシアネート化合物（ＰＩＣ）の比率は、イソシアネート基［ＮＣＯ］と、水酸基を有するポリエステルの水酸基［ＯＨ］の当量比［ＮＣＯ］／［ＯＨ］として、通常５／１〜１／１、好ましくは４／１〜１．２／１、さらに好ましくは２．５／１〜１．５／１である。［ＮＣＯ］／［ＯＨ］が５を超えると低温定着性が悪化する。［ＮＣＯ］のモル比が１未満では、ウレア変性ポリエステルを用いる場合、そのエステル中のウレア含量が低くなり、耐ホットオフセット性が悪化する。
【０１１１】
イソシアネート基を有するポリエステルプレポリマー（Ａ）中の多価イソシアネート化合物（ＰＩＣ）構成成分の含有量は、通常０．５〜４０ｗｔ％、好ましくは１〜３０ｗｔ％、さらに好ましくは２〜２０ｗｔ％である。０．５ｗｔ％未満では、耐ホットオフセット性が悪化するとともに、耐熱保存性と低温定着性の両立の面で不利になる。また、４０ｗｔ％を超えると低温定着性が悪化する。
イソシアネート基を有するポリエステルプレポリマー（Ａ）中の１分子当たりに含有されるイソシアネート基は、通常１個以上、好ましくは、平均１．５〜３個、さらに好ましくは、平均１．８〜２．５個である。１分子当たり１個未満では、ウレア変性ポリエステルの分子量が低くなり、耐ホットオフセット性が悪化する。
【０１１２】
次に、ポリエステルプレポリマー（Ａ）と反応させるアミン類（Ｂ）としては、２価アミン化合物（Ｂ１）、３価以上の多価アミン化合物（Ｂ２）、アミノアルコール（Ｂ３）、アミノメルカプタン（Ｂ４）、アミノ酸（Ｂ５）、およびＢ１〜Ｂ５のアミノ基をブロックしたもの（Ｂ６）などが挙げられる。
２価アミン化合物（Ｂ１）としては、芳香族ジアミン（フェニレンジアミン、ジエチルトルエンジアミン、４，４’−ジアミノジフェニルメタンなど）；脂環式ジアミン（４，４’−ジアミノ−３，３’−ジメチルジシクロヘキシルメタン、ジアミンシクロヘキサン、イソホロンジアミンなど）；および脂肪族ジアミン（エチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミンなど）などが挙げられる。３価以上の多価アミン化合物（Ｂ２）としては、ジエチレントリアミン、トリエチレンテトラミンなどが挙げられる。アミノアルコール（Ｂ３）としては、エタノールアミン、ヒドロキシエチルアニリンなどが挙げられる。アミノメルカプタン（Ｂ４）としては、アミノエチルメルカプタン、アミノプロピルメルカプタンなどが挙げられる。アミノ酸（Ｂ５）としては、アミノプロピオン酸、アミノカプロン酸などが挙げられる。Ｂ１〜Ｂ５のアミノ基をブロックしたもの（Ｂ６）としては、前記Ｂ１〜Ｂ５のアミン類とケトン類（アセトン、メチルエチルケトン、メチルイソブチルケトンなど）から得られるケチミン化合物、オキサゾリジン化合物などが挙げられる。これらアミン類（Ｂ）のうち好ましいものは、Ｂ１およびＢ１と少量のＢ２の混合物である。
【０１１３】
アミン類（Ｂ）の比率は、イソシアネート基を有するポリエステルプレポリマー（Ａ）中のイソシアネート基［ＮＣＯ］と、アミン類（Ｂ）中のアミノ基［ＮＨｘ］の当量比［ＮＣＯ］／［ＮＨｘ］として、通常１／２〜２／１、好ましくは１．５／１〜１／１．５、さらに好ましくは１．２／１〜１／１．２である。［ＮＣＯ］／［ＮＨｘ］が２を超えたり１／２未満では、ウレア変性ポリエステルの分子量が低くなり、耐ホットオフセット性が悪化する。
また、ウレア変性ポリエステル中には、ウレア結合と共にウレタン結合を含有していてもよい。ウレア結合含有量とウレタン結合含有量のモル比は、通常１００／０〜１０／９０であり、好ましくは８０／２０〜２０／８０、さらに好ましくは、６０／４０〜３０／７０である。ウレア結合のモル比が１０％未満では、耐ホットオフセット性が悪化する。
【０１１４】
本発明で用いられる変性ポリエステル（ｉ）は、ワンショット法、プレポリマー法により製造される。変性ポリエステル（ｉ）の重量平均分子量は、通常１万以上、好ましくは２万〜１０００万、さらに好ましくは３万〜１００万である。この時のピーク分子量は１０００〜１００００が好ましく、１０００未満では伸長反応しにくくトナーの弾性が少なくその結果耐ホットオフセット性が悪化する。また１００００を超えると定着性の低下や粒子化や粉砕において製造上の課題が高くなる。変性ポリエステル（ｉ）の数平均分子量は、後述の変性されていないポリエステル（ｉｉ）を用いる場合は特に限定されるものではなく、前記重量平均分子量とするのに得やすい数平均分子量でよい。（ｉ）単独の場合は、数平均分子量は、通常２００００以下、好ましくは１０００〜１００００、さらに好ましくは２０００〜８０００である。２００００を超えると低温定着性及びフルカラー装置に用いた場合の光沢性が悪化する。
変性ポリエステル（ｉ）を得るためのポリエステルプレポリマー（Ａ）とアミン類（Ｂ）との架橋及び／又は伸長反応には、必要により反応停止剤を用い、得られるウレア変性ポリエステルの分子量を調整することができる。反応停止剤としては、モノアミン（ジエチルアミン、ジブチルアミン、ブチルアミン、ラウリルアミンなど）、およびそれらをブロックしたもの（ケチミン化合物）などが挙げられる。
【０１１５】
（未変性ポリエステル）
本発明においては、前記変性されたポリエステル（ｉ）単独使用だけでなく、この（ｉ）と共に、未変性ポリエステル（ｉｉ）をバインダ樹脂成分として含有させることもできる。（ｉｉ）を併用することで、低温定着性及びフルカラー装置に用いた場合の光沢性が向上し、単独使用より好ましい。（ｉｉ）としては、前記（ｉ）のポリエステル成分と同様な多価アルコール（ＰＯ）と多価カルボン酸（ＰＣ）との重縮合物などが挙げられ、好ましいものも（ｉ）と同様である。また、（ｉｉ）は無変性のポリエステルだけでなく、ウレア結合以外の化学結合で変性されているものでもよく、例えばウレタン結合で変性されていてもよい。（ｉ）と（ｉｉ）は少なくとも一部が相溶していることが低温定着性、耐ホットオフセット性の面で好ましい。従って、（ｉ）のポリエステル成分と（ｉｉ）は類似の組成が好ましい。（ｉｉ）を含有させる場合の（ｉ）と（ｉｉ）の重量比は、通常５／９５〜８０／２０、好ましくは５／９５〜３０／７０、さらに好ましくは５／９５〜２５／７５、特に好ましくは７／９３〜２０／８０である。（ｉ）の重量比が５％未満では、耐ホットオフセット性が悪化するとともに、耐熱保存性と低温定着性の両立の面で不利になる。
【０１１６】
（ｉｉ）のピーク分子量は、通常１０００〜１００００、好ましくは２０００〜８０００、さらに好ましくは２０００〜５０００である。１０００未満では耐熱保存性が悪化し、１００００を超えると低温定着性が悪化する。（ｉｉ）の水酸基価は５以上であることが好ましく、さらに好ましくは１０〜１２０、特に好ましくは２０〜８０である。５未満では耐熱保存性と低温定着性の両立の面で不利になる。（ｉｉ）の酸価は１〜５が好ましく、より好ましくは２〜４である。ワックスに高酸価ワックスを使用するため、バインダは低酸価バインダが帯電や高体積抵抗につながるので二成分系現像剤に用いるトナーにはマッチしやすい。
【０１１７】
バインダ樹脂のガラス転移点（Ｔｇ）は通常３５〜７０℃、好ましくは５５〜６５℃である。３５℃未満ではトナーの耐熱保存性が悪化し、７０℃を超えると低温定着性が不十分となる。ウレア変性ポリエステルは、得られるトナー母体粒子の表面に存在しやすいため、本発明のトナーにおいては、公知のポリエステル系トナーと比較して、ガラス転移点が低くても耐熱保存性が良好な傾向を示す。
【０１１８】
（トナーバインダの製造方法）
トナーバインダは以下の方法などで製造することができる。多価アルコール（ＰＯ）と多価カルボン酸（ＰＣ）を、テトラブトキシチタネート、ジブチルチンオキサイドなど公知のエステル化触媒の存在下、１５０〜２８０℃に加熱し、必要により減圧としながら生成する水を溜去して、水酸基を有するポリエステルを得る。次いで４０〜１４０℃にて、これに多価イソシアネート化合物（ＰＩＣ）を反応させ、イソシアネート基を有するプレポリマー（Ａ）を得る。さらに（Ａ）にアミン類（Ｂ）を０〜１４０℃にて反応させ、ウレア結合で変性されたポリエステルを得る。
（ＰＩＣ）を反応させる際、及び（Ａ）と（Ｂ）を反応させる際には、必要により溶剤を用いることもできる。使用可能な溶剤としては、芳香族溶剤（トルエン、キシレンなど）；ケトン類（アセトン、メチルエチルケトン、メチルイソブチルケトンなど）；エステル類（酢酸エチルなど）；アミド類（ジメチルホルムアミド、ジメチルアセトアミドなど）及びエーテル類（テトラヒドロフランなど）などの多価イソシアネート化合物（ＰＩＣ）に対して不活性なものが挙げられる。
未変性ポリエステル（ｉｉ）を併用する場合は、水酸基を有するポリエステルと同様な方法で（ｉｉ）を製造し、これを前記（ｉ）の反応完了後の溶液に溶解し、混合する。
【０１１９】
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出来る。
【０１２０】
（着色剤）
本発明のトナーの着色剤としては公知の染料及び顔料が全て使用でき、例えば、カーボンブラック、ニグロシン染料、鉄黒、ナフト−ルイエローＳ、ハンザイエロー（１０Ｇ、５Ｇ、Ｇ）、カドミュウムイエロー、黄色酸化鉄、黄土、黄鉛、チタン黄、オイルイエロー、ハンザイエロー、（ＧＲ、Ａ、ＲＮ、Ｒ）、ピグメントイエローＬ、ベンジジンイエロー（Ｇ、ＧＲ）、パーマネントイエロー（ＮＣＧ）、バルカンファストイエロー（５Ｇ、Ｒ）、タートラジンレーキ、キノリンイエローレーキ、アンスラゲンイエローＢＧＬ、イソインドリノンイエロー、ベンガラ、鉛丹、鉛朱、カドミュウムレッド、カドミュウムマーキュリレッド、アンチモン朱、パーマネントレッド４Ｒ、パラレッド、ファイヤーレッド、パラクロルオルトニトロアニリンレッド、リソールファストスカーレットＧ、ブリリアントファストスカーレット、ブリリアントカーンミンＢＳ、パーマネントレッド（Ｆ２Ｒ、Ｆ４Ｒ、ＦＲＬ、ＦＲＬＬ、Ｆ４ＲＨ）、ファストスカレートＶＤ、ベルカンファストルビンＢ、ブリリアントスカーレットＧ、リソールルビンＧＸ、パーマネントレッドＦ５Ｒ、ブリリアントカーミン６Ｂ、ピグメントスカーレット３Ｂ、ボルドー５Ｂ、トルイジンマルーン、パーマネントボルドーＦ２Ｋ、ヘリオボルドーＢＬ、ボルドー１０Ｂ、ボンマルーンライト、ボンマルーンメジアム、エオシンレーキ、ローダミンレーキＢ、ローダミンレーキＹ、アリザリンレーキ、チオインジゴレットＢ、チオインジゴマルーン、オイルレッド、キナクリドンレッド、ピラゾロンレッド、クロームバーミリオン、ベンジジンオレンジ、ペリノンオレンジ、オイルオレンジ、コバルトブルー、セルリアンブルー、アルカリブルーレーキ、ピーコックブルーレーキ、ビクトリアブルーレーキ、無金属フタロシアニンブルー、フタロシアニンブルー、ファストスカイブルー、インダンスレンブルー（ＲＳ、ＢＣ）、インジゴ、群青、紺青、アントラキノンブルー、ファストバイオレットＢ、メチルバイオレットレーキ、コバルト紫、マンガン紫、ジオキサジンバイオレット、アントラキノンバイオレット、クロムグリーン、ジンクグリーン、酸化クロム、ピリジアンエメラルドグリーン、ピグメントグリーンＢ、ナフトールグリーンＢ、グリーンゴールド、アシッドグリーンレーキ、マラカイトグリーンレーキ、フタロシアニングリーン、アントラキノングリーン、酸化チタン、亜鉛華、リトポン及びそれらの混合物等である。使用量は一般にバインダー樹脂１００重量部に対し０．１〜５０重量部である。
【０１２１】
（マスターバッチ顔料）
本発明では、樹脂と顔料との親和性を向上させる目的で、あらかじめ樹脂と顔料を１：１程度で混合、混練りしたマスターバッチ顔料を用いることもできる。より好ましくは低極性溶媒可溶成分量の樹脂と顔料を有機溶剤を用いずに加熱混練して製造することで、環境帯電安定性の優れたマスターバッチ顔料とすることができる。さらに、乾燥粉体顔料を用い、樹脂と濡らす方法として水を用いることでより分散性をより向上できる。一般的に着色剤として使用される有機顔料は疎水性であるが、その製造工程においては水洗、乾燥という工程をとっているため、ある程度の力を加えれば顔料凝集体内部にまで水を染み込ませることが可能である。この凝集体内部に水が染み込んだ顔料と樹脂を混合したものを、開放型の混練機で、１００℃以上の設定温度で混練すると、凝集体内部の水は瞬時に沸点に達し、体積膨張するため、凝集体内部から凝集体を解砕しようとする力が加わることになる。この凝集体内部からの力は、外部から加える力に比べ非常に効率良く凝集体を解砕することが可能である。
【０１２２】
さらにこの時、樹脂は軟化点以上の温度に加熱されているため、粘度が低くなり、凝集体を効率よく濡らすようになるのと同時に、凝集体内部の沸点温度近い水といわゆるフラッシングに似た効果で置換されることにより、１次粒子に近い状態で顔料が分散したマスターバッチ顔料を得ることができる。さらに、水が蒸発している過程においては、水の蒸発に伴う気化熱を混練物から奪うため、混練物の温度は１００℃以下の比較的低温高粘度に保持されるため、剪断力が有効に顔料凝集体に加えられるという効果も合せもつ。マスターバッチ顔料製造用の開放型混練機としては通常の２本ロール、３本ロールの他、バンバリーミキサーを開放型として使用する方法や、三井鉱山社製連続式２本ロール混練機等を用いることができる。
【０１２３】
（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ー５１、含金属アゾ染料のボントロンＳー３４、オキシナフトエ酸系金属錯体のＥー８２、サリチル酸系金属錯体のＥー８４、フェノール系縮合物のＥー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ー３０２、ＴＰ一４１５（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ー９０１、ホウ素錯体であるＬＲー１４７（日本カ一リット社製）、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。
【０１２４】
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、２〜５重量部の範囲がよい。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。
【０１２５】
（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。磁性キャリアとしては、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。
【０１２６】
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。
【０１２７】
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。
【０１２８】
（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。
【０１２９】
（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。前記ワツクスは、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ツト性、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。
【０１３０】
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。
【０１３１】
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。
【０１３２】
なおワックスの分散径は３μｍ以下であることが望ましく、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。
【０１３３】
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で、前記に示した良好な結果が得られる。
【０１３４】
（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。
【０１３５】
（トナー製造方法）
本発明の製造方法は、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。
【０１３６】
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。
【０１３７】
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。
【０１３８】
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。
【０１３９】
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。
【０１４０】
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したり、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方式が好ましく用いられる。
【０１４１】
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、体積平均粒径が２〜７μｍのトナー（母体粒子）を製造する。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。
【０１４２】
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。
【０１４３】
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。
【０１４４】
（重合法１）
▲１▼　重合性モノマー、必要に応じて重合開始剤、着色剤、ワックス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。
【０１４５】
（重合法２）
▲１▼　低分子量樹脂、高分子量樹脂、着色剤、ワックス、ワックス分散剤、必要に応じて帯電制御剤等を酢酸エチル等の溶媒を用いた油層分散媒中で分散させる。
▲２▼　有機微粒子と伸長剤を含んだ水中に滴下し、乳化、収斂させる。
▲３▼　前記分散液を加熱し重合、脱溶剤させる。
▲４▼　水中で熟成させた後、洗浄、捕集、乾燥して母体粒子を得る。
【０１４６】
（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。
【０１４７】
（前記（バインダー樹脂）で記載した変性ポリエステル（ｉ）を使用するトナーの製造方法）
１）着色剤、未変性ポリエステル（ｉ）、イソシアネート基を有するポリエステルプレポリマー（Ａ）、離型剤を有機溶媒中に分散させトナー材料液を作る。
有機溶媒は、沸点が１００℃未満の揮発性であることが、トナー母体粒子形成後の除去が容易である点から好ましい。具体的には、トルエン、キシレン、ベンゼン、四塩化炭素、塩化メチレン、１，２−ジクロロエタン、１，１，２−トリクロロエタン、トリクロロエチレン、クロロホルム、モノクロロベンゼン、ジクロロエチリデン、酢酸メチル、酢酸エチル、メチルエチルケトン、メチルイソブチルケトンなどを単独あるいは２種以上組合せて用いることができる。特に、トルエン、キシレン等の芳香族系溶媒および塩化メチレン、１，２−ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン化炭化水素が好ましい。有機溶媒の使用量は、ポリエステルプレポリマー１００重量部に対し、通常０〜３００重量部、好ましくは０〜１００重量部、さらに好ましくは２５〜７０重量部である。
【０１４８】
２）トナー材料液を界面活性剤、樹脂微粒子の存在下、水系媒体中で乳化させる。
水系媒体は、水単独でも良いし、アルコール（メタノール、イソプロピルアルコール、エチレングリコールなど）、ジメチルホルムアミド、テトラヒドロフラン、セルソルブ類（メチルセルソルブなど）、低級ケトン類（アセトン、メチルエチルケトンなど）などの有機溶媒を含むものであってもよい。
トナー材料液１００重量部に対する水系媒体の使用量は、通常５０〜２０００重量部、好ましくは１００〜１０００重量部である。５０重量部未満ではトナー材料液の分散状態が悪く、所定の粒径のトナー粒子が得られない。２００００重量部を超えると経済的でない。
【０１４９】
また、水系媒体中の分散を良好にするために、界面活性剤、樹脂微粒子等の分散剤を適宜加える。
界面活性剤としては、アルキルベンゼンスルホン酸塩、α−オレフィンスルホン酸塩、リン酸エステルなどのアニオン性界面活性剤、アルキルアミン塩、アミノアルコール脂肪酸誘導体、ポリアミン脂肪酸誘導体、イミダゾリンなどのアミン塩型や、アルキルトリメチルアンモニム塩、ジアルキルジメチルアンモニウム塩、アルキルジメチルベンジルアンモニウム塩、ピリジニウム塩、アルキルイソキノリニウム塩、塩化ベンゼトニウムなどの４級アンモニウム塩型のカチオン性界面活性剤、脂肪酸アミド誘導体、多価アルコール誘導体などの非イオン界面活性剤、例えばアラニン、ドデシルジ（アミノエチル）グリシン、ジ（オクチルアミノエチル）グリシンやＮ−アルキル−Ｎ，Ｎ−ジメチルアンモニウムべタインなどの両性界面活性剤が挙げられる。
【０１５０】
また、フルオロアルキル基を有する界面活性剤を用いることにより、非常に少量でその効果をあげることができる。好ましく用いられるフルオロアルキル基を有するアニオン性界面活性剤としては、炭素数２〜１０のフルオロアルキルカルボン酸及びその金属塩、パーフルオロオクタンスルホニルグルタミン酸ジナトリウム、３−［ω−フルオロアルキル（Ｃ６〜Ｃ１１）オキシ］−１−アルキル（Ｃ３〜Ｃ４）スルホン酸ナトリウム、３−［ω−フルオロアルカノイル（Ｃ６〜Ｃ８）−Ｎ−エチルアミノ］−１−プロパンスルホン酸ナトリウム、フルオロアルキル（Ｃ１１〜Ｃ２０）カルボン酸及び金属塩、パーフルオロアルキルカルボン酸（Ｃ７〜Ｃ１３）及びその金属塩、パーフルオロアルキル（Ｃ４〜Ｃ１２）スルホン酸及びその金属塩、パーフルオロオクタンスルホン酸ジエタノールアミド、Ｎ−プロピル−Ｎ−（２−ヒドロキシエチル）パーフルオロオクタンスルホンアミド、パーフルオロアルキル（Ｃ６〜Ｃ１０）スルホンアミドプロピルトリメチルアンモニウム塩、パーフルオロアルキル（Ｃ６〜Ｃ１０）−Ｎ−エチルスルホニルグリシン塩、モノパーフルオロアルキル（Ｃ６〜Ｃ１６）エチルリン酸エステルなどが挙げられる。
商品名としては、サーフロンＳ−１１１、Ｓ−１１２、Ｓ−１１３（旭硝子社製）、フロラードＦＣ−９３、ＦＣ−９５、ＦＣ−９８、ＦＣ−１２９（住友３Ｍ社製）、ユニダインＤＳ−１０１、ＤＳ−１０２（ダイキン工業社製）、メガファックＦ−１１０、Ｆ−１２０、Ｆ−１１３、Ｆ−１９１、Ｆ−８１２、Ｆ−８３３（大日本インキ社製）、エクトップＥＦ−１０２、１０３、１０４、１０５、１１２、１２３Ａ、１２３Ｂ、３０６Ａ、５０１、２０１、２０４、（トーケムプロダクツ社製）、フタージェントＦ−１００、Ｆ１５０（ネオス社製）などが挙げられる。
【０１５１】
また、カチオン性界面活性剤としては、フルオロアルキル基を右する脂肪族１級、２級もしくは２級アミン酸、パーフルオロアルキル（Ｃ６−Ｃ１０）スルホンアミドプロピルトリメチルアンモニウム塩などの脂肪族４級アンモニウム塩、ベンザルコニウム塩、塩化ベンゼトニウム、ピリジニウム塩、イミダゾリニウム塩、商品名としてはサーフロンＳ−１２１（旭硝子社製）、フロラードＦＣ−１３５（住友３Ｍ社製）、ユニダインＤＳ−２０２（ダイキンエ業杜製）、メガファックＦ−１５０、Ｆ−８２４（大日本インキ社製）、エクトップＥＦ−１３２（トーケムプロダクツ社製）、フタージェントＦ−３００（ネオス社製）などが挙げられる。
【０１５２】
樹脂微粒子は、水系媒体中で形成されるトナー母体粒子を安定化させるために加えられる。このために、トナー母体粒子の表面上に存在する被覆率が１０〜９０％の範囲になるように加えられることが好ましい。例えば、ポリメタクリル酸メチル微粒子１μｍ、及び３μｍ、ポリスチレン微粒子０．５μｍ及び２μｍ、ポリ（スチレン―アクリロニトリル）微粒子１μｍ、商品名では、ＰＢ−２００Ｈ（花王社製）、ＳＧＰ（総研社製）、テクノポリマーＳＢ（積水化成品工業社製）、ＳＧＰ−３Ｇ（総研社製）、ミクロパール（積水ファインケミカル社製）等がある。
また、リン酸三カルシウム、炭酸カルシウム、酸化チタン、コロイダルシリカ、ヒドロキシアパタイト等の無機化合物分散剤も用いることができる。
【０１５３】
上記の樹脂微粒子、無機化合物分散剤と併用して使用可能な分散剤として、高分子系保護コロイドにより分散液滴を安定化させても良い。例えばアクリル酸、メタクリル酸、α−シアノアクリル酸、α−シアノメタクリル酸、イタコン酸、クロトン酸、フマール酸、マレイン酸または無水マレイン酸などの酸類、あるいは水酸基を含有する（メタ）アクリル系単量体、例えばアクリル酸−β−ヒドロキシエチル、メタクリル酸−β−ヒドロキシエチル、アクリル酸−β−ヒドロキシプロビル、メタクリル酸−β−ヒドロキシプロピル、アクリル酸−γ−ヒドロキシプロピル、メタクリル酸−γ−ヒドロキシプロピル、アクリル酸−３−クロロ２−ヒドロキシプロビル、メタクリル酸−３−クロロ−２−ヒドロキシプロピル、ジエチレングリコールモノアクリル酸エステル、ジエチレングリコールモノメタクリル酸エステル、グリセリンモノアクリル酸エステル、グリセリンモノメタクリル酸エステル、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミドなど、ビニルアルコールまたはビニルアルコールとのエーテル類、例えばビニルメチルエーテル、ビニルエチルエーテル、ビニルプロピルエーテルなど、またはビニルアルコールとカルボキシル基を含有する化合物のエステル類、例えば酢酸ビニル、プロピオン酸ビニル、酪酸ビニルなど、アクリルアミド、メタクリルアミド、ジアセトンアクリルアミドあるいはこれらのメチロール化合物、アクリル酸クロライド、メタクリル酸クロライドなどの酸クロライド類、ビニルピリジン、ビニルピロリドン、ビニルイミダゾール、エチレンイミンなどの含窒素化合物、またはその複素環を有するものなどのホモポリマーまたは共重合体、ポリオキシエチレン、ポリオキシプロピレン、ポリオキシエチレンアルキルアミン、ポリオキシプロピレンアルキルアミン、ポリオキシエチレンアルキルアミド、ポリオキシプロピレンアルキルアミド、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンラウリルフェニルエーテル、ポリオキシエチレンステアリルフェニルエステル、ポリオキシエチレンノニルフェニルエステルなどのポリオキシエチレン系、メチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロースなどのセルロース類などが使用できる。
【０１５４】
分散の方法としては特に限定されるものではないが、低速せん断式、高速せん断式、摩擦式、高圧ジェット式、超音波などの公知の設備が適用できる。この中でも、分散体の粒径を２〜２０μｍにするために高速せん断式が好ましい。高速せん断式分散機を使用した場合、回転数は特に限定はないが、通常１０００〜３００００ｒｐｍ、好ましくは５０００〜２００００ｒｐｍである。分散時間は特に限定はないが、バッチ方式の場合は、通常０．１〜５分である。分散時の温度としては、通常、０〜１５０℃（加圧下）、好ましくは４０〜９８℃である。
【０１５５】
３）乳化液の作製と同時に、アミン類（Ｂ）を添加し、イソシアネート基を有するポリエステルプレポリマー（Ａ）との反応を行わせる。
この反応は、分子鎖の架橋及び／又は伸長を伴う。反応時間は、ポリエステルプレポリマー（Ａ）の有するイソシアネート基構造とアミン類（Ｂ）との反応性により選択されるが、通常１０分〜４０時間、好ましくは２〜２４時間である。反応温度は、通常、０〜１５０℃、好ましくは４０〜９８℃である。また、必要に応じて公知の触媒を使用することができる。具体的にはジブチルチンラウレート、ジオクチルチンラウレートなどが挙げられる。
【０１５６】
４）反応終了後、乳化分散体（反応物）から有機溶媒を除去し、洗浄、乾燥してトナー母体粒子を得る。
有機溶媒を除去するためには、系全体を徐々に層流の攪拌状態で昇温し、一定の温度域で強い攪拌を与えた後、脱溶媒を行うことで紡錘形のトナー母体粒子が作製できる。また、分散安定剤としてリン酸カルシウム塩などの酸、アルカリに溶解可能な物を用いた場合は、塩酸等の酸により、リン酸カルシウム塩を溶解した後、水洗するなどの方法によって、トナー母体粒子からリン酸カルシウム塩を除去する。その他酵素による分解などの操作によっても除去できる。
【０１５７】
５）上記で得られたトナー母体粒子に、荷電制御剤を打ち込み、ついで、シリカ微粒子、酸化チタン微粒子等の無機微粒子を外添させ、トナーを得る。
荷電制御剤の打ち込み、及び無機微粒子の外添は、ミキサー等を用いた公知の方法によって行われる。
これにより、小粒径であって、粒径分布のシャープなトナーを容易に得ることができる。さらに、有機溶媒を除去する工程で強い攪拌を与えることで、真球状からラクビーボール状の間の形状を制御することができ、さらに、表面のモフォロジーも滑らかなものから梅干形状の間で制御することができる。
【０１５８】
（中間転写体）
本発明では、中間転写体を用いることもできる。転写システムの中間転写体の１実施形態について説明する。図１は本発明のトナー、現像剤の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。
【０１５９】
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。
【０１６０】
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。
【０１６１】
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。
【０１６２】
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。
【０１６３】
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。
【０１６４】
該中間転写体の静止摩擦係数は前述したように、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１０^３Ωｃｍ以下であることが好ましい。体積抵抗を数Ωｃｍ以上１０^３Ωｃｍ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。
【０１６５】
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。
【０１６６】
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。
【０１６７】
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。
【０１６８】
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。
【０１６９】
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出来る。
【０１７０】
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。
【０１７１】
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。
【０１７２】
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。
【０１７３】
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。
【０１７４】
ベルトの製造方法は限定されるものではない。例えば、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、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があるが、これ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。
【０１７５】
弾性ベルトト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。
【０１７６】
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。
【０１７７】
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）。
【０１７８】
（タンデム型カラー画像形成装置）
本発明では、タンデム型カラー画像形成装置としても使用できる。タンデム型カラー画像形成装置の実施形態の一例について説明する。タンデム型の電子写真装置には、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。
【０１７９】
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。
【０１８０】
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。
【０１８１】
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。
【０１８２】
以上のようなことから、最近は、タンデム型電子写真装置の中の、特に間接転写方式のものが注目されてきている。
【０１８３】
そして、この種のカラー電子写真装置では、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。
【０１８４】
以下、図面を参照しつつ、この発明のトナー、現像剤を使用する実施の形態につき説明する。
【０１８５】
図５は、この発明のトナー、現像剤を使用する一実施の形態を示すもので、タンデム型間接転写方式の電子写真装置である。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。
【０１８６】
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。
【０１８７】
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。
【０１８８】
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。
【０１８９】
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。
【０１９０】
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。
【０１９１】
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。
【０１９２】
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。
【０１９３】
さて、いまこのカラー電子写真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。
【０１９４】
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。
【０１９５】
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。
【０１９６】
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。
【０１９７】
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。
【０１９８】
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。
【０１９９】
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。
【０２００】
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。
【０２０１】
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。
【０２０２】
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。
図７に本発明のプロセスカートリッジを着脱自在に具備する画像形成装置の概略構成を示す。本発明のプロセスカ−トリッジを有する画像形成装置は、感光体が所定の周速度で回転駆動される。感光体は回転過程において、帯電手段によりその周面に正または負の所定電位の均一帯電を受け、次いで、スリット露光やレ−ザ−ビ−ム走査露光等の像露光手段からの画像露光光を受け、こうして感光体の周面に静電潜像が順次形成され、形成された静電潜像は、次いで現像手段によりトナ−現像され、現像されたトナ−像は、給紙部から感光体と転写手段との間に感光体の回転と同期されて給送された転写材に、転写手段により順次転写されていく。像転写を受けた転写材は感光体面から分離されて像定着手段へ導入されて像定着され、複写物（コピ−）として装置外へプリントアウトされる。像転写後の感光体の表面は、クリ−ニング手段によって転写残りトナ−の除去を受けて清浄面化され、更除電された後、繰り返し画像形成に使用される。
【０２０３】
【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。
【０２０４】
（評価機）
評価で用いる画像は以下の評価機Ａ，Ｂ，Ｃ，Ｄいずれかを用いて評価した。（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（２０枚〜５０枚／ｍｉｎ／Ａ４まで変化）で評価した。
【０２０５】
（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（２０枚〜５０枚／ｍｉｎ／Ａ４まで変化）で評価した。
【０２０６】
（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。
【０２０７】
（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の定着ユニッをオイルレス定着ユニットに改良し、オイル塗布型のままチューニングした評価機Ｄを用いて評価した。
【０２０８】
（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）で評価した。
【０２０９】
（評価項目）
１）添剤埋没性
４０℃、８０％の環境で１週間保存した後、現像ユニット中で１時間撹拌した後のトナー表面をＦＥ−ＳＥＭ（日立　電界放出型走査型電子顕微鏡　Ｓ−４２００）で観察して外添剤の埋め込み状態を観察した。埋め込みが少ないものが良好で、×、△、○、◎の順にランクが良くなる。具体的には×は、添加剤が全く観察されない程埋め込まれている。△は、埋め込まれているが添加剤の表面がわずかに観察できる。○は、添加剤が半分程度埋め込まれている。◎は、攪拌前と比較してほとんど埋め込みがない状態を示す。
【０２１０】
２）トナー飛散性
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、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計量した。１００ｍｇ以上が×、３０〜１００ｍｇ未満が△、５〜３０ｍｇ未満が○、５ｍｇ未満が◎となる。×、△、○、◎の順にランクが良くなる。
【０２１１】
３）文字画像内部の中抜け
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、文字部画像をリコー社製タイプＤＸのＯＨＰシートに４色重ねて出力させ、文字部の線画像内部が抜けるトナー未転写頻度を段階見本と比較した。×、△、○、◎の順にランクが良くなる。×は、明らかに内部が抜けている状態、△は、わずかに内部にトナーが残っている状態、○は、ほとんど抜けがないか、わずかに抜けている状態で許容範囲内の状態、◎は、全く抜けがない状態を示す。
【０２１２】
４）トナー転写率
単色モードで７％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、投入したトナー量と廃トナー量の関係から転写率を算出した。
転写率＝１００×（投入トナー量−廃トナー量）／（投入トナー量）
転写率９０以上を◎、９０未満７５以上を○、７５未満６０以上を△、６０未満を×とした。
【０２１３】
５）トナー補給性
９０％画像面積の画像チャートと５％画像チャートを４０００枚ごとに交互に出力して、その時のトナーの補給性を調べた。×、△、○、◎の順にトナー補給性が良くなる。×は、全くトナーが補給できなくなる状態、△は、トナー補給が不安定にできる状態で５回に１回程度トナー補給詰まりが発生する、○は、トナー補給には問題はないが、ボトル内にトナー残がわずかに残る状態、◎は、トナー補給、トナー残ともに問題ない状態。
【０２１４】
６）転写チリ
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、１０ｍｍ×１０ｍｍのベタ画像を４色重ねてリコー社製タイプ６０００ペーパーに出力させ、転写チリ度合いを段階見本と比較した。×、△、○、◎の順にランクが良くなる。×は、転写チリが非常に多く画像として問題な状態、△は、転写チリがあり画像として問題な状態、○は、転写チリがわずかにあるが画像として許容範囲内な状態（従来の電子写真画像並）、◎は、転写チリが全くない状態を示す。
【０２１５】
７）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。×は、細線のにじみが非常に多く画像として問題な状態、△は、細線のにじみがあり画像として問題な状態、○は、細線のにじみがわずかにあるが画像として許容範囲内な状態（従来の電子写真画像並）、◎は、細線のにじみが全くなく問題ない状態を示す。
【０２１６】
８）地肌汚れ
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、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（ΔＩＤ）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。ΔＩＤの値で、×は０．０５以上、△は０．０２〜０．０５未満、○は０．０１〜０．０２未満、◎は０．０１未満とした。
【０２１７】
９）画像濃度
単色モードで５０％画像面積の画像チャートを１５０，０００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。
【０２１８】
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。
【０２１９】
１１）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／ｃｍ^２、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。ヘイズ度値で、×は、５０以上。△は、３５〜５０未満。○は２０〜３５未満。◎は２０未満とした。
【０２２０】
１２）色の鮮やかさ、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、色の鮮やかさ、色再現性は、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。×は、色がくすんで見え、許容できない程度。△は、従来の電子写真画質にわずかに劣る程度。○は従来の電子写真画質並み、◎はオフセット印刷並み。
【０２２１】
１３）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、◎：１５以上、○：６以上１５未満、△：３以上〜６未満、×：３未満、とした。
【０２２２】
１４）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。帯電低下が少なく良好な順に◎、○、△、×とした。×は、帯電量の変化が大きく、２０μｃ／ｇ以上、△は１５〜２０μｃ／ｇ未満、○は１０〜１５μｃ／ｇ未満、◎は１０μｃ／ｇ未満とした。
【０２２３】
１５）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。帯電低下が少なく良好な順に◎、○、△、×とした。×は、帯電量の変化が大きく、２０μｃ／ｇ以上、△は１５〜２０μｃ／ｇ未満、○は１０〜１５μｃ／ｇ未満、◎は１０μｃ／ｇ未満とした。
【０２２４】
１６）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。特に必須の定着下限温度として、×は、１６０℃以上。△は１４５〜１６０℃未満、○は、１３０〜１４０℃未満、◎は、１００〜１３０℃未満とした。
【０２２５】
（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。
【０２２６】
（キャリアの製造）
・芯材
Ｃｕ−Ｚｎフェライト粒子（重量平均径：３５μｍ）　５０００部
・コート材
トルエン　４５０部
シリコーン樹脂ＳＲ２４００（東レ・ダウコーニング・シリコーン製、不揮発分
５０％）　　　　　　　　　　　　　　　　　　　　　　　　　　　４５０部
アミノシランＳＨ６０２０（東レ・ダウコーニング・シリコーン製）　１０部
カーボンブラック　　　　　　　　　　　　　　　　　　　　　　　　１０部
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。
【０２２７】
実施例１
（酸化物微粒子１）
蒸留精製したメチルトリメトキシシランを加熱し、ここに窒素ガスをバブリングし、メチルトリメトキシシランを窒素ガスで気流伴流して酸水素火炎バーナーに導入し、この酸水素火炎中で燃焼分解させた。このときのメチルトリメトキシシラン添加量は１２７０ｇ／ｈｒ、酸素ガス添加量は２．９Ｎｍ^３／ｈｒ、水素ガス添加量は２．１Ｎｍ^３／ｈｒ、窒素ガス添加量は０．５８Ｎｍ^３／ｈｒであり、生成した球状シリカ微粉末はバグフィルターで捕集した。この球状シリカ微粉末１ｋｇを５リットルのプラネタリミキサーに仕込み、純水１０ｇを撹拌下添加し、密閉後更に５５℃で１４時間撹拌した。次いで、室温まで冷却した後、ヘキサメチルジシラザン２０ｇを撹拌下添加し、密閉後更に２４時間撹拌した。１１５℃に昇温し、窒素ガスを通気しながら残存原料及び生成したアンモニアを除去し、酸化物微粒子１を得た。得られた該酸化物微粒子の一次粒子径、円形度はＳＦ１，ＳＦ２、元素組成の均一性は表２に示した。
【０２２８】
（酸化物微粒子２）
酸化物微粒子１において、メチルトリメトキシシラン添加量を８８０ｇ／ｈｒ、酸素ガス添加量を２．３Ｎｍ^３／ｈｒ、水素ガス添加量を１．８Ｎｍ^３／ｈｒに調整して、表２に示すように酸化物微粒子の一次粒径、標準偏差、円形度、元素組成の均一性を持った酸化物微粒子を得た以外は、酸化物微粒子１と同様にして製造した。
（酸化物微粒子３）
酸化物微粒子１において、メチルトリメトキシシラン添加量を１４３０ｇ／ｈｒ、酸素ガス添加量を３．１Ｎｍ^３／ｈｒ、水素ガス添加量を２．３Ｎｍ^３／ｈｒに調整して、表２に示すように酸化物微粒子の一次粒径、標準偏差、円形度、元素組成の均一性を持った酸化物微粒子を得た以外は、酸化物微粒子１と同様にして製造した。
（酸化物微粒子４）
酸化物微粒子１において、メチルトリメトキシシラン添加量を１５２０ｇ／ｈｒ、酸素ガス添加量を３．４Ｎｍ^３／ｈｒ、水素ガス添加量を２．５Ｎｍ^３／ｈｒに調整して、表２に示すように酸化物微粒子の一次粒径、標準偏差、円形度、元素組成の均一性を持った酸化物微粒子を得た以外は、酸化物微粒子１と同様にして製造した。
【０２２９】
（酸化物微粒子５）
蒸留精製したメチルトリメトキシシランを加熱し、ここに窒素ガスをバブリングし、メチルトリメトキシシランとチタン（Ｔｉ）金属粒子を窒素ガスで気流伴流して酸水素火炎バーナーに導入し、この酸水素火炎中で燃焼分解させた。このときのメチルトリメトキシシラン添加量は１２７０ｇ／ｈｒ、チタン金属粒子は１２７ｇ／ｈｒ、酸素ガス添加量は２．９Ｎｍ^３／ｈｒ、水素ガス添加量は２．１Ｎｍ^３／ｈｒ、窒素ガス添加量は０．５８Ｎｍ^３／ｈｒであり、生成した球状Ｔｉ含有シリカ微粉末はバグフィルターで捕集した。この球状シリカ微粉末１ｋｇを５リットルのプラネタリミキサーに仕込み、純水１０ｇを撹拌下添加し、密閉後更に５５℃で１４時間撹拌した。次いで、室温まで冷却した後、ヘキサメチルジシラザン２０ｇを撹拌下添加し、密閉後更に２４時間撹拌した。１１５℃に昇温し、窒素ガスを通気しながら残存原料及び生成したアンモニアを除去し、酸化物微粒子１を得た。得られた該酸化物微粒子の一次粒子径、円形度ＳＦ１，ＳＦ２、元素組成の均一性は表２に示した。
【０２３０】
（酸化物微粒子６）
酸化物微粒子５においてチタンの代わりに亜鉛を用いた以外は酸化物微粒子１と同様にして製造した。得られた該酸化物微粒子の一次粒子径、円形度ＳＦ１，ＳＦ２、元素組成の均一性は表２に示した。
【０２３１】
（酸化物微粒子７）
酸化物微粒子１において、酸化物微粒子製造後、酸化物微粒子１００ｇをトルエン４００ｇに分散させた後、粘度３００ｃｓのジメチルシリコーンオイル５ｇを添加し混合した。トルエンを加熱留去し酸化物微粒子７を得た。得られた該酸化物微粒子の一次粒子径、円形度ＳＦ１，ＳＦ２、元素組成の均一性は表２に示した。該酸化物微粒子のシリコーンオイルの遊離率は７５％であった。
【０２３２】
（酸化物微粒子８）
蒸留精製したメチルトリメトキシシランを加熱し、ここに窒素ガスをバブリングし、メチルトリメトキシシランを窒素ガスで気流伴流して酸水素火炎バーナーに導入し、この酸水素火炎中で燃焼分解させた。このときのメチルトリメトキシシラン添加量は９８０ｇ／ｈｒ、酸素ガス添加量は３．３Ｎｍ^３／ｈｒ、水素ガス添加量は５．０Ｎｍ^３／ｈｒ、窒素ガス添加量は１．２３Ｎｍ^３／ｈｒであり、生成した球状シリカ微粉末はバグフィルターで捕集した。この球状シリカ微粉末１ｋｇを５リットルのプラネタリミキサーに仕込み、純水１０ｇを撹拌下添加し、密閉後更に５５℃で１４時間撹拌した。次いで、室温まで冷却した後、ヘキサメチルジシラザン２０ｇを撹拌下添加し、密閉後更に２４時間撹拌した。１１５℃に昇温し、窒素ガスを通気しながら残存原料及び生成したアンモニアを除去し、酸化物微粒子８を得た。得られた該酸化物微粒子の一次粒子径、円形度はＳＦ１，ＳＦ２、元素組成の均一性は表２に示した。
【０２３３】
（酸化物微粒子９）
四塩化けい素を酸水素火炎中で火炎加水分解させてシリカ微粒子とし、耐熱性担体上に堆積すると同時に溶融してシリカ微粒子とし、シリカ微粒子から多孔質ガラス母材を作り、これを溶融して酸化物微粒子９を得た。得られた該酸化物微粒子の一次粒子径、円形度はＳＦ１，ＳＦ２、元素組成の均一性は表２に示した。
【０２３４】
（酸化物微粒子１０）
アルコキシシランをアルコール（エタノール）溶媒中で酸性触媒の存在下に加水分解してシリカゾルを合成し、これをゲルとした後乾燥し、仮焼、焼結して酸化物微粒子１０を得た。得られた該酸化物微粒子の一次粒子径、円形度はＳＦ１，ＳＦ２、元素組成の均一性は表２に示した。
【０２３５】
（酸化物微粒子１１）
蒸留精製したメチルトリメトキシシランを加熱し、ここに窒素ガスをバブリングし、メチルトリメトキシシランを窒素ガスで気流伴流して酸水素火炎バーナーに導入し、この酸水素火炎中で燃焼分解させた。このときのメチルトリメトキシシラン添加量は１２７０ｇ／ｈｒ、酸素ガス添加量は１．１Ｎｍ^３／ｈｒ、水素ガス添加量は０．９Ｎｍ^３／ｈｒ、窒素ガス添加量は１．２Ｎｍ^３／ｈｒであり、生成したシリカ微粉末はバグフィルターで捕集した。このシリカ微粉末１ｋｇを５リットルのプラネタリミキサーに仕込み、純水１０ｇを撹拌下添加し、密閉後更に５５℃で１時間撹拌した。次いで、室温まで冷却した後、ヘキサメチルジシラザン２０ｇを撹拌下添加し、密閉後更に８時間撹拌した。１１５℃に昇温し、窒素ガスを通気しながら残存原料及び生成したアンモニアを除去し、酸化物微粒子１を得た。得られた該酸化物微粒子の一次粒子径、円形度はＳＦ１，ＳＦ２、元素組成の均一性は表２に示した。
【０２３６】
（ポリオール樹脂１）
撹拌装置、温度計、Ｎ２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。
【０２３７】
（トナーの製造）
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）　　　　　　５４０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−ル表面温度１３０℃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、マスターバッチ顔料を得た。
【０２３８】

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のブラック色の着色粒子を得た。さらに、前記酸化物微粒子１を３．０ｗｔ％、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％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事によりブラックトナー１を得た。ワックスのトナー中での分散径は０．５μｍであった。
【０２３９】

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−ル表面温度１３０℃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、マスターバッチ顔料を得た。
【０２４０】

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のイエロー色の着色粒子を得た。さらに、前記酸化物微粒子１を３．０ｗｔ％、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％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事によりイエロートナー１を得た。ワックスのトナー中での分散径は０．５μｍであった。
【０２４１】

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−ル表面温度１３０℃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、マスターバッチ顔料を得た。
【０２４２】

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のマゼンタ色の着色粒子を得た。さらに、前記酸化物微粒子１を３．０ｗｔ％、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％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事によりマゼンタトナー１を得た。ワックスのトナー中での分散径は０．５μｍであった。
【０２４３】

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−ル表面温度１３０℃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、マスターバッチ顔料を得た。
【０２４４】

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のシアン色の着色粒子を得た。さらに、前記酸化物微粒子１を３．０ｗｔ％、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％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事によりマゼンタトナー１を得た。ワックスのトナー中での分散径は０．５μｍであった。
【０２４５】
実施例２〜７
実施例１において、表２に示す酸化物微粒子２〜７を使用すること以外は実施例１と同様にしてトナー、現像剤を作成して評価した。
【０２４６】
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。
【０２４７】
実施例９
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。
【０２４８】
実施例１０
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。
【０２４９】
実施例１１
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。
【０２５０】
実施例１２
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。
【０２５１】
比較例１〜４
実施例１において、酸化物微粒子を表２の酸化物微粒子８〜１１を用いた以外は実施例１と同様にしてトナー、現像剤を製造し、評価した。
【０２５２】
実施例１３
実施例１において、添加剤混合前の母体トナーを以下のように製造した以外は実施例１と同様にトナーを製造した評価した。
【０２５３】
（有機微粒子エマルションの合成）
撹拌棒および温度計をセットした反応容器に、水６８３部、メタクリル酸エチレンオキサイド付加物硫酸エステルのナトリウム塩（エレミノールＲＳ−３０、三洋化成工業製）１１部、スチレン８３部、メタクリル酸８３部、アクリル酸ブチル１１０部、過硫酸アンモニウム１部を仕込み、３８００回転／分で３０分間撹拌したところ、白色の乳濁液が得られた。加熱して、系内温度７５℃まで昇温し４時間反応させた。さらに、１％過硫酸アンモニウム水溶液３０部加え、７５℃で６時間熟成してビニル系樹脂（スチレン−メタクリル酸−アクリル酸ブチル−メタクリル酸エチレンオキサイド付加物硫酸エステルのナトリウム塩の共重合体）の水性分散液［微粒子分散液１］を得た。［微粒子分散液１］をレーザー回折／散乱式粒度分布測定装置（ＬＡ−９２０：堀場製作所製）で測定した体積平均粒径は、１１０ｎｍであった。［微粒子分散液１］の一部を乾燥して樹脂分を単離した。該樹脂分のＴｇは５８℃であり、重量平均分子量は１３万であった。
【０２５４】
（水相の調整）
水９９０部、［微粒子分散液１］８３部、ドデシルジフェニルエーテルジスルホン酸ナトリウムの４８．３％水溶液（エレミノールＭＯＮ−７：三洋化成工業製）３７部、酢酸エチル９０部を混合撹拌し、乳白色の液体を得た。これを［水相１］とする。
【０２５５】
（低分子ポリエステルの合成）
冷却管、撹拌機および窒素導入管の付いた反応容器中に、ビスフェノールＡエチレンオキサイド２モル付加物７２４　部、テレフタル酸２７６部を入れ、常圧下２３０℃で７時間重縮合し、さらに１０〜１５ｍｍＨｇの減圧下で５時間反応して［低分子ポリエステル１］を得た。［低分子ポリエステル１］は、数平均分子量２３００、重量平均分子量６７００、ピーク分子量３８００、Ｔｇ４３℃、酸価４であった。
【０２５６】
（中間体ポリエステルの合成）
冷却管、撹拌機および窒索導入管の付いた反応容器中に、ビスフェノールＡエチレンオキサイド２モル付加物６８２部、ビスフェノールＡプロピレンオキサイド２モル付加物８１部、テレフタル酸２８３部、無水トリメリット酸２２部およびジブチルチンオキサイド２部を入れ、常圧下２３０℃で７時間反応し、さらに１０〜１５ｍｍＨｇの減圧で５時間反応した［中間体ポリエステル１］を得た。［中間体ポリエステル１］は、数平均分子量２２００、重量平均分子量９７００、ピーク分子量３０００、Ｔｇ５４℃、酸価０．５、水酸基価５２であった。
次に、冷却管、撹拌機および窒素導入管の付いた反応容器中に、［中間体ポリエステル１］４１０部、イソホロンジイソシアネート８９部、酢酸エチル５００部を入れ１００℃で５時間反応し、［プレポリマー１］を得た。［プレポリマー１］の遊離イソシアネート重量％は、１．５３％であった。
【０２５７】
（ケチミンの合成）
撹拌棒および温度計をセットした反応容器に、イソホロンジアミン１７０部とメチルエチルケトン７５部を仕込み、５０℃で４時間半反応を行い、［ケチミン化合物１］を得た。［ケチミン化合物１］のアミン価は４１７であった。
【０２５８】
（マスターバッチの合成）
水１２００部、カーボンブラック（Ｐｒｉｎｔｅｘ３５：デクサ製）５４０部［ＤＢＰ吸油量＝４２ｍｌ／１００ｍｇ、ｐＨ＝９．５］、　ポリエステル樹脂１２００部を加え、ヘンシェルミキサー（三井鉱山社製）で混合し、混合物を２本ロールを用いて１３０℃で１時間混練後、圧延冷却しパルペライザーで粉砕、［マスターバッチ１］を得た。
【０２５９】
（油相の作製）
撹拌棒および温度計をセットした容器に、［低分子ポリエステル１］３７８部、カルナバワックス１００部、酢酸エチル９４７部を仕込み、撹拌下８０℃に昇温し、８０℃のまま５時間保持した後、１時間で３０℃に冷却した。次いで、容器に［マスターバッチ１］５００部、酢酸エチル５００部を仕込み、１時間混合し［原料溶解液１］を得た。
［原料溶解液１］１３２４部を容器に移し、ビーズミル（ウルトラビスコミル：アイメックス社製）を用いて、送液速度１ｋｇ／ｈｒ、ディスク周速度６ｍ／秒、０．５ｍｍジルコニアビーズを８０体積％充填、３パスの条件で、カーボンブラック、ワックスの分散を行った。次いで、［低分子ポリエステル１］の６５％酢酸エチル溶液１３２４部を加え、上記条件のビーズミルで２パスし、［顔料・ワックス分散液１］を得た。［顔料・ワックス分散液１］の固形分濃度は５０％であった。
【０２６０】
（乳化〜脱溶剤）
［顔料・ワックス分散液１］７４９部、［プレポリマー１］を１１５部、［ケチミン化合物１］２．９部を容器に入れ、ＴＫホモミキサー（特殊機化製）で５，０００ｒｐｍで２分間混合した後、容器に［水相１］１２００部を加え、ＴＫホモミキサーで、回転数１３，０００ｒｐｍで２５分間混合し［乳化スラリー１］を得た。
撹拌機および温度計をセットした容器に、［乳化スラリー１］を投入し、３０℃で７時間脱溶剤した後、４５℃で７時間熟成を行い、［分散スラリー１］を得た。
【０２６１】
（洗浄〜乾燥）
［分散スラリー１］１００部を減圧濾過した後、
▲１▼：濾過ケーキにイオン交換水１００部を加え、ＴＫホモミキサーで混合（回転数１２，０００ｒｐｍで１０分間）した後濾過した。
▲２▼：▲１▼の濾過ケーキに１０％水酸化ナトリウム水溶液１００部を加え、ＴＫホモミキサーで混合（回転数１２，０００ｒｐｍで１０分間）した後、減圧濾過した。
▲３▼：▲２▼の濾過ケーキに１０％塩酸１００部を加え、ＴＫホモミキサーで混合（回転数１２，０００ｒｐｍで１０分間）した後濾過した。
▲４▼：▲３▼の濾過ケーキにイオン交換水３００部を加え、ＴＫホモミキサーで混合（回転数１２，０００ｒｐｍで１０分間）した後濾過する操作を２回行い、［濾過ケーキ１］を得た。
［濾過ケーキ１］を循風乾燥機にて４５℃で４８時間乾燥し、目開き７５μｍメッシュで篩い、［トナー母体粒子１］を得た。その後、前記酸化物微粒子１を３．０ｗｔ％、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％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事によりトナーを得た。得られたトナーの物性を表１に、評価結果を表２に示す。
【０２６２】
【発明の効果】
上記に記載した少なくともケイ素元素を含む酸化物微粒子よりなり、該酸化物微粒子の一次粒子径Ｒが、３０ｎｍ〜３００ｎｍでかつ、Ｒの粒度分布の標準偏差σが、Ｒ／４≦σ≦Ｒの分布を持ちかつ、円形度ＳＦ１が１００〜１３０でかつ円形度ＳＦ２が１００〜１２５の実質球形であることを特徴とする電子写真トナー用外添剤を用いることで、トナーを高温高湿環境で保管後でも外添剤がトナー中に埋没せず、流動化剤、帯電補助剤としての機能を十分発揮しかつ、低温低湿環境で保存後でも異常な帯電性上昇を抑制して安定した画質を提供でき、かつトナー転写圧縮時の凝集性、現像器内でのストレス後のトナー粒子間の付着力が適正に制御された転写性、現像性に優れた高画質の画像を形成しうることを見いだした。
【０２６３】
さらにトナーの転写性を改善し、文字部中抜け等の異常画像の防止、トナー転写率の向上による廃トナー量の低減、トナー消費量の低減、トナー補給性の向上によるベタ画像の均一性、転写チリ等の減少、細線再現性の向上、高温高湿、低温低湿における帯電環境安定性の向上による地肌汚れの低減、トナー飛散の防止を達成できた。さらに耐熱保存性に優れ、色再現性、色の鮮やかさ、光沢、透明性、定着性に優れた印刷物を得ることができた。
【０２６４】
【表１】

【０２６５】
【表２】

【０２６６】
【図面の簡単な説明】
【図１】本発明のトナー、現像剤を使用する実施形態の一例を示す概略構成図である。
【図２】本発明のトナー、現像剤を使用する実施形態の一例を示す概略構成図である。
【図３】本発明のトナー、現像剤を使用する実施形態の一例を示す概略構成図である。
【図４】本発明のトナー、現像剤を使用する実施形態の一例を示す概略構成図である。
【図５】本発明のトナー、現像剤を使用する実施形態の一例を示す概略構成図である。
【図６】本発明のトナー、現像剤を使用する実施形態の一例を示す概略構成図である。
【図７】本発明のプロセスカートリッジの概略構成図である。
【０２６６】
【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]
The present invention relates to an external additive for electrophotographic toner, an electrophotographic toner, an electrophotographic developer, an image forming method, and a process cartridge.
[0002]
[Prior art]
A typical image forming process by electrophotography or electrostatic printing is to uniformly charge a photoconductive insulating layer, expose the insulating layer, and then dissipate the charge on the exposed portion. A developing step of forming an electric latent image and visualizing the latent image by attaching finely charged toner to the latent image; a transferring step of transferring the obtained visible image to a transfer material such as transfer paper; It comprises a fixing step of fixing by heating or pressing (usually using a heat roller). As a developer for developing an electrostatic image formed on the 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 method of sequentially transferring toner images of respective colors formed on a photoreceptor to an intermediate transfer body, temporarily holding the same, and then collectively transferring the toner images to a sheet again is well known.
[0003]
The toner used in such an electrophotographic or electrostatic printing method contains a binder resin and a colorant as main components, and if necessary, contains additives such as a charge controlling agent and an offset preventing agent. In addition, various performances are required in each of the above steps. For example, in the development process, in order to attach toner to an electric latent image, the toner and the binder resin for the toner are charged by a copying machine or a printer suitable for a printer without being affected by the surrounding environment such as temperature and humidity. You have to keep the quantity. Further, in the fixing step by the heat roller fixing method, the non-offset property which does not adhere to the heat roller which is usually heated to a temperature of about 100 to 230 ° C. and the fixing property to paper must be good. Further, it is also required to have blocking resistance so that the toner does not block during storage in a copying machine.
[0004]
In recent years, in the field of electrophotography, higher image quality has been studied from various angles, and among them, it has been increasingly recognized that reduction in diameter and spheroidization of toner is extremely effective. However, as the diameter of the toner decreases, the transferability tends to decrease, resulting in a poor image. On the other hand, it is known that the transferability is improved by spheroidizing the toner (Patent Document 1: Japanese Patent Application Laid-Open No. 9-258474). Under such circumstances, in the field of color copiers and color printers, higher speed image formation is desired. The “tandem method” is effective for increasing the speed (for example, Patent Document 2: JP-A-5-341617). The “tandem method” is a method in which an image formed by an image forming unit is sequentially superimposed on a single transfer sheet conveyed to a transfer belt and transferred to obtain a full-color image on the transfer sheet. The tandem-type color image forming apparatus has excellent characteristics that a wide variety of transfer papers can be used, the quality of a full-color image is high, and a full-color image can be obtained at a high speed. In particular, the characteristic that a full-color image can be obtained at a high speed is a unique characteristic not found in other types of color image forming apparatuses. On the other hand, attempts have been made to achieve high speed while achieving high image quality using spherical toner. In order to achieve high speed in an apparatus employing the above-described method, it is necessary to reduce the time required for the paper to pass through the transfer unit. Therefore, in order to obtain the same transfer capability as in the past, it is necessary to increase the transfer pressure. is there. However, if the transfer pressure is increased, the toner aggregates due to the pressure during transfer, and good transfer cannot be performed, and there is a problem that a hollow image occurs in a formed image. In order to solve such a problem, the circularity, particle size, specific gravity, BET specific surface area, 1 kg / cm²Adhesion stress during compression is 6g / cm²It is known to improve the image quality by specifying the following (Patent Document 3: JP-A-2000-3063, etc.).
[0005]
However, 1kg / cm²When the adhesive stress at the time of compression is used, since the compression pressure is too weak, there is a problem in the transferability when the transfer pressure is increased from OHP, thick paper, surface-coated paper, or the like, and in image quality such as missing in a character portion. Further, when the adhesion stress is small, there is a problem such as transfer dust. It is also known that the toner one particle adhesion is regulated to 3.0 dyne / contact point or less to improve toner dischargeability (Japanese Patent Laid-Open No. 2000-352840). However, this does not specify the toner adhesion at the time of compression, and improves the dischargeability, but has no effect on the transferability and the image quality improvement such as a missing image in a character portion.
[0006]
It is also known that the degree of cohesion at the time of compression is specified for the purpose of improving the developability and the stability over time (Patent Document 5: Japanese Patent No. 3002063). However, there is still a problem in the image quality such as a blank portion in a character portion by specifying the cohesion degree at the time of compression, and it has been difficult to sufficiently improve the transferability and the transfer rate. Further, there has been known an attempt to improve the void in a character portion by defining the product of the cohesion degree and the loose apparent density as 7 or less (Patent Document 6: JP-A-2000-267422). The effect was not sufficiently reflected in an intermediate transfer system, a strong stirring development system, etc., which are not reflected and more stress is applied to the toner. Also, an attempt is made to specify that the ratio of the loose apparent density or the apparent density is loose apparent density / hard apparent density = 0.5 to 1.0 and the cohesion is 25% or less (Patent Document 7: However, the apparent density is a value obtained by measuring the bulk density after tapping 50 times, and is close to the physical properties reflecting the fluidity, so that a mechanical stress is applied to the toner. The effect of increasing the bulk density when applied was not able to be reflected, and similarly, the intermediate transfer system, the strong agitation development system, and the like that similarly stressed the toner were not sufficiently effective.
[0007]
On the other hand, there has been proposed a method of mixing toner particles and inorganic powders such as various metal oxides and the like for the purpose of improving the flow characteristics and charging characteristics of the toner, and is called an external additive. If necessary, a method of treating with a specific silane coupling agent, a titanate coupling agent, a silicone oil, an organic acid, etc., for the purpose of modifying the hydrophobicity, charging characteristics, etc. of the surface of the inorganic powder, coating with a specific resin A method of doing so 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.
[0008]
Particularly, silica fine particles obtained by reacting silica or titanium oxide fine particles with an organic silicon compound such as dimethyldichlorosilane, hexamethyldisilazane, or silicone oil to replace the silanol group on the surface of the silica fine particles with an organic group and making the silica fine particles hydrophobic are used.
[0009]
Among these, silicone oil is known as a hydrophobizing agent which exhibits sufficient hydrophobicity and exhibits excellent transferability due to its low surface energy when contained in the toner. Patent Literature 8: Japanese Patent Publication No. 7-3600 and Patent Literature 9: Japanese Patent No. 02568244 specify the degree of hydrophobicity of silica treated with silicone oil. Patent Document 10: JP-A-7-271087 and Patent Document 11: JP-A-8-29598 specify the amount of silicone oil added and the carbon content of the additive. Hydrophobic treatment of the inorganic fine particles, which are the base material of the external additive, is sufficient to ensure the charge stability of the developer under high humidity by the silicone oil content and the degree of hydrophobicity described in the above-mentioned publications. did it. However, members that come into contact with the developer by 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 (photosensitive No attempt has been made to reduce the adhesiveness to the intermediate transfer member and the like. In particular, the background stain due to the strong adhesion of the developer to the photoreceptor, and the peeling after transfer (the portion where the developer is not transferred) of the character portion, the line portion, the edge portion and the center portion of the dot portion in the image are silicone oil. It could not be improved only by adjusting the amount of addition and the degree of hydrophobicity. Furthermore, white spots due to the inability to transfer to the concave portion during transfer to a transfer member having severe irregularities could not be similarly improved. Patent Document 12: JP-A-11-212299 discloses inorganic fine particles containing a specific amount of silicone oil as a liquid component. However, such a definition of the amount could not satisfy the above-mentioned characteristics.
[0010]
In addition, the electrophotographic toner is required to have uniform and stable charging. If these are insufficient, image quality is deteriorated due to occurrence of background stain, density unevenness, and the like. Further, since the developing mechanism has been downsized with the downsizing of the image forming apparatus, the toner charging rise has become an even more important item in order to obtain high image quality. Various proposals have been made to improve these. Among them, an example in which the improvement of the charging property is proposed by the additive of the toner for electrophotography is described in Japanese Patent Application Laid-Open No. Hei 3-294864, a non-magnetic powder containing an inorganic powder treated with silicone oil. Patent Document 14: JP-A-4-204665 discloses a one-component magnetic developer in which the coverage of an additive with respect to a toner is 3 to 30%. Patent Document 15: JP-A-4-335357. Include a toner in which fine particles having a BET non-surface area of 5 to 100 m2 / g are fixed on the toner surface and particles having a specific surface area 1.2 times or more as large as the fine particles fixed to the toner. Patent Document 16: Japanese Patent Application Laid-Open No. 7-43930 discloses a developer using a non-magnetic one-component toner containing hydrophobic silica fine powder and a specific hydrophobic titanium oxide. Document 17: organic in JP-A-8-202071 includes an organic polymeric backbone and a polysiloxane skeleton - comprising a toner additive comprising an inorganic composite particles developers are disclosed, respectively.
However, according to these proposals, sufficient charge uniformity may not be obtained yet, or the rise of the toner charge may not be sufficient. Further, the environmental stability of the toner charge, particularly the stability to humidity, Was not always sufficient. In particular, in the use of additives that have been improved in hydrophobicity by surface treatment of general oxide particles, which are found in many proposals, although the desired charge stability is initially exhibited, the additive may be used with the passage of time such as running. However, there is a problem that the toner is deteriorated due to the change in the composition. In addition, for example, in the composite particles synthesized by using a liquid phase method as described in Patent Document 17: Japanese Patent Application Laid-Open No. 8-202071, sufficient hydrophobicity is obtained due to the influence of a liquid medium substance remaining inside the particles. In some cases, the hydrophobicity did not change or the hydrophobicity changed with time.
[0011]
On the other hand, by adding large-particle inorganic fine particles having an average particle diameter of 50 to 120 nm to the toner, color shift prevention, long-term stabilization of image density and transferability, and suppression of contamination have been achieved (Patent Document 18: Patent No. 3,148,950), there was no effect on the charge rising property after printing of several other sheets, or the background stain on the non-printed portion in a high temperature and high humidity environment or a low temperature and low humidity environment.
Further, the fine particles are composed of oxide fine particles obtained by oxidizing solid solution fine particles of two or more elements, and the minimum value of the first ionization potential difference between the elements contained in the solid solution fine particles is. An electrophotographic toner additive is also known, which is 20 to 4.20 eV and the maximum value of the first ionization potential of the element contained in the solid solution fine particles is 9.00 eV or less. The particle size and shape of the fine particles have not been sufficiently studied, and the fluidity, transferability, and development stirring property of the toner were not sufficient only by specifying the ionization potential.
[0012]
On the other hand, as binder resins, polystyrene, styrene, etc. are required in terms of properties required for toner, namely, transparency, insulation, water resistance, fluidity (as a powder), mechanical strength, gloss, thermoplasticity, pulverizability, and the like. -Acrylic copolymers, polyester resins, epoxy resins, and the like are generally used, and among them, styrene resins are widely used because of their excellent crushability, water resistance, and fluidity. However, if a copy obtained with a styrene resin-containing toner is stored in a document holder made of a vinyl chloride resin sheet in order to preserve the copy, the image surface of the copy is left in close contact with the sheet. That is, the plasticizer contained in the vinyl chloride resin undergoes transfer plasticization to the fixed toner image and is fused to the sheet side. As a result, when the copy is separated from the sheet, the toner image is partially or entirely peeled off from the copy, and There was a drawback that the sheet was dirty. Such defects are also observed in the polyester resin-containing toner.
[0013]
JP-A-60-263951 and JP-A-61-24025 disclose a plasticizer for a vinyl chloride resin to a styrene resin or a polyester resin as a measure for preventing the transfer to the vinyl chloride resin sheet as described above. It has been proposed to blend an epoxy resin which is not plasticized by the above method.
[0014]
However, when such a blended resin is used particularly for a color toner, the offset property, the curl of the fixed image, and the glossiness (for a color toner image, if the gloss is low, the poor ), Coloring, transparency, and coloring are problematic. These problems cannot be all solved by conventional epoxy resins or acetylated modified epoxy resins as proposed in Patent Document 21: JP-A-61-235852.
[0015]
Therefore, it is conceivable to solve the above problem by using the epoxy resin alone, but as a new problem, reactivity of the epoxy resin with the amine occurs. An epoxy resin is generally used as a curable resin having excellent mechanical strength and chemical resistance by reacting an epoxy group with a curing agent to form a crosslinked structure. Curing agents are broadly divided into amine-based and organic acid anhydride-based curing agents. Of course, the epoxy resin used as the toner for electrophotography is used as a thermoplastic resin, but there are amine-based dyes and pigments that are kneaded with the resin as the toner, and there are amine-based ones. In some cases, a cross-linking reaction occurs and the toner cannot be used. Further, the chemical activity of this epoxy group is considered to be biochemical, that is, toxicity such as skin irritation.
[0016]
Further, since the epoxy group exhibits hydrophilicity, it absorbs water significantly under high temperature and high humidity, and causes a reduction in charge, background fouling, poor cleaning and the like. Another problem is the charging stability of the epoxy resin.
[0017]
Generally, a 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 control properties, and some of which have two functions of a colorant and a charge control agent. It has been widely practiced to use an epoxy resin as a binder resin to form a toner with the above composition, but there is a problem in dispersibility of a dye / pigment, a charge control agent and the like. In general, kneading of a binder resin, a dye and a pigment, a charge control agent and the like is performed by a hot roll mill, and it is necessary to uniformly disperse the dye and pigment, the charge control agent and the like in the binder resin. However, it is difficult to sufficiently disperse the dye, and if the dye / pigment as a colorant is poorly dispersed, the color development is poor and the degree of coloring is low. If the dispersion of the charge control agent or the like is poor, the charge distribution becomes non-uniform, which causes various failures such as poor charging, background contamination, scattering, insufficient ID, blur, and cleaning failure. Patent Document 22: Japanese Patent Application Laid-Open No. 61-219051 discloses a toner using an epoxy resin ester-modified with ε-caprolactone as a binder resin. The modified amount was as high as 15 to 90% by weight, the softening point was too low, and the gloss was too high.
[0018]
Patent Document 23: JP-A-52-86334 discloses a compound having a positive charge property by reacting an aliphatic primary or secondary amine with a terminal epoxy group of a ready-made epoxy resin. As described above, the epoxy group and the amine may cause a cross-linking reaction and may not be used as a toner. Further, Patent Document 24: JP-A-52-156632 discloses that one or both of terminal epoxy groups of an epoxy resin is reacted with alcohol, phenol, Grignard reagent, organic acid sodium acetylide, alkyl chloride or the like. Although disclosed, if an epoxy group remains, problems such as reactivity with amines, toxicity, and hydrophilicity occur as described above. In addition, some of the above reactants are hydrophilic, those that affect charging, and those that affect pulverizability in forming a toner, and are not necessarily all effective in the present invention.
[0019]
Patent Document 25: JP-A-1-267560 discloses that after reacting both terminal epoxy groups of an epoxy resin with a monovalent active hydrogen-containing compound, a monocarboxylic acid, an ester derivative thereof, or a lactone ester is used. Although the reactivity, toxicity, and hydrophilicity of the epoxy resin have been solved, curling in fixing has not been significantly improved.
[0020]
Further, in general, a solvent such as xylene is often used when synthesizing an epoxy resin or a polyol resin (for example, Patent Document 26: JP-A-11-189646), but these solvents or unreacted residual monomers such as bisphenol A are used. This is a problem because it is present in the resin after production to a considerable extent, and the residual amount of the toner using such a resin is large.
[0021]
On the other hand, as a method for producing a toner, as represented by Patent Document 27: JP-A-1-304467, the raw materials are all mixed at once and heated, melted and dispersed by a kneader or the like to obtain a uniform composition. Thereafter, a method of producing a toner having a volume average particle diameter of about 6 to 10 μm by cooling, pulverizing, and classifying is generally adopted. In particular, an electrophotographic color toner used for forming a color image generally includes various kinds of chromatic dyes or pigments dispersed and contained 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 development (coloring degree) and light transmittance (transparency) when used in an overhead projector (OHP) )Is required. Examples of the use of a dye as a colorant include those described in JP-A-57-130043 and JP-A-57-130044.
[0022]
However, when a dye is used as a colorant, the resulting image is excellent in transparency, and it is possible to form a clear color image with good coloring properties, but on the other hand, it has poor light fastness and is left under direct light. In this case, there is a problem of discoloration and fading.
[0023]
Further, as the image forming apparatus, the plurality of visible color developed images sequentially formed on the image carrier are sequentially superimposed on the intermediate transfer body that moves endlessly and primary-transferred, and the primary transfer image ( 2. Related Art An intermediate transfer type image forming apparatus that collectively and secondarily transfers a toner image) onto a transfer material is known. In recent years, an image forming apparatus using this intermediate transfer method is advantageous in terms of miniaturization and less restrictions on the type of transfer material onto which a visible image is finally transferred. They tend to be used as devices. In such an image forming apparatus, due to local transfer omission at the time of primary transfer and secondary transfer of a toner image constituting a color developed image, a final image medium is transferred onto a transfer material such as transfer paper. In some images, a so-called worm-like portion (missing characters) may be generated in which no toner is locally transferred. In the case of a bug-eating image, in the case of a solid image, the transfer is lost with a certain area. In the case of a line image, transfer omission occurs so that the line is interrupted.
[0024]
Such an abnormal image is likely to occur when a four-color full-color image is formed. This is because, in addition to the thickening of the toner layer, the primary transfer is repeated up to four times. This is because strong force (force other than electrostatic force such as van der Waals force) is generated. Further, in the process of repeatedly executing the image forming process, a filming phenomenon occurs in which the toner adheres to the surface of the intermediate transfer body in a film form, and the adhesion between the surface of the intermediate transfer body and the toner increases. Conceivable.
[0025]
Therefore, as a technique for avoiding the occurrence of such an insect-like image, a lubricant is applied to the surface of the image carrier and the intermediate transfer body to reduce the adhesive force with the toner, or the adhesive force of the toner itself is externally added. Techniques such as reduction with agents have already been put to practical use on market machines. However, the adhesion between toner and the tensile strength at break when the transfer contact pressure generated at the time of four-color full-color or high-speed transfer is increased are not taken into consideration, and especially for thick paper, surface-coated paper, OHP film, etc. There was a problem in the stability of image quality during transfer.
[0026]
Further, in Japanese Patent Application Laid-Open No. H8-211755, by adjusting the relative balance between the toner adhesion of the image carrier and the toner adhesion of the intermediate transfer member, transferability is improved, and the insect-like shape is improved. An apparatus for preventing occurrence of an abnormal image is disclosed. However, the adhesion force of the toner at this time was a value obtained by a centrifugal force method in a powder state, and was different from the physical properties when the transfer contact pressure was increased, and was insufficient.
[Patent Document 1]
JP-A-9-258474
[Patent Document 2]
JP-A-5-341617
[Patent Document 3]
JP 2000-3063
[Patent Document 4]
JP 2000-352840
[Patent Document 5]
Patent No. 3002063
[Patent Document 6]
JP-A-2000-267422
[Patent Document 7]
JP 2000-352840
[Patent Document 8]
Tokuho 7-3600
[Patent Document 9]
Patent No. 02568244
[Patent Document 10]
JP-A-7-271087
[Patent Document 11]
JP-A-8-29598
[Patent Document 12]
JP-A-11-212299
[Patent Document 13]
JP-A-3-294864
[Patent Document 14]
JP-A-4-204665
[Patent Document 15]
JP-A-4-335357
[Patent Document 16]
JP-A-7-43930
[Patent Document 17]
JP-A-8-202071
[Patent Document 18]
Patent No. 3148950
[Patent Document 19]
JP-A-60-263951
[Patent Document 20]
JP-A-61-24025
[Patent Document 21]
JP-A-61-235852
[Patent Document 22]
JP-A-61-219051
[Patent Document 23]
JP-A-52-86334
[Patent Document 24]
JP-A-52-156632
[Patent Document 25]
JP-A-1-267560
[Patent Document 26]
JP-A-11-189646
[Patent Document 27]
JP-A-1-304467
[Patent Document 28]
JP-A-57-130043
[Patent Document 29]
JP-A-57-130044
[Patent Document 30]
JP-A-8-211755
[0027]
The high temperature, high humidity, low temperature and low humidity environment during storage and transportation after production of the toner are severe for the toner, and the toner does not agglomerate even after the environmental preservation, and the charging characteristics, fluidity, transferability, and fixing. There has been a demand for a toner which has no deterioration or excellent storage stability, but no effective means has been found so far.
[0028]
[Problems to be solved by the invention]
The object of the present invention is
1. External additives do not become buried in the toner even under agitation charging after storing the toner in a high-temperature, high-humidity environment, exhibit sufficient functions as a fluidizing agent and a charging aid, and are abnormal even after storage in a low-temperature, low-humidity environment. An object of the present invention is to provide an external additive for electrophotography, a toner, a developer, an image forming method, and a process cartridge that can provide stable image quality by suppressing an increase in chargeability.
2. Aggregation after toner transfer compression and stress in the developing machine, adhesion between toner particles properly controlled, excellent transferability, developability, fixability, high image quality, less affected by transfer material To provide an external additive for electrophotography, a toner, a developer, an image forming method, and a process cartridge capable of forming an image.
3. A process cartridge and an image that form an image with less charge, less reverse charge toner, less background fouling (fogging), and less toner scattering into the machine, with excellent charge stability in high-temperature, high-humidity, low-temperature, low-humidity environments To provide a forming method.
4. To provide an image forming method having both high durability and low maintenance as an image forming system.
5. Provided is an image forming method which is excellent in replenishing property and charge rising property with sufficient fluidity at the time of non-compression simultaneously with transferability at the time of toner compression.
6. A process cartridge excellent in stability of toner charging, excellent in environment charging stability as a developer, printing speed is not inferior from a low speed to a high speed region, image density is not reduced by continuous image output, and excellent in balance between fixing property and non-offset property; An object of the present invention is to provide an image forming method.
7. An object of the present invention is to provide an image forming method in which toner transfer conditions are good, color reproducibility, color clarity, and color transparency are excellent, and gloss is stable and uniform.
8. An object of the present invention is to provide an image forming method which is excellent in environmental stability and environmental preservation.
9. An object of the present invention is to provide 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.
10. An object of the present invention is to provide an image forming method in which a fixed image does not substantially curl.
[0029]
11. An image forming apparatus in which a toner image formed on an electrostatic image carrier is primarily transferred onto an intermediate transfer member and the toner image is secondarily transferred to a transfer material, or an image capable of high-speed output by a tandem method An object of the present invention is to provide an image forming method capable of preventing occurrence of an abnormal image such as a bug-like image, image dust, and poor fine line reproducibility using a forming apparatus.
[0030]
[Means for Solving the Problems]
The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, are composed of oxide fine particles containing at least a silicon element, the primary particle size R of the oxide fine particles is 30 nm to 300 nm, and the standard particle size distribution of R is An external additive for an electrophotographic toner, wherein the deviation σ has a distribution of R / 4 ≦ σ ≦ R and is substantially spherical with a circularity SF1 of 100 to 130 and a circularity SF2 of 100 to 125. By using, the external additive does not become buried in the toner even after the toner is stored in a high temperature and high humidity environment. Stable image quality can be provided by suppressing abnormal increase in chargeability even after storage in the environment, and cohesiveness during toner transfer compression and adhesion between toner particles after stress in the developing unit are properly controlled. High image quality with excellent transferability and developability It has been found that a high quality image can be formed.
[0031]
The mechanism is currently being elucidated, but the following was inferred from some analytical data. By setting the primary particle diameter of the oxide fine particles to 30 nm to 300 nm, the oxide fine particles sufficiently exert a spacer effect of preventing aggregation of the toners, and the additives are buried at the time of storing the toner at a high temperature or at the time of strong stirring deterioration of the toner. Has the effect of preventing. Further, the standard deviation σ of the particle size distribution of R has a distribution of R / 4 ≦ σ ≦ R, so that oxide fine particles having a large particle diameter, a medium particle diameter, and a small particle diameter are contained at an appropriate ratio. Particle size particles ensure fluidity and medium and large particle size particles effectively exert the spacer effect. This has been found to work more effectively than a mixture of large, medium and small particles. Further, by giving the oxide fine particles a substantially spherical shape having a circularity SF1 of 130 or less and a circularity SF2 of 125 or less, the fluidity of the toner is improved, and the affinity between the toner and the oxide fine particles is improved. The oxide fine particles are prevented from detaching from the toner, and exhibit their original function as an external additive.
The method for producing spherical silica fine particles having this circularity is to heat and evaporate alkoxysilane and / or its partially hydrolyzed condensate to flow along an inert gas such as nitrogen gas, or to spray and spray an oxyhydrogen flame or the like. What is necessary is to introduce it into a flame and burn and decompose it in this flame, but at this time, each raw material, gas, control temperature, etc. are important, and by strictly controlling and adjusting these, the above-mentioned shape, particle size distribution Oxide fine particles could be obtained.
Conventionally, a sol-gel method (a method of synthesizing a silica sol by hydrolyzing alkoxysilane in an alcohol solvent in the presence of an acidic catalyst, forming a gel, drying, calcining, and sintering (eg, a patent) No. 3,040,310), spherical silica could be easily produced, but the particle size distribution was not in the above-mentioned range, and had a sharper distribution (standard deviation σ = R / 10 of particle size R). It is difficult to control the particle size distribution to the above-mentioned particle size distribution, and the conventional small particle size silica is generally amorphous, and only spherical small particle size silica (for example, 10 nm in diameter) is used. It has been extremely difficult to selectively produce the silica, so it is practically difficult and practical to produce, for example, only spherical small particle size silica and then to mix the particles to have the above-mentioned particle size distribution. Was not the target.
[0032]
Further, the oxide fine particles contain at least a silicon element and a metal element as an external additive for an electrophotographic toner, whereby a charge assisting agent for the toner, an electric resistance imparting agent in an appropriate range, and a fluidizing agent are provided. And a charge level and a resistance level thereof can be adjusted by a metal element (doped compound). In the case of oxide fine particles, by controlling the composition of the original solid solution fine particles and the degree of oxidation thereof, particles having various dielectric characteristics / resistance characteristics can be easily produced. Thereby, the charging characteristics of the electrophotographic toner can be easily controlled in a desired range.
[0033]
Further, in order to prevent electrostatic afterimages generated during development, it is preferable to set the electric resistance of the developer carrying member to a relatively low resistance and to quickly leak residual charge to the developer carrying body, In such a developer carrying member, even the electric charge to be held by the toner may leak. In the toner for electrophotography of the present invention, since the additive fine particles stably suppress the charge leakage, the above-mentioned disadvantages can be solved by using the silicon element and the metal element.
[0034]
Further, when the oxide fine particles contain at least a silicon element, the charging level and the resistance level can be more appropriately adjusted, and the environmental charging stability when the toner is formed can be improved. As the oxide fine particles, as long as the structure of the present invention is adopted, SiO 2 may be used.₂A general substance can be used together with, for example, MgO, CaO, BaO, Al₂O₃, TiO₂, SnO₂Or a combination of two or more. Among these, in particular, by containing at least silicon oxide and titanium oxide, excellent fluidity and charging characteristics and durability at the time of strong stirring and the like can be imparted to the toner particles.
[0035]
Further, since the composition of the oxide fine particles is uniformly dispersed in the surface portion and the inside, the dispersion of the dielectric characteristics / resistance characteristics is small, and the external additive for an electrophotographic toner having excellent stability can be obtained. Was.
The surface treatment of the oxide fine particles with at least an organosilicon compound makes it possible to impart more stable charging characteristics. The oxide fine particles obtained by the method of the present invention may become an unsaturated oxide depending on the conditions for oxidizing the solid solution fine particles, but in such a case, the oxidation progresses with time, and the additive property becomes poor. May change. In order to prevent such a change with time, a reactive portion may be inactivated with respect to the additive fine particles, and a surface treatment with an organosilicon compound surface treatment agent and / or an organotitanium compound surface treatment agent is particularly preferable. . It is even more preferable that the surface treatment is a hydrophobic treatment.
[0036]
In order to further improve environmental charging stability, R¹ ₃SiO_1/2It is preferable to use hydrophobic spherical silica fine particles into which units have been introduced. Where R¹Are the same or different monovalent hydrocarbon groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclohexyl, and phenyl. , A vinyl group, an allyl group and the like, and a methyl group is particularly preferable.
[0037]
Further, the oxide fine particles are surface-treated with at least a silicone oil, and the release rate of the silicone oil is 10 to 95%, so that an appropriately controlled amount of the silicone oil covers the toner surface, and the environmental preservation property is improved. Can be improved. Here, if it is less than 10%, characteristics as a silicone oil cannot be sufficiently exhibited. On the other hand, if it exceeds 95%, the silicone oil adheres to the electrostatic image carrier and causes filming or the like, which is not preferable. In addition, the fluidity of the toner also decreases, which is not preferable.
[0038]
Further, in the electrophotographic toner having a small particle diameter having a volume average particle diameter of at least 2 to 7 μm comprising at least a binder resin and a colorant, the oxide fine particles are mixed with the toner to form a coagulation in the small particle diameter toner. Easiness and fluidity were prevented from lowering, and charging stability and environmental storability were improved.
[0039]
The oxide fine particles and one or more external additives having an average particle diameter of primary particles smaller than this are mixed with the toner. It is possible to further improve the fluidity, which is not sufficient only with the large-diameter oxidized fine particles of 30 nm to 150 nm, improve the coverage of the external additive with respect to the toner, increase the affinity between the external additives, and improve the external additive. Has good adhesion.
[0040]
Further, since the binder resin of the toner contains at least a polyol resin, sufficient compression resistance, tensile strength at break, environmental stability, and stable fixing properties excellent in charge matching with the oxide inorganic fine particles can be obtained. The binder resin of the toner further contains at least a polyol resin having an epoxy resin part and a polyoxyalkylene part in the main chain, so that environmental stability, stable fixing characteristics, and vinyl chloride resin on the copy-fixed image surface are obtained. It is possible to prevent the transfer of the toner image to the sheet when the sheet is in close contact with the sheet, and particularly when used for a color toner, it has effects on color reproducibility, stable gloss, prevention of curling of a copy-fixed image, and the like.
[0041]
Further, when the binder resin of the toner contains at least the polyester resin portion, the toner has a good balance of elasticity and adhesiveness as well as compressive strength, and more stable transferability, developability and fixing characteristics were obtained.
[0042]
In addition, by using a two-component developing system characterized by including at least a carrier composed of the toner and the magnetic particles, the developer has a sufficient bulk density with a small amount of stress fluctuation as a developer with a well-balanced adhesion to the carrier. Developing characteristics excellent in charge rising property and environmental charging stability were obtained. Further, a developing system having excellent controllability of toner density by a bulk density sensor or the like was obtained.
[0043]
Further, the electrostatic image on the electrostatic image carrier is developed with a developer for developing an electrostatic image to form a toner image, and a transfer unit is brought into contact with the surface of the electrostatic image carrier via a transfer material to form the toner image. Wherein the developer used is a two-component developer comprising a carrier composed of magnetic particles and the above-described electrophotographic toner. Obtained.
[0044]
Thus, according to the present invention, the following (1) to (14) are provided.
(1) Distribution of oxide fine particles containing at least silicon element, wherein the primary particle diameter R of the oxide fine particles is 30 nm to 300 nm, and the standard deviation σ of the particle size distribution of R is R / 4 ≦ σ ≦ R. And a substantially spherical shape having a circularity SF1 of 100 to 130 and a circularity SF2 of 100 to 125.
[0045]
(2) The external additive for an electrophotographic toner according to the above (1), wherein the oxide fine particles contain at least a silicon element and a metal element.
[0046]
(3) The external additive for electrophotographic toner according to any one of (1) and (2), wherein the oxide fine particles contain at least a silicon element and a titanium element.
[0047]
(4) The external additive for an electrophotographic toner according to any one of (1) to (3), wherein the element composition of the oxide fine particles is uniformly dispersed in the surface portion and the inside.
[0048]
(5) The external additive for an electrophotographic toner according to any one of the above (1) to (4), wherein the oxide fine particles are surface-treated with at least an organosilicon compound.
[0049]
(6) In any one of the above (1) to (5), the oxide fine particles may have a surface with R₁ ³SiO_1/2An external additive for an electrophotographic toner, which is a hydrophobized oxide fine particle into which a unit (where R1 is the same or different, a monovalent hydrocarbon group having 1 to 8 carbon atoms) is introduced.
[0050]
(7) The electrophotographic toner according to any one of the above (1) to (6), wherein the oxide fine particles are surface-treated with at least a silicone oil, and a release rate of the silicone oil is 10 to 95%. For external additives.
[0051]
(8) An electrophotographic toner having a volume average particle diameter of 2 to 7 μm comprising at least a binder resin and a colorant, wherein at least the external additive for an electrophotographic toner according to any one of (1) to (7) above is used. A toner for electrophotography, wherein the toner is mixed.
[0052]
(9) The external additive for electrophotographic toner according to any one of the above (1) to (7) and at least one external additive having an average primary particle size smaller than that of the external additive are mixed with the toner. A toner for electrophotography, comprising:
[0053]
(10) The toner for electrophotography according to any one of the above (8) to (9), wherein the binder resin of the toner contains at least a polyol resin.
[0054]
(11) The toner for electrophotography according to any one of (8) to (9), wherein the binder resin of the toner contains at least a polyester resin.
[0055]
(12) A two-component developer containing at least the toner according to any one of (8) to (11) and a carrier comprising magnetic particles.
[0056]
(13) An image forming method using the toner or the developer according to any one of the above (8) to (12).
[0057]
Hereinafter, the present invention will be described in detail. Here, as for the external additive for toner, toner and developer used in the present invention, the production method and materials thereof, and the general system relating to the electrophotographic process, all known ones can be used as long as the conditions are satisfied.
[0058]
(Oxide fine particles)
The oxide fine particles of the present invention are spherical silica fine particles, which can be produced by burning and decomposing an alkoxysilane and / or a partially hydrolyzed condensate thereof in a flame, and non-crystalline fine particles are more preferable.
[0059]
The aforementioned alkoxysilane has the general formula R² _aSi (OR³)_4-a(Where R², R³Is a monovalent hydrocarbon group having 1 to 4 carbon atoms, a is an integer of 0 to 4), for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldi Toxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, trimethylbutoxysilane, triethylmethoxysilane, triethylethoxysilane, triethylpropoxysilane, Examples include triethylbutoxysilane, tripropylmethoxysilane, tripropylethoxysilane, tributylmethoxysilane, tributylethoxysilane, and the like, with tetramethoxysilane and methyltrimethoxysilane being particularly preferred.
[0060]
The production method includes, for example, heating and evaporating an alkoxysilane and / or a partially hydrolyzed condensate thereof to flow along with an inert gas such as a nitrogen gas, or spraying and introducing the same into a flame such as an oxyhydrogen flame, What is necessary is just to make it burn and decompose in this flame.
[0061]
The oxide fine particles of the present invention have an R surface on their surfaces to improve environmental charging stability.¹ ₃SiO_1/2It is preferable to use hydrophobic spherical silica fine particles into which units have been introduced. Where R¹Are the same or different monovalent hydrocarbon groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclohexyl, and phenyl. , A vinyl group, an allyl group and the like, and a methyl group is particularly preferable.
[0062]
This R¹ ₃SiO_1/2The units may be introduced according to a known surface modification method for fine silica powder. That is, the general formula R¹ ₃SiNHSiR¹ ₃By contacting the silazane compound represented by in the presence of water with a gas phase, a liquid phase or a solid phase at 0 to 400 ° C., and then heating at 50 to 400 ° C. to remove the excess silazane compound. Can be.
[0063]
General formula R¹ ₃SiNHSiR¹ ₃Examples of the silazane compound represented by, for example, hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, hexabutyldisilazane, hexapentyldisilazane, hexahexyldisilazane, hexacyclohexyldisilazane, hexaphenyldisilazane, Examples thereof include divinyltetramethyldisilazane, and hexamethyldisilazane is particularly preferred from the viewpoint of hydrophobicity after modification and ease of removal.
[0064]
The electrostatic image developer of the present invention can be obtained by externally adding or internally adding the above-mentioned spherical silica fine particles to the toner particles, and the compounding amount of the spherical silica fine particles is 0.01 part by weight based on 100 parts by weight of the toner. When the amount is less than 20 parts by weight, the fluidity of the toner becomes insufficient, and when the amount is more than 20 parts by weight, the chargeability and fixability of the toner are adversely affected. The range is preferably from 01 to 20 parts by weight, more preferably from 0.1 to 5 parts by weight. This mixing method may be performed by any method, for example, a V blender, a Henschel mixer, a ribbon blender, a Raikai machine, or the like.Even if the spherical silica fine particles adhere to the toner particle surface, they are fused. Or contained in the toner.
[0065]
As the element for forming the oxide fine particles of the present invention, oxide fine particles containing the following metal element (doped compound) as necessary to the silicon element (silicon compound) are more preferable. , And more preferably compounds and oxides of elements having a period of 3 or more, usually Mg, Ca, Ba, Al, Ti, V, Sr, Zr, Si, Sn, Zn, Ga, Ge, Cr, Mn, Fe , Co, Ni, Cu and the like can be used. More preferably, they are Ti and Zn.
[0066]
The oxide fine particles of the present invention have a primary particle diameter R of 30 nm to 300 nm, more preferably 50 nm to 170 nm, and a standard deviation σ of the particle size distribution of R is R / 4 ≦ σ ≦ R, more preferably R / 3 ≦ σ ≦ 2/3 × R, with a circularity SF1 of 100 to 130 (more preferably 100 to 125) and a circularity SF2 of 100 to 125 (more preferably 100 to 120). It is characterized by being spherical. Here, the primary particle diameter of the oxide fine particles is a number average particle diameter.
[0067]
The particle size of the inorganic fine particles used in the present invention can be measured by a particle size distribution measuring device using dynamic light scattering, for example, DLS-700 manufactured by Otsuka Electronics Co., Ltd. or Coulter N4 manufactured by Coulter Electronics Co., Ltd. However, since it is difficult to dissociate the secondary aggregation of the particles after the hydrophobizing treatment, it is preferable to directly determine the particle size from a photograph obtained by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). . When SEM is used, the original shape may be damaged by platinum deposition or the like. Therefore, even when the deposition is performed, the thickness of the deposited film is reduced to about 1 nm, and even when the acceleration voltage is reduced, the ultra-high resolution has sufficient resolution. It is more preferable to perform measurement by FE-SEM (for example, S-5200 manufactured by Hitachi, Ltd.) using a low acceleration voltage (several eV to 10 keV) without deposition. When SEM or TEM is used, at least 100 or more oxidized fine particles are observed, and the particle size distribution and circularity SF1, SF2 are statistically calculated by an image processing device such as Luzex, image processing software, or the like. In particular, it was introduced into an image analyzer (Luzex @ AP) manufactured by Nireco and analyzed, and the values calculated by 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 above-mentioned FE-SEM apparatus and image analysis apparatus as long as similar analysis results can be obtained.
[0068]
SF-1 = (L²/ A) × (π / 4) × 100
SF-2 = (P²/ A) × (1 / 4π) × 100
here,
The absolute maximum length of the toner is L
The projected area of toner is A
Maximum toner circumference is P
And If the sphere is a true sphere, the value becomes 100, and as the value becomes larger than 100, the shape changes from a sphere to an irregular shape. In particular, SF-1 represents the shape of the entire toner (such as an ellipse or a sphere), and SF-2 is a shape factor indicating the degree of surface irregularities.
[0069]
Further, it is more preferable that the composition of the oxide fine particles is uniformly dispersed in the surface portion and the inside. Whether or not the composition is uniformly dispersed is determined by a transmission type transmission function having a scanning function and an elemental analysis mapping function. Using an electron microscope (for example, HD-2000 manufactured by Hitachi, Ltd.), elemental analysis mapping was performed between the surface (1/4 particle diameter surface) and the inside of the oxide fine particles. If it is 0.6 to 1.4, it can be determined that the particles are uniformly dispersed.
For example, SiO₂When the number of detected Si atoms is A, the number of detected Ti elements is B, and the number of O elements is C, when the Ti element is mixed with the Ti element, / C and B / C values are calculated (this corresponds to the relative amounts of Si and Ti with respect to O), while the A '/ C' and B '/ C' values are similarly measured near the surface. I do. Thereafter, a value obtained by dividing A '/ C' by A / C (or a value obtained by dividing B '/ C' by B / C) becomes a value of the quantitative ratio.
Further, it is preferable that the size of the element particles is uniform within the particles. Here, “uniform in size” is defined as a case where the ratio of the largest mass to the smallest mass of the element mass is less than 10: 1. This can be easily calculated by image software or the like, and it is preferable to analyze about 200 element blocks.
[0070]
Examples of the surface treating agent for the oxide fine particles include silane coupling agents such as dialkyldihalogenated silanes, trialkylhalogenated silanes, alkyltrihalogenated silanes, hexaalkyldisilazane, silylating agents, and silane cups having an alkyl fluoride group. Ring agents, organic titanate-based coupling agents, aluminum-based coupling agents, silicone oils, silicone varnishes and the like can be mentioned. More preferred are an organosilicon compound surface treatment agent and a hydrophobic treatment agent.
[0071]
(External additives)
As the external additive, in addition to the oxide fine particles, inorganic fine particles and hydrophobicized inorganic fine particles can be used in combination. The average particle diameter of the hydrophobic-treated primary particles is 1 to 100 nm, more preferably 5 nm to 70 nm. It is more desirable to include at least one kind of inorganic fine particles. Further, it is more desirable that the hydrophobic-treated primary particles include at least one kind of inorganic fine particles having an average particle diameter of 20 nm or less and at least one kind of inorganic fine particles having a mean diameter of 30 nm or more. The specific surface area by the BET method is 20 to 500 m.²/ G.
[0072]
All of them can be used if they satisfy the conditions. For example, it may contain 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), and fluoropolymers.
[0073]
Particularly preferred additives include hydrophobic silica, titania, titanium oxide, and fine alumina particles. Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H1303 (above Hoechst), R972, R974, RX200, RY200, R202, R805, and R812 (both Nippon Aerosil). Further, as titania fine particles, P-25 (Nippon Aerosil), STT-30, STT-65C-S (Titanium Industry), TAF-140 (Fuji Titanium Industry), MT-150W, MT-500B, MT-600B , MT-150A (Takeka). In particular, titanium oxide fine particles subjected to hydrophobic treatment include T-805 (Nippon Aerosil), STT-30A, STT-65S-S (Titanium Industry), TAF-500T, TAF-1500T (Fuji Titanium Industry), MT -100S, MT-100T (taker), IT-S (Ishihara Sangyo), and the like.
[0074]
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, and octyltrimethoxysilane. Can be obtained. Also preferred are silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat, if necessary, to obtain inorganic fine particles.
[0075]
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, and 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, silica sand, clay, mica, and silica ash. Examples include stone, diatomaceous earth, chromium oxide, cerium oxide, pengara, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like. Among them, silica and titanium dioxide are particularly preferred. 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 it is difficult to effectively exhibit the function. On the other hand, if it is larger than this range, the surface of the photoreceptor is unevenly damaged, which is not preferable.
[0076]
The measurement of the silicone oil release rate used in the present invention can be measured by the following quantification method, but is not limited to this method, and any more optimal method can be used.
1. Extraction of free silicone oil
The sample is immersed in chloroform, stirred, and left. Chloroform is newly added to the solid content after removing the supernatant by centrifugation, and the mixture is stirred and left. This operation is repeated to remove free silicone oil.
2. Determination of carbon content
The amount of carbon was measured by a CHN elemental analyzer (for example, CHN coder @ MT-5 type (manufactured by Yanaco)).
3. Measurement of silicone oil release rate
The silicone oil release rate was determined by the following equation.
[0077]
Silicone oil release rate = (C₀-C₁) / C₀× 100 (%)
C₀: Carbon content in the sample before extraction
C₁： Amount of carbon in sample after extraction operation
(Surface treatment agent)
Examples of the surface treating agent for the external additive containing oxide fine particles include silane coupling agents such as dialkyldihalogenated silanes, trialkylhalogenated silanes, alkyltrihalogenated silanes, hexaalkyldisilazane, silylating agents, and alkyl fluorides. Examples include a silane coupling agent having a group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and silicone varnish. More preferred are an organosilicon compound surface treatment agent and a hydrophobic treatment agent.
[0078]
(Softening point, outflow starting temperature)
The softening point of the toner of the present invention was measured at a heating rate of 1 ° C./min using a softening point measuring device (manufactured by Mettler, FP90).
[0079]
(Glass transition temperature (Tg))
The Tg of the toner of the present invention was measured using the following differential scanning calorimeter under the following conditions.
[0080]
・ Differential scanning calorimeter: SEIKO1 DSC100
SEIKO1SSC5040 (Disk @ Station)
·Measurement condition:
Temperature range: 25 to 150 ° C
Heating rate: @ 10 ° C / min
Sampling time: 0.5 sec
Sample amount: $ 10mg
(Molecular weight)
The number average molecular weight (Mn), weight average molecular weight (Mw) and peak molecular weight Mp by GPC (gel permeation chromatography) were measured 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, injected with 100 μl of this sample solution into a column, and measured for the retention time under the following conditions. The retention time was measured using a 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.
[0081]
・ Column: Guard column + GLR400M + GLR400M +
GLR400 (all manufactured by Hitachi, Ltd.)
・ Column temperature: 40 ℃
・ Mobile phase (flow rate): THF (1 ml / min)
・ Peak detection method II: UV (254 nm)
[0082]
(Penetration, heat-resistant storage)
Each 10 g of the toner was weighed, placed in a 20 cc glass container, and allowed to stand in a thermostat set at 50 ° C. for 5 hours. Then, the penetration was measured with a penetration meter.
[0083]
(Average dispersed particle size of wax)
The dispersion average particle size of the wax according to the present invention can be analyzed by observing an ultrathin section of the toner with a TEM (transmission electron microscope). If necessary, the TEM image is taken into a computer, and the dispersion average particle diameter is determined by image processing software. As means other than the TEM, an optical microscope, a CCD camera image, a laser microscope, or the like can be used, and there is no particular limitation as long as the means can measure the average particle diameter.
[0084]
(Binder resin)
Examples of the binder resin of the toner of the present invention include polymers of styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene and their substituted polymers; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, and styrene- Vinyl toluene copolymer, styrene-vinyl naphthalene 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, styrene- Styrene-based copolymers such as tadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, poly Butyl 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 alicyclic Examples thereof include a hydrocarbon resin, an aromatic petroleum resin, chlorinated paraffin, and paraffin wax, which can be used alone or in combination. Particularly, a polyester resin and a polyol resin are more preferable.
[0085]
More preferably, by containing at least a polyol resin or a polyol resin having an epoxy resin part and a polyoxyalkylene part in at least the main chain, sufficient compression resistance, tensile breaking strength, environmental stability, stable fixing characteristics, copy fixing It can prevent the transfer of the toner image to the sheet when the image surface adheres to the vinyl chloride resin, especially when used for color toner, color reproducibility, stable gloss, curl prevention of copy-fixed images, etc. Effect is more preferable. Further, by including at least a polyol resin portion and a polyester resin portion, a toner having a good balance of elasticity and adhesiveness as well as compressive strength is obtained, and more stable transferability, developability, and fixing characteristics are more preferably obtained.
[0086]
The epoxy resin used in the present invention is preferably one obtained by combining bisphenol such as bisphenol A or bisphenol F with epichlorohydrin. The epoxy resin is a bisphenol A type epoxy resin having at least two kinds of different epoxy resins having different number average molecular weights in order to obtain stable fixing characteristics and gloss. The number average molecular weight of the low molecular weight component is 360 to 2000, and the high molecular weight component is It is preferable that the number average molecular weight is 3,000 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%. If the amount of the low molecular weight component is too large or the molecular weight is lower than 360, gloss may be excessively obtained and storage stability may be deteriorated. If 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 fixability may be deteriorated.
[0087]
Examples of the compound used in the present invention include the following as the alkylene oxide adduct of dihydric phenol. Examples include ethylene oxide, propylene oxide, butylene oxide, and a reaction product of a mixture thereof with a bisphenol such as bisphenol A or bisphenol F. The obtained adduct may be glycidylated with epichlorohydrin or β-methylepichlorohydrin before use. Particularly, a diglycidyl ether of an alkylene oxide adduct of bisphenol A represented by the following general formula (1) is preferable.
[0088]
Embedded image

[0089]
Further, it is preferable that an alkylene oxide adduct of dihydric phenol or its glycidyl ether is contained in an amount of 10 to 40% by weight based on the polyol resin. Here, if the amount is small, problems such as an increase in curl may occur, and if n + m is 7 or more, or if the amount is too large, gloss may be excessively obtained, and furthermore, storage stability may be deteriorated. Examples of the compound having one active hydrogen that reacts with the epoxy group in the molecule used in the present invention include monohydric phenols, secondary amines, and carboxylic acids. The following are examples of the monohydric phenols. Examples include phenol, cresol, isopropylphenol, aminophenol, nonylphenol, dodecylphenol, xylenol, p-cumylphenol and the like. Secondary amines include diethylamine, dipropylamine, dibutylamine, N-methyl (ethyl) piperazine, piperidine and the like. Examples of the carboxylic acids include propionic acid and caproic acid.
[0090]
In order to obtain a polyol resin having an epoxy resin part and an alkylene oxide part in the main chain of the present invention, various raw material combinations are possible. For example, it can be obtained by reacting an epoxy resin having glycidyl groups at both terminals and an alkylene oxide adduct of dihydric phenol having glycidyl groups at both terminals with dihalide, diisocyanate, diamine, dithiol, polyhydric phenol, or dicarboxylic acid. Of these, the reaction with dihydric phenol is most preferable in terms of reaction stability. It is also preferable to use a polyhydric phenol or a polycarboxylic acid together with a dihydric phenol within a range not causing gelation. Here, the amount of the polyhydric phenols and polycarboxylic acids is 15% or less, preferably 10% or less based on the total amount.
[0091]
Examples of the compound having two or more active hydrogens that react with the epoxy group in the molecule used in the present invention include dihydric phenols, polyhydric phenols, and polyhydric carboxylic acids. Examples of the dihydric phenol include bisphenols such as bisphenol A and bisphenol F. Examples of the polyhydric phenols include orthocresol novolaks, phenol novolaks, tris (4-hydroxyphenyl) methane, and 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] benzene. Examples of the polycarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, trimellitic acid, and trimellitic anhydride.
[0092]
Further, by using a polyol resin having an epoxy resin part, a polyoxyalkylene part and a polyester part in the main chain in the resin used in the present invention, the viscoelasticity and hardness of the resin are changed by the polyester component, and a softer resin is used. It is more preferable because it has physical properties and curling of the image can be suppressed.
[0093]
Further, by controlling the epoxy equivalent of the binder resin to 10,000 or more, preferably 30,000 or more, more preferably 50,000 or more, the thermal properties of the resin can be controlled, and low-molecular-weight epichlorohydrin, which is a reaction residue, can be used. Can be reduced, and a toner excellent in both safety and resin characteristics can be obtained.
[0094]
Here, as the polyester resin, various types can be used.
(1) at least one selected from dihydric carboxylic acids and lower alkyl esters and acid anhydrides thereof;
(2) a diol component represented by the following general formula (2)
[0095]
Embedded image

(Where R¹And R²May be the same or different and are 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. )
[0096]
(3) at least one selected from the group consisting of trivalent or higher polycarboxylic acids, lower alkyl esters and acid anhydrides thereof, and trihydric or higher polyhydric alcohols; and (1) (2) (3) It is preferably a polyester resin obtained by a reaction.
[0097]
Here, examples of the divalent carboxylic acid (1) and its lower alkyl esters and acid anhydrides include terephthalic acid, isophthalic acid, sebacic acid, isodecylsuccinic acid, maleic acid, fumaric acid, and monomethyl and monoethyl thereof. And dimethyl and diethyl esters, and phthalic anhydride and maleic anhydride, and terephthalic acid, isophthalic acid and dimethyl esters thereof 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 fixability and blocking resistance of the toner. That is, depending on the degree of condensation, the use of a large amount of aromatic terephthalic acid, isophthalic acid or the like improves the blocking resistance but lowers the fixing property. Conversely, when sebacic acid, isodecylsuccinic acid, maleic acid, fumaric acid, etc. are used in a large amount, the fixing property is improved, but the blocking resistance is lowered. Therefore, these divalent carboxylic acids are appropriately selected according to other monomer compositions, ratios, and degrees of condensation, and used alone or in combination.
[0098]
Examples of the diol component represented by the general formula (I) of (2) include polyoxypropylene- (n) -polyoxyethylene- (n ')-2,2-bis (4-hydroxyphenyl) propane, Examples thereof include polyoxypropylene- (n) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene- (n) -2,2-bis (4-hydroxyphenyl) propane. Polyoxypropylene- (n) -2,2-bis (4-hydroxyphenyl) propane where 1 ≦ n ≦ 2.5 and polyoxyethylene- (n)-where 2.0 ≦ n ≦ 2.5 2,2-bis (4-hydroxyphenyl) propane is preferred. Such a diol component has an advantage that the glass transition temperature is improved and the reaction is easily controlled.
[0099]
As the diol component, aliphatic diols such as ethylene glycol, diethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and propylene glycol can also be used. is there.
[0100]
Examples of (3) trivalent or higher polyvalent carboxylic acids and their lower alkyl esters and acid anhydrides include 1,2,4-benzenetricarboxylic acid (trimellitic acid) and 1,3,5-benzenetricarboxylic acid. 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthrenetricarboxylic 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, empoletrimer acid and monomethyl, monoethyl thereof , Dimethyl and diethyl esters.
[0101]
Examples of the trihydric or higher polyhydric alcohol of (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 And propane and 1,3,5-trihydroxymethylbenzene.
[0102]
Here, the compounding ratio of the trivalent or higher polyvalent monomer is suitably about 1 to 30 mol% of the whole monomer composition. When the amount is less than 1 mol%, the offset resistance of the toner tends to decrease, and the durability tends to deteriorate. On the other hand, when the content is 30 mol% or more, the fixability of the toner tends to deteriorate.
[0103]
Among these trivalent or higher polyvalent monomers, benzenetricarboxylic acids such as benzenetricarboxylic acid and anhydrides or esters of these acids are particularly preferred. That is, by using benzenetricarboxylic acids, it is possible to achieve both fixability and offset resistance.
[0104]
Further, modified polyester (i) is also preferable as a binder resin used in the toner of the present invention. The modified polyester (i) refers to a state in which a bonding group other than an ester bond is present in the polyester resin, or a resin component having a different configuration is bonded to the polyester resin by a covalent bond, an ionic bond, or the like. Specifically, it refers to a product obtained by introducing a functional group such as an isocyanate group which reacts with a carboxylic acid group or a hydroxyl group into a polyester terminal and further reacting with an active hydrogen-containing compound to modify the polyester terminal.
[0105]
Examples of the modified polyester (i) include a urea-modified polyester obtained by reacting a polyester prepolymer (A) having an isocyanate group with an amine (B). As the polyester prepolymer (A) having an isocyanate group, a polyester which is a polycondensate of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC) and has an active hydrogen group, and a polyvalent isocyanate compound (PIC) And the like. Examples of the active hydrogen group contained in the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, and a mercapto group. Of these, an alcoholic hydroxyl group is preferable.
[0106]
The urea-modified polyester is produced as follows.
Examples of the polyhydric alcohol compound (PO) include a dihydric alcohol (DIO) and a trihydric or higher polyhydric alcohol (TO), and a mixture of (DIO) alone or a mixture of (DIO) and a small amount of (TO). preferable. Examples of the dihydric alcohol (DIO) include alkylene glycols (such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol); and alkylene ether glycols (diethylene glycol). , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexane dimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above alicyclic diols; Alkylene oxide bisphenol (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Of these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols, and alkylene glycols having 2 to 12 carbon atoms. Is a combination of Examples of the trihydric or higher polyhydric alcohol (TO) include polyhydric aliphatic alcohols of 3 to 8 or higher (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Such as trisphenol PA, phenol novolak, and cresol novolak); and the above-mentioned trivalent or higher polyphenols alkylene oxide adducts.
[0107]
Examples of the polyvalent carboxylic acid (PC) include a divalent carboxylic acid (DIC) and a trivalent or higher carboxylic acid (TC), and (DIC) alone or a mixture of (DIC) and a small amount of (TC). Mixtures are preferred. Examples of divalent carboxylic acids (DIC) include alkylenedicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) , Naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (TC) include an aromatic polycarboxylic acid having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). The polycarboxylic acid (PC) may be reacted with a polyhydric alcohol (PO) using the above-mentioned acid anhydride or lower alkyl ester (eg, methyl ester, ethyl ester, isopropyl ester).
[0108]
The ratio between the polyhydric alcohol (PO) and the polyhydric carboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is from 1.5 / 1 to 1/1, more preferably from 1.3 / 1 to 1.02 / 1.
[0109]
Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyvalent isocyanates (such as tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,6-diisocyanatomethylcaproate); alicyclic polyisocyanates (such as isophorone diisocyanate and cyclohexylmethane diisocyanate). Aromatic diisocyanates (such as tolylene diisocyanate and diphenylmethane diisocyanate); araliphatic diisocyanates (such as α, α, α ′, α′-tetramethylxylylene diisocyanate); isocyanates; Those blocked with caprolactam and the like; and combinations of two or more of these.
[0110]
The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably 5/1 to 1/1, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the hydroxyl group-containing polyester. The ratio is from 4/1 to 1.2 / 1, more preferably from 2.5 / 1 to 1.5 / 1. If [NCO] / [OH] exceeds 5, the low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester becomes low, and the hot offset resistance deteriorates.
[0111]
The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. . If the content is less than 0.5 wt%, the hot offset resistance is deteriorated and the heat storage stability and the low-temperature fixability are both disadvantageous. On the other hand, if it exceeds 40 wt%, the low-temperature fixability deteriorates.
The number of isocyanate groups contained in one molecule in the polyester prepolymer (A) having isocyanate groups is usually one or more, preferably 1.5 to 3 on average, and more preferably 1.8 to 2 on average. There are five. If the number is less than one per molecule, the molecular weight of the urea-modified polyester becomes low, and the hot offset resistance deteriorates.
[0112]
Next, the amines (B) to be reacted with the polyester prepolymer (A) include a divalent amine compound (B1), a trivalent or higher polyamine compound (B2), an amino alcohol (B3), and an amino mercaptan (B4). ), Amino acids (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl) Methane, diaminecyclohexane, isophoronediamine, and the like; and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, and the like). Examples of the trivalent or higher polyamine compound (B2) include diethylenetriamine and triethylenetetramine. Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of the aminomercaptan (B4) include aminoethylmercaptan and aminopropylmercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the compound obtained by blocking the amino group of B1 to B5 (B6) include ketimine compounds and oxazolidine compounds obtained from the amines and ketones (such as acetone, methyl ethyl ketone, and methyl isobutyl ketone) of B1 to B5. Preferred of these amines (B) are B1 and a mixture of B1 and a small amount of B2.
[0113]
The ratio of amines (B) is equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). Is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, and more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester becomes low, and the hot offset resistance deteriorates.
Further, the urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually from 100/0 to 10/90, preferably from 80/20 to 20/80, and more preferably from 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance deteriorates.
[0114]
The modified polyester (i) used in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. The peak molecular weight at this time is preferably from 1,000 to 10,000, and if it is less than 1,000, the elongation reaction is difficult, the elasticity of the toner is small, and as a result, the hot offset resistance deteriorates. On the other hand, if it exceeds 10,000, the problems in production of fixing property decrease, particle formation and pulverization become high. The number average molecular weight of the modified polyester (i) is not particularly limited when unmodified polyester (ii) described later is used, and may be a number average molecular weight that is easily obtained to obtain the above weight average molecular weight. (I) When used alone, the number average molecular weight is usually 20,000 or less, preferably 1,000 to 10,000, and more preferably 2,000 to 8,000. If it exceeds 20,000, the low-temperature fixability and the gloss when used in a full-color device deteriorate.
In the crosslinking and / or elongation reaction between the polyester prepolymer (A) and the amines (B) for obtaining the modified polyester (i), a reaction terminator is used as necessary to adjust the molecular weight of the obtained urea-modified polyester. be able to. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).
[0115]
(Unmodified polyester)
In the present invention, not only the modified polyester (i) may be used alone, but also an unmodified polyester (ii) may be contained as a binder resin component together with the modified polyester (i). By using (ii) together, the low-temperature fixability and the glossiness when used in a full-color device are improved, and it is preferable to use alone. Examples of (ii) include the same polycondensates of polyhydric alcohol (PO) and polycarboxylic acid (PC) as in the polyester component (i), and preferable ones are also the same as (i). . Further, (ii) may be not only an unmodified polyester but also a polyester modified with a chemical bond other than a urea bond, for example, a modified urethane bond. It is preferable that (i) and (ii) are at least partially compatible with each other in view of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (i) and (ii) preferably have similar compositions. When (ii) is contained, the weight ratio of (i) to (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferably, it is 7/93 to 20/80. When the weight ratio of (i) is less than 5%, the hot offset resistance deteriorates, and the heat resistance storage stability and the low-temperature fixability are disadvantageous.
[0116]
The peak molecular weight of (ii) is usually from 1,000 to 10,000, preferably from 2,000 to 8,000, more preferably from 2,000 to 5,000. If it is less than 1,000, the heat-resistant preservability deteriorates, and if it exceeds 10,000, the low-temperature fixability deteriorates. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of compatibility between heat-resistant storage stability and low-temperature fixability. The acid value of (ii) is preferably from 1 to 5, more preferably from 2 to 4. Since a high acid value wax is used as the wax, the low acid value binder leads to electrification and high volume resistance, so that the binder easily matches the toner used for the two-component developer.
[0117]
The glass transition point (Tg) of the binder resin is usually 35 to 70 ° C, preferably 55 to 65 ° C. If the temperature is lower than 35 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the toner of the present invention tends to have good heat-resistant storage stability even at a low glass transition point as compared with known polyester-based toners. Show.
[0118]
(Production method of toner binder)
The toner binder can be manufactured by the following method. The polyhydric alcohol (PO) and polycarboxylic acid (PC) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the pressure is reduced as necessary to produce water. After distilling off, a polyester having a hydroxyl group is obtained. Next, at 40 to 140 ° C., a polyvalent isocyanate compound (PIC) is reacted therewith to obtain a prepolymer (A) having an isocyanate group. Further, (A) is reacted with an amine (B) at 0 to 140 ° C. to obtain a polyester modified with a urea bond.
When reacting (PIC) and when reacting (A) and (B), a solvent can be used if necessary. Solvents that can be used include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And the like (e.g., tetrahydrofuran), which are inert to polyvalent isocyanate compounds (PIC).
When the unmodified polyester (ii) is used in combination, (ii) is produced in the same manner as the polyester having a hydroxyl group, and this is dissolved in the solution after the completion of the reaction (i) and mixed.
[0119]
In addition, when these polyester resins and polyol resins have a high crosslinking density, it is difficult to obtain transparency and glossiness. Therefore, they are preferably non-crosslinked or weakly crosslinked (THF insoluble content is 5% or less). Is preferred.
The method for producing these binder resins is not particularly limited, and any of bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization and the like can be used.
[0120]
(Colorant)
As the colorant of the toner of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow , Yellow iron oxide, loess, graphite, titanium yellow, oil yellow, Hansa yellow, (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G, R), tartrazine lake, quinoline yellow lake, anthragen yellow BGL, isoindolinone yellow, red bengalana, lead red, lead red, cadmium red, cadmium mercury red, antimony red, permanent red 4R, Para Red, Fire Red, Para Chlor Ortho Nitro Nirin Red, Risor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Kahnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scalate VD, Belkan Fast Rubin B, Brilliant Scarlet G, Lisor Rubin GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlett 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Lite, Bon Maroon Museum, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thio Indigolet B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, black Bermidine, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC ), Indigo, ultramarine, navy blue, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, manganese purple, dioxazine violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian 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. The amount used is generally 0.1 to 50 parts by weight based on 100 parts by weight of the binder resin.
[0121]
(Master batch pigment)
In the present invention, for the purpose of improving the affinity between the resin and the pigment, a master batch pigment in which the resin and the pigment are previously mixed and kneaded at about 1: 1 can be used. More preferably, a resin and a pigment having a low polar solvent-soluble component amount are heated and kneaded without using an organic solvent to produce a masterbatch pigment having excellent environmental charge stability. Further, the dispersibility can be further improved by using a dry powder pigment and using water as a method of wetting the resin. Generally, organic pigments used as colorants are hydrophobic, but the manufacturing process involves washing and drying, so that if some force is applied, water can penetrate into the pigment aggregates. It is possible. When a mixture of a pigment and a resin impregnated with water in the aggregate is kneaded at a set temperature of 100 ° C. or more in an open kneader, the water in the aggregate reaches the boiling point instantaneously and expands in volume. Therefore, a force for breaking the aggregate is applied from inside the aggregate. The force from the inside of the aggregate can disintegrate the aggregate very efficiently compared to the force applied from the outside.
[0122]
Further, at this time, since the resin is heated to a temperature equal to or higher than the softening point, the viscosity decreases, and the aggregates are efficiently wetted, and at the same time, similar to the so-called flushing with water near the boiling point temperature inside the aggregates. By being replaced by the effect, a master batch pigment in which the pigment is dispersed in a state close to the primary particles can be obtained. Further, in the process of evaporating water, since the heat of vaporization accompanying the evaporation of water is removed from the kneaded material, the temperature of the kneaded material is kept at a relatively low temperature and high viscosity of 100 ° C. or less, so that the shearing force is effective. Has the effect of being added to the pigment aggregates. As an open-type kneader for producing a master batch pigment, a method using a Banbury mixer as an open-type in addition to a usual two-roll or three-roll, or a continuous two-roll kneader manufactured by Mitsui Mining Co., Ltd. Can be.
[0123]
(Charge control agent)
The toner of the present invention may optionally contain a charge control agent. As the charge control agent, any known charge control agents can be used. For example, 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 alone or compounds, tungsten alone or compounds, fluorinated activators, salicylic acid metal salts, and salicylic acid derivative metal salts. Specifically, bontron 03 of a nigrosine dye, bontron P-51 of a quaternary ammonium salt, bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid-based metal complex, and E-82 of a salicylic acid-based metal complex 84, E-89 of a phenolic condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium Salt copy charge PSY @ VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge @ NEGVP2036, copy charge @ NX @ VP434 (all from Hoechst), LRA-901, boron complex LR-147 ( Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinakuri Emissions, azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.
[0124]
In the present invention, the amount of the charge control agent used is determined by the type of the 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 based on 100 parts by weight of the binder resin. Preferably, the range is 2 to 5 parts by weight. If the amount exceeds 10 parts by weight, the chargeability of the toner is too large, the effect of the main charge control agent is reduced, the static electric attraction force with the developing roller increases, the fluidity of the developer decreases, and the image density decreases. Causes a decline.
[0125]
(Carrier)
When the toner of the present invention is used for a two-component developer, the toner may be mixed with a magnetic carrier, and the content ratio of the carrier and the toner in the developer may be 1 to 100 parts by weight of the carrier. 10 parts by weight are preferred. As the magnetic carrier, conventionally known ones 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. Also, polyvinyl and polyvinylidene resins, for example, acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins such as polystyrene resins and styrene acrylic copolymer resins, polychlorinated resins Halogenated olefin resin such as vinyl, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, 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.
[0126]
The coating material has a thickness of 0.01 to 3 μm, and more preferably 0.1 to 0.3 μm. When the thickness is less than 0.01 μm, it is difficult to control the film and the film cannot function as a coat film. Further, when the thickness is 3 μm or more, conductivity cannot be obtained, which is not preferable. If necessary, a conductive powder or the like may be contained in the coating resin. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide and the like can be used. These conductive powders preferably have an average particle size of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control the electric resistance.
[0127]
Further, the toner of the present invention can be used as a one-component magnetic toner or a non-magnetic toner without using a carrier.
[0128]
(Magnetic material)
Further, the toner of the present invention contains a magnetic material and can be used as a magnetic toner. When a magnetic toner is used, magnetic particles may be contained in the toner particles. As such a magnetic material, ferrite, iron or nickel such as magnetite, nickel, cobalt or other ferromagnetic metal or alloy or a compound containing these elements, does not contain a ferromagnetic element, but by performing an appropriate heat treatment Alloys that exhibit ferromagnetism, for example, manganese-copper-aluminum, manganese-copper-tin, and other manganese-copper-based Heusler alloys including manganese and copper, chromium dioxide, and the like can be given. The magnetic material is preferably contained in the form of fine powder having an average particle diameter of 0.1 to 1 μm, which is uniformly dispersed. The content ratio of the magnetic substance is preferably from 10 to 70 parts by weight, particularly preferably from 20 to 50 parts by weight, based on 100 parts by weight of the obtained toner.
[0129]
(wax)
In order to give the toner or the developer a fixing release property, it is preferable to include a wax in the toner or the developer. In particular, when an oil-less 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., preferably 50 to 110 ° C. If the melting point of the wax is too high, the fixability at low temperatures may be insufficient, while if the melting point is too low, the offset resistance and durability may be reduced. The melting point of the wax can be determined by differential scanning calorimetry (DSC). That is, the melting peak value when a few mg of sample is ripened at a constant heating 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, more preferably 0 to 10 parts by weight.
[0130]
Examples of the wax that can be used in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide-based wax, fatty acid-based wax, dead group monoketones, fatty acid metal salt-based wax, fatty acid ester-based wax, and partial ken wax. Fatty acid ester wax, silicone varnish, higher alcohol, carnauba wax and the like. Polyolefins such as low molecular weight polyethylene and polypropylene can also be used. In particular, polyolefins and esters having a softening point by a 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.
[0131]
More preferably, it is effective to contain at least one kind of wax selected from the group consisting of decarboxylated 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 sasol wax. Turned out to be relevant. The free fatty acid-type carnauba wax is obtained by desorbing free fatty acids using carnauba wax as a raw material. For this reason, the acid value is 5% or less, and the carnauba wax becomes finer crystals than the conventional carnauba wax. The dispersion average particle size in the solution becomes 1 μm or less, and the dispersibility is improved. The montan-based ester wax is refined from a mineral, becomes microcrystalline similarly to carnauba wax, has a dispersion average particle size of 1 μm or less in the binder resin, and has improved dispersibility. In the case of a montan ester wax, the acid value is particularly preferably 5 to 14.
[0132]
The dispersion diameter of the wax is preferably 3 μm or less, more preferably 2 μm or less, and further preferably 1 μm or less. When the dispersion diameter is 3 μm or more, the wax outflow property and the transfer material releasability are improved, but the high-temperature high-humidity durability, charge stability and the like of the toner are reduced.
[0133]
Moreover, oxidized lasiss wax is obtained by air-oxidizing rice bran wax. The acid value is preferably from 10 to 30, and if it is less than 10, the fixing lower limit temperature rises and the low-temperature fixability becomes insufficient. If it is more than 30, the cold offset temperature rises and the low-temperature fixability also becomes insufficient. As the Sasol wax, Sasol wax H1, H2, A1, A2, A3, A4, A6, A7, A14, C1, C2, SPRAY30, SPRAY40, etc. manufactured by Sasol can be used, and among them, H1, H2, SPRAY30, SPRAY40 are available. Is preferred because of its excellent low-temperature fixing and storage stability. The above wax may be used alone or in combination. The content of 1 to 15 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the binder resin, The result is obtained.
[0134]
(Cleaning improver)
It is more preferable that the cleaning property improving agent for removing the developer after transfer 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 property improver include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, and polymer fine particles produced by soap-free emulsion polymerization of polymethyl methacrylate fine particles, polystyrene fine particles, and the like. . 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 property improver is preferably 0.001 to 5 parts by weight, more preferably 0.001 to 1 part by weight.
[0135]
(Toner production method)
The production method of the present invention is a toner having a step of mechanically mixing a developer component containing at least a binder resin, a main charge control agent and a pigment, a step of melt-kneading, a step of pulverizing, and a step of classifying. Can be applied. Further, in the step of mechanically mixing and the step of melt-kneading, a production method in which powder other than the particles serving as a product obtained in the step of pulverization or classification is returned and reused is also included.
[0136]
The powder (by-product) other than the particles that become the product referred to here is mixed with the fine particles and coarse particles other than the components that become the product having the desired particle size obtained in the pulverization step after the step of melt-kneading, and in the subsequent classification step. It means fine particles and coarse particles other than the components that generate the desired particle size. In the mixing step or the melt-kneading step of such a by-product, it is preferable to mix the raw materials and preferably the by-product 1 at a weight ratio of the other raw material 50 to the by-product 50 from the other raw material 99.
[0137]
The mixing step of mechanically mixing at least the binder resin, the main charge control agent and the pigment, and the developer components including the by-products may be performed under normal conditions using a normal mixer or the like with a rotating blade, particularly No restrictions.
[0138]
After the completion of the above mixing step, 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, a KTK twin screw extruder manufactured by Kobe Steel, a TEM extruder manufactured by Toshiba Machine Co., a twin screw extruder manufactured by Kay Kay, a PCM twin screw extruder manufactured by Ikegai Iron Works, Bus A co-kneader or the like is preferably used.
[0139]
It is important that the melt-kneading be performed under appropriate conditions so as not to cut the molecular chains of the binder resin. More specifically, the melt-kneading temperature should be determined with reference to the softening point of the binder resin. If the temperature is lower 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 volatile components remaining at that time.
[0140]
After the completion of the above-described melt-kneading process, the kneaded material is then pulverized. In this pulverization step, it is preferable to first perform coarse pulverization and then finely pulverize. At this time, a method of pulverizing by colliding with a collision plate in a jet stream or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.
[0141]
After the completion of the pulverizing step, the pulverized product is classified in an air stream by centrifugal force or the like, thereby producing a toner (base particles) having a predetermined particle size and a volume average particle size of 2 to 7 μm. The volume average particle size can be measured using, for example, COULTERTA-II (COULTER ELECTRONICS, INC).
[0142]
Further, when preparing the toner, in order to enhance the fluidity and storage properties of the toner, developability, transferability, the oxide fine particles of the present invention further mentioned above in the toner produced as described above, Inorganic fine particles such as hydrophobic silica fine powder may be added and mixed. A general powder mixer is used for mixing the external additives, but it is preferable that the internal temperature can be adjusted by providing a jacket or the like. In order to change the history of the load applied to the external additive, the external additive may be added during or gradually. Of course, the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. A strong load may be applied first, followed by a relatively weak load, or vice versa.
[0143]
Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Lodige mixer, a Nauter mixer, and a Henschel mixer.
Further, as other production methods, a polymerization method, a capsule method, and the like can be used. The outline of these production methods is described below.
[0144]
(Polymerization method 1)
{Circle around (1)} A polymerizable monomer, and if necessary, a polymerization initiator, a colorant, a wax and the like are granulated in an aqueous dispersion medium.
{Circle around (2)} The granulated monomer composition particles are classified to an appropriate particle size.
{Circle around (3)} Polymerizing the monomer composition particles having a specified internal particle diameter obtained by the above classification.
{Circle around (4)} After removing the dispersant by appropriate treatment, the polymerization product obtained above is filtered, washed with water and dried to obtain base particles.
[0145]
(Polymerization method 2)
{Circle around (1)} A low molecular weight resin, a high molecular weight resin, a colorant, a wax, a wax dispersant, and, if necessary, a charge control agent are dispersed in an oil layer dispersion medium using a solvent such as ethyl acetate.
{Circle around (2)} Dropping into water containing organic fine particles and an extender to emulsify and converge.
{Circle around (3)} The dispersion is heated to polymerize and remove the solvent.
(4) After aging in water, washing, collecting and drying are performed to obtain base particles.
[0146]
(Capsule method)
{Circle around (1)} A resin, a coloring agent and the like, if necessary, are kneaded with a kneader or the like to obtain a toner core material in a molten state.
{Circle around (2)} Put the toner core material into water and stir vigorously to produce a fine particle core material.
{Circle around (3)} The core material fine particles are put in the shell material solution, and the poor solvent is added dropwise with stirring, and the core material is encapsulated by covering the surface of the core material with the shell material.
{Circle around (4)} The capsules obtained above are filtered and dried to obtain base particles.
[0147]
(Production method of toner using modified polyester (i) described in (Binder resin))
1) A toner material liquid is prepared by dispersing a colorant, an unmodified polyester (i), a polyester prepolymer having an isocyanate group (A), and a release agent in an organic solvent.
It is preferable that the organic solvent is volatile having a boiling point of less than 100 ° C. from the viewpoint of easy removal after the formation of the toner base particles. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone or the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are preferred. The amount of the organic solvent to be used is generally 0 to 300 parts by weight, preferably 0 to 100 parts by weight, more preferably 25 to 70 parts by weight, based on 100 parts by weight of the polyester prepolymer.
[0148]
2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
The aqueous medium may be water alone, or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), and lower ketones (acetone, methylethylketone, etc.). May be included.
The amount of the aqueous medium to be used per 100 parts by weight of the toner material liquid is usually 50 to 2,000 parts by weight, preferably 100 to 1,000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner material liquid is poor, and toner particles having a predetermined particle size cannot be obtained. If it exceeds 20,000 parts by weight, it is not economical.
[0149]
In order to improve the dispersion in the aqueous medium, a dispersant such as a surfactant and resin fine particles is appropriately added.
Examples of the surfactant include an alkyl benzene sulfonate, an α-olefin sulfonate, an anionic surfactant such as a phosphate, an alkylamine salt, an amino alcohol fatty acid derivative, a polyamine fatty acid derivative, and an amine salt type such as imidazoline. Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like.
[0150]
Further, by using a surfactant having a fluoroalkyl group, the effect can be improved with a very small amount. Preferred examples of the anionic surfactant having a fluoroalkyl group include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonylglutamate, and 3- [ω-fluoroalkyl (C6 to C11). ) Oxy] -1-alkyl (C3-C4) sulfonic acid sodium salt, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium salt, fluoroalkyl (C11-C20) carboxylic acid Acid and metal salt, perfluoroalkylcarboxylic acid (C7-C13) and its metal salt, perfluoroalkyl (C4-C12) sulfonic acid and its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl) perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. No.
As trade names, Surflon S-111, S-112, S-113 (manufactured by Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (manufactured by Sumitomo 3M), Unidyne DS-101 , DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink and Chemicals), Ectop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, and 204 (manufactured by Tochem Products), and Fagents F-100 and F150 (manufactured by Neos).
[0151]
Examples of the cationic surfactant include aliphatic quaternary ammonium such as an aliphatic primary, secondary or secondary amino acid, and a perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, which is a fluoroalkyl group. Salt, benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, with trade names of Surflon S-121 (manufactured by Asahi Glass Co., Ltd.), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (Daikin Industries Morifa), Megafac F-150, F-824 (manufactured by Dainippon Ink and Chemicals), Ectop EF-132 (manufactured by Tochem Products), Futagent F-300 (manufactured by Neos) and the like.
[0152]
The resin fine particles are added to stabilize the toner base particles formed in the aqueous medium. For this reason, it is preferable that the toner be added so that the coverage existing on the surface of the toner base particles is in the range of 10 to 90%. For example, polymethyl methacrylate microparticles 1 μm and 3 μm, polystyrene microparticles 0.5 μm and 2 μm, poly (styrene-acrylonitrile) microparticles 1 μm, trade names are PB-200H (manufactured by Kao Corporation), SGP (manufactured by Sokensha), Techno Polymer SB (manufactured by Sekisui Chemical Co., Ltd.), SGP-3G (manufactured by Soken Co., Ltd.), Micropearl (manufactured by Sekisui Fine Chemical Co., Ltd.) and the like.
Further, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.
[0153]
As a dispersant that can be used in combination with the resin fine particles and the inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer-based protective colloid. For example, an acid such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or a (meth) acrylic monomer containing a hydroxyl group Such as -β-hydroxyethyl acrylate, -β-hydroxyethyl methacrylate, -β-hydroxypropyl acrylate, -β-hydroxypropyl methacrylate, -γ-hydroxypropyl acrylate, -γ-hydroxy methacrylate Propyl, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin monoacrylate, glycerin monomethacrylate Vinyl alcohol or ethers with vinyl alcohol, such as luic acid ester, N-methylol acrylamide, N-methylol methacrylamide, for example, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or a compound containing vinyl alcohol and a carboxyl group Esters, for example, vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinylpyridine, vinylpyrrolidone, vinyl Nitrogen-containing compounds such as imidazole and ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring, polyoxyethylene, and polyoxyethylene. Xypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearylphenyl ester, polyoxy Polyoxyethylenes such as ethylene nonyl phenyl ester and celluloses such as methyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose can be used.
[0154]
The dispersing method is not particularly limited, but known equipment such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. Among these, a high-speed shearing type is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the number of revolutions is not particularly limited, but it is usually 1,000 to 30,000 rpm, preferably 5,000 to 20,000 rpm. The dispersion time is not particularly limited, but is usually 0.1 to 5 minutes in the case of a batch system. The temperature at the time of dispersion is usually 0 to 150 ° C (under pressure), preferably 40 to 98 ° C.
[0155]
3) Simultaneously with the preparation of the emulsion, the amines (B) are added to react with the polyester prepolymer (A) having isocyanate groups.
This reaction involves crosslinking and / or elongation of the molecular chains. The reaction time is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer (A) and the amines (B), and is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0-150C, preferably 40-98C. In addition, a known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.
[0156]
4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the whole system is gradually heated in a laminar stirring state, and after strong stirring is given in a certain temperature range, the solvent is removed to produce spindle-shaped toner base particles. . When an acid such as a calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Is removed. In addition, it can be removed by an operation such as decomposition with an enzyme.
[0157]
5) A charge controlling agent is injected into the toner base particles obtained above, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are externally added to obtain a toner.
The charging of the charge control agent and the external addition of the inorganic fine particles are performed by a known method using a mixer or the like.
As a result, a toner having a small particle size and a sharp particle size distribution can be easily obtained. Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between a true sphere and a rugby ball can be controlled, and the morphology of the surface can be controlled between a smooth and a umeboshi shape. be able to.
[0158]
(Intermediate transfer member)
In the present invention, an intermediate transfer member can be used. One embodiment of the intermediate transfer member of the transfer system will be described. FIG. 1 is a schematic configuration diagram of a copying machine according to an embodiment of the toner and the developer of the present invention. Around a photoreceptor drum (hereinafter, referred to as a photoreceptor) 10 as an image carrier, a charging roller 20 as a charging device, an exposing device 30, a cleaning device 60 having a cleaning blade, a discharging lamp 70 as a discharging device, and a developing device An apparatus 40 and an intermediate transfer member 50 as an intermediate transfer member are provided. The intermediate transfer body 50 is suspended by a plurality of suspension rollers 51, and is configured to run endlessly in a direction indicated by an arrow by driving means 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. A transfer roller 80 is provided as a transfer unit for transferring a developed image to a transfer paper 100 as a final transfer material, facing the intermediate transfer body 50. The transfer roller 80 is connected to a transfer bias by a power supply (not shown). Supplied. A corona charger 52 is provided around the intermediate transfer member 50 as charge applying means.
[0159]
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, and a magenta (hereinafter, referred to as a magenta). The developing unit 45 includes a magenta (hereinafter referred to as magenta) developing unit 45M and a cyan (hereinafter referred to as C) developing unit 45C. The developing belt 41 is stretched over a plurality of belt rollers, and is configured to run endlessly in a direction indicated by an arrow by driving means such as a motor (not shown). It moves at almost the same speed as 10.
[0160]
Since the configuration of each developing unit is common, the following description will be made only for the Bk developing unit 50Bk, and the other developing units 50Y, 50M, and 50C will be described in the same portions as those in the Bk developing unit 50Bk in the drawing. The Y, M, and C are appended to the numbers assigned to the units in the unit, and the description is omitted. The developing unit 50Bk is provided with a developing tank 42Bk containing a high-viscosity, high-concentration liquid developer containing toner particles and a carrier liquid component, and a lower portion immersed in the liquid developer in the developing tank 42Bk. And a coating roller 44Bk for thinning the developer pumped from the pumping roller 43Bk and applying it to the developing belt 41. The application roller 44Bk has conductivity, and a predetermined bias is applied from a power supply (not shown).
[0161]
Note that, in addition to the apparatus configuration shown in FIG. 1, the apparatus configuration of the copying machine according to the present embodiment includes an apparatus configuration in which developing units 45 for each color are provided around the photoconductor 10 as shown in FIG. 2. It may be.
[0162]
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 a 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 exposure device 30 using an optical system (not shown). To form an electrostatic latent image. This electrostatic latent image is developed by the developing device 40 to form a toner image as a visible image. The thin developer layer on the developing belt 41 is separated from the belt 41 in a thin layer state by contact with the photoconductor in the developing area, and shifts to a portion on the photoconductor 10 where a latent image is formed. The toner image developed by the developing device 40 is transferred to the surface of the intermediate transfer body 50 at the contact portion (primary transfer area) between the photoconductor 10 and the intermediate transfer body 50 moving at a constant speed (primary transfer area). Transcription). When performing a transfer in which three or four colors are superimposed, this process is repeated for each color, and a color image is formed on the intermediate transfer body 50.
[0163]
The corona charger 52 for applying an electric charge to the superimposed toner image on the intermediate transfer member is provided at a position where the photosensitive member 10 contacts 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 body 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. An electric charge is applied to the toner image. After being charged by the corona charger 52, the toner image is collectively transferred onto 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 (2). Next transfer). Thereafter, the transfer paper 100 on which the toner image has been transferred is separated from the photoreceptor 10 by a separating device (not shown), and is discharged from the device after being subjected to a fixing process by a fixing device (not shown). On the other hand, the untransferred toner is collected and removed from the photoreceptor 10 after the transfer by the cleaning device 60, and the remaining charge is removed by the charge removing lamp 70 in preparation for the next charging.
[0164]
As described above, the coefficient of static friction of the intermediate transfer member is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is several Ωcm or more and 10³It is preferably Ωcm or less. Volume resistance of several Ωcm or more 10³By setting the resistance to Ωcm or less, the charge of the intermediate transfer body itself is prevented, and the charge applied by the charge applying unit is less likely to remain on the intermediate transfer body. Therefore, transfer unevenness during secondary transfer can be prevented. Further, the transfer bias can be easily applied at the time of the secondary transfer.
[0165]
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, and is made of PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) / PAT ( Blend material of polyalkylene terephthalate), 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 due to the stress during image formation is small, and particularly, the resist is not easily shifted during color image formation. (2) A two- or three-layer belt 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. It has a performance capable of preventing the dropout of the line image generated due to this. (3) A belt having a relatively low Young's modulus using rubber and an elastomer, and these belts have an advantage that the center of a line image hardly occurs due to its softness. Further, since the width of the belt is made larger than that of the driving roll and the stretching roll, and the meandering is prevented by utilizing the elasticity of the belt ears protruding from the roll, low cost can be realized without the need for a rib or a meandering prevention device. .
[0166]
As the intermediate transfer belt, a fluorine resin, a polycarbonate resin, a polyimide resin, or the like has been conventionally used, but in recent years, an elastic belt in which all layers of the belt or a part of the belt is an elastic member has been used. Transfer of a color image using a resin belt has the following problems.
[0167]
A color image is usually formed with four colored toners. One to four toner layers are formed on one color image. The toner layer receives pressure by passing through primary transfer (transfer from the photoreceptor to the intermediate transfer belt) and 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 is increased, the phenomenon of missing characters in a character or missing edges of a solid image tends to occur. Since the resin belt has a high hardness and does not deform in accordance with the toner layer, the toner layer is easily compressed, and the character missing phenomenon easily occurs.
[0168]
In recent years, there has been a growing demand for full-color images to be formed on various types of paper, for example, Japanese paper, intentionally having irregularities, and forming images on paper. However, paper having poor smoothness tends to generate voids with the toner at the time of transfer, and transfer loss tends to occur. If the transfer pressure of the secondary transfer portion is increased in order to enhance the adhesion, the condensing force of the toner layer will be increased, and the above-described character void will occur.
[0169]
The elastic belt is used for the following purposes. The elastic belt is deformed in the transfer section corresponding to the toner layer and the paper having poor smoothness. In other words, the elastic belt is deformed following the local irregularities, so that the transfer pressure is not excessively increased with respect to the toner layer, good adhesiveness is obtained, and there is no missing characters in the paper, and the paper has poor flatness. A transfer image with excellent uniformity can be obtained.
[0170]
The resin of the elastic belt is polycarbonate, fluororesin (ETFE, PVDF), polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer Copolymer, styrene-maleic acid copolymer, styrene-acrylate copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylic acid Octyl copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylate copolymer (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-phenyl methacrylate copolymer) Styrene-α-chloroacrylic) Styrene-based resins (homopolymers or copolymers containing styrene or styrene substituents) such as methyl acrylate copolymer, styrene-acrylonitrile-acrylate copolymer, methyl methacrylate resin, butyl methacrylate resin, acrylic 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 copolymer Polymer, rosin-modified maleic resin, phenolic resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene, polyvinylidene chloride, ionomer resin, polyurethane resin, silicone resin, ketone resin, d 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.
[0171]
Elastic rubbers and elastomers 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 tar Polymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, silicone rubber, fluorine rubber, polysulfide rubber, polynorbornene rubber, hydrogenated nitrile rubber Selected from the group consisting of thermoplastic elastomers (eg, polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide, polyurea, polyester, and 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.
[0172]
Although there is no particular limitation on the conductive agent for adjusting the resistance value, for example, carbon black, graphite, metal powder such as aluminum or nickel, tin oxide, titanium oxide, antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite Conductive metal oxides such as oxide (ATO) and indium oxide-tin oxide (ITO), and conductive metal oxides are coated with insulating fine particles such as barium sulfate, magnesium silicate, and calcium carbonate. May be. Naturally, the conductive agent is not limited to the above.
[0173]
The surface layer material is required to prevent contamination of the photoreceptor with an elastic material, and to reduce surface frictional resistance to the transfer belt surface to reduce toner adhesion, thereby improving cleaning performance and secondary transferability. . For example, one or more kinds of polyurethane, polyester, epoxy resin and the like are used to reduce surface energy and enhance lubricity, for example, powders of fluorine resin, fluorine compound, fluorocarbon, titanium dioxide, silicon carbide, etc. One or more kinds of bodies and particles or those having different particle diameters can be dispersed and used. Also, by performing a heat treatment like a fluorine-based rubber material, a fluorine-rich layer is formed on the surface to reduce the surface energy. A smaller one can also be used.
[0174]
The method for manufacturing the belt is not limited. For example, a centrifugal molding method in which a material is poured into a rotating cylindrical mold to form a belt, a spray coating method in which a liquid paint is sprayed to form a film, a dipping method in which a cylindrical mold is immersed in a material solution and pulled up, There are casting methods of pouring into inner and outer dies, and a method of wrapping a compound around a cylindrical mold and performing vulcanization polishing. However, the method is not limited to this, and a belt is formed by combining a plurality of manufacturing methods. It is common to manufacture.
[0175]
Methods for preventing elongation by elastic belting include a method of forming a rubber layer on a core resin layer with low elongation and a method of adding a material for preventing elongation to the core layer, but are not particularly concerned with the manufacturing 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 obtained by using more than one kind. Of course, it is not limited to the above materials.
[0176]
The yarn may be of any kind, such as twisted one or more filaments, single twisted yarn, multiple twisted yarn, twin yarn and 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.
[0177]
On the other hand, as the woven fabric, any woven fabric such as a knitted woven fabric can be used. Needless to say, a woven fabric obtained by cross-weaving can also be used, and naturally a conductive treatment can be applied. The manufacturing method of providing the core layer is not particularly limited.For example, a method of covering a woven fabric woven in a cylindrical shape on a mold or the like and providing a coating layer thereon, a method of forming a woven fabric in a cylindrical shape on a liquid rubber And a method of providing a coating layer on one or both surfaces of the core layer by immersing the yarn in a spiral shape at an arbitrary pitch around a die or the like, 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 expansion and contraction of the surface becomes large and cracks easily occur in the surface layer. Further, it is not preferable that the thickness is too large (about 1 mm or more) because the amount of expansion and contraction becomes large and the bleeding of the image becomes large.
[0178]
(Tandem type color image forming apparatus)
In the present invention, it can also be used as a tandem type color image forming apparatus. An example of an embodiment of a tandem type color image forming apparatus will be described. As shown in FIG. 3, a tandem type electrophotographic apparatus includes a direct transfer type in which an image on each photoconductor 1 is sequentially transferred to a sheet s conveyed by a sheet conveying belt 3 by a transfer device 2, and FIG. As shown in FIG. 4, the image on each photoconductor 1 is sequentially transferred to the intermediate transfer member 4 by the primary transfer device 2 once, and then the image on the intermediate transfer member 4 is transferred to the sheet s by the secondary transfer device 5. There is an indirect transfer type that performs batch transfer. The transfer device 5 is a transfer conveyance belt, but may have a roller shape or a type.
[0179]
Comparing the direct transfer type and the indirect transfer type, the former disposes the paper feeder 6 upstream of the tandem type image forming apparatus T in which the photoconductors 1 are arranged and the fixing device 7 downstream thereof. And there is a disadvantage in that the size increases in the sheet conveying direction.
On the other hand, in the latter, the secondary transfer position can be set relatively freely. The sheet feeding device 6 and the fixing device 7 can be disposed so as to overlap with the tandem-type image forming device T, and there is an advantage that the size can be reduced.
[0180]
In the former case, the fixing device 7 is arranged close to the tandem-type image forming apparatus T in order not to increase the size in the sheet conveying direction. For this reason, the fixing device 7 cannot be arranged with a sufficient margin to allow the sheet s to bend, and the impact when the leading edge of the sheet s enters the fixing device 7 (particularly remarkable for a thick sheet) and the fixing There is a disadvantage that the fixing device 7 easily affects the image formation on the upstream side due to the speed difference between the sheet conveyance speed when passing through the device 7 and the sheet conveyance speed by the transfer conveyance belt.
[0181]
On the other hand, in the latter, since the fixing device 7 can be arranged with a sufficient margin to allow the sheet s to bend, the fixing device 7 can hardly affect image formation.
[0182]
In view of the above, attention has recently been paid to a tandem type electrophotographic apparatus, particularly an indirect transfer type.
[0183]
In this type of color electrophotographic apparatus, as shown in FIG. 4, the transfer residual toner remaining on the photoconductor 1 after the primary transfer is removed by the photoconductor cleaning device 8 to clean the surface of the photoconductor 1. In preparation for the second 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 and prepare for the image formation again.
[0184]
Hereinafter, an embodiment using a toner and a developer of the present invention will be described with reference to the drawings.
[0185]
FIG. 5 shows an embodiment using the toner and the developer of the present invention, which is an electrophotographic apparatus of a tandem type indirect transfer system. In the figure, reference numeral 100 denotes a copying apparatus main body, 200 denotes a sheet feeding table on which the copying apparatus is mounted, 300 denotes a scanner mounted on the copying apparatus main body 100, and 400 denotes an automatic document feeder (ADF) mounted thereon. An endless belt-shaped intermediate transfer body 10 is provided at the center of the copying apparatus main body 100.
[0186]
Then, as shown in FIG. 5, in the example shown in the figure, it is wrapped around three support rollers 14, 15, 16 so as to be rotatable clockwise in the figure.
[0187]
In the 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 to the left of the second support roller 15 among the three.
[0188]
On the intermediate transfer member 10 extending between the first support roller 14 and the second support roller 15 among the three, four images of yellow, cyan, magenta, and black are arranged along the transport direction. The tandem image forming apparatus 20 is configured by arranging the forming units 18 side by side.
[0189]
An exposure device 21 is further provided on the tandem image forming device 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 device 20 with the intermediate transfer member 10 therebetween. In the illustrated example, the secondary transfer device 22 is configured by wrapping a secondary transfer belt 24, which is an endless belt, between two rollers 23, and pressing the secondary transfer belt 24 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.
[0190]
A fixing device 25 for fixing a transferred image on a 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 which is an endless belt.
[0191]
The above-described secondary transfer device 22 also has a sheet conveying function of conveying the sheet after image transfer to the fixing device 25. Of course, a transfer roller or a non-contact charger may be disposed as the secondary transfer device 22, and in such a case, it is difficult to additionally provide the sheet conveying function.
[0192]
In the illustrated example, a sheet reversing device 28 that reverses the sheet so as to record an image on both sides of the sheet is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 20 described above. Is provided.
[0193]
Now, when making a copy using this color electrophotographic apparatus, an original is set on the original table 30 of the automatic original transport apparatus 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.
[0194]
When a start switch (not shown) is pressed, when the original is set on the automatic document feeder 400, the original is conveyed and moved onto the contact glass 32, and then the original is set on the other contact glass 32. At this time, the scanner 300 is immediately driven to travel on 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 to the second traveling body 34, is reflected by the mirror of the second traveling body 34, and passes through the imaging lens 35. The original is read by a reading sensor 36 and read.
[0195]
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. I do. At the same time, the photoreceptors 40 are rotated by the individual image forming means 18 to form black, yellow, magenta, and cyan monochromatic images on the respective photoreceptors 40, respectively. Then, as the intermediate transfer body 10 is transported, the monochrome images are sequentially transferred to form a composite color image on the intermediate transfer body 10.
[0196]
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 a sheet is fed out from one of the paper feed cassettes 44 provided in the paper bank 43 in multiple stages. The sheet is separated one by one into a sheet feeding path 46, conveyed by a conveying roller 47, guided to a sheet feeding path 48 in the copying machine main body 100, and stopped against a registration roller 49.
[0197]
Alternatively, the sheet feeding roller 50 is rotated to feed out the sheet on the manual feed tray 51, separated one by one by the separation roller 52, and then put into the manual sheet feeding path 53, and similarly hit against the registration roller 49 and stopped.
[0198]
Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer body 10, the sheet is fed between the intermediate transfer body 10 and the secondary transfer device 22, and the sheet is transferred by the secondary transfer device 22. Record a color image on the sheet.
[0199]
The sheet after the image transfer is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the transfer image is fixed by applying heat and pressure by the fixing device 25, and then switched by the switching claw 55 to discharge the sheet. The sheet is discharged at 56 and stacked on a sheet discharge tray 57. Alternatively, the sheet is switched into the sheet reversing device 28 by the switching claw 55, reversed and guided again to the transfer position, the image is recorded on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.
[0200]
On the other hand, the intermediate transfer member 10 after the image transfer is removed by an intermediate transfer member cleaning device 17 to remove the residual toner remaining on the intermediate transfer member 10 after the image transfer, and the tandem image forming device 20 prepares for another image formation.
[0201]
Here, the registration roller 49 is generally used with being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.
[0202]
Now, in the tandem image forming apparatus 20 described above, the individual image forming units 18 are, for example, as shown in FIG. 6, around a drum-shaped photoconductor 40, a charging device 60, a developing device 61, and a primary device. It includes a transfer device 62, a photoconductor cleaning device 63, a charge removing device 64, and the like.
FIG. 7 shows a schematic configuration of an image forming apparatus having the process cartridge of the present invention detachably. In the image forming apparatus having the process cartridge of the present invention, the photosensitive member is driven to rotate at a predetermined peripheral speed. In the rotation process, the photoreceptor is uniformly charged on its peripheral surface with a predetermined positive or negative potential by the charging means, and then the image exposure light from the image exposure means such as slit exposure or laser beam scanning exposure. Then, an electrostatic latent image is sequentially formed on the peripheral surface of the photoreceptor, and the formed electrostatic latent image is then toner-developed by a developing unit, and the developed toner image is exposed from a sheet feeding unit. The image is sequentially transferred by the transfer means to the transfer material fed between the body and the transfer means in synchronization with the rotation of the photoconductor. The transfer material having undergone the image transfer is separated from the photoreceptor surface, introduced into an image fixing means, where the image is fixed, and printed out of the apparatus as a copy (copy). After the transfer of the image, the surface of the photoreceptor is cleaned to remove the toner remaining after the transfer by a cleaning means, and the surface of the photoreceptor is further removed.
[0203]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples. In the following examples, parts and% are based on weight unless otherwise specified. The evaluation machine used, the obtained characteristics and the evaluation results are shown in Table 1. In the examples, evaluation was performed as follows.
[0204]
(Evaluation machine)
The images used in the evaluation were evaluated using any of the following evaluators A, B, C and D. (Evaluation machine A)
Using a tandem type Ricoh full-color laser printer "IPSiO Color 8000" fixing unit having a non-magnetic two-component developing unit for four colors and a photoreceptor for four colors, an oilless fixing unit and an evaluator A tuned. Was evaluated. The printing speed was evaluated by high-speed printing (changed from 20 sheets to 50 sheets / min / A4).
[0205]
(Evaluator B)
A tandem type Ricoh full-color laser printer "IPSiO Color 8000" having a four-color non-magnetic two-component developing part and a four-color photoreceptor is improved and primary-transferred onto an intermediate transfer member. The evaluation was performed using an evaluator B, which was changed to an intermediate transfer system for secondary transfer to a transfer material, and the fixing unit was changed to an oilless fixing unit and tuned. The printing speed was evaluated by high-speed printing (changed from 20 sheets to 50 sheets / min / A4).
[0206]
(Evaluator C)
A full-color laser copying machine manufactured by Ricoh Co., Ltd. of a system in which a developing unit for four colors develops a two-component developer on one drum-shaped photoreceptor for each color, sequentially transfers it to an intermediate transfer body, and collectively transfers four colors to a transfer material. The evaluation unit C was evaluated by using a color # 2800 fixing unit modified to an oilless fixing unit and tuned.
[0207]
(Evaluation machine D)
A full-color laser printer manufactured by Ricoh that uses a four-color developing unit to sequentially develop a non-magnetic one-component developer on one belt photoreceptor for each color, sequentially transfers it to an intermediate transfer member, and collectively transfers four colors to a transfer material. The fixing unit of IPSiO Color 5000 was improved to an oilless fixing unit, and evaluated using an evaluation machine D tuned with an oil-coated fixing unit.
[0208]
(Evaluator E)
A tandem Ricoh full-color laser printer "IPSiO Color 8000" having a four-color non-magnetic two-component type developing unit and a four-color photoreceptor was evaluated using an evaluator E tuned with an oil-coated fixing unit. . The printing speed was evaluated by high-speed printing (changed from 20 sheets to 50 sheets / min / A4).
[0209]
(Evaluation item)
1) Implantability of additives
After storing for 1 week in an environment of 40 ° C. and 80%, the toner surface after stirring in a developing unit for 1 hour is observed with an FE-SEM (Hitachi {field emission scanning electron microscope} S-4200) and an external additive is added. Was observed. The one with less embedding is better, and the rank becomes better in the order of ×, Δ, ○, ◎. Specifically, x is embedded so that no additive is observed. △ indicates that the surface of the additive is slightly observed although it is embedded. ○ indicates that about half of the additive is embedded. ◎ indicates that there is almost no embedding as compared to before stirring.
[0210]
2) Toner scattering
After outputting 30,000 sheets of an image chart having a 50% image area in the monochrome mode, the amount of toner scattered from the developing unit was measured with the developing unit opened. X is 100 mg or more, Δ is 30 to less than 100 mg, ○ is 5 to less than 30 mg, and ◎ is less than 5 mg. The rank becomes better in the order of ×, Δ, ○, ◎.
[0211]
3) Inside of character image
After running 30,000 sheets of an image chart with a 50% image area in the single color mode, the character portion image is output by superimposing four colors on a Ricoh type DX OHP sheet, and toner inside the line image of the character portion is removed. The transcription frequency was compared with a step sample. The rank becomes better in the order of ×, Δ, ○, ◎. × indicates a state where the inside is clearly missing, Δ indicates a state where the toner is slightly left inside, ○ indicates a state where there is little or no toner and the state is within the allowable range, and ◎ indicates Shows a state where there is no omission at all.
[0212]
4) Toner transfer rate
After outputting 200,000 sheets of an image chart having a 7% image area in the monochromatic mode, the transfer rate was calculated from the relationship between the amount of toner input and the amount of waste toner.
Transfer rate = 100 × (input toner amount−waste toner amount) / (input toner amount)
A transfer rate of 90 or more was rated as ◎, less than 90 and 75 or more as ○, less than 75 and 60 or more as Δ, and less than 60 as x.
[0213]
5) Toner supply
An image chart with a 90% image area and a 5% image chart were alternately output every 4000 sheets, and the toner replenishability at that time was examined. ×, Δ, 、, 順 に, the toner replenishing property is improved. × indicates that toner cannot be supplied at all, Δ indicates that toner supply can be unstable, and toner supply clogging occurs about once every five times, ○ indicates that there is no problem with toner supply, Is a state where a small amount of toner remains, and ◎ indicates a state where there is no problem in both toner supply and toner remaining.
[0214]
6) Transfer chile
After running 30,000 sheets of an image chart having a 50% image area in the single color mode, a solid image of 10 mm × 10 mm was superimposed with four colors and output on a Ricoh type 6000 paper, and the degree of transfer dust was compared with a step sample. . The rank becomes better in the order of ×, Δ, ○, ◎. × indicates a state in which transfer dust is very large and is a problem as an image, Δ indicates a state where transfer dust is present and is a problem as an image, and ○ indicates a state in which transfer dust is slight but within an allowable range as an image (conventional electrophotography). (Average of image) and 示 す indicate a state where there is no transfer dust.
[0215]
7) Fine line reproducibility
After running 30,000 sheets of an image chart with a 50% image area in the monochromatic mode, a 600 dpi fine line image was output on a Ricoh type 6000 paper, and the degree of thin line bleeding was compared with a step sample. The rank becomes better in the order of ×, Δ, ○, ◎. This was performed by overlapping four colors. × indicates a state in which fine lines are very bleeding and is a problem as an image, Δ indicates a state in which fine lines are bleeding and is a problem as an image, and ○ indicates a state in which fine lines are slightly bleeding but is within an allowable range as an image (conventionally.並 indicates that there is no problem with no fine line bleeding.
[0216]
8) Background dirt
After running 30,000 sheets of the image chart of the 50% image area in the monochromatic mode, the blank image is stopped during the development, the developer on the photoconductor after the development is transferred to the tape, and the image density of the untransferred tape is transferred. (ΔID) was measured with a 938 spectrodensitometer (manufactured by X-Rite). The smaller the difference between the image densities, the better the background stain, and the rank improves in the order of ×, Δ, ○, ◎. In the ΔID values, x was 0.05 or more, Δ was 0.02 to less than 0.05, ○ was 0.01 to less than 0.02, and ◎ was less than 0.01.
[0219]
9) Image density
After outputting 150,000 sheets of an image chart having a 50% image area in the monochromatic mode, a solid image was output on Ricoh 6000 paper, and the image density was measured by X-Rite (X-Rite). This was performed independently for four colors, and the average was determined. When this value is less than 1.2, it is ×, when it is 1.2 or more and less than 1.4, it is Δ, when it is 1.4 or more and less than 1.8, or when it is 1.8 or more and less than 2.2. ◎
[0218]
10) Heat resistant storage
10 g of each color toner was weighed, placed in a 20 ml glass container, and the glass bottle was tapped 100 times, then left in a constant temperature bath set at 55 ° C. for 24 hours, and the penetration was measured with a penetration meter. ◎: 20 mm or more, ：: 15 mm or more and less than 20 mm, Δ: 10 mm or more to less than 15 mm, and X: less than 10 mm.
[0219]
11) Transparency
After outputting 100,000 sheets of an image chart having a 50% image area in the single color mode, an image density of 1.0 mg / cm is printed on a RDX type DX OHP sheet in a single color.²Fixing temperature: 140 ° C., and measured by a haze computer HGM-2DP type manufactured by Suga Test Instruments Co., Ltd. ◎, △, Δ, and × were given in order of good transparency. In the haze value, x is 50 or more. Δ is less than 35 to 50.は is less than 20-35. ◎ is less than 20.
[0220]
12) Color vividness and color reproducibility
After running 100,000 sheets of an image chart with a 50% image area in the single color mode, the image output on Ricoh 6000 paper was visually evaluated for color vividness and color reproducibility. ◎, △, Δ, × were given in the order of goodness. ×: Color is dull and unacceptable. △ is a degree slightly inferior to the conventional electrophotographic image quality. ○ indicates the same level as the conventional electrophotographic image quality, and ◎ indicates the same level as the offset printing.
[0221]
13) Gloss
After running 100,000 sheets of an image chart with a 50% image area in the single-color mode, the image output on Ricoh 6000 paper was projected using a gloss meter (VG-1D) (Nippon Denshoku). The light angle and the light receiving angle were adjusted to 60 °, respectively, and the S and S / 10 switching SW were adjusted to S. After the preparation of 0 and standard setting using a standard plate, measurement was performed.も の: 15 or more, ：: 6 or more and less than 15, Δ: 3 or more to less than 6 and X: less than 3 from those having good glossiness.
[0222]
14) High temperature and high humidity environment charging stability
In an environment of a temperature of 40 ° C. and a humidity of 90%, while running 100,000 image charts having a 7% image area in the monochromatic mode, a developer is partially sampled every 1000 sheets and the charge amount is measured by a blow-off method. Measurement was made to evaluate the charging stability. ◎, △, Δ, and × were given in the order of decreasing charge reduction and good order. × indicates that the change in the charge amount is large and is 20 μc / g or more, Δ indicates 15 to less than 20 μc / g, ○ indicates 10 to less than 15 μc / g, and ◎ indicates less than 10 μc / g.
[0223]
15) Low temperature and low humidity environment charging stability
In an environment of a temperature of 10 ° C. and a humidity of 15%, while a running output of 100,000 image charts having a 7% image area is performed in the monochrome mode, a part of the developer is sampled every 1000 sheets and the charge amount is measured by a blow-off method. Measurement was made to evaluate the charging stability. ◎, △, Δ, and × were given in the order of decreasing charge reduction and good order. × indicates that the change in the charge amount is large and is 20 μc / g or more, Δ indicates 15 to less than 20 μc / g, ○ indicates 10 to less than 15 μc / g, and ◎ indicates less than 10 μc / g.
[0224]
16) Fixing property
The fixing lower limit temperature and the fixing upper limit temperature of the toner are sufficiently within the fixing temperature range, hot offset and cold offset do not occur, wrapping, paper jam, etc., and transport troubles are less likely to occur. , Δ, and × were evaluated for overall fixability. X is 160 ° C. or more, which is a particularly essential fixing minimum temperature. △ was less than 145 to 160 ° C, ○ was 130 to less than 140 ° C, and ◎ was 100 to less than 130 ° C.
[0225]
(Evaluation of two-component developer)
When an image is evaluated using a two-component developer, a ferrite carrier having an average particle size of 50 μm coated with a silicone resin at an average thickness of 0.3 μm is used as follows, and a toner 5 of each color is used for 100 parts by weight of the carrier. The parts by weight were uniformly mixed and charged using a turbuler mixer of a type in which the container was rolled and stirred to prepare a developer.
[0226]
(Manufacture of carrier)
・ Core material
Cu-Zn ferrite particles (weight average diameter: 35 μm) 5000 parts
・ Coating material
Toluene 450 parts
Silicone resin SR2400 (made by Dow Corning Toray Silicone, non-volatile
50%) 450 copies
Aminosilane SH6020 (Dow Corning Toray Silicone) 10 parts
Carbon black 10 parts
The coating material is dispersed by a stirrer for 10 minutes to prepare a coating solution, and the coating solution and the core material are applied to a coating apparatus for performing coating while forming a swirling flow provided with a rotating bottom plate disk and a stirring blade in a fluidized bed. Then, the coating solution was applied onto the core material. The obtained coating was fired in an electric furnace at 250 ° C. for 2 hours to obtain the carrier.
[0227]
Example 1
(Oxide fine particles 1)
Distilled and purified methyltrimethoxysilane was heated, nitrogen gas was bubbled into the trimethylsilane, and methyltrimethoxysilane was introduced into an oxyhydrogen flame burner by flowing a stream of nitrogen gas into the oxyhydrogen flame burner to be decomposed in the oxyhydrogen flame. At this time, the addition amount of methyltrimethoxysilane was 1270 g / hr, and the addition amount of oxygen gas was 2.9 Nm.³/ Hr, the amount of hydrogen gas added is 2.1 Nm³/ Hr, nitrogen gas addition amount is 0.58 Nm³/ Hr, and the resulting spherical silica fine powder was collected by a bag filter. 1 kg of this spherical silica fine powder was charged into a 5 liter planetary mixer, 10 g of pure water was added with stirring, and the mixture was sealed and further stirred at 55 ° C. for 14 hours. Next, after cooling to room temperature, 20 g of hexamethyldisilazane was added with stirring, and the mixture was stirred and further stirred for 24 hours. The temperature was raised to 115 ° C., and the remaining raw material and the generated ammonia were removed while passing nitrogen gas through, to thereby obtain oxide fine particles 1. The primary particle diameter and circularity of the obtained oxide fine particles are SF1 and SF2, and the uniformity of the elemental composition is shown in Table 2.
[0228]
(Oxide fine particles 2)
In the oxide fine particles 1, the addition amount of methyltrimethoxysilane was 880 g / hr, and the addition amount of oxygen gas was 2.3 Nm.³/ Hr, the amount of hydrogen gas added is 1.8 Nm³/ Hr, and the same as oxide fine particle 1 except that oxide fine particles having a primary particle diameter, a standard deviation, a circularity, and a uniform element composition as shown in Table 2 were obtained as shown in Table 2. It was manufactured.
(Oxide fine particles 3)
In the oxide fine particles 1, the addition amount of methyltrimethoxysilane was 1430 g / hr, and the addition amount of oxygen gas was 3.1 Nm.³/ Hr, the amount of hydrogen gas added is 2.3 Nm³/ Hr, and the same as oxide fine particle 1 except that oxide fine particles having a primary particle diameter, a standard deviation, a circularity, and a uniform element composition as shown in Table 2 were obtained as shown in Table 2. It was manufactured.
(Oxide fine particles 4)
In the oxide fine particles 1, the addition amount of methyltrimethoxysilane was 1520 g / hr, and the addition amount of oxygen gas was 3.4 Nm.³/ Hr, the amount of hydrogen gas added is 2.5 Nm³/ Hr, and the same as oxide fine particle 1 except that oxide fine particles having a primary particle diameter, a standard deviation, a circularity, and a uniform element composition as shown in Table 2 were obtained as shown in Table 2. It was manufactured.
[0229]
(Oxide fine particles 5)
Distilled and purified methyltrimethoxysilane is heated, nitrogen gas is bubbled into the trimethylsilane, and methyltrimethoxysilane and titanium (Ti) metal particles are introduced into the oxyhydrogen flame burner by flowing a stream of nitrogen gas into the oxyhydrogen flame burner. Combustion decomposition in. At this time, the addition amount of methyltrimethoxysilane was 1270 g / hr, the titanium metal particle was 127 g / hr, and the addition amount of oxygen gas was 2.9 Nm.³/ Hr, the amount of hydrogen gas added is 2.1 Nm³/ Hr, nitrogen gas addition amount is 0.58 Nm³/ Hr, and the generated spherical Ti-containing silica fine powder was collected by a bag filter. 1 kg of this spherical silica fine powder was charged into a 5 liter planetary mixer, 10 g of pure water was added with stirring, and the mixture was sealed and further stirred at 55 ° C. for 14 hours. Next, after cooling to room temperature, 20 g of hexamethyldisilazane was added with stirring, and the mixture was stirred and further stirred for 24 hours. The temperature was raised to 115 ° C., and the remaining raw material and the generated ammonia were removed while passing nitrogen gas through, to thereby obtain oxide fine particles 1. Table 2 shows the primary particle diameter, circularity SF1, SF2, and uniformity of the elemental composition of the obtained oxide fine particles.
[0230]
(Oxide fine particles 6)
The oxide fine particles 5 were produced in the same manner as the oxide fine particles 1 except that zinc was used instead of titanium. Table 2 shows the primary particle diameter, circularity SF1, SF2, and uniformity of the elemental composition of the obtained oxide fine particles.
[0231]
(Oxide fine particles 7)
In the oxide fine particles 1, after manufacturing the oxide fine particles, 100 g of the oxide fine particles were dispersed in 400 g of toluene, and 5 g of dimethyl silicone oil having a viscosity of 300 cs was added and mixed. The toluene was removed by heating to obtain oxide fine particles 7. Table 2 shows the primary particle diameter, circularity SF1, SF2, and uniformity of the elemental composition of the obtained oxide fine particles. The release rate of silicone oil from the oxide fine particles was 75%.
[0232]
(Oxide fine particles 8)
Distilled and purified methyltrimethoxysilane was heated, nitrogen gas was bubbled into the trimethylsilane, and methyltrimethoxysilane was introduced into an oxyhydrogen flame burner by flowing a stream of nitrogen gas into the oxyhydrogen flame burner to be decomposed in the oxyhydrogen flame. At this time, the addition amount of methyltrimethoxysilane was 980 g / hr, and the addition amount of oxygen gas was 3.3 Nm.³/ Hr, the amount of hydrogen gas added is 5.0 Nm³/ Hr, nitrogen gas addition amount is 1.23 Nm³/ Hr, and the resulting spherical silica fine powder was collected by a bag filter. 1 kg of this spherical silica fine powder was charged into a 5 liter planetary mixer, 10 g of pure water was added with stirring, and the mixture was sealed and further stirred at 55 ° C. for 14 hours. Next, after cooling to room temperature, 20 g of hexamethyldisilazane was added with stirring, and the mixture was stirred and further stirred for 24 hours. The temperature was raised to 115 ° C., and the residual raw material and the generated ammonia were removed while passing a nitrogen gas through to obtain oxide fine particles 8. The primary particle diameter and circularity of the obtained oxide fine particles are SF1 and SF2, and the uniformity of the elemental composition is shown in Table 2.
[0233]
(Oxide fine particles 9)
The silicon tetrachloride is flame-hydrolyzed in an oxyhydrogen flame to form silica fine particles, which are deposited on a heat-resistant carrier and melted at the same time as silica fine particles. Oxide fine particles 9 were obtained. The primary particle diameter and circularity of the obtained oxide fine particles are SF1 and SF2, and the uniformity of the elemental composition is shown in Table 2.
[0234]
(Oxide fine particles 10)
The alkoxysilane was hydrolyzed in an alcohol (ethanol) solvent in the presence of an acidic catalyst to synthesize a silica sol, which was gelled, dried, calcined, and sintered to obtain oxide fine particles 10. The primary particle diameter and circularity of the obtained oxide fine particles are SF1 and SF2, and the uniformity of the elemental composition is shown in Table 2.
[0235]
(Oxide fine particles 11)
Distilled and purified methyltrimethoxysilane was heated, nitrogen gas was bubbled into the trimethylsilane, and methyltrimethoxysilane was introduced into an oxyhydrogen flame burner by flowing a stream of nitrogen gas into the oxyhydrogen flame burner to be decomposed in the oxyhydrogen flame. At this time, the addition amount of methyltrimethoxysilane was 1270 g / hr, and the addition amount of oxygen gas was 1.1 Nm.³/ Hr, the amount of hydrogen gas added is 0.9 Nm³/ Hr, the amount of nitrogen gas added is 1.2 Nm³/ Hr, and the generated silica fine powder was collected by a bag filter. 1 kg of this silica fine powder was charged into a 5 liter planetary mixer, and 10 g of pure water was added with stirring. After sealing, the mixture was further stirred at 55 ° C. for 1 hour. Next, after cooling to room temperature, 20 g of hexamethyldisilazane was added with stirring, and the mixture was stirred and further stirred for 8 hours. The temperature was raised to 115 ° C., and the residual raw material and the generated ammonia were removed while passing nitrogen gas through, to thereby obtain oxide fine particles 1. The primary particle diameter and circularity of the obtained oxide fine particles are SF1 and SF2, and the uniformity of the elemental composition is shown in Table 2.
[0236]
(Polyol resin 1)
In a separable flask equipped with a stirrer, thermometer, N2 inlet, and condenser, 378.4 g of low-molecular bisphenol A type epoxy resin (number average molecular weight: about 360) and high molecular bisphenol A type epoxy resin (number average molecular weight: about 2700) 86.0 g, diglycidylated bisphenol A-type propylene oxide adduct [n + m in the general formula (1): about 2.1] 191.0 g, bisphenol F 274.5 g, p-cumylphenol 70.1 g, xylene 200 g were added. N₂The temperature was raised to 70 to 100 ° C under an atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C, water was added under reduced pressure, and water and xylene were bubbled by bubbling water and xylene. The polar solvent-soluble component was removed, and polymerization was carried out at a reaction temperature of 180 ° C. for 6 to 9 hours. Mn; 3800, Mw / Mn; 3.9, Mp; 5000, softening point 109 ° C., Tg 58 ° C., epoxy equivalent 1000 g of a polyol resin of 20,000 or more was obtained (polyol resin 1). In the polymerization reaction, the reaction conditions were controlled so that no monomer component remained. The polyoxyalkylene part of the main chain was confirmed by NMR.
[0237]
(Manufacture of toner)
Black toner
Water 1000 copies
Phthalocyanine green water-containing cake (solid content 30%) ¥ 200 parts
Carbon black (MA60, manufactured by Mitsubishi Chemical Corporation) 540 parts
Polyol resin 1 1200 parts
The above raw materials were mixed with a Henschel mixer to obtain a mixture in which water was permeated into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., cooled by rolling, and pulverized with a pulperizer to obtain a master batch pigment.
[0238]

After mixing the above materials with a mixer, the mixture was melt-kneaded three times or more with a two-roll mill, and the kneaded product was rolled and cooled. After that, an impingement plate type pulverizer (type I mill; manufactured by Nippon Pneumatic Industries, Ltd.) using a jet mill and a wind classification using a swirling flow (DS classifier; manufactured by Nippon Pneumatics, Inc.) were performed, and the volume average particle size was 5.5 μm. To obtain black colored particles. Further, 3.0 wt% of the oxide fine particles 1 and 1.0 wt% of hydrophobic silica (HDK @ H2000, Clariant Japan) having a primary particle diameter of 10 nm were added, mixed with a Henschel mixer, and passed through a sieve having an opening of 50 μm to aggregate. The black toner 1 was obtained by removing the matter. The dispersion diameter of the wax in the toner was 0.5 μm.
[0239]

The above raw materials were mixed with a Henschel mixer to obtain a mixture in which water was permeated into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., cooled by rolling, and pulverized with a pulperizer to obtain a master batch pigment.
[0240]

After mixing the above materials with a mixer, the mixture was melt-kneaded three or more times with a two-roll mill, and the kneaded product was rolled and cooled. After that, an impingement plate type pulverizer (type I mill; manufactured by Nippon Pneumatic Industries, Ltd.) using a jet mill and a wind classification using a swirling flow (DS classifier; manufactured by Nippon Pneumatics, Inc.) were performed, and the volume average particle size was 5.5 μm. To obtain yellow colored particles. Further, 3.0 wt% of the oxide fine particles 1 and 1.0 wt% of hydrophobic silica (HDK @ H2000, Clariant Japan) having a primary particle diameter of 10 nm were added, mixed with a Henschel mixer, and passed through a sieve having an opening of 50 μm to aggregate. The yellow toner 1 was obtained by removing the substance. The dispersion diameter of the wax in the toner was 0.5 μm.
[0241]

The above raw materials were mixed with a Henschel mixer to obtain a mixture in which water was permeated into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., cooled by rolling, and pulverized with a pulperizer to obtain a master batch pigment.
[0242]

After mixing the above materials with a mixer, the mixture was melt-kneaded three or more times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, an impingement plate type pulverizer (type I mill; manufactured by Nippon Pneumatic Industries, Ltd.) using a jet mill and a wind classifier (DS classifier; manufactured by Nippon Pneumatics Co., Ltd.) using a swirling flow were used to obtain a volume average particle size of 5.5 μm. Magenta colored particles were obtained. Further, 3.0 wt% of the oxide fine particles 1 and 1.0 wt% of hydrophobic silica (HDK @ H2000, Clariant Japan) having a primary particle diameter of 10 nm were added, mixed with a Henschel mixer, and passed through a sieve having an opening of 50 μm to aggregate. Magenta toner 1 was obtained by removing the material. The dispersion diameter of the wax in the toner was 0.5 μm.
[0243]

The above raw materials were mixed with a Henschel mixer to obtain a mixture in which water was permeated into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., cooled by rolling, and pulverized with a pulperizer to obtain a master batch pigment.
[0244]

After mixing the above materials with a mixer, the mixture was melt-kneaded three or more times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, an impingement plate type pulverizer (type I mill; manufactured by Nippon Pneumatic Industries, Ltd.) using a jet mill and a wind classifier (DS classifier; manufactured by Nippon Pneumatics Co., Ltd.) using a swirling flow were used to obtain a volume average particle size of 5.5 μm. Of cyan colored particles were obtained. Further, 3.0 wt% of the oxide fine particles 1 and 1.0 wt% of hydrophobic silica (HDK @ H2000, Clariant Japan) having a primary particle diameter of 10 nm were added, mixed with a Henschel mixer, and passed through a sieve having an opening of 50 μm to aggregate. Magenta toner 1 was obtained by removing the material. The dispersion diameter of the wax in the toner was 0.5 μm.
[0245]
Examples 2 to 7
In Example 1, a toner and a developer were prepared and evaluated in the same manner as in Example 1 except that oxide fine particles 2 to 7 shown in Table 2 were used.
[0246]
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 The temperature was evaluated in the same manner as in Example 1 except that the temperature was changed to 108 ° C.).
[0247]
Example 9
The evaluation was performed in the same manner as in Example 1 except that the evaluation machine B was used.
[0248]
Example 10
Evaluation was performed in the same manner as in Example 1 except that the evaluation machine C was used.
[0249]
Example 11
Evaluation was performed in the same manner as in Example 1 except that the evaluation machine D was used.
[0250]
Example 12
In Example 1, the production and evaluation were performed in the same manner as in Example 1 except that the toner was manufactured without adding the wax and the evaluation machine E was used.
[0251]
Comparative Examples 1-4
In Example 1, a toner and a developer were manufactured and evaluated in the same manner as in Example 1 except that oxide fine particles 8 to 11 in Table 2 were used as the oxide fine particles.
[0252]
Example 13
In Example 1, a toner was manufactured in the same manner as in Example 1 except that the base toner before mixing the additives was manufactured as described below.
[0253]
(Synthesis of organic fine particle emulsion)
683 parts of water, 11 parts of sodium salt of methacrylic acid ethylene oxide adduct sulfate (Eleminor RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid were placed in a reaction vessel equipped with a stirring rod and a thermometer. 110 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred at 3800 rpm for 30 minutes to obtain a white emulsion. The mixture was heated to a temperature in the system of 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and the aqueous solution of the vinyl resin (copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-ethylene methacrylate ethylene oxide adduct) was obtained. A dispersion liquid [fine particle dispersion liquid 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured with a laser diffraction / scattering particle size distribution analyzer (LA-920: manufactured by Horiba, Ltd.) was 110 nm. A part of [fine particle dispersion 1] was dried to isolate a resin component. The resin component had a Tg of 58 ° C. and a weight average molecular weight of 130,000.
[0254]
(Adjustment of aqueous phase)
990 parts of water, 83 parts of [Particle Dispersion 1], 37 parts of a 48.3% aqueous solution of sodium dodecyldiphenyletherdisulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries), and 90 parts of ethyl acetate are mixed and stirred to give a milky white liquid. Got. This is designated as [aqueous phase 1].
[0255]
(Synthesis of low molecular polyester)
In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introducing pipe, 724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid were put, and polycondensed at 230 ° C. under normal pressure for 7 hours, and further 10 to 15 mmHg. For 5 hours to obtain [low molecular weight polyester 1]. [Low-molecular polyester 1] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, a peak molecular weight of 3,800, a Tg of 43 ° C, and an acid value of 4.
[0256]
(Synthesis of intermediate polyester)
In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 682 parts of a 2-mol adduct of bisphenol A ethylene oxide, 81 parts of a 2-mol adduct of bisphenol A propylene oxide, 283 parts of terephthalic acid, and 22 parts of trimellitic anhydride 22 And 2 parts of dibutyltin oxide, and reacted at 230 ° C. for 7 hours under normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [intermediate polyester 1]. [Intermediate polyester 1] had a number average molecular weight of 2,200, a weight average molecular weight of 9,700, a peak molecular weight of 3,000, a Tg of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.
Next, 410 parts of [intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate were placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. The free isocyanate weight% of [Prepolymer 1] was 1.53%.
[0257]
(Synthesis of ketimine)
170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stir bar and a thermometer, and reacted at 50 ° C. for 4.5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.
[0258]
(Synthesis of master batch)
1200 parts of water, 540 parts of carbon black (Printex 35: manufactured by Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], 1200 parts of polyester resin were added, and the mixture was mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Was kneaded at 130 ° C. for 1 hour using two rolls, rolled and cooled, and pulverized with a pulperizer to obtain [Master Batch 1].
[0259]
(Preparation of oil phase)
A container equipped with a stirring rod and a thermometer was charged with 378 parts of [low-molecular polyester 1], 100 parts of carnauba wax, and 947 parts of ethyl acetate, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. And cooled to 30 ° C. for 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged into a container and mixed for 1 hour to obtain [raw material solution 1].
[Material Dissolution 1] 1324 parts was transferred to a container, and a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.) was used to feed the liquid at a speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads at 80% by volume. Filling and dispersion of carbon black and wax were performed under three pass conditions. Next, 1324 parts of a 65% ethyl acetate solution of [low-molecular polyester 1] was added, and two passes were performed with a bead mill under the above conditions to obtain [pigment / wax dispersion 1]. [Pigment / wax dispersion 1] had a solid content of 50%.
[0260]
(Emulsification-Desolvation)
749 parts of [Pigment / Wax Dispersion 1], 115 parts of [Prepolymer 1], and 2.9 parts of [Ketimine Compound 1] are placed in a container, and are mixed with a TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes. After mixing, 1200 parts of [aqueous phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 25 minutes to obtain [emulsified slurry 1].
[Emulsified slurry 1] was charged into a container equipped with a stirrer and a thermometer, the solvent was removed at 30 ° C. for 7 hours, and then ripened at 45 ° C. for 7 hours to obtain [Dispersed slurry 1].
[0261]
(Washing-drying)
[Dispersion Slurry 1] After 100 parts of filtered under reduced pressure
{Circle around (1)} 100 parts of ion-exchanged water were added to the filter cake, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered.
(4): 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered twice to obtain [filter cake 1]. Obtained.
[Filter cake 1] was dried at 45 ° C. for 48 hours with a circulating drier and sieved with a mesh having a mesh size of 75 μm to obtain [Toner base particles 1]. Thereafter, 3.0 wt% of the oxide fine particles 1 and 1.0 wt% of hydrophobic silica (HDK @ H2000, Clariant Japan) having a primary particle diameter of 10 nm were added, mixed with a Henschel mixer, and passed through a sieve with openings of 50 μm to aggregate. The toner was obtained by removing the objects. Table 1 shows the physical properties of the obtained toner, and Table 2 shows the evaluation results.
[0262]
【The invention's effect】
The oxide fine particles containing at least the silicon element described above, wherein the primary particle diameter R of the oxide fine particles is 30 nm to 300 nm, and the standard deviation σ of the particle size distribution of R is R / 4 ≦ σ ≦ R. By using an external additive for an electrophotographic toner having a distribution and having a circularity SF1 of 100 to 130 and a circularity SF2 of 100 to 125 being substantially spherical, the toner can be used in a high temperature and high humidity environment. The external additives do not become buried in the toner even after storage, exhibiting sufficient functions as a fluidizing agent and a charge auxiliary agent, and suppress abnormal increase in chargeability even after storage in a low-temperature and low-humidity environment to achieve stable image quality. It is possible to form a high-quality image with excellent cohesiveness during toner transfer compression, transferability with properly controlled adhesion between toner particles after stress in a developing device, and excellent developability. I found it.
[0263]
Furthermore, the transferability of the toner has been improved, preventing abnormal images such as missing characters in the text area, reducing the amount of waste toner by improving the toner transfer rate, reducing toner consumption, and improving uniformity of solid images by improving toner replenishment. It was possible to achieve a reduction in transfer dust and the like, an improvement in reproducibility of fine lines, a reduction in background fouling due to an improvement in charging environment stability at high temperature, high humidity, and low temperature and low humidity, and prevention of toner scattering. Further, a printed matter having excellent heat-resistant storage stability, excellent color reproducibility, vivid color, gloss, transparency, and fixability was obtained.
[0264]
[Table 1]

[0265]
[Table 2]

[0266]
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram showing an example of an embodiment using a toner and a developer of the present invention.
FIG. 2 is a schematic configuration diagram showing an example of an embodiment using a toner and a developer of the present invention.
FIG. 3 is a schematic configuration diagram showing an example of an embodiment using a toner and a developer of the present invention.
FIG. 4 is a schematic configuration diagram showing an example of an embodiment using a toner and a developer of the present invention.
FIG. 5 is a schematic configuration diagram showing an example of an embodiment using a toner and a developer of the present invention.
FIG. 6 is a schematic configuration diagram showing an example of an embodiment using a toner and a developer of the present invention.
FIG. 7 is a schematic configuration diagram of a process cartridge of the present invention.
[0266]
[Explanation of symbols]
10 photoconductor
20 charging roller
30mm exposure equipment
40mm developing device
41 developing belt
42 development tank
43 mm pumping roller
44 coating roller
45 development unit
50 ° intermediate transfer body
51 suspension 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 (14)

It is composed of oxide fine particles containing at least a silicon element, and the primary particle size R (number average) of the oxide fine particles is 30 nm to 300 nm, and the standard deviation σ of the particle size distribution of R is R / 4 ≦ σ ≦ R. An external additive for an electrophotographic toner, having a distribution and a substantially spherical shape having a circularity SF1 of 100 to 130 and a circularity SF2 of 100 to 125. 2. The external additive for an electrophotographic toner according to claim 1, wherein the oxide fine particles contain at least a silicon element and a metal element. 3. The external additive for an electrophotographic toner according to claim 1, wherein the oxide fine particles contain at least a silicon element and a titanium element. 4. The external additive for an electrophotographic toner according to claim 1, wherein the element composition of the oxide fine particles is uniformly dispersed in the surface portion and the inside. 5. The external additive for an electrophotographic toner according to claim 1, wherein said oxide fine particles are surface-treated with at least an organosilicon compound. In the claims 1~5, ^R ₁ 3 _{SiO 1/2} units oxide particles on the surface (where, ^{R 1} is a monovalent hydrocarbon group having 1 to 8 carbon atoms of the same or different) hydrophobized oxide obtained by introducing An external additive for an electrophotographic toner, which is an organic fine particle. 7. The external additive for an electrophotographic toner according to claim 1, wherein the oxide fine particles are surface-treated with at least silicone oil, and a release rate of the silicone oil is 10 to 95%. 8. An electrophotographic toner having a volume average particle diameter of at least 2 to 7 μm comprising at least a binder resin and a colorant, wherein at least the electrophotographic toner external additive according to claim 1 is mixed with the toner. A toner for electrophotography, comprising: 8. An electrophotographic apparatus comprising: an electrophotographic toner external additive according to claim 1; and one or more external additives having an average primary particle size smaller than the toner. For toner. The electrophotographic toner according to claim 8, wherein the binder resin of the toner contains at least a polyol resin. The electrophotographic toner according to any one of claims 8 and 9, wherein the binder resin of the toner contains at least a polyester resin. A two-component developer containing at least a carrier comprising the toner according to any one of claims 8 to 11 and magnetic particles. 13. A process cartridge which integrally supports a photosensitive member and at least one unit selected from a developing unit, a charging unit, and a cleaning unit and is detachable from an image forming apparatus main body, wherein the developing unit is any one of claims 1 to 12. A process cartridge holding the toner or the developer according to claim 1. An image forming method using the toner or the developer according to claim 8.

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