JP3762131B2 - Image forming method and image forming apparatus - Google Patents

Description

を介して結合するものである。
【００７３】
本発明のトナーに含有される結着樹脂は、ビニル系重合体ユニット中の全カルボン酸エステルのポリエステルユニットとの反応率、すなわちグラフト化率がビニル系重合体に含有される（メタ）アクリル酸エステルを基準にして、好ましくは１０乃至６０モル％、より好ましくは１５乃至５５モル％、更に好ましくは２０乃至５０モル％含有することが良い。グラフト化率が１０モル％未満となる場合にはビニル系重合体ユニットとポリエステルユニットの相溶性が悪化し、ワックスの分散性も悪化することがあり好ましくなく、６０モル％超となる場合には相対的に分子量の大きな成分が増大する結果トナーの低温定着性が悪化する場合があり好ましくない。
【００７４】
酢酸エチルに不溶な成分（Ｗ４）は、ポリエステル樹脂成分（Ｇｐ）を４０乃至９８重量％含有していることが良く、好ましくは５０乃至９５重量％、更に好ましくは６０乃至９０重量％含有していることが良い。ポリエステル樹脂成分（Ｇｐ）含有量が４０重量％未満となる場合には、トナーの定着性が悪化する可能性があり好ましくなく、９８重量％超となる場合には、炭化水素系ワックスとの相溶性が悪くなりやすく好ましくない。
【００７５】
酢酸エチルに溶解する成分（Ｗ３）は、ポリエステル樹脂成分（Ｓｐ）を２０乃至９０重量％含有していることが良く、好ましくは２５乃至８５重量％、更に好ましくは３０乃至８０重量％含有していることが良い。ポリエステル樹脂成分（Ｓｐ）の含有量が２０重量％未満となる場合には、炭化水素系ワックスがトナーに含有される結着樹脂全体で均一に分散されるために定着性が改良されず、９０重量％超となる場合には、炭化水素系ワックスとの相溶性が悪くなりやすく局在化が生じ、ホットオフセットが発生しやすくない。
【００７６】
比（Ｓｐ／Ｇｐ）は、０．５０乃至１．００であることが良く、好ましくは０．６０乃至０．９５、更に好ましくは０．６５乃至０．９０であることが良い。比（Ｓｐ／Ｇｐ）が０．５未満となる場合、及び比（Ｓｐ／Ｇｐ）が１．００超となる場合には、いずれも酢酸エチルに不溶な成分と溶解する成分とが均一に混合されず、トナーの現像性が悪化する場合があり好ましくない。
【００７７】
本発明においては、トナーの結着樹脂全体の酸価（ＡＶ１）は、７〜４０ｍｇＫＯＨ／ｇであればよいが、好ましくは１０〜３７ｍｇＫＯＨ／ｇ、より好ましくは１５〜３５ｍｇＫＯＨ／ｇ、さらに好ましくは１７〜３０ｍｇＫＯＨ／ｇであることが良い。
【００７８】
さらに、トナーの酢酸エチル可溶分（Ｗ３）の酸価（ＡＶ２）は、１０〜４５ｍｇＫＯＨ／ｇであればよいが、好ましくは１５〜４５ｍｇＫＯＨ／ｇ、より好ましくは１７〜４０ｍｇＫＯＨ／ｇ、さらに好ましくは２０〜３５ｍｇＫＯＨ／ｇであることが良い。
【００７９】
このトナーの結着樹脂全体の酸価（ＡＶ１）とトナーの酢酸エチル可溶分（Ｗ３）の酸価（ＡＶ２）との比（ＡＶ１／ＡＶ２）は、好ましくは０．７〜２．０、より好ましくは０．９〜１．７、さらに好ましくは１．０〜１．５であることが良い。
【００８０】
トナーの結着樹脂全体の酸価（ＡＶ１）が７ｍｇＫＯＨ／ｇ未満の場合及び４０ｍｇＫＯＨ／ｇを超える場合、ともに耐久によって画像濃度が低下する場合があり好ましくない。
【００８１】
トナーの酢酸エチル可溶分（Ｗ３）の酸価（ＡＶ２）が、１０ｍｇＫＯＨ／ｇ未満の場合にはトナーの耐高温オフセット性が損なわれる場合があり好ましくなく、４５ｍｇＫＯＨ／ｇを超える場合にはトナーの低温定着性が損なわれる場合があり好ましくない。
【００８２】
ＡＶ１／ＡＶ２の値が０．７未満の場合には耐久による画像濃度が低下する場合があり好ましくなく、２．０を超える場合にはトナーの耐高温オフセット性が損なわれる場合があり好ましくない。
【００８３】
本発明のトナーにおいて、ポリエステルユニットは、好ましくは、式（１）乃至（４）で表わせる２価のカルボン酸、式（５）で表せる１価のカルボン酸または式（６）で表わせる１価のアルコールの少なくとも１種以上を含有するものである。
【００８４】
【化４】

［式中、Ｒ₁は炭素数１４以上の直鎖、分岐または環状のアルキル基、アルケニル基を表わし、Ｒ₃，Ｒ₄，Ｒ₅及びＲ₆は水素原子、炭素数３以上の直鎖、分岐または環状のアルキル基、アルケニル基を表わし、同一の置換基であってもよいが、同時に水素原子になることはなく、Ｒ₇及びＲ₈は炭素数１２以上の直鎖、分岐または環状のアルキル基、アルケニル基を表わし、ｎは１２乃至４０の整数を表わす。］
【００８５】
式（１）で表わせる化合物としては、例えば、下記化合物（１−１）〜（１−６）が挙げられる。
【００８６】
【化５】

【００８７】
式（２）で表わせる化合物としては、例えば、下記化合物（２−１）〜（２−４）が挙げられる。
【００８８】
【化６】

【００８９】
式（３）で表わせる化合物としては、例えば、下記化合物（３−１）〜（３−３）が挙げられる。
【００９０】
【化７】

【００９１】
式（４）で表わせる化合物としては、例えば、下記化合物（４−１）〜（４−２）が挙げられる。
【００９２】
【化８】

【００９３】
式（５）で表わせる化合物としては、例えば、下記化合物（５−１）〜（５−５）が挙げられる。
【００９４】
【化９】

【００９５】
式（６）で表わせる化合物としては、例えば、下記化合物（６−１）〜（６−５）が挙げられる。
【００９６】
【化１０】

【００９７】
更に、本発明者らは、高温高湿下におけるクリーニング不良、トナー融着及び画像流れに関して検討を続け、以下のことを見出した。
【００９８】
感光体上の残余トナー及び生成又は付着した紙粉、オゾン付加物等をクリーニングする方法としては、磁気ブラシによる静電吸着法、クリーニングブレードによるかき落とし法等が考えられている。
【００９９】
しかし、磁気ブラシ法においては、残余トナーのクリーニングに対しては有効であるが、感光体上に生成又は付着した紙粉、オゾン付加物等をクリーニングする方法としては問題がある。また、クリーニングブレードによるかき落とし法においては、使用されるブレードの材質、感光体に対する当接方法により、得られる効果が違ってくる。
【０１００】
固いブレードを感光体へ当接させ、感光体上の残余トナー及び生成又は付着した紙粉、オゾン付加物等をクリーニングする場合、感光体とブレードとの密着性が得られにくく、すり抜け等によるクリーニング不良が発生しやすい。また、この現象を回避する目的で感光体への当接圧力を強くした場合には、感光体削れや感光体上へのトナー融着等の問題が発生する。
【０１０１】
逆に柔らかいブレードを感光体へ当接させ、感光体上の残余トナー及び生成又は付着した紙粉、オゾン付加物等をクリーニングする場合、感光体とブレードとの密着性は高まるが、ブレード捲れや感光体の回転時振動の影響によるびびり等から発生するクリーニング不良が発生する。また、この現象を回避する目的で感光体への当接圧力を弱くした場合には、本来の目的である感光体上の残余トナー及び生成又は付着した紙粉、オゾン付加物等をクリーニングする上で問題が発生する。
【０１０２】
更に、クリーニング性と研磨性を両立させる目的で、クリーニングブレードと磁気ブラシを併用する方法等も考えられているが、複写機自体の軽量、コンパクト化に対応できない点及び設定の自由度が狭くなる点等の問題がある。
【０１０３】
また、上記のブレードの材質に対して、常温常湿における反発弾性を規定すること及び有機感光体表面層に無機微粉末を含有させて面粗さを規定し、感光体に対してブレードをカウンターで当接させ、かつブレード自体を振動させてクリーニングを行う方法も考えられているが、感光体上の残余トナーのクリーニングには有効であっても、高温高湿下において生成又は付着した紙粉、オゾン付加物等をクリーニングする場合には問題がある。
【０１０４】
更に、クリーニング助剤として研磨効果を持った第三成分をトナーに添加する方法では、感光体上の生成又は付着した紙粉、オゾン付加物等をクリーニングする効果はあるが、感光体削れと現像性及びクリーニング性を全て満足するものでは無い。
【０１０５】
そこで、本発明者らは、特に高温高湿下におけるトナーの現像性、クリーニング性を考え、前記クリーニングにおける問題を詳細に検討した結果、特に高速複写機において、クリーニングブレードの粘弾性特性とトナーの粘弾性特性には密接な関係が存在することを見出した。更に、本条件を満たすブレードとトナーにおいて、そのトナーに無機微粉体として複合酸化物を用いることが、いっそう本効果を高めることを見出した。
【０１０６】
感光体に当接するクリーニングブレードは、連続複写中は感光体との摩擦により昇温する。この現象は複写機が設置される環境により、更に顕著となる。つまり、高温高湿下での昇温が非常に厳しいものとなり、高速複写機においては、感光体に当接しているブレード温度は４０〜７０℃にもなる。
【０１０７】
そこで、本発明者らは、種々のトナー、ブレードに関し、温度依存特性としての粘弾性特性を測定し、これらの組み合わせにおける、高温高湿下での現像性及び画像流れ、感光体削れに着目して検討を行い、以下のことを見出した。
【０１０８】
現像剤が下記式（１）で示される無機微粉体である複合酸化物（Ａ）粒子を有することにより、感光体上からの紙粉及びオゾン付加物に対する研磨性は向上する。
【０１０９】
［Ｍ₁］_a［Ｍ₂］_bＯ_c （１）
（式中、Ｍ₁はＳｒ，Ｍｇ，Ｚｎ，Ｃｏ，Ｍｎ，Ｃａ及びＣｅからなるグループから選択される金属元素を示し、Ｍ₂はＴｉ又はＳｉから選択される金属元素を示し、ａは１〜９の整数を示し、ｂは１〜９の整数を示し、ｃは３〜９の整数を示す。）
【０１１０】
また、トナーの現像器内ブロッキング、感光体への融着等に関しては、トナーとブレードとの粘弾特性を以下の範囲とすることにより防止することができる。
【０１１１】
トナーが温度５０乃至７５℃において、
ａ）貯蔵弾性率（Ｇ’Ｔ）と損失弾性率（Ｇ”Ｔ）とが等しくなる温度（ＴＴ．Ｃ）が存在し、
ｂ）損失正接（ｔａｎδＴ．Ｐ）が極大となる温度（ＴＴ．Ｐ）が存在し、
該クリーニングブレードが、
ｃ）温度４０乃至８０℃で、貯蔵弾性率（Ｇ’Ｂ）が、５×１０⁵乃至１×１０⁷Ｐａであり、
ｄ）温度４０乃至８０℃で、損失弾性率（Ｇ”Ｂ）が、５×１０³乃至１×１０⁶Ｐａであり、
ｅ）温度４０乃至８０℃で、損失正接（ｔａｎδＢ．Ｐ）が極小となる温度（ＴＴ．Ｂ）が存在し、
ｆ）温度７０乃至１３０℃に、損失正接（ｔａｎδＢ．Ｐ）が極大となる温度（ＴＢ．Ｐ）が存在し、
該トナー及び該クリーニングブレードの損失正接において、
ｇ）差（ＴＴ．Ｐ−ＴＢ．Ｐ）が、−４０乃至２０℃であり、
ｈ）温度（ＴＴ．Ｃ）におけるクリーニングブレードの損失弾性率（Ｇ”Ｂ．Ｃ）の比（Ｇ”Ｔ／Ｇ”Ｂ．Ｃ）が５×１０²乃至５×１０⁴である。
【０１１２】
なお、１Ｐａ＝１０ｄｙｎ／ｃｍ²である。
【０１１３】
以上のことから、特に高速複写機を用いて高温高湿環境下で連続複写を行う場合においても、高画質、高画像濃度を維持し、感光体上の残余トナー及び感光体上に生成又は付着する紙粉やオゾン付加物を取り除くことで、クリーニング不良、画像流れ等の発生を防止するためには、トナーとブレードとの粘弾特性を規定することが重要であり、更に好ましくは結着樹脂としてハイブリッド樹脂を含有させ、トナーとブレードとの粘弾特性を規定したトナーに対して、前述の式（１）で示される複合酸化物を使用することが重要である。
【０１１４】
本発明のトナーにおいて、温度５０乃至７５℃に貯蔵弾性率（Ｇ’Ｔ）と損失弾性率（Ｇ’）が等しくなる温度（Ｔ．ＴＣ）が存在し、損失正接（ｔａｎδＴ．Ｐ）が極大となる温度（Ｔ．ＴＰ）が存在するものであるが、好ましくは、温度５３乃至７３℃にＴ．ＴＣ及びＴ．ＴＰが存在する場合であり、更に好ましくは温度５５乃至７０℃にＴ．ＴＣ及びＴ．ＴＰが存在する場合である。
【０１１５】
もし、温度５０℃未満にＴ．ＴＣ及びＴ．ＴＰが存在すると、クリーニングブレードの粘弾性的性質によらずトナーがクリーニング時に電子写真感光体上に固着するドラム融着と呼ばれる現象が起きる場合があり好ましくない。温度７５℃超にＴ．ＴＣ及びＴ．ＴＰが存在すると、クリーニングブレードの粘弾性的性質によらずトナーがクリーニング時に電子写真感光体表面に大きな傷を形成する場合があり好ましくない。
【０１１６】
本発明において、クリーニングブレードは温度４０乃至８０℃で、貯蔵弾性率（Ｇ’Ｂ）は５×１０⁵乃至１×１０⁷Ｐａであればよいが、好ましくは７×１０⁵乃至７×１０⁶Ｐａとなる場合であり、更に好ましくは１×１０⁶乃至５×１０⁶Ｐａとなる場合である。もし、Ｇ’Ｂが５×１０⁵Ｐａ未満となる場合には、トナーの粘弾性的性質によらずクリーニング時に電子写真感光体上のトナーが完全にクリーニングされないクリーニング不良と呼ばれる現象が起きる場合があり好ましくない。Ｇ’Ｂが１×１０⁷Ｐａ超となる場合には、電子写真感光体表面の摩耗が著しくなるドラム削れと呼ばれる現象が起きる場合があり好ましくない。
【０１１７】
本発明において、クリーニングブレードは温度４０乃至８０℃で、損失弾性率（Ｇ”Ｂ）は５×１０³乃至１×１０⁶Ｐａあればよいが、好ましくは７×１０³乃至７×１０⁵Ｐａとなる場合であり、更に好ましくは１×１０⁴乃至５×１０⁵Ｐａとなる場合である。もし、Ｇ”Ｂが５×１０³Ｐａ未満となる場合には、トナーの粘弾性的性質によらずクリーニング時にドラム融着現象が起きる場合があり好ましくない。Ｇ”Ｂが１×１０⁶Ｐａ超となる場合には、クリーニング不良と呼ばれる現象が起きる場合があり好ましくない。
【０１１８】
本発明において、クリーニングブレードは温度４０乃至８０℃で、損失正接（ｔａｎδＢ．Ｐ）が極小となる温度（ＴＴ．Ｂ）が存在すれば良いが、好ましくは温度４２乃至７５℃で損失正接（ｔａｎδＢ．Ｐ）が極小となる温度（ＴＴ．Ｂ）が存在する場合であり、更に好ましくは温度４５乃至７０℃で損失正接（ｔａｎδＢ．Ｐ）が極小となる温度（ＴＴ．Ｂ）が存在する場合である。
【０１１９】
もし、（ｔａｎδＢ．Ｐ）が極小となる温度ＴＴ．Ｂが４０℃未満となる場合には、トナーの粘弾性的性質によらずクリーニング時にドラム融着が起きる場合があり好ましくない。（ｔａｎδＢ．Ｐ）が極小となる温度ＴＴ．Ｂが８０℃超となる場合には、ドラム削れが起きる場合があり好ましくない。
【０１２０】
本発明において、クリーニングブレードは温度７０乃至１３０℃で、損失正接（ｔａｎδＢ．Ｐ）が極大となる温度（ＴＢ．Ｐ）が存在すれば良いが、好ましくはＴＢ．Ｐが温度７５乃至１２０℃となる場合であり、更に好ましくはＴＢ．Ｐが温度８０乃至１１０℃となる場合である。
【０１２１】
もし、温度ＴＢ．Ｐが７０℃未満及び温度ＴＢ．Ｐが１３０℃超となる場合には、クリーニング不良が起きる場合があり好ましくない。
【０１２２】
本発明において、差（ＴＴ．Ｐ−ＴＢ．Ｐ）は−４０乃至２０℃であれば良いが、好ましくは−３０乃至１０℃となる場合であり、更に好ましくは−２０乃至５℃となる場合である。
【０１２３】
もし、差（ＴＴ．Ｐ−ＴＢ．Ｐ）が−４０℃未満及び差（ＴＴ．Ｐ−ＴＢ．Ｐ）が２０℃超となる場合には、ドラム上からの十分な除去効果が得られず、ドラム融着、クリーニング不良等が起きる場合があり好ましくない。
【０１２４】
本発明において、温度（ＴＴ．Ｃ）でのトナー及びクリーニングブレードの損失弾性率の比（Ｇ”Ｔ／Ｇ”Ｂ．Ｃ）は５×１０²乃至５×１０⁴Ｐａであれば良いが、好ましくは７×１０²乃至３×１０⁴Ｐａとなる場合であり、更に好ましくは１×１０³乃至１×１０⁴Ｐａとなる場合である。
【０１２５】
もし、比（Ｇ”Ｔ／Ｇ”Ｂ．Ｃ）が５×１０²未満となる場合には、ドラム削れが起きる場合があり好ましくなく、比（Ｇ”Ｔ／Ｇ”Ｂ．Ｃ）が５×１０⁴超となる場合には、ドラム融着が起きる場合があり好ましくない。
【０１２６】
更に本発明において、より好ましいトナーの構成を以下に詳述する。
【０１２７】
本発明に用いられるポリエステル樹脂のモノマーとしては以下のものが挙げられる。
【０１２８】
アルコール成分としては、エチレングリコール、プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、２，３−ブタンジオール、ジエチレングリコール、トリエチレングリコール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、２−エチル１，３−ヘキサンジオール、水素化ビスフェノールＡ、下記（７−１）式で表わされるビスフェノール誘導体及び下記（７−２）式で示されるジオール類が挙げられる。
【０１２９】
【化１１】

【０１３０】
【化１２】

【０１３１】
酸性分としては、フタル酸、イソフタル酸及びテレフタル酸の如き芳香族ジカルボン酸類又はその無水物；こはく酸、アジピン酸、セバシン酸及びアゼライン酸の如きアルキルジカルボン酸類又はその無水物；炭素数６〜１２のアルキル基で置換されたこはく酸もしくはその無水物；フマル酸、マレイン酸及びシトラコン酸の如き不飽和ジカルボン酸類又はその無水物；が挙げられる。
【０１３２】
ビニル系樹脂を生成するためのビニル系モノマーとしては、次のようなものが挙げられる。
【０１３３】
スチレン；ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ｐ−フェニルスチレン、ｐ−エチルスチレン、２，４−ジメチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−デシルスチレン、ｐ−ｎ−ドデシルスチレン、ｐ−メトキシスチレン、ｐ−クロルスチレン、３，４−ジクロルスチレン、ｍ−ニトロスチレン、ｏ−ニトロスチレン、ｐ−ニトロスチレンの如きスチレン及びその誘導体；エチレン、プロピレン、ブチレン、イソブチレンの如きスチレン不飽和モノオレフィン類；ブタジエン、イソプレンの如き不飽和ポリエン類；塩化ビニル、塩化ビニルデン、臭化ビニル、フッ化ビニルの如きハロゲン化ビニル類；酢酸ビニル、プロピオン酸ビニル、ベンゾエ酸ビニルの如きビニルエステル類；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸ｎ−オクチル、メタクリル酸ドデシル、メタクリル酸２−エチルヘキシル、メタクリル酸ステアリル、メタクリル酸フェニル、メタクリル酸ジメチルアミノエチル、メタクリル酸ジエチルアミノエチルの如きα−メチレン脂肪族モノカルボン酸エステル類；アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸ｎ−オクチル、アクリル酸ドデシル、アクリル酸２−エチルヘキシル、アクリル酸ステアリル、アクリル酸２−クロルエチル、アクリル酸フェニルの如きアクリル酸エステル類；ビニルメチルエーテル、ビニルエチルエーテル、ビニルイソブチルエーテルの如きビニルエーテル類；ビニルメチルケトン、ビニルヘキシルケトン、メチルイソプロペニルケトンの如きビニルケトン類；Ｎ−ビニルピロール、Ｎ−ビニルカルバゾール、Ｎ−ビニルインドール、Ｎ−ビニルピロリドンの如きＮ−ビニル化合物；ビニルナフタリン類；アクリロニトリル、メタクリロニトリル、アクリルアミドの如きアクリル酸もしくはメタクリル酸誘導体等が挙げられる。
【０１３４】
さらに、マレイン酸、シトラコン酸、イタコン酸、アルケニルコハク酸、フマル酸、メサコン酸の如き不飽和二塩基酸；マレイン酸無水物、シトラコン酸無水物、イタコン酸無水物、アルケニルコハク酸無水物の如き不飽和二塩基酸無水物；マレイン酸メチルハーフエステル、マレイン酸エチルハーフエステル、マレイン酸ブチルハーフエステル、シトラコン酸メチルハーフエステル、シトラコン酸エチルハーフエステル、シトラコン酸ブチルハーフエステル、イタコン酸メチルハーフエステル、アルケニルコハク酸メチルハーフエステル、フマル酸メチルハーフエステル、メサコン酸メチルハーフエステルの如き不飽和二塩基酸のハーフエステル；ジメチルマレイン酸、ジメチルフマル酸の如き不飽和二塩基酸エステル；アクリル酸、メタクリル酸、クロトン酸、ケイヒ酸の如きα，β−不飽和酸；クロトン酸無水物、ケイヒ酸無水物の如きα，β−不飽和酸無水物、該α，β−不飽和酸と低級脂肪酸との無水物；アルケニルマロン酸、アルケニルグルタル酸、アルケニルアジピン酸、これらの酸無水物及びこれらのモノエステルの如きカルボキシル基を有するモノマーが挙げられる。
【０１３５】
さらに、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレートなどのアクリル酸またはメタクリル酸エステル類；４−（１−ヒドロキシ−１−メチルブチル）スチレン、４−（１−ヒドロキシ−１−メチルヘキシル）スチレンの如きヒドロキシ基を有するモノマーが挙げられる。
【０１３６】
本発明のトナーにおいて、結着樹脂のポリエステルユニットは、三価以上の多価カルボン酸またはその無水物、または、三価以上の多価アルコールで架橋された架橋構造を有しているものである。三価以上の多価カルボン酸またはその無水物としては、例えば、１，２，４−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、１，２，４−ナフタレントリカルボン酸、ピロメリット酸及びこれらの酸無水物または低級アルキルエステル等が挙げられ、三価以上の多価アルコールとしては、例えば、１，２，３−プロパントリオール、トリメチロールプロパン、ヘキサントリオール、ペンタエリスリトール等が挙げられるが、好ましくは１，２，４−ベンゼントリカルボン酸及びその酸無水物である。
【０１３７】
本発明のトナーにおいて、結着樹脂のビニル系重合体ユニットは、ビニル基を２個以上有する架橋剤で架橋された架橋構造を有していてもよいが、この場合に用いられる架橋剤は、芳香族ジビニル化合物として例えば、ジビニルベンゼン、ジビニルナフタレンが挙げられ；アルキル鎖で結ばれたジアクリレート化合物類として例えば、エチレングリコールジアクリレート、１，３−ブチレングリコールジアクリレート、１，４−ブタンジオールジアクリレート、１，５−ペンタンジオールジアクリレート、１，６ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられ；エーテル結合を含むアルキル鎖で結ばれたジアクリレート化合物類としては、例えば、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコール＃４００ジアクリレート、ポリエチレングリコール＃６００ジアクリレート、ジプロピレングリコールジアクリレート及び以上の化合物のアクリレートをメタアクリレートに代えたものが挙げられ；芳香族基及びエーテル結合を含む鎖で結ばれたジアクリレート化合物類として例えば、ポリオキシエチレン（２）−２，２−ビス（４−ヒドロキシフェニル）プロパンジアクリレート、ポリオキシエチレン（４）−２，２−ビス（４−ヒドロキシフェニル）プロパンジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられ；ポリエステル型ジアクリレート類として例えば、商品名ＭＡＮＤＡ（日本化薬）が挙げられる。
【０１３８】
多官能の架橋剤としては、ペンタエリスリトールトリアクリレート、トリメチロールエタントリアクリレート、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラアクリレート、オリゴエステルアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたもの；トリアリルシアヌレート、トリアリルトリメリテートが挙げられる。
【０１３９】
これらの架橋剤は、他のモノマー成分１００重量部に対して、０．０１〜１０重量部（さらに好ましくは０．０３〜５重量部）用いることができる。
【０１４０】
これらの架橋性モノマーのうち、トナー用樹脂に定着性、耐オフセット性の点から好適に用いられるものとして、芳香族ジビニル化合物（特にジビニルベンゼン）、芳香族基及びエーテル結合を含む鎖で結ばれたジアクリレート化合物類が挙げられる。
【０１４１】
本発明ではビニル系共重合体成分及び／又はポリエステル樹脂成分中に、両樹脂成分と反応し得るモノマー成分を含むことが好ましい。ポリエステル樹脂成分を構成するモノマーのうちビニル系共重合体と反応し得るものとしては、例えば、フタル酸、マレイン酸、シトラコン酸、イタコン酸の如き不飽和ジカルボン酸又はその無水物などが挙げられる。ビニル系共重合体成分を構成するモノマーのうちポリエステル樹脂成分と反応し得るものとしては、カルボキシル基又はヒドロキシ基を有するものや、アクリル酸もしくはメタクリル酸エステル類が挙げられる。
【０１４２】
ビニル系樹脂とポリエステル樹脂の反応生成物を得る方法としては、先に挙げたビニル系樹脂及びポリエステル樹脂のそれぞれと反応しうるモノマー成分を含むポリマーが存在しているところで、どちらか一方もしくは両方の樹脂の重合反応をさせることにより得る方法が好ましい。
【０１４３】
本発明のビニル系共重合体を製造する場合に用いられる重合開始剤としては、例えば、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２’−アゾビス（−２，４−ジメチルバレロニトリル）、２，２’−アゾビス（−２メチルブチロニトリル）、ジメチル−２，２’−アゾビスイソブチレート、１，１’−アゾビス（１−シクロヘキサンカルボニトリル）、２−（カーバモイルアゾ）−イソブチロニトリル、２，２’−アゾビス（２，４，４−トリメチルペンタン）、２−フェニルアゾ−２，４−ジメチル−４−メトキシバレロニトリル、２，２’−アゾビス（２−メチル−プロパン）、メチルエチルケトンパーオキサイド、アセチルアセトンパーオキサイド、シクロヘキサノンパーオキサイドの如きケトンパーオキサイド類、２，２−ビス（ｔ−ブチルパーオキシ）ブタン、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、１，１，３，３−テトラメチルブチルハイドロパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルクミルパーオキサイド、ジ−クミルパーオキサイド、α，α’−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン、イソブチルパーオキサイド、オクタノイルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、３，５，５−トリメチルヘキサノイルパーオキサイド、ベンゾイルパーオキサイド、ｍ−トリオイルパーオキサイド、ジ−イソプロピルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ジ−ｎ−プロピルパーオキシジカーボネート、ジ−２−エトキシエチルパーオキシカーボネート、ジ−メトキシイソプロピルパーオキシジカーボネート、ジ（３−メチル−３−メトキシブチル）パーオキシカーボネート、アセチルシクロヘキシルスルホニルパーオキサイド、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシネオデカノエイト、ｔ−ブチルパーオキシ２−エチルヘキサノエイト、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシベンゾエイト、ｔ−ブチルパーオキシイソプロピルカーボネート、ジ−ｔ−ブチルパーオキシイソフタレート、ｔ−ブチルパーオキシアリルカーボネート、ｔ−アミルパーオキシ２−エチルヘキサノエート、ジ−ｔ−ブチルパーオキシヘキサハイドロテレフタレート，ジ−ｔ−ブチルパーオキシアゼレートがあげられる。
【０１４４】
本発明のトナーに用いられる結着樹脂を調製できる製造方法としては、例えば、以下の（１）〜（６）に示す製造方法を挙げることができる。
【０１４５】
（１）ビニル系樹脂、ポリエステル樹脂及びハイブリッド樹脂成分をそれぞれ製造後にブレンドする方法であり、ブレンドは有機溶剤（例えば、キシレン）に溶解・膨潤した後に有機溶剤を留去するものであり、好ましくは、このブレンド工程でワックスを添加して製造される。尚、ハイブリッド樹脂成分は、ビニル系重合体とポリエステル樹脂を別々に製造後、少量の有機溶剤に溶解・膨潤させ、エステル化触媒及びアルコールを添加し、加熱することによりエステル交換反応を行なって合成されるエステル化合物を用いることができる。
【０１４６】
（２）ビニル系重合体ユニット製造後に、これの存在下にポリエステルユニット及びハイブリッド樹脂成分を製造する方法である。ハイブリッド樹脂成分はビニル系重合体ユニット（必要に応じてビニル系モノマーも添加できる）とポリエステルモノマー（アルコール、カルボン酸）及び／またはポリエステルとの反応により製造される。この場合も適宜、有機溶剤を使用することができる。好ましくは、この工程でワックスを添加する。
【０１４７】
（３）ポリエステルユニット製造後に、これの存在下にビニル系重合体ユニット及びハイブリッド樹脂成分を製造する方法である。ハイブリッド樹脂成分はポリエステルユニット（必要に応じてポリエステルモノマーも添加できる）とビニル系モノマー及び／またはビニル系重合体ユニットとの反応により製造される。好ましくは、この工程でワックスを添加する。
【０１４８】
（４）ビニル系重合体ユニット及びポリエステルユニット製造後に、これらの重合体ユニット存在下にビニル系モノマー及び／またはポリエステルモノマー（アルコール、カルボン酸）を添加することによりハイブリッド樹脂成分を製造される。この場合も適宜、有機溶剤を使用することができる。好ましくは、この工程でワックスを添加する。
【０１４９】
（５）ハイブリッド樹脂成分を製造後、ビニル系モノマー及び／またはポリエステルモノマー（アルコール、カルボン酸）を添加して付加重合及び／又は縮重合反応を行うことによりビニル系重合体ユニット及びポリエステルユニットが製造される。この場合、ハイブリッド樹脂成分は上記（２）乃至（４）の製造方法により製造されるものを使用することもでき、必要に応じて公知の製造方法により製造されたものを使用することもできる。さらに、適宜、有機溶剤を使用することができる。好ましくは、この工程でワックスを添加する。
【０１５０】
（６）ビニル系モノマー及びポリエステルモノマー（アルコール、カルボン酸等）を混合して付加重合及び縮重合反応を連続して行うことによりビニル系重合体ユニット、ポリエステルユニット及びハイブリッド樹脂成分が製造される。さらに、適宜、有機溶剤を使用することができる。好ましくは、この工程でワックスを添加する。
【０１５１】
上記（１）乃至（５）の製造方法において、ビニル系重合体ユニット及び／またはポリエステルユニットは複数の異なる分子量、架橋度を有する重合体ユニットを使用することができる。
【０１５２】
上記の（１）〜（６）の製造方法の中でも、特に（３）の製造方法が、ビニル系重合体ユニットの分子量制御が容易であり、ハイブリッド樹脂成分の生成を制御することができ、かつワックスを添加する場合にはその分散状態を制御できる点で好ましい。
【０１５３】
本発明のトナー、ワックスを含有するトナーの示差走査熱量計で測定されるＤＳＣ曲線において、好ましくは温度７０乃至１６０℃、より好ましくは温度７０乃至１４０℃、さらに好ましくは７５乃至１４０℃、最も好ましくは８０乃至１３５℃の領域に吸熱メインピークを有することがトナーの低温定着性及び耐オフセット性の点で良い。
【０１５４】
さらに好ましくは、ワックスを含有するトナーは、示差走査熱量計で測定されるＤＳＣ曲線において、温度８０〜１５５℃、好ましくは９０〜１３０℃の領域に吸熱メインピーク及び吸熱サブピーク又は吸熱ショルダーを有していることが低温定着性，耐オフセット性及び耐ブロッキング性の点で好ましい。
【０１５５】
トナーのＤＳＣ曲線において、温度７０乃至１６０℃の領域に明瞭な吸熱ピークを形成するためには、使用するワックスが限定される。後述の示差走査熱量計による温度３０〜２００℃の範囲におけるワックスのＤＳＣ曲線において、最大吸熱ピークに対応する温度をワックスの融点と定義すると、ワックスとしては、融点が好ましくは７０〜１６０℃、より好ましくは７５〜１６０℃、さらに好ましくは７５〜１４０℃、最も好ましくは８０〜１３５℃であるものが使用される。
【０１５６】
このようなワックスとしては、例えば、低分子ポリエチレン、低分子ポリプロピレン、マイクロクリスタリンワックス及びパラフィンワックスの如き脂肪族炭化水素系ワックス；酸化ポリエチレンワックスの如き脂肪族炭化水素系ワックスの酸化物；それら脂肪族炭化水素系ワックスのブロック共重合物；カルナバワックス、サゾールワックス及びモンタン酸エステルワックスの如き脂肪酸エステルを主成分とするワックス類；脱酸カルナバワックスの如き脂肪酸エステル類を一部または全部を脱酸化したものが挙げられる。さらに、パルミチン酸、ステアリン酸、モンタン酸、あるいは更に長鎖のアルキル基を有する長鎖アルキルカルボン酸類の如き飽和直鎖脂肪酸類；ブランジン酸、エレオステアリン酸、バリナリン酸の如き不飽和脂肪酸類；ステアリンアルコール、アラルキルアルコール、ベヘニルアルコール、カルナウビルアルコール、セリルアルコール、メリシルアルコール、あるいは更に長鎖のアルキル基を有する長鎖アルキルアルコール類の如き飽和アルコール類；ソルビトールの如き多価アルコール類；ステアリン酸カルシウム、ラウリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸マグネシウムの如き脂肪酸金属塩（一般に金属石けんといわれているもの）；脂肪族炭化水素系ワックスにスチレンやアクリル酸などのビニル系モノマーを用いてグラフト化させたワックス類；ベヘニン酸モノグリセリドの如き脂肪酸と多価アルコールの部分エステル化物；植物性油脂の水素添加によって得られるヒドロキシル基を有するメチルエステル化合物が挙げられる。
【０１５７】
本発明において好ましく用いられる低融点ワックス成分としては、分岐の少ない長鎖アルキル基を有する炭化水素からなり、具体的には例えばアルキレンを高圧下でラジカル重合あるいは低圧下でチーグラー触媒で重合した低分子量のアルキレンポリマー、高分子量のアルキレンポリマーを熱分解して得られるアルキレンポリマー、一酸化炭素・水素からなる合成ガスからアーゲ法により得られる炭化水素の蒸留残分から、あるいはこれらを水素添加して得られる合成炭化水素などのワックスがよい。更に、プレス発汗法、溶剤法、真空蒸留の利用や分別結晶方式により炭化水素ワックスの分別を行なったものがより好ましく用いられる。母体としての炭化水素は、金属酸化物系触媒（多くは２種以上の多元系）を使用した、一酸化炭素と水素の反応によって合成されたもの、例えばジントール法、ヒドロコール法（流動触媒床を使用）、あるいはワックス状炭化水素が多く得られるアーゲ法（固定触媒床を使用）により得られる。
【０１５８】
本発明において好ましく用いられる高融点ワックス成分としては、分岐の少ない長鎖アルキル基を有する炭化水素からなり、具体的には例えばアルキレンを高圧下でラジカル重合あるいは低圧下でチーグラー触媒で重合した低分子量のアルキレンポリマー、高分子量のアルキレンポリマーを熱分解して得られるアルキレンポリマー、一酸化炭素・水素からなる合成ガスからアーゲ法により得られる炭化水素の蒸留残分から、あるいはこれらを水素添加して得られる合成炭化水素などのワックスがよい。それ以外の好ましく用いられるワックスとしては、水酸基、カルボキシル基等の置換機を有する置換アルキルワックスがある。
【０１５９】
本発明において好ましく用いられる炭化水素ワックスとしては、具体的には例えばエチレンやプロピレンの如きアルキレンを高圧下でラジカル重合あるいは低圧下でチーグラー触媒で重合した低分子量のアルキレンポリマー、高分子量のアルキレンポリマーを熱分解して得られるアルキレンポリマー、一酸化炭素及び水素からなる合成ガスからアーゲ法により得られる炭化水素の蒸留残分から、あるいはこれらを水素添加して得られる合成炭化水素などのワックスが用いられる。更に、プレス発汗法、溶剤法、真空蒸留の利用や分別結晶方式により分別を行なったものが、より好ましく用いられる。
【０１６０】
石油系ワックスとしては、パラフィンワックス、マイクロクリスタリンワックス、ペトロラクタムの如き石油より分離されたワックスが使用される。
【０１６１】
本発明における炭化水素ワックス、石油系ワックスは実質的に官能基を有しない。「実質的」とは、官能基の数が１分子あたり０．１個以下であるものを指す。
【０１６２】
本発明において使用される炭化水素ワックスもしくは石油系ワックスは、ワックスを含有するトナーの示差走査熱量計で測定されるＤＳＣ曲線において、温度７０〜１４０℃の領域に吸熱メインピークを有することが、トナーの低温定着性及び耐オフセット性の点で好ましい。
【０１６３】
より好ましくは、炭化水素ワックスもしくは石油系ワックスを含有するトナーは、示差走査熱量計で測定されるＤＳＣ曲線において温度８０〜１３５℃の領域に吸熱メインピークを有することが好ましい。さらに好ましくは、ワックスを含有するトナーは、示差走査熱量計で測定されるＤＳＣ曲線において、温度９０〜１３０℃の領域に吸熱メインピーク及び吸熱サブピーク又は吸熱ショルダーを有していることが低温定着性、耐オフセット性及び耐ブロッキング性の点で好ましい。
【０１６４】
本発明において用いられるワックスの含有量は、結着樹脂１００重量部あたり０．１〜３０重量部、好ましくは０．５〜２０重量部が好ましい。
【０１６５】
複合酸化物（Ａ）としてはＭ₁として、マグネシウム、亜鉛、コバルト、マンガン、ストロンチウム、カルシウム、セリウムが挙げられる。Ｍ₂としては、チタン、シリカがあげられる。特に本発明の効果をより発揮できることから、珪酸ストロンチウム〔Ｓｒ〕_a〔Ｓｉ〕_bＯ_c及びチタン酸ストロンチウム〔Ｓｒ〕_a〔Ｔｉ〕_bＯ_cが好ましい。より具体的には、ＳｒＳｉＯ₃、Ｓｒ₃ＳｉＯ₅、Ｓｒ₂ＳｉＯ₄、ＳｒＳｉＯ₅、Ｓｒ₃Ｓｉ₂Ｏ₇及びＳｒＴｉＯ₃、Ｓｒ₂ＴｉＯ₄、Ｓｒ₃Ｔｉ₂Ｏ₇が挙げられ、中でもＳｒＳｉＯ₃及びＳｒＴｉＯ₃が好ましい。
【０１６６】
本発明で使用する複合酸化物を有する粒子は、例えば焼結法によって生成し、機会粉砕した後、風力分級し、所望の粒度分布であるものを用いるのが良い。
【０１６７】
本発明における複合酸化物は、トナー粒子１００重量部に対して、複合酸化物（Ａ）を有する微粒子を０．１０〜１０重量部、好ましくは０．２〜５．０重量部用いるのが良い。複合酸化物を含む粒子は、重量平均粒径が０．１〜５．０μｍ、好ましくは０．３〜３．０μｍ、より好ましくは０．５〜２．５μｍである。
【０１６８】
本発明のトナーを磁性トナーとして用いる場合、磁性トナーに含まれる磁性材料としては、マグネタイト、マグヘマイト、フェライトの如き酸化鉄、及び他の金属酸化物を含む酸化鉄；Ｆｅ，Ｃｏ，Ｎｉのような金属、あるいは、これらの金属とＡｌ，Ｃｏ，Ｃｕ，Ｐｂ，Ｍｇ，Ｎｉ，Ｓｎ，Ｚｎ，Ｓｂ，Ｂｅ，Ｂｉ，Ｃｄ，Ｃａ，Ｍｎ，Ｓｅ，Ｔｉ，Ｗ，Ｖのような金属との合金、およびこれらの混合物等が挙げられる。
【０１６９】
具体的には、磁性材料としては、四三酸化鉄（Ｆｅ₃Ｏ₄）、三二酸化鉄（γ−Ｆｅ₂Ｏ₃）、酸化鉄亜鉛（ＺｎＦｅ₂Ｏ₄）、酸化鉄イットリウム（Ｙ₃Ｆｅ₅Ｏ₁₂）、酸化鉄カドミウム（ＣｄＦｅ₂Ｏ₄）、酸化鉄ガドリニウム（Ｇｄ₃Ｆｅ₅−Ｏ₁₂）、酸化鉄銅（ＣｕＦｅ₂Ｏ₄）、酸化鉄鉛（ＰｂＦｅ₁₂−Ｏ₁₉）、酸化鉄ニッケル（ＮｉＦｅ₂Ｏ₄）、酸化鉄ネオジム（ＮｄＦｅ₂Ｏ₃）、酸化鉄バリウム（ＢａＦｅ₁₂Ｏ₁₉）、酸化鉄マグネシウム（ＭｇＦｅ₂Ｏ₄）、酸化鉄マンガン（ＭｎＦｅ₂Ｏ₄）、酸化鉄ランタン（ＬａＦｅＯ₃）、鉄粉（Ｆｅ）、コバルト粉（Ｃｏ）、ニッケル粉（Ｎｉ）等が挙げられる。上述した磁性材料を単独で或いは２種以上の組合せて使用する。特に好適な磁性材料は、四三酸化鉄又はγ−三二酸化鉄の微粉末である。
【０１７０】
これらの強磁性体は平均粒径が０．０５〜２μｍで、７９５．８ｋＡ／ｍ印加での磁気特性が抗磁力１．６〜１２．０ｋＡ／ｍ、飽和磁化５０〜２００Ａｍ²／ｋｇ（好ましくは５０〜１００Ａｍ²／ｋｇ）、残留磁化２〜２０Ａｍ²／ｋｇのものが好ましい。
【０１７１】
結着樹脂１００重量部に対して、磁性体１０〜２００重量部、好ましくは２０〜１５０重量部使用するのが良い。
【０１７２】
本発明のトナーに使用できる非磁性の着色剤としては、任意の適当な顔料又は染料が挙げられる。例えば顔料として、カーボンブラック、アニリンブラック、アセチレンブラック、ナフトールイエロー、ハンザイエロー、ローダミンレーキ、アリザリンレーキ、ベンガラ、フタロシアニンブルー、インダンスレンブルー等がある。これらは結着樹脂１００重量部に対し０．１〜２０重量部、好ましくは１〜１０重量部の添加量が良い。また、同様に染料が用いられ、例えば、アントラキノン系染料、キサンテン系染料、メチン系染料があり、結着樹脂１００重量部に対し０．１〜２０重量部、好ましくは０．３〜１０重量部の添加量が良い。
【０１７３】
本発明のトナーは、その帯電性をさらに安定化させる為に必要に応じて荷電制御剤を用いても良い。荷電制御剤は、結着樹脂１００重量部当り好ましくは０．１〜１０重量部、より好ましくは０．２〜５重量部使用するのが好ましい。
【０１７４】
荷電制御剤としては、以下のものが挙げられる。
【０１７５】
例えば有機金属錯体、キレート化合物、有機金属塩が挙げられる。具体的には、モノアゾ金属錯体；芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸化合物の金属錯体又は金属塩が挙げられる。他には、芳香族ハイドロキシカルボン酸、芳香族モノ及びポリカルボン酸及びその無水物、そのエステル類；ビスフェノールのフェノール誘導体類が挙げられる。
【０１７６】
本発明のトナーに流動性向上剤を添加しても良い。流動性向上剤は、トナー粒子に外添することにより、流動性が添加前後を比較すると増加し得るものである。例えば、フッ化ビニリデン微粉末、ポリテトラフルオロエチレン微粉末の如きフッ素系樹脂粉末；湿式製法シリカ、乾式製法シリカの如き微粉末シリカ、微粉末酸化チタン、微粉末アルミナ、それらをシランカップリング剤、チタンカップリング剤、シリコーンオイルにより表面処理を施した処理シリカ等がある。
【０１７７】
好ましい流動性向上剤としては、ケイ素ハロゲン化合物の蒸気相酸化により生成された微粉体であり、いわゆる乾式法シリカ又はヒュームドシリカと称されるものである。例えば、四塩化ケイ素ガスの酸水素焔中における熱分解酸化反応を利用するもので、基礎となる反応式は次の様なものである。
【０１７８】
ＳｉＣｌ₂＋２Ｈ₂＋Ｏ₂→ＳｉＯ₂＋４ＨＣｌ
【０１７９】
この製造工程において、塩化アルミニウム又は塩化チタン等の他の金属ハロゲン化合物をケイ素ハロゲン化合物と共に用いることによってシリカと他の金属酸化物の複合微粉体を得ることも可能であり、シリカとしてはそれらも包含する。その粒径は、平均の一次粒径として、０．００１〜２μｍの範囲内であることが好ましく、特に好ましくは、０．００２〜０．２μｍの範囲内のシリカ微粉体を使用するのが良い。
【０１８０】
ケイ素ハロゲン化合物の蒸気相酸化により生成された市販のシリカ微粉体としては、例えば以下の様な商品名で市販されているものがある。
【０１８１】

【０１８２】
さらには、該ケイ素ハロゲン化合物の気相酸化により生成されたシリカ微粉体に疎水化処理した処理シリカ微粉体がより好ましい。該処理シリカ微粉体において、メタノール滴定試験によって測定された疎水化度が３０〜８０の範囲の値を示すようにシリカ微粉体を処理したものが特に好ましい。
【０１８３】
疎水化方法としては、シリカ微粉体と反応あるいは物理吸着する有機ケイ素化合物等で化学的に処理することによって付与される。好ましい方法としては、ケイ素ハロゲン化合物の蒸気相酸化により生成されたシリカ微粉体を有機ケイ素化合物で処理する。
【０１８４】
有機ケイ素化合物としては、ヘキサメチルジシラザン、トリメチルシラン、トリメチルクロルシラン、トリメチルエトキシシラン、ジメチルジクロルシラン、メチルトリクロルシラン、アリルジメチルクロルシラン、アリルフェニルジクロルシラン、ベンジルジメチルクロルシラン、ブロムメチルジメチルクロルシラン、α−クロルエチルトリクロルシラン、ρ−クロルエチルトリクロルシラン、クロルメチルジメチルクロルシラン、トリオルガノシリルメルカプタン、トリメチルシリルメルカプタン、トリオルガノシリルアクリレート、ビニルジメチルアセトキシシラン、ジメチルエトキシシラン、ジメチルジメトキシシラン、ジフェニルジエトキシシラン、ヘキサメチルジシロキサン、１，３−ジビニルテトラメチルジシロキサン、１，３−ジフェニルテトラメチルジシロキサンおよび１分子当り２から１２個のシロキサン単位を有し末端に位置する単位にそれぞれ１個宛のＳｉに結合した水酸基を含有するジメチルポリシロキサン等がある。さらに、ジメチルシリコーンオイルの如きシリコーンオイルが挙げられる。これらは１種あるいは２種以上の混合物で用いられる。
【０１８５】
流動性向上剤は、ＢＥＴ法で測定した窒素吸着による比表面積が３０ｍ²／ｇ以上、好ましくは５０ｍ²／ｇ以上のものが良好な結果を与える。トナー１００重量部に対して流動性向上剤０．０１〜８重量部、好ましくは０．１〜４重量部使用するのが良い。
【０１８６】
本発明のトナーを作製するには、結着樹脂、着色剤及び／又は磁性体、荷電制御剤またはその他の添加剤を、ヘンシェルミキサー、ボールミルの如き混合機により充分混合し、ニーダー、エクストルーダーの如き熱混練機を用いて溶融・混練して樹脂類を互いに相溶せしめ、溶融混練物を冷却固化後に固化物を粉砕し、粉砕物を分級して本発明のトナーを得ることができる。
【０１８７】
トナー粒子は、画像濃度や解像度の面で、重量平均粒径が、好ましくは３〜１２μｍ、より好ましくは３〜９μｍであるのが良い。
【０１８８】
更に、流動性向上剤とトナー粒子をヘンシェルミキサーの如き混合機により十分混合し、トナー粒子表面に流動性向上剤を有するトナーを得ることができる。
【０１８９】
次に本発明の画像形成方法に関して説明する。
【０１９０】
図８及び図９を参照しながら、本発明の画像形成方法を実施し得る画像形成装置の一例について説明する。一次帯電器２で静電荷像担持体（感光体）１表面を負極性又は正極性に帯電し、アナログ露光又はレーザ光による露光５により静電荷像（例えば、イメージスキャニングによりデジタル潜像）を形成し、磁性ブレード１１と、磁極Ｎ₁，Ｎ₂，Ｓ₁及びＳ₂を有する磁石２３を内包している現像スリーブ４とを具備する現像器９の磁性トナー１３で静電荷像を反転現像又は正規現像により現像する。現像部において感光体１の導電性基体１６と現像スリーブ４との間で、バイアス印加手段１２により交互バイアス，パルスバイアス及び／又は直流バイアスが印加されている。磁性トナー像は、中間転写体を介して、又は、介さずに転写材へ転写される。転写紙Ｐが搬送されて、転写部にくると転写帯電器３により転写紙Ｐの背面（感光体側と反対面）から正極性または負極性の帯電をすることにより、感光体表面上の負荷電性磁性トナー像または正荷電性磁性トナー像が転写紙Ｐ上へ静電転写される。除電手段２２で除電後、感光体１から分離された転写紙Ｐは、ヒータ２１を内包している加熱加圧ローラ定着器７により転写紙Ｐ上のトナー画像は、加熱加圧定着される。
【０１９１】
転写工程後の感光体１に残留する磁性トナーは、クリーニングブレード８を有するクリーニング手段で除去される。クリーニング後の感光体１は、イレース露光６により除電され、再度、一次帯電器２により帯電工程から始まる工程が繰り返される。
【０１９２】
次に、以下の実施例中で測定した各種物性データの測定方法に関して以下に説明する。
【０１９３】
（１）トナーのテトラヒドロフラン（ＴＨＦ）、酢酸エチル及びクロロホルム不溶成分の定量
トナー２ｇを精秤（ＴＷ１）して円筒濾紙（例えば、東洋濾紙社製Ｎｏ．８６Ｒ）に入れてソックスレー抽出器にかけ、ＴＨＦは２００ｍｌ用いる。約１２０℃に温度調整されたオイルバスを用いて１０時間還流する。ＴＨＦに可溶な成分（Ｗ１）はＴＨＦを濃縮、乾固した後に６０℃で２４時間真空乾燥することにより定量できる。トナーのＴＨＦ不溶成分（Ｗ２）を定量する場合は、着色剤（磁性体）等の結着樹脂以外のＴＨＦ不溶成分（ＴＷ２）から下記式により算出される。
【０１９４】
【数１】

【０１９５】
同様にして、溶媒を酢酸エチル及びクロロホルムに変更することにより、それぞれの溶媒に対する結着樹脂の可溶成分及び不溶成分を定量することができる。
【０１９６】
ソックスレー抽出装置の一例を図７に示す。
【０１９７】
容器５１に入っているＴＨＦ５２は、ヒータ５３で加熱され気化し、気化したＴＨＦは管５４を通って冷却器５５に導かれる。冷却器５５は、冷却水５６で常時、冷却されている。冷却器５５で冷却されて液化したＴＨＦは円筒ろ紙５７を有する貯留部５８にたまり、ＴＨＦの液面が中管５９よりも高くなると、貯留部からＴＨＦが容器５１に排出される。円筒ろ紙５７に入っているトナーまたは樹脂は、循環するＴＨＦによって抽出処理される。
【０１９８】
（２）¹Ｈ−ＮＭＲ及び¹³Ｃ−ＮＭＲ測定による酢酸エチルに不溶な成分及び可溶な成分中のポリエステル樹脂の定量
^１Ｈ−ＮＭＲ及び¹³Ｃ−ＮＭＲを用いて各モノマー組成存在比率をモル比率で求め、このモル比率での各モノマー組成存在比率から各モノマーの分子量を用い、エステル化に伴う脱水量は無視してポリエステル樹脂成分の含有量を重量％で算出する。
【０１９９】
（¹Ｈ−ＮＭＲ（核磁気共鳴）スペクトルの測定）
測定装置 ：ＦＴ ＮＭＲ装置 ＪＮＭ−ＥＸ４００（日本電子社製）
測定周波数：４００ＭＨｚ
パルス条件：５．０μｓ
データポイント：３２７６８
周波数範囲：１０５００Ｈｚ
積算回数 ：１００００回
測定温度 ：６０℃
試料 ：測定試料５０ｍｇをφ５ｍｍのサンプルチューブに入れ、溶媒としてＣＤＣｌ₃を添加し、これを６０℃の恒温槽内で溶解させて調製する。
【０２００】
（¹³Ｃ−ＮＭＲ（核磁気共鳴）スペクトルの測定）
測定装置 ：ＦＴ ＮＭＲ装置 ＪＮＭ−ＥＸ４００（日本電子社製）
測定周波数：４００ＭＨｚ
パルス条件：５．０μｓ
データポイント：３２７６８
遅延時間：２５ｓｅｃ．
周波数範囲：１０５００Ｈｚ
積算回数 ：１６回
測定温度 ：４０℃
試料 ：測定試料２００ｍｇをφ５ｍｍのサンプルチューブに入れ、溶媒としてＣＤＣｌ₃（ＴＭＳ０．０５％）を添加し、これを４０℃の恒温槽内で溶解させて調製する。
【０２０１】
^１Ｈ−ＮＭＲ及び¹³Ｃ−ＮＭＲ測定による酢酸エチルに不溶な成分中及び可溶な成分中のポリエステル樹脂の含有量の定量の一具体例を図３及び４乃至６を用いて下記に記載する。
【０２０２】
▲１▼ ¹ Ｈ−ＮＭＲ測定によるアルコール成分の存在比率の決定（図４及び５参照）
プロポキシ化ビスフェノールＡ（ＰＯ−ＢＰＡ）及びエトキシ化ビスフェノールＡ（ＥＯ−ＢＰＡ）の存在比率は、¹Ｈ−ＮＭＲスペクトルにおける５．２ｐｐｍ、５．３ｐｐｍ及び５．４ｐｐｍ付近のプロポキシ基の水素（各１Ｈ相当：図６参照）のシグナルと４．３ｐｐｍ及び４．６５ｐｐｍ付近のエトキシ基の水素（各４Ｈ相当）のシグナルとの強度比から求める。
【０２０３】
▲２▼ ¹ Ｈ−ＮＭＲ測定による芳香族カルボン酸成分の存在比率の決定（図４及び５参照）
テレフタル酸及びトリメリット酸の存在比率は、¹Ｈ−ＮＭＲスペクトルにおける８ｐｐｍ付近のテレフタル酸の水素（４Ｈ相当）のシグナルと７．６ｐｐｍ７．８ｐｐｍ及び８．４ｐｐｍ付近のトリメリット酸の水素（各１Ｈ相当）のシグナルとの強度比から求める。
【０２０４】
▲３▼ ¹ ＨＮＭＲ測定によるスチレンの存在比率の決定（図４及び５参照）
スチレンの存在比率は、¹Ｈ−ＮＭＲスペクトルにおける６．６ｐｐｍ付近の水素（１Ｈ相当）のシグナルの強度比から求める。
【０２０５】
▲４▼ ¹³ Ｃ−ＮＭＲ測定による脂肪族カルボン酸、（メタ）アクリル酸エステル及びＰＯ−ＢＰＡ、ＥＯ−ＢＰＡの（メタ）アクリル酸エステル化合物（ビニル系重合体とポリエステル樹脂との反応生成物）の存在比率の決定（図３参照）
脂肪族カルボン酸、（メタ）アクリル酸エステル及びビニル系重合体とポリエステル樹脂との反応生成物の存在比率は、¹³Ｃ−ＮＭＲスペクトルにおける１７３．５ｐｐｍ及び１７４ｐｐｍ付近の脂肪族カルボン酸のカルボキシル基の炭素（各１Ｃ相当）のシグナルと１７６ｐｐｍ付近の（メタ）アクリル酸エステルのカルボキシル基の炭素（１Ｃ相当）のシグナルと１６９ｐｐｍ付近の新たに検出されたピークの（メタ）アクリル酸エステルのカルボキシル基の炭素（１Ｃ相当）のシグナルと強度比から求める。
【０２０６】
▲５▼ ¹³ Ｃ−ＮＭＲ測定による脂肪族カルボン酸と芳香族カルボン酸の存在比率の決定（図３参照）
脂肪族カルボン酸と芳香族カルボン酸の存在比率は、¹³Ｃ−ＮＭＲスペクトルにおける１６５ｐｐｍ付近のテレフタル酸及びトリメリット酸のカルボキシル基の炭素（１Ｃ相当）のシグナルと上記▲４▼の脂肪族カルボン酸のカルボキシル基の炭素（各１Ｃ相当）のシグナルの強度比の比較から求める。
【０２０７】
▲６▼ ¹³ Ｃ−ＮＭＲ測定によるスチレンの存在比率の決定（図３参照）
スチレンの存在比率は、¹³Ｃ−ＮＭＲスペクトルにおける１２５ｐｐｍ付近のパラ位の炭素（１Ｃ相当）のシグナルの強度比から求める。
【０２０８】
▲７▼酢酸エチルに不溶な成分中及び可溶な成分中のポリエステル樹脂成分の含有量の決定
上記▲１▼乃至▲３▼の¹Ｈ−ＮＭＲスペクトルから、ＰＯ−ＢＰＡ、ＥＯ−ＢＰＡ、テレフタル酸、トリメリット酸及びスチレンの各モノマー組成存在比率をモル比率で算出し、さらに上記▲４▼乃至▲６▼の¹³Ｃ−ＮＭＲスペクトルから、ＰＯ−ＢＰＡ、ＥＯ−ＢＰＡの（メタ）アクリル酸エステル化合物（ビニル系重合体とポリエステル樹脂との反応生成物）、脂肪族カルボン酸、芳香族カルボン酸及びスチレンの各モノマー組成存在比率をモル比率で算出することにより、全構成モノマーの組成存在比率をモル比率で算出する。このモル比率での各モノマー組成存在比率から各モノマーの分子量を用い、エステル化に伴う脱水量は無視してポリエステル樹脂成分の含有量を重量％で算出する。
【０２０９】
（３）ワックスの融点測定
示差走査熱量計（ＤＳＣ測定装置），ＤＳＣ−７（パーキンエルマー社製）を用いてＡＳＴＭ Ｄ３４１８−８２に準じて測定する。
【０２１０】
測定試料は２〜１０ｍｇ、好ましくは５ｍｇを精密に秤量する。
【０２１１】
これをアルミパン中に入れ、リファレンスとして空のアルミパンを用い、測定温度範囲３０〜２００℃の間で、昇温速度１０℃／ｍｉｎで常温常湿下で測定を行う。
【０２１２】
この昇温過程で、温度３０〜２００℃の範囲におけるＤＳＣ曲線のメインピークの吸熱ピークが得られる。
【０２１３】
この吸熱メインピークの温度をもってワックスの融点とする。
【０２１４】
（４）トナーのＤＳＣ曲線の測定
上記ワックスの融点の測定と同様にして、トナーの昇温過程におけるＤＳＣ曲線を測定する。
【０２１５】
（５）結着樹脂のガラス転移温度（Ｔｇ）の測定
示差走査熱量計（ＤＳＣ測定装置），ＤＳＣ−７（パーキンエルマー社製）を用いてＡＳＴＭ Ｄ３４１８−８２に準じて測定する。
【０２１６】
測定試料は５〜２０ｍｇ、好ましくは１０ｍｇを精密に秤量する。
【０２１７】
これをアルミパン中に入れ、リファレンスとして空のアルミパンを用い、測定温度範囲３０〜２００℃の間で、昇温速度１０℃／ｍｉｎで常温常湿下で測定を行う。
【０２１８】
この昇温過程で、温度４０〜１００℃の範囲におけるメインピークの吸熱ピークが得られる。
【０２１９】
このときの吸熱ピークが出る前と出た後のベースラインの中間点の線と示差熱曲線との交点を本発明におけるガラス転移温度Ｔｇとする。
【０２２０】
（６）ワックスの分子量分布の測定
ゲルパーミエーションクロマトグラフィ（ＧＰＣ）測定装置：ＧＰＣ−１５０Ｃ（ウォーターズ社）
カラム：ＧＭＨ−ＨＴ３０ｃｍ２連（東ソー社製）
温度：１３５℃
溶媒：ｏ−ジクロロベンゼン（０．１％アイオノール添加）
流速：１．０ｍｌ／ｍｉｎ
試料：０．１５％の試料を０．４ｍｌ注入
【０２２１】
以上の条件で測定し、試料の分子量算出にあたっては単分散ポリスチレン標準試料により作成した分子量較正曲線を使用する。さらに、Ｍａｒｋ−Ｈｏｕｗｉｎｋ粘度式から導き出される換算式でポリエチレン換算することによって算出される。
【０２２２】
（７）結着樹脂原料又はトナーの結着樹脂の分子量分布の測定
ＧＰＣによるクロマトグラムの分子量は次の条件で測定される。
【０２２３】
４０℃のヒートチャンバー中でカラムを安定化させ、この温度におけるカラムに、溶媒としてテトラヒドロフラン（ＴＨＦ）を毎分１ｍｌの流速で流す。試料が結着樹脂原料の場合は、結着樹脂原料をロールミルに素通し（１３０℃，１５分）したものを用いる。試料がトナーの場合は、トナーをＴＨＦに溶解後０．２μｍフィルターで濾過し、その濾液を試料として用いる。試料濃度として０．０５〜０．６重量％に調整した樹脂のＴＨＦ試料溶液を５０〜２００μｌ注入して測定する。試料の分子量測定にあたっては、試料の有する分子量分布を、数種の単分散ポリスチレン標準試料により作製された検量線の対数値とカウント数との関係から算出する。検量線作成用の標準ポリスチレン試料としては、例えば、Ｐｒｅｓｓｕｒｅ Ｃｈｅｍｉｃａｌ Ｃｏ．製あるいは、東洋ソーダ工業社製の分子量が６×１０² ，２．１×１０³ ，４×１０³ ，１．７５×１０⁴ ，５．１×１０⁴ ，１．１×１０⁵ ，３．９×１０⁵ ，８．６×１０⁵ ，２×１０⁶ ，４．４８×１０⁶ のものを用い、少なくとも１０点程度の標準ポリスチレン試料を用いるのが適当である。検出器にはＲＩ（屈折率）検出器を用いる。
【０２２４】
カラムとしては、１０³ 〜２×１０⁶ の分子量領域を適確に測定するために、市販のポリスチレンゲルカラムを複数組合せるのが良く、例えば、Ｗａｔｅｒｓ社製のμ−ｓｔｙｒａｇｅｌ ５００，１０³ ，１０⁴ ，１０⁵ の組合せや、昭和電工社製のｓｈｏｄｅｘ ＫＡ−８０１，８０２，８０３，８０４，８０５，８０６，８０７の組合せが好ましい。
【０２２５】
（８）トナーに含有される結着樹脂の¹³Ｃ−ＮＭＲ測定
測定装置 ：ＦＴ ＮＭＲ装置 ＪＮＭ−ＥＸ４００（日本電子社製）
測定周波数：１００．４０ＭＨｚ
パルス条件：５．０μｓ（４５°）ＤＥＰＴ法による
データポイント：３２７６８
遅延時間 ：２５ｓｅｃ．
積算回数 ：５００００回
測定温度 ：２６℃
試料 ：室温でトナー１０ｇを１００ｍｌの濃塩酸（約１２Ｍ）に添加して
約７０時間撹拌して、トナーに含有される磁性体を溶解する。次に、濾液が弱酸性（約ｐＨ５）になるまで濾過・洗浄する。得られた樹脂組成物を６０℃で約２０時間真空乾燥して測定試料とする。この測定試料約１ｇをφ１０ｍｍのサンプルチューブに入れ、溶媒として重クロロホルム（ＣＤＣｌ₃）３ｍｌを添加し、これを５５℃の恒温槽内で溶解させて調整する。
【０２２６】
（９）酸価の測定
ＪＩＳ Ｋ００７０−１９９２に記載の測定方法に準拠して行う。
測定装置 ：電位差自動滴定装置 ＡＴ−４００（京都電子社製）
装置の校正：トルエン１２０ｍｌとエタノール３０ｍｌの混合溶媒を使用する。
測定温度 ：２５℃
試料調整 ：トナー０．５ｇ（酢酸エチル可溶成分では０．３ｇ）をトルエン１２０ｍｌに添加して室温（約２５℃）で約１０時間撹拌して溶解する。更にエタノール３０ｍｌを添加して試料溶液とする。
【０２２７】
（１０）ＯＨ価（水酸基価）の測定
試料０．５ｇを１００ｍｌのメスフラスコに精秤し、これにアセチル化試薬５ｍｌを正しく加える。その後１００℃±５℃の浴中に浸して加熱する。１〜２時間後フラスコを浴から取り出し、放冷後水を加えて振り動かして無水酢酸を分解する。更に分解を完全にするため再びフラスコを浴中で１０分間以上加熱し放冷後、有機溶剤でフラスコの壁を良く洗う。この液をガラス電極を用いてＮ／２水酸化カリウムエチルアルコール溶液で電位差滴定を行いＯＨ価を求める（ＪＩＳ
Ｋ００７０−１９６６に準ずる。）。
【０２２８】
（１１）Ｘ線回折の測定

【０２２９】
上記成型装置を使用して、測定検体を圧縮プレスする。成型した試料をＸ線回折装置にセットし、以下の条件で測定する。得られたＸ線回折パターンのピーク強度と２θ角度より構造を決定する。
Ｔａｒｇｅｔ Ｆｉｌｔｅｒ Ｃｕ，Ｎｉ
Ｖｏｌｔａｇｅ Ｃｕｒｒｅｎｔ ３２．５ｋＶ、１５ｍＡ
Ｃｏｕｎｔｅｒ Ｓｅ
Ｔｉｍｅ Ｃｏｎｓｔａｎｔ １ｓｅｃ
Ｄｉｖｅｒｇｅｎｃｅ Ｓｌｉｔ １°
Ｒｅｃｅｉｖｉｎｇ Ｓｌｉｔ ０．１５ｍｍ
Ｓｃａｔｔｅｒ Ｓｌｉｔ １°
Ａｎｇｌｅ Ｒａｎｇｅ ６０〜２０°
【０２３０】
（１２）トナー中の複合酸化物の定量方法

【０２３１】
▲１▼検量線の作成
磁性トナー（Ｘ）に対し、定量目的の複合酸化物をコーヒーミルを用いて以下の比率（重量％）で各々混合し、検量線用サンプルを作成する。
０％，０．５％，１．０％，２．０％，３．０％，５．０％，１０．０％
試料プレス成型機を用いて上記サンプル７点をプレス成形する。２θテーブルより複合酸化物中〔Ｍ〕Ｋαピーク角度（ａ）を決定する。蛍光Ｘ線分析装置中へ検量線サンプルを入れ、試料室を減圧し真空にする。以下の条件にて各々のサンプルのＸ線強度を求め検量線を作成する。
【０２３２】
〔測定条件〕
測定電位，電圧 ５０ｋＶ−５０ｍＡ
２θ角度 ａ
結晶板 ＬｉＦ
測定時間 ６０秒
【０２３３】
▲２▼トナー中の複合酸化物の定量
上記▲１▼と同様の方法でサンプル成形した後、同じ測定条件にてＸ線強度をもとめ、検量線より添加量を算出する。
【０２３４】
（１３）粒度分布の測定
粒度分布については、種々の方法によって測定できるが、本発明においてはコールターカウンターのマルチサイザーを用いて行った。
【０２３５】
測定装置としてはコールターカウンターのマルチサイザーＩＩ型（コールター社製）を用い、個数分布，体積分布を出力するインターフェイス（日科機製）及びＣＸ−１パーソナルコンピューター（キヤノン製）を接続し、電解液は特級または１級塩化ナトリウムを用いて１％ＮａＣｌ水溶液を調製する。測定法としては前記電解水溶液１００〜１５０ｍｌ中に分散剤として界面活性剤（好ましくはアルキルベンゼンスルホン酸塩）を０．１〜５ｍｌ加え、さらに測定試料を２〜２０ｍｇ加える。試料を懸濁した電解液は超音波分散器で約１〜３分間分散処理を行い、前記コールターカウンターのマルチサイザーＩＩ型により、アパーチャーとして、トナー粒径を測定するときは１００μｍアパーチャーを用い、無機微粉末粒径を測定するときは１３μｍアパーチャーを用いて測定する。トナー及び無機微粉末の体積，個数を測定して、体積分布と、個数分布とを算出した。それから体積分布から求めた重量基準の重量平均径を求める。
【０２３６】
（１４）トナー及びクリーニングブレードの粘弾性特性の測定）
粘弾性測定装置（レオメーター）ＲＤＡ−ＩＩ（レオメトリックス社製）を用いて測定を行う。
測定治具：直径７．９ｍｍのパラレルプレート
測定試料：トナーは加熱、溶解後に直径８ｍｍ、高さ２乃至５ｍｍの円盤状試料に成型して使用する。測定治具への固定は常法に従って行う。
【０２３７】
クリーニングブレードは厚さ１乃至５ｍｍのシート状試料から直径約８ｍｍの円盤状に打ち抜くか、または切り出して使用する。測定治具への固定は瞬間接着剤等を使用して接着固定する。
測定周波数：６．２８ラジアン／秒
測定温度：室温より１７０℃まで、毎分１℃の割合で昇温する。
【０２３８】
【実施例】
以下、実施例によって本発明を説明するが、本発明はこれらの実施例に限定されるものではない。
【０２３９】
結着樹脂の製造例Ｉ：
（樹脂製造例Ｉ−１）
（Ｉ−ａ）低架橋度樹脂組成物の製造
（クロロホルム不溶分を実質的に０乃至１０重量％含有する樹脂組成物の製造）
・テレフタル酸 ：５．０ｍｏｌ
・式（１−３）で表せるコハク酸誘導体 ：１．０ｍｏｌ
・無水トリメリット酸 ：１．０ｍｏｌ
・ＰＯ−ＢＰＡ ：７．０ｍｏｌ
・ＥＯ−ＢＰＡ ：３．０ｍｏｌ
【０２４０】
上記ポリエステルモノマーをエステル化触媒とともにオートクレーブに仕込み、減圧装置、水分離装置、窒素ガス導入装置、温度測定装置及び撹拌装置を装着して窒素雰囲気下、減圧しながら常法に従って２１０℃まで加熱しながら縮重合反応を行うことにより、クロロホルム不溶分を約３重量％含有する低架橋度ポリエステル樹脂を得た。
【０２４１】
次に、キシレン５０重量部に、ここで得られたポリエステル樹脂８０重量部、スチレン１６重量部、２−エチルヘキシルアクリレート４重量部及びエステル化触媒としてジブチルスズオキサイド０．３重量部を添加して、１１０℃まで加熱して溶解・膨潤した。窒素雰囲気下、ラジカル重合開始剤であるｔ−ブチルハイドロパーオキサイド１重量部をキシレン１０重量部に溶解したものを約３０分かけて滴下した。その温度で更に１０時間保持してラジカル重合反応を終了した。更に加熱しながら減圧して、脱溶剤することにより、低架橋度ポリエステル樹脂、ビニル系重合体及びポリエステルユニットとビニル系重合体ユニットを有しているハイブリッド樹脂成分からなり、クロロホルム不溶分を約７重量％含有する低架橋度樹脂組成物（ａ−１）を得た。
【０２４２】
（Ｉ−ｂ）高架橋度樹脂組成物の製造
（クロロホルム不溶分を１５乃至７０重量％含有する樹脂組成物の製造）
・テレフタル酸 ：２．０ｍｏｌ
・式（１−３）で表せるコハク酸誘導体 ：４．０ｍｏｌ
・無水トリメリット酸 ：４．０ｍｏｌ
・ＰＯ−ＢＰＡ ：１０．０ｍｏｌ
・ＥＯ−ＢＰＡ ：４．０ｍｏｌ
【０２４３】
上記ポリエステルモノマーをエステル化触媒とともにオートクレーブに仕込み、減圧装置、水分離装置、窒素ガス導入装置、温度測定装置及び撹拌装置を装着して窒素雰囲気下、減圧しながら常法に従って２１０℃まで加熱しながら縮重合反応を行うことにより、クロロホルム不溶分を約２５重量％含有する高架橋度ポリエステル樹脂を得た。
【０２４４】
次に、キシレン５０重量部に、ここで得られたポリエステル樹脂８０重量部、スチレン１０重量部、２−エチルヘキシルアクリレート１０重量部、ジビニルベンゼン０．０１重量部及びエステル化触媒としてジブチルスズオキサイド０．３重量部を添加して、１１０℃まで加熱して溶解・膨潤した。窒素雰囲気下、ラジカル重合開始剤であるｔ−ブチルハイドロパーオキサイド１重量部をキシレン１０重量部に溶解したものを約３０分かけて滴下した。その温度で更に１０時間保持してラジカル重合反応を終了した。更に加熱しながら減圧して、脱溶剤することにより、高架橋度ポリエステル樹脂、ビニル系重合体及びポリエステルユニットとビニル系重合体ユニットを有しているハイブリッド樹脂成分からなり、クロロホルム不溶分を約３３重量％含有する高架橋度樹脂組成物（ｂ−１）を得た。
【０２４５】
（Ｉ−ｃ）結着樹脂の製造
キシレン１００重量部に低架橋度樹脂組成物（ａ−１）６０重量部、高架橋度樹脂組成物（ｂ−１）３０重量部、スチレン５重量部、２−エチルヘキシルアクリレート５重量部及びジビニルベンゼン０．０１重量部を添加して１１０℃まで加熱して膨潤・溶解した。窒素雰囲気下、ラジカル重合開始剤であるｔ−ブチルハイドロパーオキサイド１重量部をキシレン１０重量部に溶解したものを約３０分かけて滴下した。その温度で更に１０時間保持してラジカル重合反応を終了した。更に加熱しながら減圧して、脱溶剤することにより、低架橋度ポリエステル樹脂、高架橋度ポリエステル樹脂、ビニル系重合体及びポリエステルユニットとビニル系重合体ユニットを有しているハイブリッド樹脂成分からなり、クロロホルム不溶分を約２８重量％含有する結着樹脂（Ｃ−１）を得た。
【０２４６】
（樹脂製造例Ｉ−２）
樹脂製造例Ｉ−１において、高架橋度樹脂組成物（ｂ−１）を製造する際に、ポリエステル樹脂８０重量部に対して１６．６重量部の炭化水素系ワックス（融点１００℃、重量平均分子量１８００）をスチレン及び２−エチルヘキシルアクリレートと共に添加して、ワックスを含有し、かつクロロホルム不溶分を３７重量％含有する高架橋度樹脂組成物（ｂ−２）を得た。高架橋度樹脂組成物（ｂ−２）３５重量部（ワックス５重量部を含む）を使用した以外は製造例Ｉ−１と同様にして、低架橋度ポリエステル樹脂、高架橋度ポリエステル樹脂、ビニル系重合体及びポリエステルユニットとビニル系重合体ユニットを有しているハイブリッド樹脂成分からなり、クロロホルム不溶分を約３０重量％含有する結着樹脂（Ｃ−２）を得た。
【０２４７】
（樹脂製造例Ｉ−３〜Ｉ−５）
モノマーの種類及び組成比を変更することにより、表１乃至３に示す結着樹脂（Ｃ−３）〜（Ｃ−５）を得た。
【０２４８】
（樹脂比較製造例Ｉ−１）
樹脂製造例Ｉ−１において、コハク酸誘導体（１−３）のかわりにテレフタル酸を使用した以外は同様にして、表１乃至３に示す比較用結着樹脂（ウ−１）を得た。
【０２４９】
（樹脂比較製造例Ｉ−２）
樹脂製造例Ｉ−１において、コハク酸誘導体（１−３）のかわりにテレフタル酸を使用し、無水トリメリット酸を増量した低架橋度樹脂組成物を使用した以外は同様にして、表１乃至３に示す比較用結着樹脂（ウ−２）を得た。
【０２５０】
【表１】

【０２５１】
【表２】

【０２５２】
【表３】

【０２５３】
（複合酸化物の製造例１：珪酸ストロンチウム）
炭酸ストロンチウム１５００ｇと酸化珪素６００ｇをボールミルにて、８時間湿式混合した後、ろ過乾燥し、この混合物を５ｋｇ／ｃｍ²の圧力で成形して１３００℃で８時間仮焼した。これを、機械粉砕して、重量平均径２．０μｍの珪酸ストロンチウム微粉体（Ｍ−１）を得た。更に、この得られた（Ｍ−１）に対してＸ線回折を実施し、図１２のピークパターンより製造した複合酸化物がＳｒＳｉＯ₃（式（１）のａ＝１，ｂ＝１，ｃ＝３）及びＳｒ₂ＳｉＯ₄（式（１）のａ＝２，ｂ＝１，ｃ＝４）を有することを確認した。
【０２５４】
（複合酸化物の製造例２：チタン酸ストロンチウム）
炭酸ストロンチウム６００ｇと酸化チタン３２０ｇをボールミルにて、８時間湿式混合した後、ろ過乾燥し、この混合物を５ｋｇ／ｃｍ²の圧力で成形して１１００℃で８時間仮焼した。これを、機械粉砕して、重量平均径１．７μｍのチタン酸ストロンチウム微粉体（Ｍ−２）を得た。
【０２５５】
（複合酸化物の製造例３：酸化セリウム（比較用））
炭酸セリウム１５００ｇと酸素存在下にて１３００℃で１０時間燃焼した。これを、機械粉砕して、重量平均径２．０μｍの酸化セリウム微粉体（Ｍ−３）を得た。
【０２５６】
（テストブレード）
表４に示すブレードＡ〜Ｋを本検討用ブレードとして準備した。なお、ブレードの寸法は全て長さ３３１．５±１．０ｍｍ，幅２０±０．２ｍｍ，厚さ３±０．１ｍｍとした。
【０２５７】
ブレードＢの粘弾性データー（データー：１）を図１０として添付する。
【０２５８】
【表４】

【０２５９】
（トナーの製造例）
・結着樹脂（Ｃ−１） １００重量部
・磁性酸化鉄 ９０重量部
（平均粒径０．１５μｍ、Ｈｃ９．２ｋＡ／ｍ（１２０エルステッド）、σｓ＝８３Ａｍ²／ｋｇ（８３ｅｍｕ／ｇ）、σｒ＝１１．５Ａｍ²／ｋｇ（１１．５ｅｍｕ／ｇ））
・アゾ系鉄錯体化合物（負荷電性制御剤） ２重量部
・低分子量ポリエチレンワックス ５重量部
（融点１１０℃、重量平均分子量１８８０）
【０２６０】
上記材料をヘンシェルミキサーで混合した後、１３０℃で二軸混練押出機によって溶融混練を行い、混合物を冷却後、カッターミルで粗粉砕した後、ジェット気流を用いた微粉砕機を用いて粉砕し、更に風力分級機を用いて分級して、重量平均径６．３μｍの負荷電性の磁性トナー粒子（Ｐ）を得た。
【０２６１】
このトナー（Ｐ）を用いて、結着樹脂に含有されるテトラヒドロフラン（ＴＨＦ）、酢酸エチル及びクロロホルムの可溶成分及び不溶分をソックスレー抽出により定量したところ、混在するワックスを除外した樹脂組成物は、ＴＨＦ不溶分（Ｗ２）が３１重量％であり、酢酸エチル不溶分（Ｗ４）が３４重量％であり、クロロホルム不溶分（Ｗ６）が１５重量％であり、比（Ｗ４／Ｗ６）が２．７であり、ＴＨＦ不溶分（Ｗ２）中のクロロホルム不溶分（Ｗ６Ａ）が６．７重量％であり、酢酸エチル不溶分（Ｗ４）中のクロロホルム不溶分（Ｗ６Ｂ）が８．３重量％であった。
【０２６２】
テトラヒドロフランの可溶成分（Ｗ１）のＧＰＣによる分子量測定を行ったところ、メインピークとなる分子量が４４００、分子量５００以上１万未満の領域の成分（Ａ１）が４８．９％、分子量１万以上１０万未満の領域の成分（Ａ２）が２６．７％、分子量１０万以上の領域の成分（Ａ３）が２４．４％であり、比（Ａ１／Ａ２）は１．８３であった。
【０２６３】
トナーの結着樹脂及びトナーの酢酸エチルの可溶成分（Ｗ３）の酸価を測定したところ、トナーに含有されている結着樹脂の酸価（ＡＶ１）は２６．７ｍｇＫＯＨ／ｇであり、トナーの酢酸エチル可溶成分の酸価（ＡＶ２）は２１．６ｍｇＫＯＨ／ｇであり、比（ＡＶ１／ＡＶ２）の値は１．２であった。
【０２６４】
¹Ｈ−ＮＭＲ及び¹³Ｃ−ＮＭＲにより、トナー中にビニル系共重合体、ポリエステル樹脂及びポリエステルユニットとビニル系重合体ユニットを有しているハイブリッド樹脂成分が存在していることを確認した。
【０２６５】
トナーにおいて、ポリエステルユニットとビニル系重合体ユニットを有しているハイブリッド樹脂成分は、¹³Ｃ−ＮＭＲにより新たに生成するエステル結合のシグナルを検出することにより検証することができる。
【０２６６】
一般的にスチレンと共重合したアクリル酸エステルのエステル基の¹³Ｃ−ＮＭＲにより測定されるシグナルは、アクリル酸エステルの単独重合体のそれよりスチレンのベンゼン環の影響により数ｐｐｍ高磁場側にシフトする現象が知られている。これは、アクリル酸エステルのアルコール成分がポリエステルのアルコール成分とエステル交換反応して得られるハイブリッド樹脂成分の場合も同様であり、エステル交換によって導入されるポリエステルユニットに含有されるベンゼン環の影響も受け、シグナルは上記ビニル系重合体ユニットのアクリル酸エステルより更に高磁場側のシグナルとして検出される。
【０２６７】
低架橋度ポリエステルの¹³Ｃ−ＮＭＲ測定結果を図１に、スチレン−２−エチルヘキシルアクリレート共重合体の測定結果を図２に、トナーに含有される結着樹脂（Ｃ−１）の測定結果を図３に示す。この結果より、アクリル酸エステルの約２２モル％がポリエステルユニットとエステル化したハイブリッド樹脂成分として存在することがわかった。
【０２６８】
各々の¹³Ｃ−ＮＭＲ測定結果を表５に示す。
【０２６９】
【表５】

【０２７０】
さらにＮＭＲにより酢酸エチルに不溶な結着樹脂成分（Ｗ４）及び溶解する結着樹脂成分（Ｗ３）に含有されるポリエステル樹脂成分（Ｇｐ）及び（Ｓｐ）を定量したところ、Ｇｐ＝約８３重量％、Ｓｐ＝約７７重量％であり、比（Ｓｐ／Ｇｐ）＝０．９３であり、式（１−３）で表わせるコハク酸誘導体の存在量を定量したところ、酢酸エチルに不溶な成分に全仕込み量の約７４重量％含有されていた。
【０２７１】
酢酸エチルに不溶な成分（Ｗ４）に含有されるワックス量はＤＳＣにより測定され溶解エンタルピーから定量でき、その結果、トナーに添加して全ワックスの約６１重量％が存在していることがわかった。
【０２７２】
トナー分析結果は表６及び表７に記載した。
【０２７３】
この磁性トナー粒子（Ｐ）１００重量部に対して、疎水性シリカ（比表面積２００ｍ²／ｇ）１．０重量部と複合酸化物（Ｍ−１）３．０重量部をヘンシェルミキサーにて外添混合して評価用磁性トナー（Ｐ−１）とした。
【０２７４】
＜評価−１＞
トナー定着性評価としての濃度低下率及び高温オフセットは、以下の評価方法に基づいて実施した。低温定着性に関しては、濃度低下率３％と良好な結果を示し、高温オフセットに関しても問題はなかった。評価結果は表８に示した。
【０２７５】
低温定着性試験：
キヤノン製デジタル複写機ＧＰ２１５改造機（現像、ドラム、光学、紙搬送系等を全て調整して複写速度を２０％アップさせた。）を低温低湿室（温度：５℃、湿度：５％）に設置する。
【０２７６】
評価用磁性トナー（Ｐ−１）にて、ハーフトーン画像を原稿として、連続通紙１００枚の画出しを行い、１００枚目の画像をサンプリングし、その画像を４９００Ｎ／ｍ²（５０ｇ／ｃｍ²）の荷重をかけて、柔和な薄紙により摺擦し、この前後における画像濃度差（画像濃度低下率（％））で評価した。
【０２７７】
（低温定着性評価レベル）
Ａ：濃度低下率が５％未満
Ｂ：濃度低下率が５％以上１０％未満
Ｃ：濃度低下率が１０％以上１５％未満
Ｄ：濃度低下率が１５％以上２５％未満
Ｅ：濃度低下率が２５％以上
【０２７８】
高温オフセット試験：
キヤノン製複写機ＮＰ６０８５の定着器を取り外し、外部駆動及び温度制御装置を設置する。
【０２７９】
キヤノン製複写機ＮＰ６０８５を用いて評価用磁性トナー（Ｐ−１）を使用して未定着画像を作り、上記の定着装置の定着温度を変化させて、高温オフセットの発生の有無を、定着ローラー上及び定着画像上へのトナー付着を目視確認することで判断し、評価した。
【０２８０】
（耐高温オフセット性評価レベル）
Ａ：２５０℃にてオフセット発生無し
Ｂ：２５０℃にて、軽微なオフセット発生
Ｃ：２３０℃〜２４０℃にて、軽微なオフセット発生
Ｄ：２２０℃〜２３０℃にてオフセット発生
Ｅ：２１０℃以下でオフセット発生
【０２８１】
＜評価−２＞
トナー材料中の結着樹脂を（ａ−２）に、負荷電性制御剤をＡｌ錯体化合物に変えた以外は上記トナーの製造例と同様にして、重量平均径７．０μｍの磁性トナー粒子（Ｑ）を得た。
【０２８２】
この磁性トナー粒子（Ｑ）１００重量部に対して、疎水性シリカ（比表面積２００ｍ²／ｇ）１．０重量部と複合酸化物（Ｍ−２）４．０重量部をヘンシェルミキサーにて外添混合して評価用磁性トナー（Ｑ−１）とした。
【０２８３】
このトナーを用いて、評価−１と同様の評価を行った。低温定着性及び耐高温オフセット性に関しては良好な結果であった。評価結果を表８に示した。
【０２８４】
＜評価−３〜５＞
トナー材料中の結着樹脂を（ａ−３）、（ａ−４）、（ａ−５）に変えた以外は評価−１と同様にして、各々重量平均径６．４μｍ、６．８μｍ、６．６μｍの磁性トナー粒子（Ｒ）、（Ｓ）、（Ｔ）を得た。
【０２８５】
この各々の磁性トナー粒子（Ｒ）、（Ｓ）、（Ｔ）１００重量部に対して、疎水性シリカ（比表面積２００ｍ²／ｇ）１．０重量部と複合酸化物（Ｍ−２）４．０重量部をヘンシェルミキサーにて外添混合して評価用磁性トナー（Ｒ−１）、（Ｓ−１）、（Ｔ−１）とした。
【０２８６】
このトナーを用いて、評価−１と同様の評価を行った。低温定着性及び耐高温オフセット性に関しては良好な結果であった。評価結果を表８に示した。
【０２８７】
＜評価−６〜７：比較例＞
トナー材料中の結着樹脂を（ア−１）、（ア−２）に変えた以外は上記トナーの製造例と同様にして、各々重量平均径６．４μｍ及び６．８μｍの磁性トナー粒子（サ）及び（シ）を得た。
【０２８８】
この各々の磁性トナー粒子（サ）及び（シ）１００重量部に対して、疎水性シリカ（比表面積２００ｍ²／ｇ）１．０重量部と複合酸化物（Ｍ−２）４．０重量部をヘンシェルミキサーにて外添混合して比較評価用磁性トナー（サ−１）及び（シ−１）とした。
【０２８９】
このトナーを用いて、評価−１と同様の評価を行った。（サ−１）に関しては耐高温オフセット性に、（シ−１）に関しては低温定着性に問題が生じた。評価結果を表８に示した。
【０２９０】
＜評価−８＞
上記のトナー（Ｑ）、（Ｒ）、（Ｓ）、（Ｔ）、（サ）及び（シ）に関して、トナー（Ｐ）と同様の分析を行い、表６及び表７の結果を得た。
【０２９１】
＜評価−９＞
キヤノン製複写機ＮＰ６０８５改造機（現像、ドラム、光学、紙搬送系等を全て調整して複写速度を２０％アップさせた。）を高温高湿室（温度：３２．５℃、湿度：８５％）に設置する。この時、クリーニングブレードには表４中のＢをドラムに対して総圧６８０ｇにて当接させた。
【０２９２】
評価用磁性トナー（Ｐ−１）を使用して連続３０万枚画出しを行い、画像濃度、カブリ、画像流れとドラム削れ量に関して評価した。結果は耐久初期から最終の３０万枚に至るまで、画像濃度は安定しており、カブリも無い高画質が得られた。また、画像流れは発生しなかった。更に、耐久前後でのドラム膜厚を測定したところ、削れ量は１０Åであった。詳細な結果は表９に示した。
【０２９３】
画像濃度の評価レベルは、耐久中最大画像濃度−耐久終了３０万枚時画像濃度によって判断した。
【０２９４】
カブリの評価レベルは、耐久終了３０万枚時のベタ白画像におけるカブリによって判断した。
【０２９５】
カブリ測定は、カブリ測定用反射測定機ＲＥＦＬＥＣＴＭＥＴＥＲ（東京電色（株））にて、上記のベタ白画像及び未使用紙の反射率を測定して、両者の差をカブリとする。未使用紙反射率−ベタ白反射率＝カブリ％
【０２９６】
画像流れの評価は、耐久中に画像上にて抜けが発生した場合、この最大抜け画像面積で評価した。
【０２９７】
ドラム削れ量の評価は、耐久前ドラムと耐久後ドラムとの膜厚（ドラム軸方向１０点平均）差で判断した。
【０２９８】
（画像濃度評価レベル）
Ａ：最大画像濃度−耐久終了時画像濃度 ０．０５未満
Ｂ：最大画像濃度−耐久終了時画像濃度 ０．０５以上０．１０未満
Ｃ：最大画像濃度−耐久終了時画像濃度 ０．１０以上０．１５未満
Ｄ：最大画像濃度−耐久終了時画像濃度 ０．１５以上０．２５未満
Ｅ：最大画像濃度−耐久終了時画像濃度 ０．２５以上
【０２９９】
（カブリ評価レベル）
Ａ：カブリ ０．１％未満
Ｂ：カブリ ０．１以上０．５％未満
Ｃ：カブリ ０．５以上１．０％未満
Ｄ：カブリ １．０以上１．５％未満
Ｅ：カブリ １．５以上
【０３００】
（画像流れ評価レベル）
Ａ：抜け画像面積 なし
Ｂ：抜け画像面積 ０．１５ｃｍ²未満
Ｃ：抜け画像面積 ０．１５以上５．０ｃｍ²未満
Ｄ：抜け画像面積 ５．０以上１０．０ｃｍ²未満
Ｅ：抜け画像面積 １０．０ｃｍ²以上
【０３０１】
（ドラム削れ量評価レベル）
Ａ：削れ量 １０．０Å未満
Ｂ：削れ量 １０．０以上２５．０Å未満
Ｃ：削れ量 ２５．０以上５０．０Å未満
Ｄ：削れ量 ５０．０以上１５０．０Å未満
Ｅ：削れ量 １５０．０Å以上
【０３０２】
＜評価−１０〜１４＞
クリーニングブレードをＣ，Ｄ，Ｆ，Ｇ，Ｈに変更して、評価−９と同様の評価を行った。画像濃度は高く、安定しており、カブリの無い解像力の高い画質が得られた。更に画像流れは問題の無いレベルであった。詳細な結果は表９に示した。
【０３０３】
＜評価−１５〜１９：比較例＞
クリーニングブレードをＡ，Ｅ，Ｉ，Ｊ，Ｋに変更して、評価−９と同様の評価を行った。画像濃度は高く、安定しており、カブリも問題の無いレベルで解像力の高い画質が得られた。更に画像流れは問題の無いレベルであったが、Ａ，Ｅ，Ｉ，Ｋに関しては耐久途中からクリーニング不良が、Ｊに関しては耐久途中からドラム融着が発生した。詳細な結果は表９に示した。
【０３０４】
＜評価−２０〜２３＞
評価用磁性トナーを（Ｑ−１）、（Ｒ−１）、（Ｓ−１）、（Ｔ−１）に変更して、評価−９と同様の評価を行った。画像濃度は高く、安定しており、カブリも問題の無いレベルで解像力の高い画質が得られた。更に画像流れは問題の無いレベルであった。詳細な結果は表９に示した。
【０３０５】
＜評価−２４〜２５：比較例＞
評価用磁性トナーを（サ−１）及び（シ−１）に変更して、評価−９と同様の評価を行った。いずれのトナーも画像濃度は低下傾向があり、カブリ抑制の悪い画質が得られた。更に、画像流れは問題の無いレベルであったが、（シ−１）においてはクリーニング不良が、（サ−１）に関してはドラム融着が発生した。詳細な結果は表９に示した。
【０３０６】
＜評価−２６〜２９：比較例＞
この各々の磁性トナー粒子（Ｑ），（Ｒ），（サ），（シ）１００重量部に対して、疎水性シリカ（比表面積２００ｍ²／ｇ）１．０重量部と複合酸化物（Ｍ−３）４．０重量部をヘンシェルミキサーにて外添混合して比較評価用磁性トナー（Ｑ−２）、（Ｒ−２）、（サ−２）及び（シ−２）とした。
【０３０７】
このトナーを用いて、評価−９と同様の評価を行った。いずれのトナーも、耐久により、ドラム削れが発生したため、画像濃度は低下傾向があり、カブリ抑制の悪い画質が得られた。ただし、画像流れは問題の無いレベルであった。詳細な結果は表９に示した。
【０３０８】
＜評価−３０：比較例＞
磁性トナー粒子（Ｑ）１００重量部に対して、疎水性シリカ（比表面積２００ｍ²／ｇ）１．０重量部をヘンシェルミキサーにて外添混合して比較評価用磁性トナー（Ｑ−３）とした。
【０３０９】
このトナーを用いて、評価−９と同様の評価を行った。結果は、耐久により画像濃度は低下傾向があり、カブリ抑制の悪い画質が得られた。更に、画像流れは耐久初期より発生した。また、ドラム削れは問題の無いレベルであったが、ドラム融着が発生していった。詳細な結果は表９に示した。
【０３１０】
【表６】

【０３１１】
【表７】

【０３１２】
【表８】

【０３１３】
【表９】

【０３１４】
（トナー及びブレードの粘弾特性）
磁性トナー（Ｐ），（Ｑ），（Ｒ），（Ｓ），（Ｔ），（サ）及び（シ）に関して、粘弾性を測定した。結果は表１０となった。（Ｐ）の粘弾性測定チャートを図１１として添付する。
【０３１５】
さらに、表１１に本検討で使用したトナー（Ｐ）とブレードとの粘弾特性を示す。
【０３１６】
【表１０】

【０３１７】
【表１１】

【０３１８】
【発明の効果】
本発明によれば、上記の如く使用するトナー及びクリーニングブレードの改良を行ったことから、高温高湿下においても高画質、高画像濃度が得られ、さらにクリーニング不良やトナー融着及び画像流れ等を発生させない画像形成方法及び画像形成装置を提供することができる。
【図面の簡単な説明】
【図１】低架橋度ポリエステル樹脂組成物の¹³Ｃ−ＮＭＲスペクトルを示す。
【図２】スチレン・２−エチルヘキシルアクリレート共重合体の¹³Ｃ−ＮＭＲスペクトルを示す。
【図３】本発明に係る結着樹脂（Ｃ−１）の¹³Ｃ−ＮＭＲスペクトルを示す。
【図４】本発明に係る結着樹脂（Ｃ−１）の酢酸エチル可溶成分の¹Ｈ−ＮＭＲスペクトルを示す。
【図５】本発明に係る結着樹脂（Ｃ−１）の酢酸エチル不溶成分の¹Ｈ−ＮＭＲスペクトルを示す。
【図６】ＰＯ−ＢＰＡのＰＯ基の¹Ｈ−ＮＭＲシグナルの帰属を示す説明図である。
【図７】ソックスレー抽出に使用するソックスレー抽出装置の一具体例を示す概略図である。
【図８】本発明の画像形成方法を実施し得る画像形成装置の一例を示す説明図である。
【図９】図８に示す画像形成装置の現像部の拡大図を示す。
【図１０】ブレードＢの粘弾性データーを示すグラフである。
【図１１】トナー（Ｐ）の粘弾性データーを示すグラフである。
【図１２】製造例１の複合酸化物のＸ線回折ピークパターンを示すグラフである。
【符号の説明】
１ 静電潜像保持体（感光体）
４ トナー担持体（現像スリーブ）
７ 定着器
８ クリーニングブレード
９ 現像器
１１ 磁性ブレード
１３ トナー
Ｐ 記録材（転写材）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an image forming method and an image forming apparatus using toner for developing an electrostatic charge latent image.
[0002]
[Prior art]
Many electrophotographic methods are known as described in US Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748. In general, a photoconductive material is used to form an electrostatic charge image on a photoreceptor by various means, and then the electrostatic charge image is developed with toner, and a toner image is formed on a transfer material such as paper as necessary. After the toner is transferred, the toner image is fixed on the transfer material by heating, pressure, heating and pressurization, or solvent vapor.
[0003]
Various methods and apparatuses have been developed with respect to the process of fixing the toner image on the sheet as a transfer material, which is the final process described above. The most common method at present is a pressure heating method using a fixed heating heater via a heat roller or a heat-resistant film.
[0004]
The pressure heating method using a heating roller fixes the toner image by allowing the surface of the heat roller having releasability to the toner and the toner image surface of the fixing sheet to pass through the fixing sheet while contacting under pressure. It is. In this method, the surface of the heat roller and the toner image on the fixing sheet come into contact with each other under pressure, so that the thermal efficiency when fusing the toner image on the fixing sheet is extremely good, and the fixing is performed quickly. Can do.
[0005]
Since the surface of the heating roller and the toner image are in contact with each other in a molten state and under pressure, a part of the toner image adheres to and is transferred to the surface of the fixing roller, which is transferred again to the next fixing sheet and stains the fixing sheet. The so-called offset phenomenon is greatly affected by the fixing speed and fixing temperature. In general, when the fixing speed is low, the surface temperature of the heating roller is set to be relatively low, and when the fixing speed is high, the surface temperature of the heating roller is set to be relatively high. This is to make the amount of heat applied from the heating roller to the toner to fix the toner substantially constant regardless of the fixing speed.
[0006]
Since the toner image on the fixing sheet has several toner layers, in a system where the fixing speed is particularly high and the surface temperature of the heating roller is high, the toner layer contacting the heating roller and the fixing target The temperature difference with the lowermost toner layer in contact with the sheet becomes large. Therefore, when the surface temperature of the heating roller is high, a phenomenon of high temperature offset that causes the toner on the uppermost layer to transfer to the heating roller is likely to occur, and when the surface temperature of the heating roller is low, the toner on the lowermost layer is sufficiently melted. Therefore, the toner is not fixed on the fixing sheet and a phenomenon of low temperature offset is likely to occur.
[0007]
In order to solve this problem, when the fixing speed is high, it is usual to increase the pressure at the time of fixing and anchor the toner to the fixing sheet. With this method, the temperature of the heating roller can be lowered to some extent, and the high temperature offset phenomenon of the uppermost toner layer can be prevented. However, since the shearing force applied to the toner becomes very large, the fixing sheet is wound around the fixing roller, so that a so-called winding offset phenomenon occurs or the fixing sheet is separated from the fixing roller. The separation nail is likely to appear in the fixed image. Furthermore, since the pressure is high, the line image is crushed at the time of fixing, or the toner is blown off, so that the image quality of the fixed image is likely to deteriorate.
[0008]
Conventionally, vinyl copolymers such as polyester resins and styrene resins are mainly used as binder resins for toners.
[0009]
Polyester resins have excellent performance at low temperature fixability, but on the other hand, they have a problem that offset phenomenon is likely to occur at high temperatures. In order to compensate for this problem, attempts have been made to improve the viscoelastic properties by increasing the molecular weight of the polyester resin. In this case, however, there is a problem that the low-temperature fixability is impaired, and pulverization during toner production As a result, the binder resin becomes unsuitable for toner fine particles.
[0010]
Vinyl copolymers such as styrene resins are excellent in high-temperature offset resistance because of their excellent pulverization properties during toner production and easy high molecular weight, but they have a low molecular weight to improve low-temperature fixability. In addition, there is a problem that blocking resistance and developability deteriorate when the glass transition temperature is lowered.
[0011]
In order to make effective use of the advantages of these two types of resins and to make up for the drawbacks, several methods of mixing and using these resins have been studied.
[0012]
For example, Japanese Patent Laid-Open No. 54-114245 discloses a toner containing a resin obtained by mixing a polyester resin and a vinyl copolymer. However, since the chemical structure of the polyester resin and the vinyl copolymer are largely different, the compatibility is poor, and it is difficult to satisfy all of the low-temperature fixability, the high-temperature offset resistance, and the blocking resistance.
[0013]
Furthermore, it is difficult to uniformly disperse various additives added at the time of toner production, particularly wax, and not only the toner fixing performance but also developability is likely to occur. This problem becomes remarkable.
[0014]
Japanese Patent Application Laid-Open Nos. 56-116043 and 58-159546 disclose a toner containing a polymer obtained by polymerizing a monomer in the presence of a polyester resin. .
[0015]
JP-A-58-102246 and JP-A-1-156759 disclose a toner containing a polymer obtained by polymerizing a vinyl copolymer in the presence of an unsaturated polyester. Yes.
[0016]
Japanese Patent Publication No. 8-16796 discloses a toner comprising a polyester resin having a specific acid value and a block copolymer obtained by esterifying a styrene resin having a specific acid value and molecular weight. Yes.
[0017]
Japanese Patent Application Laid-Open No. 8-54753 discloses a toner in which the binder resin is composed of a condensation polymerization resin and a vinyl resin and has a specific chloroform insoluble content and a peak in a specific molecular weight range.
[0018]
In the above binder resin, the condensation polymerization resin and the addition polymerization resin can maintain a stable phase separation state. However, although the high-temperature offset resistance is improved to some extent with toners using these binder resins, the low-temperature fixability of the toner is still insufficient, and when the toner contains wax, the dispersion state of the wax is reduced. It is difficult to control. When a toner is used, there are still problems to be improved not only in low-temperature fixability but also in developability.
[0019]
JP-A-62-195681 and JP-A-62-195682 describe a developer composition for electrophotography comprising a vinyl resin-containing polyester resin containing a specific amount of vinyl resin relative to the polyester resin. is doing.
[0020]
However, the binder resin used in these electrophotographic developer compositions is a mixture in which a vinyl resin is dispersed and mixed in a polyester resin, and satisfies the low temperature fixability and the high temperature offset resistance. It is difficult.
[0021]
In recent years, there has been a demand for multifunctional copying machines and high-quality copy images by digitizing copying machines and making toner fine particles. However, in the case of finely divided toner, the colorant (magnetic material) contained in the toner is relatively large, and it becomes difficult to maintain the low-temperature fixability of the toner, and the developability is more severe than ever. become.
[0022]
Furthermore, as an effort to deal with environmental problems, in medium- and low-speed machines, power consumption is reduced by the pressure heating method using a heat-resistant film that requires little residual heat or heat storage. In high-speed copiers, power is supplied to the fixing roller. As a reduction, body design from the viewpoint of energy saving such as fixing roller wage down is also becoming important.
[0023]
The decrease in low-temperature fixability of the toner is particularly noticeable in the halftone part. This is because the amount of toner on the fixing sheet that forms a halftone image is smaller than that of the solid image portion. In other words, in a solid image, even if the toner can maintain low-temperature fixability by the synergistic effect of the adhesion force between the toners in addition to the adhesion force between the toner and the fixing sheet, In a halftone image in which the applied amount is reduced, it is difficult to maintain low-temperature fixability. Furthermore, in the pressure heating method using heat-resistant film, it is necessary to suppress the pressure during fixing to some extent in order to maintain the durability of the film and the fixing device itself, which is severe for low-temperature fixability in halftone images. It becomes.
[0024]
As a countermeasure, when a countermeasure is taken by increasing the amount of heat supplied to the heater, a temperature rise problem occurs in the non-sheet passing portion. This is because when A4 paper is continuously fed vertically, the portion where the paper continuously passes on the fixing member is deprived of heat, so that the fixing heater is turned on to maintain the temperature necessary for fixing. . However, in the non-sheet passing portion, heat is not taken away by the paper, and the temperature is increased by heat storage. As a countermeasure, not only a main body design that does not cause cracking of the heater but also a toner resistant to high temperature offset is required.
[0025]
Further, when the toner image is transferred onto the transfer material from the photoconductor during the process of obtaining the toner image, there is residual toner on the photoconductor. In order to perform continuous copying promptly, it is necessary to clean the remaining toner on the photoreceptor. If this cleaning is insufficient, various image defects may be caused. As this cleaning means, magnetic brush cleaning, blade cleaning, or the like is used.
[0026]
In the above-described cleaning method, in the magnetic brush cleaning method, the toner remaining on the photosensitive member is electrostatically attracted and collected on the carrier of the cleaning material. However, this method has problems such as scattering of toner from the magnetic brush and poor cleaning that occur when the charge amount of the carrier of the cleaning material decreases. As a method for solving these problems, Japanese Patent Application Laid-Open No. 5-88595 discloses a method for preventing toner scattering by changing the rotational speed of the cleaning roller itself depending on the charged state of the cleaning material. However, this method cannot completely remove paper dust, ozone deposits, and the like that are generated or adhered to the photoreceptor.
[0027]
In addition, since the cleaning method using a blade directly scrapes residual toner from the surface of the photoreceptor, various problems such as filming, toner fusion, and photoconductor scraping have occurred.
[0028]
In addition, the organic photoreceptor and the amorphous silicon photoreceptor cause a phenomenon of image flow due to the influence of paper dust, ozone deposits, and the like attached to the surface of the photoreceptor, particularly in a high temperature and high humidity environment. As a method for solving these problems, in Japanese Patent Application Laid-Open No. 2-110475, a paper powder produced or adhered on a photoreceptor using two kinds of inorganic fine powders in a toner using a metal-crosslinked styrene-acrylic resin, A method for removing ozone adducts and improving toner scattering, image flow, and image density reduction under high temperature and high humidity has been disclosed. However, this method has a problem in image stability during continuous copying because the photoconductor itself is also scraped.
[0029]
In recent years, digitalization of copiers and finer toner particles have increased the functionality of copiers, improved the image quality of copy images, and also addressed environmental issues. No internal heater (drum heater) is desired.
[0030]
Furthermore, further improvement is required in the method of removing the residual toner on the photosensitive member and removing the paper dust, ozone adduct, etc. generated or adhered on the photosensitive member by increasing the copying speed and the material of the transfer paper.
[0031]
In JP-A-9-190125, a blade having a rebound resilience of 35 to 60% at room temperature is used, and inorganic particles are contained on the surface of the organic photoconductor, so that the photoconductor surface roughness Rz is 0.05 to 1.0 μm. A method is disclosed in which a cleaning blade is brought into contact with a photoconductor against a counter, and the cleaning blade is vibrated to 10 to 200 μm for cleaning. Although it is possible to improve the cleanability under normal temperature and normal humidity by this method, there is a problem in achieving both prevention of image flow and photoconductor abrasion under high temperature and high humidity.
[0032]
In other words, the above-mentioned problems, in particular, the half-tone low-temperature fixability is good, the high-temperature offset is strong, the wax dispersion state in the toner is uniform and no image defect occurs, and the cleaning is performed under high temperature and high humidity. At present, no image forming method or apparatus that does not cause defects, toner fusion, image flow, or the like has been realized.
[0033]
[Problems to be solved by the invention]
An object of the present invention is to provide an image forming method and an image forming apparatus that solve the above-mentioned problems.
[0034]
An object of the present invention is to provide an image forming method and an image forming apparatus using a toner in which wax is uniformly dispersed in a binder resin.
[0035]
An object of the present invention is to provide an image forming method and an image forming apparatus capable of obtaining a high image quality and a high image density even with a fine particle toner having an increased content of a colorant (particularly a magnetic material).
[0036]
An object of the present invention is to provide an image forming method and an image forming apparatus capable of obtaining good low-temperature fixability in a halftone image even in a fine particle toner having an increased content of a colorant (particularly a magnetic material).
[0037]
The object of the present invention is to exhibit good low-temperature fixability and high-temperature offset even in a medium to low-speed machine using a high-speed machine using a heat roll fixing device and a pressure heating method using a fixed heating heater through a heat-resistant film. It is an object of the present invention to provide an image forming method and an image forming apparatus that exhibit a wide fixing temperature region in which no occurrence of the toner occurs.
[0038]
SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method and an image forming apparatus which are controlled in a dispersed state without adversely affecting the toner fixing property and developing property regardless of the type and amount of wax.
[0039]
An object of the present invention is to provide an image forming method and an image forming apparatus capable of continuously obtaining an image faithful to a latent image even in a long-term durability.
[0040]
An object of the present invention is to provide an image forming method and an image forming apparatus that do not cause image flow even under high temperature and high humidity.
[0041]
SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method and an image forming apparatus that do not cause photoconductor abrasion even when used in a high-speed copying machine and are excellent in durability of a large number of sheets.
[0042]
[Means for Solving the Problems]
In the present invention, an electrostatic charge image formed on an electrostatic charge image carrier is developed using toner to form a toner image, and the formed toner image is transferred from the electrostatic charge image carrier to an intermediate transfer member. Or an image forming method having a step of transferring to a transfer material without intervention, and cleaning the transfer residual toner on the electrostatic charge image carrier using a cleaning blade,
The toner is a toner having toner particles containing at least a binder resin, a wax and a colorant and an inorganic fine powder,
The binder resin is
(1) A vinyl resin, a polyester resin, and a hybrid resin component having a vinyl polymer unit and a polyester unit,
(2) Soxhlet extraction for 10 hours using tetrahydrofuran (THF) as a solvent, containing 50 to 85% by weight (W1) of a THF-soluble component and 15 to 50% (W2) of a THF-insoluble component,
(3) 10-hour Soxhlet extraction using ethyl acetate as a solvent, containing 40 to 98% by weight (W3) of an ethyl acetate soluble component, 2 to 60% by weight (W4) of an ethyl acetate insoluble component,
(4) Soxhlet extraction for 10 hours using chloroform as a solvent, containing 55 to 90% by weight (W5) of a chloroform soluble component and 10 to 45% by weight (W6) of a chloroform insoluble component,
(5) The value of W4 / W6 is 1.1 to 4.0,
When the toner is at a temperature of 50 to 75 ° C.
(A) There exists a temperature (TT.C) at which the storage elastic modulus (G′T) and the loss elastic modulus (G ″ T) become equal,
(B) There exists a temperature (TT.P) at which the loss tangent (tan δTP) becomes maximum,
The cleaning blade
(C) Storage modulus (G′B) of 5 × 10 5 at a temperature of 40 to 80 ° C.^FiveTo 1 × 10⁷Pa,
(D) At a temperature of 40 to 80 ° C., the loss elastic modulus (G ″ B) is 5 × 10^ThreeTo 1 × 10⁶Pa,
(E) At a temperature of 40 to 80 ° C., there is a temperature (TT.B) at which the loss tangent (tan δB.P) is minimized,
(F) There exists a temperature (TB.P) at which the loss tangent (tan δB.P) is maximized at a temperature of 70 to 130 ° C.
In the loss tangent of the toner and the cleaning blade,
(G) the difference (TT.P-TB.P) is −40 to 20 ° C .;
(H) Ratio (G ″ T) of the loss elastic modulus (G ″ T) of the toner at the temperature (TT.C) and the loss elastic modulus (G ″ BC) of the cleaning blade at the temperature (TT.C). ) / (G ″ B.C) is 5 × 10²To 5 × 10^FourIs
The present invention relates to an image forming method.
[0043]
Further, the present invention provides a developing means for developing an electrostatic image formed on an electrostatic image carrier with toner and forming a toner image, and intermediate transfer of the formed toner image from the electrostatic image carrier. In an image forming apparatus having at least a transfer unit for transferring to a transfer material with or without a body, and a cleaning unit for cleaning the transfer residual toner on the electrostatic charge image carrier using a cleaning blade,
The toner is a toner having toner particles containing at least a binder resin, a wax and a colorant and an inorganic fine powder,
The binder resin is
(1) A vinyl resin, a polyester resin, and a hybrid resin component having a vinyl polymer unit and a polyester unit,
(2) Soxhlet extraction for 10 hours using tetrahydrofuran (THF) as a solvent, containing 50 to 85% by weight (W1) of a THF-soluble component and 15 to 50% (W2) of a THF-insoluble component,
(3) 10-hour Soxhlet extraction using ethyl acetate as a solvent, containing 40 to 98% by weight (W3) of an ethyl acetate soluble component, 2 to 60% by weight (W4) of an ethyl acetate insoluble component,
(4) Soxhlet extraction for 10 hours using chloroform as a solvent, containing 55 to 90% by weight (W5) of a chloroform soluble component and 10 to 45% by weight (W6) of a chloroform insoluble component,
(5) The value of W4 / W6 is 1.1 to 4.0,
When the toner is at a temperature of 50 to 75 ° C.
(A) There exists a temperature (TT.C) at which the storage elastic modulus (G′T) and the loss elastic modulus (G ″ T) become equal,
(B) There exists a temperature (TT.P) at which the loss tangent (tan δTP) becomes maximum,
The cleaning blade
(C) Storage modulus (G′B) of 5 × 10 5 at a temperature of 40 to 80 ° C.^FiveTo 1 × 10⁷Pa,
(D) At a temperature of 40 to 80 ° C., the loss elastic modulus (G ″ B) is 5 × 10^ThreeTo 1 × 10⁶Pa,
(E) At a temperature of 40 to 80 ° C., there is a temperature (TT.B) at which the loss tangent (tan δB.P) is minimized,
(F) There exists a temperature (TB.P) at which the loss tangent (tan δB.P) is maximized at a temperature of 70 to 130 ° C.
In the loss tangent of the toner and the cleaning blade,
(G) the difference (TT.P-TB.P) is −40 to 20 ° C .;
(H) Ratio (G ″ T) of the loss elastic modulus (G ″ T) of the toner at the temperature (TT.C) and the loss elastic modulus (G ″ BC) of the cleaning blade at the temperature (TT.C). ) / (G ″ B.C) is 5 × 10²To 5 × 10^FourIs
The present invention relates to an image forming apparatus.
[0044]
DETAILED DESCRIPTION OF THE INVENTION
According to the study of the present inventor, even a toner having a reduced particle size with an increased content of a colorant (especially a magnetic material), good low-temperature fixability even in a halftone image regardless of the heating method of the fixing device. In order to obtain a toner having a high temperature offset occurrence temperature and difficult to offset, the toner binder resin should contain a certain amount of components having a composition and molecular weight that can be selectively dissolved in a plurality of specific solvents. is important.
[0045]
Conventionally, the resin component insoluble in any one solvent of tetrahydrofuran, chloroform or ethyl acetate contained in the binder resin of the toner is quantified, and it corresponds to the high temperature offset occurrence temperature of the toner to some extent. However, this is not an evaluation from the viewpoint of evaluating the dispersion state of the wax contained in the toner, which may greatly affect not only the toner fixability but also the toner developability.
[0046]
According to the study of the present inventors, tetrahydrofuran (THF) is a good solvent for the vinyl polymer unit of the binder resin contained in the toner of the present invention, but is not necessarily good for the polyester unit. It is not a solvent. Quantifying components insoluble in THF can be achieved by quantifying components having a very large molecular weight in polyester resins or components having a relatively high proportion of polyester units in hybrid resin components. is there. The component insoluble in THF can evaluate the low-temperature fixability of the toner. Furthermore, in order to achieve better low-temperature fixability, it is important that the component soluble in THF has a specific molecular weight and molecular weight component.
[0047]
Ethyl acetate is a good solvent for the polyester unit of the binder resin contained in the toner of the present invention, but is not necessarily a good solvent for the vinyl polymer unit. Quantifying components that are insoluble in ethyl acetate means that components having a very high molecular weight in vinyl resins or components having a relatively high proportion of highly crosslinked components and vinyl polymer units in hybrid resin components Is to quantify. The ethyl acetate insoluble component contains a component that is soluble in chloroform and a component that is insoluble in chloroform. It is possible to evaluate the dispersion state of the wax, which has a significant influence on imparting not only the toner fixability but also a stable developability (for example, environment dependency such as image density and fog) to the toner.
[0048]
Chloroform is a good solvent for both the vinyl polymer unit and the polyester unit of the binder resin contained in the toner of the present invention. Quantifying components that are insoluble in chloroform can be achieved by hybridizing extremely high molecular weight components or highly cross-linked components in vinyl-based resins with extremely high molecular weight components or highly cross-linked components in polyester resins. Quantifying the component having a very large molecular weight or the highly crosslinked component in the resin component. Such a component having a very large molecular weight or a crosslinked component in the hybrid resin component is closely related to the high temperature offset occurrence temperature of the toner.
[0049]
Therefore, the ratio of ethyl acetate insoluble component to chloroform insoluble component contained in the binder resin of the toner not only shows the balance of wax dispersion and high temperature resistant offset, but also the toner is stable without causing image defects. It becomes an index for showing good developability.
[0050]
In the present invention, the binder resin preferably contains 15 to 50% by weight of THF insolubles (W2), preferably 20 to 45% by weight, more preferably 25 to 40% by weight. . When the content of the THF-insoluble component is less than 15% by weight, the high temperature offset occurrence temperature of the toner is lowered to cause a problem in hot offset resistance and the storage stability of the toner may be deteriorated. . If the THF-insoluble content exceeds 50% by weight, the low-temperature fixability of the toner may deteriorate, which is not preferable.
[0051]
In the present invention, the binder resin may contain 2 to 60% by weight of ethyl acetate insoluble (W4), preferably 5 to 50% by weight, more preferably 10 to 40% by weight. good. If the ethyl acetate insoluble content is less than 2% by weight, there is a problem with the resistance to hot offset of the toner, and it becomes difficult to control the dispersion state of the wax contained in the toner. May decrease, which is not preferable. When the content of ethyl acetate insoluble is more than 60% by weight, there is a problem in the low-temperature fixability of the toner, and the fog density may increase due to durability, which is not preferable.
[0052]
In the present invention, the binder resin preferably contains 10 to 45% by weight of chloroform-insoluble matter (W6), preferably 15 to 40% by weight, and more preferably 17 to 37% by weight. When the content of the chloroform-insoluble component is less than 10% by weight, not only the problem of hot offset resistance is caused, but also a phenomenon that the toner is fused on the photosensitive member due to durability may occur. When the content of the chloroform-insoluble component exceeds 45% by weight, not only the problem of low-temperature fixability of the toner occurs, but also the toner on the photoconductor may become difficult to clean due to durability, which is not preferable.
[0053]
The value of the ratio (W4 / W6) of ethyl acetate insoluble matter (W4) to chloroform insoluble matter (W6) should be 1.1 to 4.0, preferably 1.2 to 3.5, Preferably it is 1.3 to 3.0. In any case where the ratio (W4 / W6) is less than 1.1 or more than 4.0, the image density decreases due to durability.
[0054]
Further, in the present invention, the binder resin contains (i) THF-insoluble matter (W2), and the THF-insoluble matter (W2) further contains chloroform-insoluble matter (W6A) as A weight% (binder resin). (Ii) containing ethyl acetate insoluble matter (W4), ethyl acetate insoluble matter (W4) further containing chloroform insoluble matter (W6B) in B wt% (binder resin) (On a weight basis).
[0055]
The content of the chloroform insoluble component (W6A) contained in the THF insoluble component (W2) and the content of the chloroform insoluble component (W6B) contained in the ethyl acetate insoluble component (W4) satisfy the following conditions. Preferably
3 wt% ≤ W6A ≤ 25 wt%
7 wt% ≤ W6B ≤ 30 wt%
10 wt% ≤ W6A + W6B ≤ 45 wt%
W6A: W6B = 1: 1-3
More preferably, the following conditions are satisfied.
[0056]
5 wt% ≤ W6A ≤ 20 wt%
10 wt% ≤ W6B ≤ 25 wt%
15 wt% ≤ W6A + W6B ≤ 40 wt%
W6A: W6B = 1: 1.5-2.5
[0057]
When the THF-insoluble matter (W2) contains less than 3% by weight of the chloroform-insoluble matter (W6A), not only the high temperature offset resistance of the toner is impaired, but also the image density due to the durability of the toner may be lowered. There is not preferable.
[0058]
If the THF-insoluble content (W2) contains more than 25% by weight of the chloroform-insoluble content (W6A), the low-temperature fixability of the toner may be impaired, which is not preferable.
[0059]
When the ethyl acetate insoluble component (W4) contains less than 7% by weight of the chloroform insoluble component (W6B), not only the high temperature offset resistance of the toner is impaired but also the toner blocking resistance may be impaired. There is not preferable.
[0060]
When the ethyl acetate insoluble content (W4) contains more than 30% by weight of the chloroform insoluble content (W6B), the low-temperature fixability of the toner may be impaired.
[0061]
The total amount (W6A + W6B) of the content of chloroform insoluble matter (W6A) contained in THF insoluble matter (W2) and the content of chloroform insoluble matter (W6B) contained in ethyl acetate insoluble matter (W4) is , Which corresponds to the content of the chloroform-insoluble content (W6) of the binder resin. Therefore, if the total amount (W6A + W6B) deviates from the upper and lower limits, the content of the above-mentioned chloroform-insoluble content (W6) The result is the same as when the value falls below the lower limit.
[0062]
Furthermore, the ratio of the content of chloroform insoluble matter (W6A) contained in THF insoluble matter (W2) to the content of chloroform insoluble matter (W6B) contained in ethyl acetate insoluble matter (W4) is 1: 1. If the ratio is less than 1, not only the high temperature offset resistance of the toner is impaired, but also the toner blocking resistance may be impaired.
[0063]
When the ratio exceeds 1: 3, not only the low-temperature fixability of the toner is impaired, but also the image density may decrease due to durability, which is not preferable.
[0064]
In the molecular weight distribution measured by gel permeation chromatography (GPC), the THF soluble component has a main peak in the region of molecular weight 4000 to 9000, preferably in the region of molecular weight 5000 to 8500. More preferably, it has a molecular weight of 4500 to 8000. When the main peak is in a region having a molecular weight of less than 4000, the hot offset resistance of the toner may deteriorate, and when the main peak is in a region having a molecular weight of more than 9000, the low-temperature fixability of the toner may be impaired. There is not preferable.
[0065]
The component (A1) having a molecular weight of 500 to less than 10,000 is preferably contained in an amount of 35.0 to 65.0%, preferably 37.0 to 60.0%, more preferably 40.0 to 55. It is good to contain 0.0%. When the content of the component in the molecular weight region of 500 to less than 10,000 is less than 35.0%, the low-temperature fixability of the toner may deteriorate, and when it exceeds 65.0%, the toner is stored. It may be worse, and is not preferable.
[0066]
The component (A2) having a molecular weight of 10,000 to less than 100,000 is preferably contained in an amount of 25.0 to 45.0%, preferably 27.0 to 42.0%, more preferably 30.0 to It is good to contain 40.0%. When the content of the component in the region having a molecular weight of 10,000 to less than 100,000 is less than 25.0%, the hot offset resistance of the toner may deteriorate, and when it exceeds 45.0%, the toner The low temperature fixability of the toner may deteriorate, which is not preferable.
[0067]
The component (A3) having a molecular weight of 100,000 or more is preferably contained in an amount of 10.0 to 30.0%, preferably 12.0 to 25.0%, more preferably 15.0 to 22.0. % Content is good. When the content of the component in the region having a molecular weight of 100,000 or more is less than 10.0%, the hot offset resistance of the toner may deteriorate, and when it exceeds 30.0%, the toner is fixed at low temperature. It may be worse, and is not preferable.
[0068]
The value of the ratio (A1 / A2) is preferably 1.05 to 2.00, preferably 1.10 to 1.90, and more preferably 1.15 to 1.80. When the ratio (A1 / A2) is less than 1.05, the low temperature fixability of the toner may be deteriorated, and when it exceeds 2.00, the hot offset resistance of the toner may be deteriorated. Absent.
[0069]
In the present invention, the charging ratio of the monomer for synthesizing the polyester resin used for synthesizing the binder resin and the vinyl monomer is 10% by weight of the vinyl monomer to 100 parts by weight of the monomer for synthesizing the polyester resin. Or 100 to 100 parts by weight, preferably 15 to 80 parts by weight, and more preferably 20 to 70 parts by weight.
[0070]
In the binder resin contained in the toner of the present invention, the “hybrid resin component” means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are formed by a transesterification reaction, preferably a vinyl polymer. Is used to form a graft copolymer (or block copolymer) having a backbone polymer and a polyester unit as a branch polymer.
[0071]
Therefore, in the present invention, the vinyl polymer unit and polyester unit of the hybrid resin component are:
[0072]
[Chemical Formula 3]

It connects through.
[0073]
The binder resin contained in the toner of the present invention is a (meth) acrylic acid in which the reaction rate with the polyester unit of all carboxylic acid esters in the vinyl polymer unit, that is, the grafting rate, is contained in the vinyl polymer. The content is preferably 10 to 60 mol%, more preferably 15 to 55 mol%, still more preferably 20 to 50 mol% based on the ester. When the grafting rate is less than 10 mol%, the compatibility between the vinyl polymer unit and the polyester unit is deteriorated, and the dispersibility of the wax may be deteriorated. As a result of an increase in a component having a relatively large molecular weight, the low-temperature fixability of the toner may deteriorate, which is not preferable.
[0074]
The component (W4) insoluble in ethyl acetate preferably contains 40 to 98% by weight of the polyester resin component (Gp), preferably 50 to 95% by weight, more preferably 60 to 90% by weight. Good to be. When the content of the polyester resin component (Gp) is less than 40% by weight, the fixability of the toner may be deteriorated, which is not preferable. When the content exceeds 98% by weight, it is not compatible with the hydrocarbon wax. It is not preferable because the solubility tends to deteriorate.
[0075]
The component (W3) dissolved in ethyl acetate preferably contains 20 to 90% by weight of the polyester resin component (Sp), preferably 25 to 85% by weight, more preferably 30 to 80% by weight. Good to be. When the content of the polyester resin component (Sp) is less than 20% by weight, the fixing property is not improved because the hydrocarbon wax is uniformly dispersed throughout the binder resin contained in the toner. If it exceeds wt%, the compatibility with the hydrocarbon-based wax tends to be poor, localization occurs, and hot offset does not easily occur.
[0076]
The ratio (Sp / Gp) is preferably 0.50 to 1.00, preferably 0.60 to 0.95, and more preferably 0.65 to 0.90. When the ratio (Sp / Gp) is less than 0.5 and when the ratio (Sp / Gp) exceeds 1.00, the components that are insoluble in ethyl acetate and the components that are soluble are mixed uniformly. In this case, the developability of the toner may be deteriorated, which is not preferable.
[0077]
In the present invention, the acid value (AV1) of the entire binder resin of the toner may be 7 to 40 mgKOH / g, preferably 10 to 37 mgKOH / g, more preferably 15 to 35 mgKOH / g, and still more preferably. It is good that it is 17-30 mgKOH / g.
[0078]
Further, the acid value (AV2) of the ethyl acetate soluble component (W3) of the toner may be 10 to 45 mgKOH / g, preferably 15 to 45 mgKOH / g, more preferably 17 to 40 mgKOH / g, and still more preferably. Is preferably 20 to 35 mg KOH / g.
[0079]
The ratio (AV1 / AV2) of the acid value (AV1) of the entire binder resin of the toner to the acid value (AV2) of the ethyl acetate soluble part (W3) of the toner is preferably 0.7 to 2.0, More preferably, it is 0.9-1.7, More preferably, it is 1.0-1.5.
[0080]
When the acid value (AV1) of the entire binder resin of the toner is less than 7 mgKOH / g or more than 40 mgKOH / g, the image density may decrease due to durability, which is not preferable.
[0081]
When the acid value (AV2) of the ethyl acetate-soluble component (W3) of the toner is less than 10 mgKOH / g, the high temperature offset resistance of the toner may be impaired, and when it exceeds 45 mgKOH / g, the toner The low temperature fixability of the resin may be impaired, which is not preferable.
[0082]
When the value of AV1 / AV2 is less than 0.7, the image density due to durability may decrease, which is not preferable. When the value exceeds 2.0, the high temperature offset resistance of the toner may be impaired.
[0083]
In the toner of the present invention, the polyester unit is preferably a divalent carboxylic acid represented by formulas (1) to (4), a monovalent carboxylic acid represented by formula (5), or 1 represented by formula (6). It contains at least one kind of hydric alcohol.
[0084]
[Formula 4]

[Wherein R₁Represents a linear, branched or cyclic alkyl group or alkenyl group having 14 or more carbon atoms;_Three, R_Four, R_FiveAnd R₆Represents a hydrogen atom, a linear, branched or cyclic alkyl group or alkenyl group having 3 or more carbon atoms, and may be the same substituent, but at the same time, it does not become a hydrogen atom.₇And R₈Represents a linear, branched or cyclic alkyl group or alkenyl group having 12 or more carbon atoms, and n represents an integer of 12 to 40. ]
[0085]
Examples of the compound represented by the formula (1) include the following compounds (1-1) to (1-6).
[0086]
[Chemical formula 5]

[0087]
Examples of the compound that can be represented by the formula (2) include the following compounds (2-1) to (2-4).
[0088]
[Chemical 6]

[0089]
Examples of the compound that can be represented by the formula (3) include the following compounds (3-1) to (3-3).
[0090]
[Chemical 7]

[0091]
Examples of the compound represented by the formula (4) include the following compounds (4-1) to (4-2).
[0092]
[Chemical 8]

[0093]
As a compound represented by Formula (5), the following compounds (5-1)-(5-5) are mentioned, for example.
[0094]
[Chemical 9]

[0095]
Examples of the compound that can be represented by the formula (6) include the following compounds (6-1) to (6-5).
[0096]
Embedded image

[0097]
Furthermore, the present inventors have continued investigations regarding poor cleaning under high temperature and high humidity, toner fusion, and image flow, and have found the following.
[0098]
As a method for cleaning the residual toner on the photosensitive member, paper dust generated or adhered, ozone adducts, and the like, an electrostatic adsorption method using a magnetic brush, a scraping method using a cleaning blade, and the like are considered.
[0099]
However, the magnetic brush method is effective for cleaning residual toner, but there is a problem as a method for cleaning paper dust, ozone adducts and the like generated or adhered on the photosensitive member. Further, in the scraping method using a cleaning blade, the effect obtained varies depending on the material of the blade used and the contact method with the photosensitive member.
[0100]
When a hard blade is brought into contact with the photoconductor to clean the residual toner on the photoconductor and the generated or adhered paper dust, ozone adduct, etc., the adhesion between the photoconductor and the blade is difficult to obtain, and cleaning by slipping etc. Defects are likely to occur. Further, when the contact pressure on the photoconductor is increased for the purpose of avoiding this phenomenon, problems such as photoconductor scraping and toner fusion onto the photoconductor occur.
[0101]
Conversely, when a soft blade is brought into contact with the photoconductor to clean the residual toner on the photoconductor and the generated or adhered paper powder, ozone adducts, etc., the adhesion between the photoconductor and the blade increases, A cleaning failure occurs due to chatter or the like due to the influence of vibration during rotation of the photosensitive member. In addition, when the contact pressure on the photosensitive member is reduced in order to avoid this phenomenon, the residual toner on the photosensitive member and the generated or adhered paper dust, ozone adduct, etc. are cleaned. Will cause problems.
[0102]
Furthermore, in order to achieve both cleanability and polishability, a method of using a cleaning blade and a magnetic brush together is considered, but the copying machine itself cannot be made lightweight and compact, and the setting flexibility is narrow. There are problems such as points.
[0103]
In addition, for the blade material described above, the rebound resilience at room temperature and normal humidity is defined, and the surface roughness is defined by adding inorganic fine powder to the surface of the organic photoreceptor, and the blade is countered against the photoreceptor. Although it is also considered that the cleaning is performed by causing the blade itself to abut and vibrating the blade itself, it is effective for cleaning the residual toner on the photoreceptor, but the paper dust generated or adhered under high temperature and high humidity is effective. There is a problem when cleaning ozone adducts and the like.
[0104]
Furthermore, the method of adding a third component having an abrasive effect as a cleaning aid to the toner has an effect of cleaning paper dust, ozone adducts, etc. produced or adhered to the photoconductor, but the photoconductor is scraped and developed. This does not satisfy all of the properties and cleaning properties.
[0105]
Therefore, the present inventors considered the developing property and cleaning property of the toner especially under high temperature and high humidity, and as a result of examining the problems in the cleaning in detail, the viscoelastic property of the cleaning blade and the toner We found that there is a close relationship between viscoelastic properties. Furthermore, it has been found that, in a blade and a toner satisfying this condition, the use of a complex oxide as an inorganic fine powder in the toner further enhances this effect.
[0106]
The cleaning blade in contact with the photoreceptor heats up due to friction with the photoreceptor during continuous copying. This phenomenon becomes more prominent depending on the environment where the copying machine is installed. That is, the temperature rise under high temperature and high humidity becomes very severe, and in the high speed copying machine, the temperature of the blade in contact with the photosensitive member is 40 to 70 ° C.
[0107]
Therefore, the present inventors have measured viscoelastic characteristics as temperature-dependent characteristics for various toners and blades, and paid attention to developability and image flow under high temperature and high humidity, and photoconductor scraping in these combinations. And found the following.
[0108]
When the developer has composite oxide (A) particles that are inorganic fine powders represented by the following formula (1), the abrasiveness to paper dust and ozone adduct from the photoreceptor is improved.
[0109]
[M₁]_a[M₂]_bO_c                (1)
(Where M₁Represents a metal element selected from the group consisting of Sr, Mg, Zn, Co, Mn, Ca and Ce, and M₂Represents a metal element selected from Ti or Si, a represents an integer of 1 to 9, b represents an integer of 1 to 9, and c represents an integer of 3 to 9. )
[0110]
Further, blocking of the toner in the developing unit, fusion to the photosensitive member, and the like can be prevented by setting the viscoelastic characteristics of the toner and the blade within the following ranges.
[0111]
When the toner is at a temperature of 50 to 75 ° C.
a) There exists a temperature (TT.C) at which the storage elastic modulus (G′T) and the loss elastic modulus (G ″ T) become equal,
b) There is a temperature (TT.P) at which the loss tangent (tan δTP) is a maximum,
The cleaning blade
c) Storage modulus (G′B) of 5 × 10 5 at a temperature of 40 to 80 ° C.^FiveTo 1 × 10⁷Pa,
d) At a temperature of 40 to 80 ° C., the loss elastic modulus (G ″ B) is 5 × 10^ThreeTo 1 × 10⁶Pa,
e) At a temperature of 40 to 80 ° C., there is a temperature (TT.B) at which the loss tangent (tan δB.P) is minimized,
f) There exists a temperature (TB.P) at which the loss tangent (tan δB.P) is maximized at a temperature of 70 to 130 ° C.
In the loss tangent of the toner and the cleaning blade,
g) The difference (TT.P-TB.P) is −40 to 20 ° C.,
h) The ratio (G "T / G" B.C) of the loss elastic modulus (G "B.C) of the cleaning blade at the temperature (TT.C) is 5 × 10.²To 5 × 10^FourIt is.
[0112]
1 Pa = 10 dyn / cm²It is.
[0113]
From the above, especially when performing continuous copying in a high-temperature and high-humidity environment using a high-speed copying machine, it maintains high image quality and high image density, and generates or adheres to the residual toner on the photoreceptor and the photoreceptor. In order to prevent the occurrence of poor cleaning, image flow, etc. by removing paper dust and ozone adduct, it is important to define the viscoelastic characteristics of toner and blade, and more preferably binder resin It is important to use the composite oxide represented by the above formula (1) for the toner containing the hybrid resin and defining the viscoelastic characteristics of the toner and the blade.
[0114]
In the toner of the present invention, the temperature (T.TC) at which the storage elastic modulus (G′T) and the loss elastic modulus (G ′) are equal exists at a temperature of 50 to 75 ° C., and the loss tangent (tan δTP) is the maximum. Temperature (T.TP) is present, but preferably, the temperature is 53 to 73 ° C. TC and T.W. In the presence of TP, more preferably at a temperature of 55 to 70 ° C. TC and T.W. This is a case where TP exists.
[0115]
If the temperature is below 50 ° C. TC and T.W. If TP is present, a phenomenon called drum fusion in which the toner is fixed onto the electrophotographic photosensitive member during cleaning may occur regardless of the viscoelastic property of the cleaning blade. When the temperature exceeds 75 ° C. TC and T.W. The presence of TP is not preferable because the toner may form large scratches on the surface of the electrophotographic photosensitive member during cleaning regardless of the viscoelastic properties of the cleaning blade.
[0116]
In the present invention, the cleaning blade has a temperature of 40 to 80 ° C. and a storage elastic modulus (G′B) of 5 × 10 5.^FiveTo 1 × 10⁷It may be Pa, but preferably 7 × 10^FiveTo 7 × 10⁶Pa, more preferably 1 × 10⁶To 5 × 10⁶This is the case when Pa is reached. If G’B is 5 × 10^FiveWhen the pressure is less than Pa, a phenomenon called poor cleaning in which the toner on the electrophotographic photosensitive member is not completely cleaned may occur during cleaning regardless of the viscoelastic property of the toner. G’B is 1 × 10⁷If the pressure exceeds Pa, a phenomenon called drum scraping that causes significant wear on the surface of the electrophotographic photosensitive member may occur, which is not preferable.
[0117]
In the present invention, the cleaning blade has a temperature of 40 to 80 ° C. and a loss elastic modulus (G ″ B) of 5 × 10^ThreeTo 1 × 10⁶Pa is sufficient, but preferably 7 × 10^ThreeTo 7 × 10^FivePa, more preferably 1 × 10^FourTo 5 × 10^FiveThis is the case when Pa is reached. If G ″ B is 5 × 10^ThreeIf it is less than Pa, the drum fusion phenomenon may occur during cleaning regardless of the viscoelastic properties of the toner, which is not preferable. G ″ B is 1 × 10⁶If it exceeds Pa, a phenomenon called cleaning failure may occur, which is not preferable.
[0118]
In the present invention, the cleaning blade may have a temperature (TT.B) at which the loss tangent (tan δB.P) is minimal at a temperature of 40 to 80 ° C., but preferably has a loss tangent (tan δB at a temperature of 42 to 75 ° C. .P) is present when there is a minimum temperature (TT.B), more preferably when there is a temperature (TT.B) at which the loss tangent (tan δB.P) is minimized at a temperature of 45 to 70 ° C. It is.
[0119]
If the temperature TT. At which (tan δB.P) is minimized. When B is less than 40 ° C., drum fusion may occur during cleaning regardless of the viscoelastic properties of the toner, which is not preferable. The temperature TT. At which (tan δB.P) is minimized. When B exceeds 80 ° C., drum scraping may occur, which is not preferable.
[0120]
In the present invention, the cleaning blade may have a temperature of 70 to 130 ° C. and a temperature (TB.P) at which the loss tangent (tan δB.P) becomes maximum. P is a temperature of 75 to 120 ° C., more preferably TB. This is the case where P is at a temperature of 80 to 110 ° C.
[0121]
If the temperature TB. P is less than 70 ° C. and temperature TB. When P exceeds 130 ° C., cleaning failure may occur, which is not preferable.
[0122]
In the present invention, the difference (TT.P-TB.P) may be −40 to 20 ° C., preferably −30 to 10 ° C., more preferably −20 to 5 ° C. It is.
[0123]
If the difference (TT.P-TB.P) is less than −40 ° C. and the difference (TT.P-TB.P) exceeds 20 ° C., a sufficient removal effect from the drum cannot be obtained. Drum fusion, poor cleaning, etc. may occur, which is not preferable.
[0124]
In the present invention, the loss elastic modulus ratio (G "T / G" BC) of the toner and the cleaning blade at the temperature (TT.C) is 5 × 10.²To 5 × 10^FourPa may be used, but preferably 7 × 10.²To 3 × 10^FourPa, more preferably 1 × 10^ThreeTo 1 × 10^FourThis is the case when Pa is reached.
[0125]
If the ratio (G "T / G" BC) is 5 × 10²If the ratio is less than 1, drum scraping may occur, which is not preferable, and the ratio (G "T / G" BC) is 5 × 10.^FourWhen it exceeds, drum fusion may occur, which is not preferable.
[0126]
Further, in the present invention, a more preferable toner configuration will be described in detail below.
[0127]
The following are mentioned as a monomer of the polyester resin used for this invention.
[0128]
As alcohol components, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexane Examples include diol, neopentyl glycol, 2-ethyl 1,3-hexanediol, hydrogenated bisphenol A, bisphenol derivatives represented by the following formula (7-1), and diols represented by the following formula (7-2).
[0129]
Embedded image

[0130]
Embedded image

[0131]
Acidic components include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides; Succinic acid substituted with an alkyl group or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof;
[0132]
The following are mentioned as a vinyl-type monomer for producing | generating a vinyl-type resin.
[0133]
Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- n-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene Styrene and its derivatives such as m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride Halogen such as vinylidene chloride, vinyl bromide, vinyl fluoride Vinyl esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, methacrylic acid Α-methylene aliphatic monocarboxylic acid esters such as dodecyl, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, propyl acrylate , N-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, acrylic Acrylic esters such as phenyl oxalate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N- N-vinyl compounds such as vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.
[0134]
In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester unsaturated dibasic acid half ester; dimethylmaleic acid, dimethyl fumaric acid unsaturated dibasic acid ester; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.
[0135]
Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.
[0136]
In the toner of the present invention, the polyester unit of the binder resin has a crosslinked structure crosslinked with a trivalent or higher polyvalent carboxylic acid or an anhydride thereof, or a trivalent or higher polyhydric alcohol. . Examples of the trivalent or higher polyvalent carboxylic acid or anhydride thereof include 1,2,4-benzenetricarboxylic acid, 1,2,4, -cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and pyromellitic. Examples thereof include acids and acid anhydrides or lower alkyl esters thereof. Examples of trihydric or higher polyhydric alcohols include 1,2,3-propanetriol, trimethylolpropane, hexanetriol, and pentaerythritol. Are preferably 1,2,4-benzenetricarboxylic acid and acid anhydrides thereof.
[0137]
In the toner of the present invention, the vinyl polymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. In this case, the crosslinking agent used is Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butanediol di Examples include acrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and the above compounds in which acrylate is replaced by methacrylate; linked by an alkyl chain containing an ether bond. As diacrylate compounds For example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate Examples of diacrylate compounds connected by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene ( 4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate; For example, as the rate class, like the trade name MANDA (Nippon Kayaku) is.
[0138]
Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallylcia Examples include nurate and triallyl trimellitate.
[0139]
These crosslinking agents can be used in an amount of 0.01 to 10 parts by weight (more preferably 0.03 to 5 parts by weight) with respect to 100 parts by weight of other monomer components.
[0140]
Among these crosslinkable monomers, those which are preferably used for toner resins from the viewpoint of fixing property and offset resistance, are bonded with an aromatic divinyl compound (particularly divinylbenzene), a chain containing an aromatic group and an ether bond. And diacrylate compounds.
[0141]
In this invention, it is preferable that the monomer component which can react with both resin components is contained in a vinyl-type copolymer component and / or a polyester resin component. Examples of the monomer constituting the polyester resin component that can react with the vinyl copolymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
[0142]
As a method for obtaining a reaction product of a vinyl resin and a polyester resin, a polymer containing a monomer component capable of reacting with each of the vinyl resin and the polyester resin listed above is present. A method obtained by polymerizing a resin is preferred.
[0143]
Examples of the polymerization initiator used for producing the vinyl copolymer of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4- Dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone peroxide, siku Ketone peroxides such as hexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide , Di-t-butyl peroxide, t-butyl cumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide Oxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate , Di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide , T-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate, t-butyl Peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl peroxy F Sa Hydro terephthalate, di -t- butyl peroxy azelate and the like.
[0144]
As a manufacturing method which can prepare binder resin used for the toner of this invention, the manufacturing method shown to the following (1)-(6) can be mentioned, for example.
[0145]
(1) A method in which a vinyl resin, a polyester resin and a hybrid resin component are blended after production, respectively, and the blend dissolves and swells in an organic solvent (for example, xylene), and then the organic solvent is distilled off. In this blending process, the wax is added and manufactured. The hybrid resin component is synthesized by separately producing a vinyl polymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and performing a transesterification reaction by heating. The ester compound used can be used.
[0146]
(2) A method of producing a polyester unit and a hybrid resin component in the presence of a vinyl polymer unit in the presence of the vinyl polymer unit. The hybrid resin component is produced by a reaction between a vinyl polymer unit (a vinyl monomer can be added if necessary) and a polyester monomer (alcohol, carboxylic acid) and / or polyester. Also in this case, an organic solvent can be appropriately used. Preferably, wax is added in this step.
[0147]
(3) A method for producing a vinyl polymer unit and a hybrid resin component in the presence of the polyester unit after the production. The hybrid resin component is produced by a reaction between a polyester unit (a polyester monomer can be added if necessary) and a vinyl monomer and / or vinyl polymer unit. Preferably, wax is added in this step.
[0148]
(4) After the production of the vinyl polymer unit and the polyester unit, the hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. Also in this case, an organic solvent can be appropriately used. Preferably, wax is added in this step.
[0149]
(5) After producing the hybrid resin component, vinyl polymer units and / or polyester units (alcohol, carboxylic acid) are added to carry out addition polymerization and / or polycondensation reaction to produce vinyl polymer units and polyester units. Is done. In this case, as the hybrid resin component, those produced by the production methods (2) to (4) can be used, and those produced by a known production method can be used as necessary. Furthermore, an organic solvent can be used as appropriate. Preferably, wax is added in this step.
[0150]
(6) A vinyl polymer unit, a polyester unit, and a hybrid resin component are produced by mixing a vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reaction. Furthermore, an organic solvent can be used as appropriate. Preferably, wax is added in this step.
[0151]
In the production methods (1) to (5), the vinyl polymer unit and / or the polyester unit can use a plurality of polymer units having different molecular weights and crosslinking degrees.
[0152]
Among the production methods (1) to (6) above, in particular, the production method (3) can easily control the molecular weight of the vinyl polymer unit, can control the production of the hybrid resin component, and When wax is added, it is preferable in that the dispersion state can be controlled.
[0153]
In the DSC curve measured with the differential scanning calorimeter of the toner of the present invention and the toner containing wax, the temperature is preferably 70 to 160 ° C, more preferably 70 to 140 ° C, still more preferably 75 to 140 ° C, and most preferably. The toner may have an endothermic main peak in the region of 80 to 135 ° C. from the viewpoint of low-temperature fixability and offset resistance of the toner.
[0154]
More preferably, the toner containing the wax has an endothermic main peak and an endothermic subpeak or endothermic shoulder in a temperature range of 80 to 155 ° C., preferably 90 to 130 ° C., in a DSC curve measured with a differential scanning calorimeter. It is preferable in terms of low-temperature fixability, offset resistance, and blocking resistance.
[0155]
In the DSC curve of the toner, the wax used is limited in order to form a clear endothermic peak in the temperature range of 70 to 160 ° C. When the temperature corresponding to the maximum endothermic peak is defined as the melting point of the wax in the DSC curve of the wax in the temperature range of 30 to 200 ° C. by a differential scanning calorimeter described later, the melting point of the wax is preferably 70 to 160 ° C. Preferably 75-160 ° C, more preferably 75-140 ° C, most preferably 80-135 ° C are used.
[0156]
Examples of such waxes include aliphatic hydrocarbon waxes such as low molecular polyethylene, low molecular polypropylene, microcrystalline wax and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; Block copolymers of hydrocarbon waxes; waxes based on fatty acid esters such as carnauba wax, sazol wax and montanic acid ester wax; partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax The thing which was done is mentioned. In addition, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a long-chain alkyl group; unsaturated fatty acids such as brandic acid, eleostearic acid, and valinal acid; Saturated alcohols such as stearic alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, melyl alcohol, or long chain alkyl alcohols having a long chain alkyl group; polyhydric alcohols such as sorbitol; , Fatty acid metal salts such as calcium laurate, zinc stearate and magnesium stearate (generally called metal soap); vinyl monomers such as styrene and acrylic acid are used in aliphatic hydrocarbon waxes Partial esters of such fatty acids with polyhydric alcohols behenic acid monoglyceride; obtained by grafting waxes and methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oil and the like.
[0157]
The low melting point wax component preferably used in the present invention comprises a hydrocarbon having a long-chain alkyl group with little branching, and specifically, for example, a low molecular weight obtained by polymerizing alkylene with radical polymerization under high pressure or Ziegler catalyst under low pressure. An alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer, a hydrocarbon distillation residue obtained by the age method from a synthesis gas composed of carbon monoxide and hydrogen, or obtained by hydrogenating these A wax such as a synthetic hydrocarbon is preferable. Furthermore, the thing which fractionated hydrocarbon wax by the use of the press perspiration method, the solvent method, the vacuum distillation, or the fractional crystallization system is used more preferably. The hydrocarbon as a base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (mostly two or more multi-component systems), for example, the jintole method, hydrocol method (fluidized catalyst bed) Or an age method (using a fixed catalyst bed) in which a large amount of waxy hydrocarbons can be obtained.
[0158]
The high melting point wax component preferably used in the present invention comprises a hydrocarbon having a long-chain alkyl group with little branching, and specifically, for example, a low molecular weight obtained by polymerizing alkylene with radical polymerization under high pressure or Ziegler catalyst under low pressure. An alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer, a hydrocarbon distillation residue obtained by the age method from a synthesis gas composed of carbon monoxide and hydrogen, or obtained by hydrogenating these A wax such as a synthetic hydrocarbon is preferable. Other preferable waxes include substituted alkyl waxes having a substituent such as a hydroxyl group or a carboxyl group.
[0159]
Specific examples of the hydrocarbon wax preferably used in the present invention include a low molecular weight alkylene polymer obtained by polymerizing an alkylene such as ethylene or propylene under high pressure by radical polymerization or a Ziegler catalyst under low pressure, or a high molecular weight alkylene polymer. A wax such as an alkylene polymer obtained by thermal decomposition, a hydrocarbon distillation residue obtained by an age method from a synthesis gas composed of carbon monoxide and hydrogen, or a synthetic hydrocarbon obtained by hydrogenating them is used. Further, those subjected to fractionation by press sweating method, solvent method, vacuum distillation or fractional crystallization method are more preferably used.
[0160]
As the petroleum wax, wax separated from petroleum such as paraffin wax, microcrystalline wax, and petrolactam is used.
[0161]
The hydrocarbon wax and petroleum wax in the present invention have substantially no functional group. “Substantially” means that the number of functional groups is 0.1 or less per molecule.
[0162]
The hydrocarbon wax or petroleum wax used in the present invention has an endothermic main peak in a temperature range of 70 to 140 ° C. in a DSC curve measured with a differential scanning calorimeter of the toner containing the wax. From the viewpoints of low-temperature fixability and offset resistance.
[0163]
More preferably, the toner containing a hydrocarbon wax or a petroleum wax preferably has an endothermic main peak in the region of a temperature of 80 to 135 ° C. in a DSC curve measured with a differential scanning calorimeter. More preferably, the toner containing the wax has an endothermic main peak and an endothermic subpeak or endothermic shoulder in a temperature range of 90 to 130 ° C. in a DSC curve measured with a differential scanning calorimeter. In view of offset resistance and blocking resistance, it is preferable.
[0164]
The content of the wax used in the present invention is 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight per 100 parts by weight of the binder resin.
[0165]
The complex oxide (A) is M₁As examples, magnesium, zinc, cobalt, manganese, strontium, calcium, and cerium can be given. M₂Examples thereof include titanium and silica. In particular, the strontium silicate [Sr] is effective because the effects of the present invention can be more exhibited_a[Si]_bO_cAnd strontium titanate [Sr]_a[Ti]_bO_cIs preferred. More specifically, SrSiO_Three, Sr_ThreeSiO_Five, Sr₂SiO_Four, SrSiO_Five, Sr_ThreeSi₂O₇And SrTiO_Three, Sr₂TiO_Four, Sr_ThreeTi₂O₇Among them, SrSiO_ThreeAnd SrTiO_ThreeIs preferred.
[0166]
The particles having a composite oxide used in the present invention are preferably produced by, for example, a sintering method, subjected to opportunity pulverization, air classification, and particles having a desired particle size distribution.
[0167]
In the composite oxide of the present invention, 0.10 to 10 parts by weight, preferably 0.2 to 5.0 parts by weight of the fine particles having the composite oxide (A) are used with respect to 100 parts by weight of the toner particles. . The particles containing the composite oxide have a weight average particle size of 0.1 to 5.0 μm, preferably 0.3 to 3.0 μm, more preferably 0.5 to 2.5 μm.
[0168]
When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite and ferrite, and iron oxides including other metal oxides; Fe, Co, Ni, etc. Metals or alloys of these metals with metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, V , And mixtures thereof.
[0169]
Specifically, as the magnetic material, triiron tetroxide (Fe_ThreeO_Four), Iron sesquioxide (γ-Fe₂O_Three), Zinc iron oxide (ZnFe₂O_Four), Iron yttrium oxide (Y_ThreeFe_FiveO₁₂), Cadmium oxide (CdFe₂O_Four), Iron gadolinium oxide (Gd)_ThreeFe_Five-O₁₂), Copper iron oxide (CuFe₂O_Four), Lead iron oxide (PbFe₁₂-O₁₉), Nickel iron oxide (NiFe)₂O_Four), Neodymium iron oxide (NdFe₂O_Three), Iron barium oxide (BaFe)₁₂O₁₉), Magnesium iron oxide (MgFe₂O_Four), Iron manganese oxide (MnFe₂O_Four), Iron lanthanum oxide (LaFeO)_Three), Iron powder (Fe), cobalt powder (Co), nickel powder (Ni) and the like. The magnetic materials described above are used alone or in combination of two or more. A particularly suitable magnetic material is a fine powder of triiron tetroxide or γ-iron sesquioxide.
[0170]
These ferromagnets have an average particle size of 0.05 to 2 μm, a magnetic property of 795.8 kA / m applied, a coercive force of 1.6 to 12.0 kA / m, and a saturation magnetization of 50 to 200 Am.²/ Kg (preferably 50-100 Am²/ Kg), residual magnetization 2-20 Am²/ Kg is preferred.
[0171]
The magnetic material is used in an amount of 10 to 200 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of the binder resin.
[0172]
The nonmagnetic colorant that can be used in the toner of the present invention includes any appropriate pigment or dye. Examples of the pigment include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengara, phthalocyanine blue, and indanthrene blue. These are added in an amount of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the binder resin. Similarly, dyes are used, for example, anthraquinone dyes, xanthene dyes, and methine dyes, and 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The addition amount of is good.
[0173]
In the toner of the present invention, a charge control agent may be used as necessary in order to further stabilize the chargeability. The charge control agent is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight per 100 parts by weight of the binder resin.
[0174]
Examples of the charge control agent include the following.
[0175]
For example, an organometallic complex, a chelate compound, and an organometallic salt can be given. Specific examples include monoazo metal complexes; metal complexes or metal salts of aromatic hydroxycarboxylic acid and aromatic dicarboxylic acid compounds. Others include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their anhydrides, esters thereof; phenol derivatives of bisphenols.
[0176]
A fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner particles to increase the fluidity before and after the addition. For example, fluororesin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder; wet powder silica, fine powder silica such as dry process silica, fine powder titanium oxide, fine powder alumina, silane coupling agent, There are a titanium coupling agent, a treated silica surface-treated with silicone oil, and the like.
[0177]
A preferable fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, and is called so-called dry silica or fumed silica. For example, a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame is used, and the basic reaction formula is as follows.
[0178]
SiCl₂+ 2H₂+ O₂→ SiO₂+ 4HCl
[0179]
In this production process, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. To do. The average primary particle size is preferably within a range of 0.001 to 2 μm, and particularly preferably a fine silica powder within a range of 0.002 to 0.2 μm is used. .
[0180]
Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include those sold under the following trade names.
[0181]

[0182]
Furthermore, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of the silicon halide is more preferable. Among the treated silica fine powders, those obtained by treating the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is in the range of 30 to 80 are particularly preferable.
[0183]
As a hydrophobizing method, it is applied by chemically treating with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound.
[0184]
Examples of organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, and bromomethyldimethyl. Chlorsilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyl Diethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3 -Diphenyltetramethyldisiloxane and dimethylpolysiloxane containing 2 to 12 siloxane units per molecule, each containing a hydroxyl group bonded to one Si at each terminal unit. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These are used alone or in a mixture of two or more.
[0185]
The fluidity improver has a specific surface area of 30 m by nitrogen adsorption measured by the BET method.²/ G or more, preferably 50 m²/ G or more gives good results. The flow improver is used in an amount of 0.01 to 8 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the toner.
[0186]
To prepare the toner of the present invention, a binder resin, a colorant and / or a magnetic material, a charge control agent or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. The toner of the present invention can be obtained by melting and kneading using such a heat kneader to make the resins compatible with each other, cooling and solidifying the melt-kneaded product, pulverizing the solidified product, and classifying the pulverized product.
[0187]
The toner particles preferably have a weight average particle diameter of 3 to 12 μm, more preferably 3 to 9 μm in terms of image density and resolution.
[0188]
Further, the fluidity improver and the toner particles can be sufficiently mixed by a mixer such as a Henschel mixer to obtain a toner having the fluidity improver on the toner particle surface.
[0189]
Next, the image forming method of the present invention will be described.
[0190]
An example of an image forming apparatus that can carry out the image forming method of the present invention will be described with reference to FIGS. The surface of the electrostatic charge image carrier (photoconductor) 1 is charged negatively or positively by the primary charger 2, and an electrostatic charge image (for example, a digital latent image by image scanning) is formed by analog exposure or laser light exposure 5. Magnetic blade 11 and magnetic pole N₁, N₂, S₁And S₂The electrostatic charge image is developed by reversal development or normal development with the magnetic toner 13 of the developing device 9 including the developing sleeve 4 including the magnet 23 having the. An alternating bias, a pulse bias, and / or a direct current bias is applied by the bias applying means 12 between the conductive substrate 16 of the photoreceptor 1 and the developing sleeve 4 in the developing unit. The magnetic toner image is transferred to the transfer material with or without the intermediate transfer member. When the transfer paper P is conveyed and arrives at the transfer section, the transfer charger 3 charges the positive or negative polarity from the back surface (the opposite surface to the photoconductor side) of the transfer paper P by the transfer charger 3. The electrostatic magnetic toner image or the positively charged magnetic toner image is electrostatically transferred onto the transfer paper P. The transfer paper P separated from the photosensitive member 1 after being neutralized by the static eliminating means 22 is heated and pressurized and fixed on the toner image on the transfer paper P by the heat and pressure roller fixing device 7 including the heater 21.
[0191]
The magnetic toner remaining on the photoreceptor 1 after the transfer process is removed by a cleaning unit having a cleaning blade 8. After the cleaning, the photoreceptor 1 is neutralized by the erase exposure 6, and the process starting from the charging process by the primary charger 2 is repeated again.
[0192]
Next, a method for measuring various physical property data measured in the following examples will be described below.
[0193]
(1) Determination of toner insoluble components in tetrahydrofuran (THF), ethyl acetate and chloroform
2 g of the toner is precisely weighed (TW1), put in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kaisha, Ltd.), passed through a Soxhlet extractor, and 200 ml of THF is used. Reflux for 10 hours using an oil bath whose temperature is adjusted to about 120 ° C. The component soluble in THF (W1) can be quantified by concentrating and drying the THF, followed by vacuum drying at 60 ° C. for 24 hours. When the THF-insoluble component (W2) of the toner is quantified, it is calculated from the THF-insoluble component (TW2) other than the binder resin such as a colorant (magnetic material) by the following formula.
[0194]
[Expression 1]

[0195]
Similarly, by changing the solvent to ethyl acetate and chloroform, the soluble component and insoluble component of the binder resin in each solvent can be quantified.
[0196]
An example of a Soxhlet extraction apparatus is shown in FIG.
[0197]
The THF 52 contained in the container 51 is heated and vaporized by the heater 53, and the vaporized THF is guided to the cooler 55 through the pipe 54. The cooler 55 is constantly cooled by cooling water 56. The THF cooled and liquefied by the cooler 55 accumulates in the storage part 58 having the cylindrical filter paper 57, and when the liquid level of THF becomes higher than the middle tube 59, the THF is discharged from the storage part to the container 51. The toner or resin contained in the cylindrical filter paper 57 is extracted by circulating THF.
[0198]
(2)¹H-NMR and¹³Determination of polyester resin insoluble and soluble in ethyl acetate by C-NMR measurement
¹H-NMR and¹³C-NMR is used to determine the abundance ratio of each monomer composition in terms of a molar ratio. The molecular weight of each monomer is used from the abundance ratio of each monomer composition at this molar ratio, and the amount of dehydration associated with esterification is ignored. The amount is calculated in weight%.
[0199]
(¹Measurement of H-NMR (nuclear magnetic resonance) spectrum)
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Data points: 32768
Frequency range: 10500Hz
Integration count: 10,000 times
Measurement temperature: 60 ° C
Sample: 50 mg of a measurement sample is put in a φ5 mm sample tube, and CDCl is used as a solvent._ThreeIs added and dissolved in a constant temperature bath at 60 ° C. to prepare.
[0200]
(¹³Measurement of C-NMR (nuclear magnetic resonance) spectrum)
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Data points: 32768
Delay time: 25 sec.
Frequency range: 10500Hz
Integration count: 16 times
Measurement temperature: 40 ° C
Sample: 200 mg of a measurement sample is put in a φ5 mm sample tube, and CDCl is used as a solvent._Three(TMS 0.05%) is added and dissolved in a constant temperature bath at 40 ° C. to prepare.
[0201]
¹H-NMR and¹³One specific example of the determination of the content of the polyester resin in the component insoluble in ethyl acetate and in the soluble component by C-NMR measurement is described below with reference to FIGS.
[0202]
▲ 1 ▼ ¹ Determination of abundance ratio of alcohol component by H-NMR measurement (see FIGS. 4 and 5)
The abundance ratio of propoxylated bisphenol A (PO-BPA) and ethoxylated bisphenol A (EO-BPA) is:¹In the H-NMR spectrum, signals of propoxy group hydrogen (corresponding to each 1H: see FIG. 6) near 5.2 ppm, 5.3 ppm and 5.4 ppm and hydrogen of ethoxy group around 4.3 ppm and 4.65 ppm (each 4 H (Equivalent) signal and the intensity ratio.
[0203]
▲ 2 ▼ ¹ Determination of abundance ratio of aromatic carboxylic acid component by H-NMR measurement (see FIGS. 4 and 5)
The existing ratio of terephthalic acid and trimellitic acid is¹It is determined from the intensity ratio between the signal of hydrogen of terephthalic acid near 8 ppm (equivalent to 4H) and the signal of hydrogen of trimellitic acid near 7.6 ppm and 8.4 ppm (equivalent to 1H each) in the H-NMR spectrum.
[0204]
▲ 3 ▼ ¹ Determination of abundance ratio of styrene by HNMR measurement (see FIGS. 4 and 5)
The abundance ratio of styrene is¹Obtained from the intensity ratio of the signal of hydrogen (corresponding to 1H) in the vicinity of 6.6 ppm in the H-NMR spectrum.
[0205]
▲ 4 ▼ ¹³ The abundance ratio of aliphatic carboxylic acid, (meth) acrylic acid ester and PO-BPA, EO-BPA (meth) acrylic acid ester compound (reaction product of vinyl polymer and polyester resin) by C-NMR measurement Decision (see Figure 3)
The abundance ratio of the reaction product of aliphatic carboxylic acid, (meth) acrylic acid ester and vinyl polymer and polyester resin is¹³In the C-NMR spectrum, signals of the carboxyl group carbon (corresponding to 1C each) of the aliphatic carboxylic acid around 173.5 ppm and 174 ppm and the signal of the carbon of the carboxyl group (corresponding to 1C) of the (meth) acrylic acid ester around 176 ppm It is determined from the signal and intensity ratio of carbon (corresponding to 1C) of the carboxyl group of the (meth) acrylic acid ester of the newly detected peak around 169 ppm.
[0206]
▲ 5 ▼ ¹³ Determination of abundance ratio of aliphatic carboxylic acid and aromatic carboxylic acid by C-NMR measurement (see FIG. 3)
The abundance ratio of aliphatic carboxylic acid and aromatic carboxylic acid is¹³Intensity ratio of the signal of carbon (1C equivalent) of the carboxyl group of terephthalic acid and trimellitic acid in the C-NMR spectrum to the carbon of the carboxyl group of aliphatic carboxylic acid (4) above (equivalent to 1C each). Calculate from the comparison.
[0207]
▲ 6 ▼ ¹³ Determination of the abundance ratio of styrene by C-NMR measurement (see FIG. 3)
The abundance ratio of styrene is¹³It is determined from the signal intensity ratio of para-positioned carbon (corresponding to 1C) near 125 ppm in the C-NMR spectrum.
[0208]
(7) Determination of polyester resin component content in components insoluble and soluble in ethyl acetate
Above (1) to (3)¹From the H-NMR spectrum, the respective monomer composition existing ratios of PO-BPA, EO-BPA, terephthalic acid, trimellitic acid and styrene were calculated as molar ratios, and the above (4) to (6)¹³From C-NMR spectrum, (meth) acrylic acid ester compound (reaction product of vinyl polymer and polyester resin) of PO-BPA and EO-BPA, aliphatic carboxylic acid, aromatic carboxylic acid and styrene monomer By calculating the composition abundance ratio as a molar ratio, the composition abundance ratio of all constituent monomers is calculated as a molar ratio. The molecular weight of each monomer is used from the monomer composition abundance ratio at this molar ratio, and the dehydration amount accompanying esterification is ignored, and the content of the polyester resin component is calculated by weight%.
[0209]
(3) Melting point measurement of wax
It measures according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device) and DSC-7 (manufactured by Perkin Elmer).
[0210]
The measurement sample is precisely weighed in an amount of 2 to 10 mg, preferably 5 mg.
[0211]
This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rise rate of 10 ° C./min at room temperature and normal humidity within a measurement temperature range of 30 to 200 ° C.
[0212]
In this temperature raising process, an endothermic peak of the main peak of the DSC curve in the temperature range of 30 to 200 ° C. is obtained.
[0213]
The temperature of this endothermic main peak is taken as the melting point of the wax.
[0214]
(4) Measurement of toner DSC curve
The DSC curve in the process of raising the temperature of the toner is measured in the same manner as the measurement of the melting point of the wax.
[0215]
(5) Measurement of glass transition temperature (Tg) of binder resin
It measures according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device) and DSC-7 (manufactured by Perkin Elmer).
[0216]
The sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg.
[0217]
This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rise rate of 10 ° C./min at room temperature and normal humidity within a measurement temperature range of 30 to 200 ° C.
[0218]
In this temperature raising process, an endothermic peak of the main peak in the temperature range of 40 to 100 ° C. is obtained.
[0219]
At this time, the point of intersection between the base line midpoint before and after the endothermic peak and the differential heat curve is defined as the glass transition temperature Tg in the present invention.
[0220]
(6) Measurement of molecular weight distribution of wax
Gel permeation chromatography (GPC) measuring device: GPC-150C (Waters)
Column: GMH-HT 30 cm 2 series (manufactured by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% ionol added)
Flow rate: 1.0 ml / min
Sample: 0.4ml injection of 0.15% sample
[0221]
Measurement is performed under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used in calculating the molecular weight of the sample. Furthermore, it calculates by converting into polyethylene by the conversion formula derived from the Mark-Houwink viscosity formula.
[0222]
(7) Measurement of molecular weight distribution of binder resin raw material or toner binder resin
The molecular weight of the chromatogram by GPC is measured under the following conditions.
[0223]
The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min. When the sample is a binder resin raw material, a material obtained by passing the binder resin raw material through a roll mill (130 ° C., 15 minutes) is used. When the sample is toner, the toner is dissolved in THF, filtered through a 0.2 μm filter, and the filtrate is used as a sample. Measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by weight. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Manufactured by Toyo Soda Industry Co., Ltd.²2.1 × 10^Three, 4 × 10^Three, 1.75 × 10^Four, 5.1 × 10^Four1.1 × 10^Five, 3.9 × 10^Five8.6 × 10^Five, 2 × 10⁶, 4.48 × 10⁶It is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
[0224]
As column, 10^Three~ 2x10⁶In order to accurately measure the molecular weight region, it is preferable to combine a plurality of commercially available polystyrene gel columns, for example, μ-stergel 500, 10 manufactured by Waters.^Three, 10^Four, 10^FiveAnd combinations of shodex KA-801, 802, 803, 804, 805, 806 and 807 manufactured by Showa Denko KK are preferred.
[0225]
(8) of the binder resin contained in the toner¹³C-NMR measurement
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 100.40 MHz
Pulse condition: 5.0 μs (45 °) by DEPT method
Data points: 32768
Delay time: 25 sec.
Integration count: 50000 times
Measurement temperature: 26 ° C
Sample: Add 10g of toner to 100ml of concentrated hydrochloric acid (about 12M) at room temperature
Stir for about 70 hours to dissolve the magnetic material contained in the toner. Next, it is filtered and washed until the filtrate is slightly acidic (about pH 5). The obtained resin composition is vacuum-dried at 60 ° C. for about 20 hours to obtain a measurement sample. About 1 g of this measurement sample is placed in a φ10 mm sample tube, and deuterated chloroform (CDCl) as a solvent._Three3) Add 3ml and adjust it by dissolving in a constant temperature bath at 55 ° C.
[0226]
(9) Measurement of acid value
The measurement is performed according to the measurement method described in JIS K0070-1992.
Measuring apparatus: Automatic potentiometric titrator AT-400 (manufactured by Kyoto Electronics Co., Ltd.)
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
Measurement temperature: 25 ° C
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate-soluble component) is added to 120 ml of toluene and dissolved by stirring at room temperature (about 25 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to prepare a sample solution.
[0227]
(10) Measurement of OH value (hydroxyl value)
Weigh accurately 0.5 g of sample into a 100 ml volumetric flask and add 5 ml of acetylating reagent correctly. Then, it is immersed in a bath at 100 ° C. ± 5 ° C. and heated. After 1-2 hours, the flask is removed from the bath, allowed to cool, water is added and shaken to decompose acetic anhydride. Furthermore, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using a glass electrode to obtain an OH number (JIS
According to K0070-1966. ).
[0228]
(11) Measurement of X-ray diffraction

[0229]
Using the molding apparatus, the measurement specimen is compressed and pressed. The molded sample is set in an X-ray diffractometer and measured under the following conditions. The structure is determined from the peak intensity and 2θ angle of the obtained X-ray diffraction pattern.
Target Filter Cu, Ni
Voltage Current 32.5kV, 15mA
Counter Se
Time Constant 1sec
Divergence Slit 1 °
Receiving slit 0.15mm
Scatter slit 1 °
Angle Range 60-20 °
[0230]
(12) Quantitative determination method of complex oxide in toner

[0231]
(1) Creating a calibration curve
To the magnetic toner (X), a complex oxide for quantitative purposes is mixed in the following ratio (% by weight) using a coffee mill to prepare a sample for a calibration curve.
0%, 0.5%, 1.0%, 2.0%, 3.0%, 5.0%, 10.0%
The above seven samples are press-molded using a sample press molding machine. [M] Kα peak angle (a) in the composite oxide is determined from the 2θ table. The calibration curve sample is put into the X-ray fluorescence analyzer, and the sample chamber is depressurized and vacuumed. A calibration curve is created by obtaining the X-ray intensity of each sample under the following conditions.
[0232]
〔Measurement condition〕
Measurement potential, voltage 50kV-50mA
2θ angle a
Crystal plate LiF
Measurement time 60 seconds
[0233]
(2) Determination of complex oxide in toner
After forming the sample by the same method as in the above (1), the X-ray intensity is obtained under the same measurement conditions, and the addition amount is calculated from the calibration curve.
[0234]
(13) Measurement of particle size distribution
The particle size distribution can be measured by various methods. In the present invention, the particle size distribution was performed using a multisizer of a Coulter counter.
[0235]
As a measuring device, a multisizer type II (manufactured by Coulter Co.), a Coulter counter, was connected to an interface (manufactured by Nikka) and a CX-1 personal computer (manufactured by Canon) that output number distribution and volume distribution. A 1% NaCl aqueous solution is prepared using special grade or first grade sodium chloride. As a measuring method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes. When measuring the toner particle size with the Coulter Counter Multisizer II type, a 100 μm aperture is used, and an inorganic material is used. When measuring the particle size of fine powder, it is measured using a 13 μm aperture. The volume and number of toner and inorganic fine powder were measured, and the volume distribution and number distribution were calculated. Then, a weight-based weight average diameter obtained from the volume distribution is obtained.
[0236]
(14) Measurement of viscoelastic characteristics of toner and cleaning blade)
Measurement is performed using a viscoelasticity measuring device (rheometer) RDA-II (manufactured by Rheometrics).
Measuring jig: Parallel plate with a diameter of 7.9 mm
Measurement sample: The toner is used after being heated and melted and molded into a disk-shaped sample having a diameter of 8 mm and a height of 2 to 5 mm. Fixing to the measuring jig is performed according to a conventional method.
[0237]
The cleaning blade is used by punching or cutting out a disk-like sample having a diameter of about 8 mm from a sheet-like sample having a thickness of 1 to 5 mm. Fixing to the measuring jig is performed using an instantaneous adhesive or the like.
Measurement frequency: 6.28 radians / second
Measurement temperature: The temperature is raised from room temperature to 170 ° C. at a rate of 1 ° C. per minute.
[0238]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
[0239]
Production Example I of Binder Resin:
(Resin Production Example I-1)
(Ia) Production of low-crosslinking resin composition
(Production of resin composition containing substantially 0 to 10% by weight of chloroform-insoluble matter)
・ Terephthalic acid: 5.0 mol
-Succinic acid derivative represented by formula (1-3): 1.0 mol
-Trimellitic anhydride: 1.0 mol
・ PO-BPA: 7.0 mol
・ EO-BPA: 3.0 mol
[0240]
The polyester monomer is charged into an autoclave together with an esterification catalyst, and equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirring device, and heated to 210 ° C. in a nitrogen atmosphere under reduced pressure. By performing the condensation polymerization reaction, a low-crosslinking degree polyester resin containing about 3% by weight of chloroform-insoluble matter was obtained.
[0241]
Next, 80 parts by weight of the polyester resin obtained here, 16 parts by weight of styrene, 4 parts by weight of 2-ethylhexyl acrylate, and 0.3 parts by weight of dibutyltin oxide as an esterification catalyst were added to 50 parts by weight of xylene. It melted and swollen by heating to ° C. Under a nitrogen atmosphere, a solution obtained by dissolving 1 part by weight of t-butyl hydroperoxide as a radical polymerization initiator in 10 parts by weight of xylene was dropped over about 30 minutes. The temperature was further maintained for 10 hours to complete the radical polymerization reaction. Further, by depressurizing and removing the solvent while heating, it comprises a low cross-linking polyester resin, a vinyl polymer, and a hybrid resin component having a polyester unit and a vinyl polymer unit, and the chloroform-insoluble content is reduced to about 7 A low-crosslinking resin composition (a-1) containing wt% was obtained.
[0242]
(Ib) Production of highly crosslinked resin composition
(Production of resin composition containing 15 to 70% by weight of chloroform insoluble)
・ Terephthalic acid: 2.0 mol
-Succinic acid derivative represented by formula (1-3): 4.0 mol
-Trimellitic anhydride: 4.0 mol
・ PO-BPA: 10.0 mol
-EO-BPA: 4.0 mol
[0243]
The polyester monomer is charged into an autoclave together with an esterification catalyst, and equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirring device, and heated to 210 ° C. in a nitrogen atmosphere under reduced pressure. By performing the condensation polymerization reaction, a highly crosslinked polyester resin containing about 25% by weight of a chloroform-insoluble component was obtained.
[0244]
Next, 50 parts by weight of xylene, 80 parts by weight of the polyester resin obtained here, 10 parts by weight of styrene, 10 parts by weight of 2-ethylhexyl acrylate, 0.01 part by weight of divinylbenzene and 0.3 parts of dibutyltin oxide as an esterification catalyst. Part by weight was added and heated to 110 ° C. to dissolve and swell. Under a nitrogen atmosphere, a solution obtained by dissolving 1 part by weight of t-butyl hydroperoxide as a radical polymerization initiator in 10 parts by weight of xylene was dropped over about 30 minutes. The temperature was further maintained for 10 hours to complete the radical polymerization reaction. Further, the solvent is depressurized while heating, and the solvent is removed, thereby comprising a highly crosslinked polyester resin, a vinyl polymer, and a hybrid resin component having a polyester unit and a vinyl polymer unit. % -Containing highly crosslinked resin composition (b-1) was obtained.
[0245]
(Ic) Production of binder resin
100 parts by weight of xylene, 60 parts by weight of a low-crosslinking resin composition (a-1), 30 parts by weight of a high-crosslinking resin composition (b-1), 5 parts by weight of styrene, 5 parts by weight of 2-ethylhexyl acrylate, and 0 divinylbenzene .01 part by weight was added and heated to 110 ° C. to swell and dissolve. Under a nitrogen atmosphere, a solution obtained by dissolving 1 part by weight of t-butyl hydroperoxide as a radical polymerization initiator in 10 parts by weight of xylene was dropped over about 30 minutes. The temperature was further maintained for 10 hours to complete the radical polymerization reaction. Further, by depressurizing while heating and removing the solvent, it comprises a low-crosslinking polyester resin, a high-crosslinking polyester resin, a vinyl polymer, and a hybrid resin component having a polyester unit and a vinyl polymer unit. A binder resin (C-1) containing about 28% by weight of insoluble matter was obtained.
[0246]
(Resin Production Example I-2)
In Resin Production Example I-1, when producing a highly crosslinked resin composition (b-1), 16.6 parts by weight of a hydrocarbon wax (melting point: 100 ° C., weight average molecular weight with respect to 80 parts by weight of the polyester resin) 1800) was added together with styrene and 2-ethylhexyl acrylate to obtain a highly crosslinked resin composition (b-2) containing wax and 37% by weight of chloroform-insoluble matter. Except for using 35 parts by weight of a highly crosslinked resin composition (b-2) (including 5 parts by weight of wax), the same as in Production Example I-1, low-crosslinked polyester resin, highly crosslinked polyester resin, vinyl heavy A binder resin (C-2) comprising a combined resin and a hybrid resin component having a polyester unit and a vinyl polymer unit and containing about 30% by weight of chloroform-insoluble matter was obtained.
[0247]
(Resin production examples I-3 to I-5)
Binder resins (C-3) to (C-5) shown in Tables 1 to 3 were obtained by changing the type and composition ratio of the monomers.
[0248]
(Resin Comparative Production Example I-1)
In Comparative Example I-1, except that terephthalic acid was used in place of the succinic acid derivative (1-3), comparative binder resins (U-1) shown in Tables 1 to 3 were obtained.
[0249]
(Resin Comparative Production Example I-2)
In the same manner as in Resin Production Example I-1, except that terephthalic acid was used in place of the succinic acid derivative (1-3), and a low-crosslinking resin composition with an increased amount of trimellitic anhydride was used, the same as in Tables 1 to The comparative binder resin (U-2) shown in 3 was obtained.
[0250]
[Table 1]

[0251]
[Table 2]

[0252]
[Table 3]

[0253]
(Production Example of Composite Oxide 1: Strontium Silicate)
1500 g of strontium carbonate and 600 g of silicon oxide were wet mixed in a ball mill for 8 hours and then filtered and dried.²And calcined at 1300 ° C. for 8 hours. This was mechanically pulverized to obtain strontium silicate fine powder (M-1) having a weight average diameter of 2.0 μm. Further, the obtained (M-1) was subjected to X-ray diffraction, and the composite oxide produced from the peak pattern of FIG._Three(A = 1, b = 1, c = 3 in formula (1)) and Sr₂SiO_FourIt was confirmed that (= 2 in the formula (1), b = 1, c = 4).
[0254]
(Production Example 2 of Complex Oxide: Strontium Titanate)
600 g of strontium carbonate and 320 g of titanium oxide were wet mixed in a ball mill for 8 hours and then filtered and dried.²And then calcined at 1100 ° C. for 8 hours. This was mechanically pulverized to obtain strontium titanate fine powder (M-2) having a weight average diameter of 1.7 μm.
[0255]
(Production Example 3 of Complex Oxide: Cerium Oxide (For Comparison))
Combustion was performed at 1500 ° C. for 10 hours in the presence of 1500 g of cerium carbonate and oxygen. This was mechanically pulverized to obtain a fine cerium oxide powder (M-3) having a weight average diameter of 2.0 μm.
[0256]
(Test blade)
Blades A to K shown in Table 4 were prepared as blades for this study. The dimensions of the blades were all 331.5 ± 1.0 mm in length, 20 ± 0.2 mm in width, and 3 ± 0.1 mm in thickness.
[0257]
The viscoelasticity data (data: 1) of blade B is attached as FIG.
[0258]
[Table 4]

[0259]
(Example of toner production)
・ Binder resin (C-1) 100 parts by weight
・ 90 parts by weight of magnetic iron oxide
(Average particle size 0.15 μm, Hc 9.2 kA / m (120 oersted), σs = 83 Am²/ Kg (83 emu / g), σr = 11.5 Am²/ Kg (11.5 emu / g))
・ Azo-based iron complex compound (negative charge control agent) 2 parts by weight
・ Low molecular weight polyethylene wax 5 parts by weight
(Melting point 110 ° C., weight average molecular weight 1880)
[0260]
After mixing the above materials with a Henschel mixer, melt kneading with a twin-screw kneading extruder at 130 ° C., cooling the mixture, coarsely crushing with a cutter mill, and then crushing with a fine crusher using a jet stream Further, classification was performed using an air classifier to obtain negatively charged magnetic toner particles (P) having a weight average diameter of 6.3 μm.
[0261]
Using this toner (P), the soluble components and insoluble components of tetrahydrofuran (THF), ethyl acetate and chloroform contained in the binder resin were quantified by Soxhlet extraction, and the resin composition excluding the mixed wax was The THF-insoluble matter (W2) is 31% by weight, the ethyl acetate-insoluble matter (W4) is 34% by weight, the chloroform-insoluble matter (W6) is 15% by weight, and the ratio (W4 / W6) is 2. The chloroform insoluble matter (W6A) in the THF insoluble matter (W2) was 6.7% by weight, and the chloroform insoluble matter (W6B) in the ethyl acetate insoluble matter (W4) was 8.3% by weight. It was.
[0262]
When the molecular weight of the soluble component (W1) of tetrahydrofuran was measured by GPC, the molecular weight of the main peak was 4400, the component (A1) in the region having a molecular weight of 500 to less than 10,000 was 48.9%, and the molecular weight was 10,000 or more 10 The component (A2) in the region of less than 10,000 was 26.7%, the component (A3) in the region of molecular weight of 100,000 or more was 24.4%, and the ratio (A1 / A2) was 1.83.
[0263]
When the acid value of the toner binder resin and the toner ethyl acetate soluble component (W3) was measured, the acid value (AV1) of the binder resin contained in the toner was 26.7 mgKOH / g. The acid value (AV2) of the ethyl acetate-soluble component was 21.6 mgKOH / g, and the ratio (AV1 / AV2) was 1.2.
[0264]
¹H-NMR and¹³It was confirmed by C-NMR that a vinyl copolymer, a polyester resin, and a hybrid resin component having a polyester unit and a vinyl polymer unit were present in the toner.
[0265]
In the toner, the hybrid resin component having a polyester unit and a vinyl polymer unit is¹³It can verify by detecting the signal of the ester bond newly produced | generated by C-NMR.
[0266]
In general, the ester group of an acrylate ester copolymerized with styrene¹³It is known that the signal measured by C-NMR shifts to the high magnetic field side by several ppm due to the influence of the benzene ring of styrene rather than that of the homopolymer of acrylate ester. The same applies to the hybrid resin component obtained by transesterifying the alcohol component of the acrylate ester with the alcohol component of the polyester, and is also affected by the benzene ring contained in the polyester unit introduced by transesterification. The signal is detected as a signal on the higher magnetic field side than the acrylic ester of the vinyl polymer unit.
[0267]
Low cross-linking polyester¹³FIG. 1 shows the C-NMR measurement results, FIG. 2 shows the measurement results of the styrene-2-ethylhexyl acrylate copolymer, and FIG. 3 shows the measurement results of the binder resin (C-1) contained in the toner. From this result, it was found that about 22 mol% of the acrylate ester was present as a hybrid resin component esterified with the polyester unit.
[0268]
Each¹³Table 5 shows the C-NMR measurement results.
[0269]
[Table 5]

[0270]
Further, when the polyester resin components (Gp) and (Sp) contained in the binder resin component (W4) insoluble in ethyl acetate and the soluble binder resin component (W3) were quantified by NMR, Gp = about 83 wt% Sp = approx. 77% by weight, ratio (Sp / Gp) = 0.93, and the amount of succinic acid derivative represented by formula (1-3) was quantified. About 74% by weight of the total charge was contained.
[0271]
The amount of wax contained in the component (W4) insoluble in ethyl acetate was measured by DSC and could be determined from the enthalpy of dissolution, and as a result, it was found that about 61% by weight of the total wax was present when added to the toner. .
[0272]
The toner analysis results are shown in Tables 6 and 7.
[0273]
Hydrophobic silica (specific surface area: 200 m) with respect to 100 parts by weight of the magnetic toner particles (P)²/ G) 1.0 part by weight and 3.0 parts by weight of the composite oxide (M-1) were externally added and mixed with a Henschel mixer to obtain a magnetic toner (P-1) for evaluation.
[0274]
<Evaluation-1>
Density reduction rate and high temperature offset as toner fixability evaluation were performed based on the following evaluation methods. Concerning the low-temperature fixability, an excellent result was obtained with a density reduction rate of 3%, and there was no problem with the high-temperature offset. The evaluation results are shown in Table 8.
[0275]
Low temperature fixability test:
Canon digital copying machine GP215 remodeling machine (development, drum, optics, paper transport system etc. all adjusted to increase copying speed by 20%) to low temperature and low humidity chamber (temperature: 5 ° C, humidity: 5%) Install.
[0276]
With the evaluation magnetic toner (P-1), using a halftone image as a manuscript, 100 sheets of continuous paper are drawn, the 100th image is sampled, and the image is 4900 N / m.²(50 g / cm²) And a soft thin paper, and evaluated by the image density difference (image density reduction rate (%)) before and after this.
[0277]
(Low-temperature fixability evaluation level)
A: Density reduction rate is less than 5%
B: Density reduction rate is 5% or more and less than 10%
C: Density reduction rate is 10% or more and less than 15%
D: Density reduction rate is 15% or more and less than 25%
E: Density reduction rate is 25% or more
[0278]
High temperature offset test:
Remove the fuser of Canon copier NP6085 and install external drive and temperature control device.
[0279]
An unfixed image is created using the magnetic toner for evaluation (P-1) using a Canon copier NP6085, and the fixing temperature of the fixing device is changed to determine whether a high temperature offset has occurred on the fixing roller. In addition, the toner adhesion on the fixed image was judged by visual confirmation and evaluated.
[0280]
(High temperature offset resistance evaluation level)
A: No offset at 250 ° C
B: Slight offset occurs at 250 ° C
C: Slight offset generation at 230-240 ° C
D: Offset occurs at 220 ° C to 230 ° C
E: Offset occurs below 210 ° C
[0281]
<Evaluation-2>
Magnetic toner particles having a weight average diameter of 7.0 μm (same as in the above toner production example) except that the binder resin in the toner material is changed to (a-2) and the negative charge control agent is changed to an Al complex compound. Q) was obtained.
[0282]
Hydrophobic silica (specific surface area: 200 m) with respect to 100 parts by weight of the magnetic toner particles (Q)²/ G) 1.0 part by weight and 4.0 parts by weight of the composite oxide (M-2) were externally added and mixed with a Henschel mixer to obtain a magnetic toner (Q-1) for evaluation.
[0283]
Evaluation similar to Evaluation-1 was performed using this toner. Good results were obtained with respect to low-temperature fixability and high-temperature offset resistance. The evaluation results are shown in Table 8.
[0284]
<Evaluation-3-5>
Weight average diameters of 6.4 μm, 6.8 μm, respectively, in the same manner as in Evaluation-1, except that the binder resin in the toner material was changed to (a-3), (a-4), and (a-5). 6.6 μm magnetic toner particles (R), (S), and (T) were obtained.
[0285]
Hydrophobic silica (specific surface area 200 m) with respect to 100 parts by weight of each of the magnetic toner particles (R), (S), (T).²/ G) Magnetic toners (R-1), (S-1), (T) for 1.0 part by weight and 4.0 parts by weight of the composite oxide (M-2) were externally added and mixed with a Henschel mixer. -1).
[0286]
Evaluation similar to Evaluation-1 was performed using this toner. Good results were obtained with respect to low-temperature fixability and high-temperature offset resistance. The evaluation results are shown in Table 8.
[0287]
<Evaluation-6-7: Comparative Example>
Magnetic toner particles having weight average diameters of 6.4 μm and 6.8 μm, respectively, were obtained in the same manner as in the toner production example except that the binder resin in the toner material was changed to (A-1) and (A-2). Sa) and (shi) were obtained.
[0288]
Hydrophobic silica (specific surface area of 200 m) is used for 100 parts by weight of each of the magnetic toner particles (sa) and (si).²/ G) 1.0 parts by weight and 4.0 parts by weight of the composite oxide (M-2) were externally added and mixed with a Henschel mixer to obtain magnetic toners (S-1) and (S-1) for comparative evaluation. .
[0289]
Evaluation similar to Evaluation-1 was performed using this toner. There was a problem with high temperature offset resistance for (S-1) and low temperature fixability for (S-1). The evaluation results are shown in Table 8.
[0290]
<Evaluation-8>
The toners (Q), (R), (S), (T), (S), and (S) were analyzed in the same manner as the toner (P), and the results shown in Tables 6 and 7 were obtained.
[0291]
<Evaluation-9>
Canon copy machine NP6085 modified machine (development, drum, optics, paper transport system etc. are all adjusted to increase the copying speed by 20%) in a high temperature and high humidity chamber (temperature: 32.5 ° C, humidity: 85%) ). At this time, B in Table 4 was brought into contact with the drum at a total pressure of 680 g on the cleaning blade.
[0292]
Using the evaluation magnetic toner (P-1), 300,000 continuous images were printed, and the image density, fog, image flow and drum scraping amount were evaluated. As a result, the image density was stable from the initial durability to the final 300,000 sheets, and high image quality without fogging was obtained. Also, no image flow occurred. Furthermore, when the film thickness of the drum before and after durability was measured, the amount of scraping was 10 mm. Detailed results are shown in Table 9.
[0293]
The evaluation level of the image density was determined by the maximum image density during endurance−the image density at the end of endurance of 300,000 sheets.
[0294]
The evaluation level of fog was determined based on fog in a solid white image at the end of endurance of 300,000 sheets.
[0295]
In the fog measurement, the reflectance of the solid white image and the unused paper is measured with a reflection measurement machine REFECTMETER (Tokyo Denshoku Co., Ltd.) for fog measurement, and the difference between the two is fogged. Unused paper reflectance-solid white reflectance = fog%
[0296]
The evaluation of image flow was evaluated based on the maximum missing image area when missing on the image occurred during durability.
[0297]
The evaluation of the amount of drum abrasion was judged by the difference in film thickness (average of 10 points in the drum axis direction) between the drum before durability and the drum after durability.
[0298]
(Image density evaluation level)
A: Maximum image density-end-of-end image density less than 0.05
B: Maximum image density-end-of-end image density 0.05 to less than 0.10
C: Maximum image density-end-of-end image density 0.10 or more and less than 0.15
D: Maximum image density-end-of-end image density 0.15 or more and less than 0.25
E: Maximum image density-end-of-end image density 0.25 or more
[0299]
(Fog evaluation level)
A: fog less than 0.1%
B: fog 0.1 to less than 0.5%
C: fog 0.5 to less than 1.0%
D: fog 1.0 to less than 1.5%
E: fog 1.5 or more
[0300]
(Image flow evaluation level)
A: missing image area None
B: missing image area 0.15 cm²Less than
C: missing image area 0.15 to 5.0 cm²Less than
D: Missing image area 5.0 or more 10.0 cm²Less than
E: missing image area 10.0 cm²more than
[0301]
(Drum scraping evaluation level)
A: Abrasion amount less than 10.0 mm
B: Abrasion amount 10.0 to less than 25.0 mm
C: Abrasion amount 25.0 or more and less than 50.0 mm
D: Abrasion amount 50.0 or more and less than 150.0 mm
E: Abrasion amount 150.0 mm or more
[0302]
<Evaluation-10-14>
The cleaning blade was changed to C, D, F, G, and H, and the same evaluation as in Evaluation-9 was performed. The image density was high and stable, and a high-resolution image without fog was obtained. Furthermore, the image flow was at a level with no problem. Detailed results are shown in Table 9.
[0303]
<Evaluation-15-19: Comparative Example>
The cleaning blade was changed to A, E, I, J, and K, and the same evaluation as in Evaluation-9 was performed. The image density was high and stable, and the image quality with high resolving power was obtained at a level where there was no problem with fogging. Further, the image flow was at a level with no problem. However, A, E, I, and K had poor cleaning from the middle of durability, and J had drum fusion from the middle of durability. Detailed results are shown in Table 9.
[0304]
<Evaluation-20 to 23>
Evaluation was made in the same manner as Evaluation-9, except that the evaluation magnetic toner was changed to (Q-1), (R-1), (S-1), and (T-1). The image density was high and stable, and the image quality with high resolving power was obtained at a level where there was no problem with fogging. Furthermore, the image flow was at a level with no problem. Detailed results are shown in Table 9.
[0305]
<Evaluation-24-25: Comparative Example>
Evaluation was made in the same manner as Evaluation-9, except that the evaluation magnetic toner was changed to (S-1) and (S-1). All the toners tended to decrease the image density, and an image quality with poor fog suppression was obtained. Further, although the image flow was at a level with no problem, cleaning failure occurred in (S-1), and drum fusion occurred in (S-1). Detailed results are shown in Table 9.
[0306]
<Evaluation -26 to 29: Comparative Example>
With respect to 100 parts by weight of each of the magnetic toner particles (Q), (R), (sa), (si), hydrophobic silica (specific surface area 200 m)²/ G) 1.0 parts by weight and 4.0 parts by weight of the composite oxide (M-3) were externally added and mixed with a Henschel mixer, and magnetic toners for comparison evaluation (Q-2), (R-2), ( Sa-2) and (Sh-2).
[0307]
Evaluation similar to Evaluation-9 was performed using this toner. In any of the toners, drum scraping occurred due to durability, so that the image density tended to decrease, and an image quality with poor fog suppression was obtained. However, the image flow was at a level with no problem. Detailed results are shown in Table 9.
[0308]
<Evaluation-30: Comparative Example>
Hydrophobic silica (specific surface area 200 m) with respect to 100 parts by weight of magnetic toner particles (Q)²/ G) 1.0 part by weight was externally mixed with a Henschel mixer to obtain a comparative evaluation magnetic toner (Q-3).
[0309]
Evaluation similar to Evaluation-9 was performed using this toner. As a result, the image density tended to decrease due to durability, and an image quality with poor fog suppression was obtained. Furthermore, image flow occurred from the beginning of durability. Drum scraping was at a level with no problem, but drum fusion occurred. Detailed results are shown in Table 9.
[0310]
[Table 6]

[0311]
[Table 7]

[0312]
[Table 8]

[0313]
[Table 9]

[0314]
(Viscoelastic properties of toner and blade)
Viscoelasticity was measured for the magnetic toners (P), (Q), (R), (S), (T), (S), and (S). The result is shown in Table 10. The viscoelasticity measurement chart of (P) is attached as FIG.
[0315]
Further, Table 11 shows viscoelastic characteristics of the toner (P) and the blade used in this study.
[0316]
[Table 10]

[0317]
[Table 11]

[0318]
【The invention's effect】
According to the present invention, since the toner and the cleaning blade to be used are improved as described above, high image quality and high image density can be obtained even under high temperature and high humidity, and further, poor cleaning, toner fusion, image flow, etc. It is possible to provide an image forming method and an image forming apparatus that do not generate the image.
[Brief description of the drawings]
FIG. 1 shows a polyester resin composition having a low crosslinking degree.¹³A C-NMR spectrum is shown.
[Fig. 2] Styrene-2-ethylhexyl acrylate copolymer¹³A C-NMR spectrum is shown.
FIG. 3 shows the binder resin (C-1) according to the present invention.¹³A C-NMR spectrum is shown.
FIG. 4 shows the ethyl acetate-soluble component of the binder resin (C-1) according to the present invention.¹H-NMR spectrum is shown.
FIG. 5 shows the ethyl acetate insoluble component of the binder resin (C-1) according to the present invention.¹H-NMR spectrum is shown.
FIG. 6 shows the PO group of PO-BPA.¹It is explanatory drawing which shows attribution of a H-NMR signal.
FIG. 7 is a schematic diagram showing a specific example of a Soxhlet extraction apparatus used for Soxhlet extraction.
FIG. 8 is an explanatory diagram showing an example of an image forming apparatus that can carry out the image forming method of the present invention.
9 is an enlarged view of a developing unit of the image forming apparatus shown in FIG.
10 is a graph showing viscoelasticity data of blade B. FIG.
FIG. 11 is a graph showing viscoelasticity data of toner (P).
12 is a graph showing an X-ray diffraction peak pattern of the composite oxide of Production Example 1. FIG.
[Explanation of symbols]
1 Electrostatic latent image carrier (photoconductor)
4 Toner carrier (Developing sleeve)
7 Fixing device
8 Cleaning blade
9 Developer
11 Magnetic blade
13 Toner
P Recording material (transfer material)

Claims (106)

The electrostatic image formed on the electrostatic image carrier is developed with toner to form a toner image, and the formed toner image is passed from the electrostatic image carrier through the intermediate transfer member or not. In the image forming method including the step of transferring to the transfer material, and cleaning the transfer residual toner on the electrostatic charge image carrier using a cleaning blade,
The toner is a toner having toner particles containing at least a binder resin, a wax and a colorant and an inorganic fine powder,
The binder resin is
(1) A vinyl resin, a polyester resin, and a hybrid resin component having a vinyl polymer unit and a polyester unit,
(2) Soxhlet extraction for 10 hours using tetrahydrofuran (THF) as a solvent, containing 50 to 85% by weight (W1) of a THF-soluble component and 15 to 50% (W2) of a THF-insoluble component,
(3) 10-hour Soxhlet extraction using ethyl acetate as a solvent, containing 40 to 98% by weight (W3) of an ethyl acetate soluble component, 2 to 60% by weight (W4) of an ethyl acetate insoluble component,
(4) Soxhlet extraction for 10 hours using chloroform as a solvent, containing 55 to 90% by weight (W5) of a chloroform soluble component and 10 to 45% by weight (W6) of a chloroform insoluble component,
(5) The value of W4 / W6 is 1.1 to 4.0,
When the toner is at a temperature of 50 to 75 ° C.
(A) There exists a temperature (TT.C) at which the storage elastic modulus (G′T) and the loss elastic modulus (G ″ T) become equal,
(B) There exists a temperature (TT.P) at which the loss tangent (tan δTP) becomes maximum,
The cleaning blade
(C) at a temperature of 40 to 80 ° C., the storage elastic modulus (G′B) is 5 × 10 ^{5 to} 1 × 10 ⁷ Pa,
(D) At a temperature of 40 to 80 ° C., the loss elastic modulus (G ″ B) is 5 × 10 ^{3 to} 1 × 10 ⁶ Pa,
(E) At a temperature of 40 to 80 ° C., there is a temperature (TT.B) at which the loss tangent (tan δB.P) is minimized,
(F) There exists a temperature (TB.P) at which the loss tangent (tan δB.P) is maximized at a temperature of 70 to 130 ° C.
In the loss tangent of the toner and the cleaning blade,
(G) The difference (TT.P-TB.P) is −40 to 20 ° C.,
(H) Ratio (G ″ T) of the loss elastic modulus (G ″ T) of the toner at the temperature (TT.C) and the loss elastic modulus (G ″ BC) of the cleaning blade at the temperature (TT.C). ) / (G ″ B.C) is 5 × 10 ^{2 to} 5 × 10 ⁴ . The binder resin has a main peak in the molecular weight region of 4000 to 9000 in the molecular weight distribution measured by gel permeation chromatography (GPC) of the THF-soluble component, and the component in the molecular weight region of 500 to less than 10,000 is 35. 0.06 to 65.0% (A1), components having a molecular weight of 10,000 to less than 100,000 are 25.0 to 45.0% (A2), and components having a molecular weight of 100,000 or more are 10.0 to 2. The image forming method according to claim 1, wherein the image forming method is 30.0% (A3), and the value of A1 / A2 is 1.05 to 2.00. The polyester resin and the polyester unit of a binder resin are characterized by having a crosslinked structure crosslinked with a trivalent or higher polyvalent carboxylic acid or an anhydride thereof, or a trivalent or higher polyhydric alcohol. The image forming method according to claim 1 or 2. 4. The binder resin according to claim 1, wherein the vinyl resin and the vinyl polymer unit of the binder resin have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. The image forming method described in 1. 5. The image forming method according to claim 1, wherein the binder resin contains 20 to 45% by weight of a THF-insoluble component (W2). 5. The image forming method according to claim 1, wherein the binder resin contains 25 to 40% by weight of a THF-insoluble component (W2). The image forming method according to any one of claims 1 to 6, wherein the binder resin contains 5 to 50% by weight of an ethyl acetate insoluble component (W4). 7. The image forming method according to claim 1, wherein the binder resin contains 10 to 40% by weight of an ethyl acetate insoluble component (W4). 9. The image forming method according to claim 1, wherein the binder resin contains 15 to 40% by weight of a chloroform-insoluble component (W6). 9. The image forming method according to claim 1, wherein the binder resin contains 17 to 37% by weight of a chloroform-insoluble component (W6). The binder resin has a ratio (W4 / W6) of an ethyl acetate insoluble component (W4) to a chloroform insoluble component (W6) of 1.2 to 3.5. The image forming method according to any one of the above. The binder resin has a ratio (W4 / W6) of an ethyl acetate insoluble component (W4) to a chloroform insoluble component (W6) of 1.5 to 3.0. The image forming method according to any one of the above. The content of the chloroform-insoluble component (W6A) contained in the THF-insoluble component (W2) and the content of the chloroform-insoluble component (W6B) contained in the ethyl acetate-insoluble component (W4) are as follows: Wt% ≦ W6A ≦ 25 wt%
7 wt% ≤ W6B ≤ 30 wt%
10 wt% ≤ W6A + W6B ≤ 45 wt%
W6A: W6B = 1: 1-3
The image forming method according to claim 1, wherein: The content of the chloroform-insoluble component (W6A) contained in the THF-insoluble component (W2) and the content of the chloroform-insoluble component (W6B) contained in the ethyl acetate-insoluble component (W4) are as follows: Wt% ≦ W6A ≦ 20 wt%
10 wt% ≤ W6B ≤ 25 wt%
15 wt% ≤ W6A + W6B ≤ 40 wt%
W6A: W6B = 1: 1.5-2.5
The image forming method according to claim 1, wherein: The hybrid polymer component vinyl polymer unit and polyester unit are:

The image forming method according to claim 1, wherein the image forming method is coupled via a gap. The hybrid resin component is a copolymer formed by transesterification of a polyester unit and a vinyl polymer unit obtained by polymerization of a monomer having a carboxylic acid ester group. The image forming method according to any one of the above. 17. The image forming method according to claim 1, wherein the hybrid resin component is a graft polymer in which a vinyl polymer unit is a trunk polymer and a polyester unit is a branch polymer. 18. The image forming method according to claim 1, wherein the binder resin has a grafting ratio of 10 to 60 mol%. 18. The image forming method according to claim 1, wherein the binder resin has a grafting ratio of 15 to 55 mol%. The binder resin is
(1) containing 2 to 60% by weight of the component (W4) insoluble in ethyl acetate with respect to 100 parts by weight of the binder resin;
(2) The component (W4) insoluble in ethyl acetate contains 40 to 98% by weight of the polyester resin component (Gp),
(3) The component (W3) dissolved in ethyl acetate contains 20 to 90% by weight of the polyester resin component (Sp),
(4) Ratio of content of polyester resin component (Gp) contained in component (W4) insoluble in ethyl acetate and content of polyester resin component (Sp) contained in component (W3) dissolved in ethyl acetate ( Sp / Gp) is 0.50 to 1.00,
The image forming method according to claim 1, wherein the wax includes a hydrocarbon-based wax. 21. The image forming method according to claim 20, wherein the component (W4) insoluble in ethyl acetate contains 55 to 95% by weight of a polyester resin component (Gp). 21. The image forming method according to claim 20, wherein the component (W4) insoluble in ethyl acetate contains 60 to 90% by weight of a polyester resin component (Gp). 23. The image forming method according to claim 20, wherein the component (W3) dissolved in ethyl acetate contains 25 to 85% by weight of a polyester resin component (Sp). The image forming method according to any one of claims 20 to 22, wherein the component (W3) dissolved in ethyl acetate contains 30 to 80% by weight of a polyester resin component (Sp). The ratio (Sp / Gp) between the content of the polyester resin component (Gp) contained in the component (W4) insoluble in ethyl acetate and the polyester resin component (Sp) contained in the component (W3) dissolved in ethyl acetate is The image forming method according to claim 20, wherein the image forming method is 0.60 to 0.95. The ratio (Sp / Gp) between the content of the polyester resin component (Gp) contained in the component (W4) insoluble in ethyl acetate and the polyester resin component (Sp) contained in the component (W3) dissolved in ethyl acetate is The image forming method according to claim 20, wherein the image forming method is 0.65 to 0.90. 27. The image forming method according to claim 1, wherein the total binder resin of the toner has an acid value (AV1) of 7 to 40 mg KOH / g. 27. The image forming method according to claim 1, wherein the total binder resin of the toner has an acid value (AV1) of 10 to 37 mg KOH / g. The image forming method according to any one of claims 1 to 28, wherein the ethyl acetate soluble component (W3) of the toner has an acid value (AV2) of 10 to 45 mg KOH / g. 29. The image forming method according to claim 1, wherein the ethyl acetate-soluble component (W3) of the toner has an acid value (AV2) of 15 to 45 mg KOH / g. The ratio (AV1 / AV2) of the acid value (AV1) of the total binder resin of the toner to the acid value (AV2) of the ethyl acetate soluble component (W3) of the toner is 0.7 to 2.0. The image forming method according to claim 1, wherein the image forming method is an image forming method. The ratio (AV1 / AV2) of the acid value (AV1) of the total binder resin of the toner to the acid value (AV2) of the ethyl acetate soluble component (W3) of the toner is 1.0 to 1.5. The image forming method according to claim 1, wherein the image forming method is an image forming method. 33. The melting point defined by the endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC) is 70 to 140 ° C. Image forming method. 33. The melting point defined by the endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC) is 80 to 135 ° C., wherein the wax is any one of claims 1 to 32. Image forming method. 33. The melting point defined by the endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC) is 90 to 130 ° C. Image forming method. 36. The image forming method according to claim 1, wherein the toner contains a binder resin containing a wax produced in the presence of a wax at the time of producing the binder resin. . The image forming method according to any one of claims 1 to 36, wherein the inorganic fine powder has composite oxide (A) particles represented by the following formula (1).
[M ₁ ] _a [M ₂ ] _b O _c (1)
(Wherein M ₁ represents a metal element selected from the group consisting of Sr, Mg, Zn, Co, Mn, Ca and Ce, M ₂ represents a metal element selected from Ti or Si, and a is 1 ) Represents an integer of ˜9, b represents an integer of 1 to 9, and c represents an integer of 3 to 9.) 38. The image forming method according to claim 1, wherein 0.10 to 10 parts by weight of composite oxide (A) particles are externally added to 100 parts by weight of toner particles. 38. The image forming method according to claim 1, wherein 0.20 to 5 parts by weight of composite oxide (A) particles are externally added to 100 parts by weight of toner particles. 40. The image forming method according to claim _{1, wherein} (M1) is Sr. The image forming method according to any one of claims 1 to 40, characterized in that (M ₂₎ is Ti. 42. The image forming method according to claim 1, wherein the composite oxide (A) is strontium titanate (SrTiO ₃ ). The image forming method according to any one of claims 1 to 40 (M ₂₎ is equal to or is Si. The image forming method according to claim 43, wherein the composite oxide (A) is a strontium silicate (SrSiO _3). The image forming method according to claim 1, wherein the composite oxide (A) particles are generated by a sintering method. The image forming method according to claim 1, wherein the composite oxide (A) particles have a weight average diameter of 0.1 to 5.0 μm. The image forming method according to claim 1, wherein the composite oxide (A) particles have a weight average diameter of 0.3 to 3.0 μm. The image forming method according to claim 1, wherein the composite oxide (A) particles have a weight average diameter of 0.5 to 2.5 μm. 49. The image forming method according to claim 1, wherein the colorant is a magnetic material. 50. The image forming method according to claim 1, wherein the toner particles have a weight average diameter larger than that of the composite oxide (A) particles. 51. The image forming method according to claim 50, wherein the toner particles have a weight average diameter of 3 to 12 [mu] m. 51. The image forming method according to claim 50, wherein the toner particles have a weight average diameter of 3 to 9 [mu] m. The cleaning blade
(A) At a temperature of 40 to 80 ° C., the storage elastic modulus (G′B) is 1 × 10 ^{6 to} 5 × 10 ⁶ Pa,
23. The image forming method according to claim 1, wherein the loss elastic modulus (G ″ B) is 1 × 10 ^{4 to} 5 × 10 ⁵ Pa at a temperature of 40 to 80 ° C. . The electrostatic charge image formed on the electrostatic charge image carrier is developed with toner, developing means for forming a toner image, and the formed toner image is transferred from the electrostatic charge image carrier to the intermediate transfer member. Or an image forming apparatus having at least a transfer means for transferring to a transfer material without intervention, and a cleaning means for cleaning the transfer residual toner on the electrostatic charge image carrier using a cleaning blade,
The toner is a toner having toner particles containing at least a binder resin, a wax and a colorant and an inorganic fine powder,
The binder resin is
(1) A vinyl resin, a polyester resin, and a hybrid resin component having a vinyl polymer unit and a polyester unit,
(2) Soxhlet extraction for 10 hours using tetrahydrofuran (THF) as a solvent, containing 50 to 85% by weight (W1) of a THF-soluble component and 15 to 50% (W2) of a THF-insoluble component,
(3) 10-hour Soxhlet extraction using ethyl acetate as a solvent, containing 40 to 98% by weight (W3) of an ethyl acetate soluble component, 2 to 60% by weight (W4) of an ethyl acetate insoluble component,
(4) Soxhlet extraction for 10 hours using chloroform as a solvent, containing 55 to 90% by weight (W5) of a chloroform soluble component and 10 to 45% by weight (W6) of a chloroform insoluble component,
(5) The value of W4 / W6 is 1.1 to 4.0,
When the toner is at a temperature of 50 to 75 ° C.
(A) There exists a temperature (TT.C) at which the storage elastic modulus (G′T) and the loss elastic modulus (G ″ T) become equal,
(B) There exists a temperature (TT.P) at which the loss tangent (tan δTP) becomes maximum,
The cleaning blade
(C) at a temperature of 40 to 80 ° C., the storage elastic modulus (G′B) is 5 × 10 ^{5 to} 1 × 10 ⁷ Pa,
(D) At a temperature of 40 to 80 ° C., the loss elastic modulus (G ″ B) is 5 × 10 ^{3 to} 1 × 10 ⁶ Pa,
(E) At a temperature of 40 to 80 ° C., there is a temperature (TT.B) at which the loss tangent (tan δB.P) is minimized,
(F) There exists a temperature (TB.P) at which the loss tangent (tan δB.P) is maximized at a temperature of 70 to 130 ° C.
In the loss tangent of the toner and the cleaning blade,
(G) The difference (TT.P-TB.P) is −40 to 20 ° C.,
(H) Ratio (G ″ T) of the loss elastic modulus (G ″ T) of the toner at the temperature (TT.C) and the loss elastic modulus (G ″ BC) of the cleaning blade at the temperature (TT.C). ) / (G ″ B.C) is 5 × 10 ^{2 to} 5 × 10 ⁴ . The binder resin has a main peak in the molecular weight region of 4000 to 9000 in the molecular weight distribution measured by gel permeation chromatography (GPC) of the THF-soluble component, and the component in the molecular weight region of 500 to less than 10,000 is 35. 0.06 to 65.0% (A1), components having a molecular weight of 10,000 to less than 100,000 are 25.0 to 45.0% (A2), and components having a molecular weight of 100,000 or more are 10.0 to 55. The image forming apparatus according to claim 54, wherein the image forming apparatus is 30.0% (A3) and the value of A1 / A2 is 1.05 to 2.00. The polyester resin and the polyester unit of a binder resin are characterized by having a crosslinked structure crosslinked with a trivalent or higher polyvalent carboxylic acid or an anhydride thereof, or a trivalent or higher polyhydric alcohol. The image forming apparatus according to claim 54 or 55. 57. The binder resin according to claim 54, wherein the vinyl resin and the vinyl polymer unit of the binder resin have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. The image forming apparatus described in 1. 58. The image forming apparatus according to claim 54, wherein the binder resin contains 20 to 45% by weight of a THF insoluble component (W2). 58. The image forming apparatus according to claim 54, wherein the binder resin contains 25 to 40% by weight of a THF-insoluble component (W2). 60. The image forming apparatus according to claim 54, wherein the binder resin contains 5 to 50% by weight of an ethyl acetate insoluble component (W4). 60. The image forming apparatus according to claim 54, wherein the binder resin contains 10 to 40% by weight of an ethyl acetate insoluble component (W4). 62. The image forming apparatus according to claim 54, wherein the binder resin contains 15 to 40% by weight of a chloroform-insoluble component (W6). 62. The image forming apparatus according to claim 54, wherein the binder resin contains 17 to 37% by weight of a chloroform-insoluble component (W6). The binder resin has a ratio (W4 / W6) of an ethyl acetate insoluble component (W4) to a chloroform insoluble component (W6) of 1.2 to 3.5. The image forming apparatus according to any one of the above. The binder resin has a ratio (W4 / W6) of an ethyl acetate insoluble component (W4) to a chloroform insoluble component (W6) of 1.5 to 3.0. The image forming apparatus according to any one of the above. The content of the chloroform-insoluble component (W6A) contained in the THF-insoluble component (W2) and the content of the chloroform-insoluble component (W6B) contained in the ethyl acetate-insoluble component (W4) are as follows: Wt% ≦ W6A ≦ 25 wt%
7 wt% ≤ W6B ≤ 30 wt%
10 wt% ≤ W6A + W6B ≤ 45 wt%
W6A: W6B = 1: 1-3
66. The image forming apparatus according to claim 54, wherein: The content of the chloroform-insoluble component (W6A) contained in the THF-insoluble component (W2) and the content of the chloroform-insoluble component (W6B) contained in the ethyl acetate-insoluble component (W4) are as follows: Wt% ≦ W6A ≦ 20 wt%
10 wt% ≤ W6B ≤ 25 wt%
15 wt% ≤ W6A + W6B ≤ 40 wt%
W6A: W6B = 1: 1.5-2.5
66. The image forming method according to any one of claims 54 to 65, wherein: The hybrid polymer component vinyl polymer unit and polyester unit are:

68. The image forming apparatus according to claim 54, wherein the image forming apparatuses are coupled via a gap. 69. The hybrid resin component is a copolymer formed by a transesterification reaction between a polyester unit and a vinyl polymer unit obtained by polymerization of a monomer having a carboxylic ester group. The image forming apparatus according to any one of the above. 70. The image forming apparatus according to claim 54, wherein the hybrid resin component is a graft polymer in which a vinyl polymer unit is a trunk polymer and a polyester unit is a branch polymer. 71. The image forming apparatus according to claim 54, wherein the binder resin has a grafting ratio of 10 to 60 mol%. 71. The image forming apparatus according to claim 54, wherein the binder resin has a grafting ratio of 15 to 55 mol%. The binder resin is
(1) containing 2 to 60% by weight of the component (W4) insoluble in ethyl acetate with respect to 100 parts by weight of the binder resin;
(2) The component (W4) insoluble in ethyl acetate contains 40 to 98% by weight of the polyester resin component (Gp),
(3) The component (W3) dissolved in ethyl acetate contains 20 to 90% by weight of the polyester resin component (Sp),
(4) Ratio of content of polyester resin component (Gp) contained in component (W4) insoluble in ethyl acetate and content of polyester resin component (Sp) contained in component (W3) dissolved in ethyl acetate ( Sp / Gp) is 0.50 to 1.00,
55. The image forming apparatus according to claim 54, wherein the wax includes a hydrocarbon wax. The image forming apparatus according to claim 73, wherein the component (W4) insoluble in ethyl acetate contains 55 to 95% by weight of a polyester resin component (Gp). The image forming apparatus according to claim 73, wherein the component (W4) insoluble in ethyl acetate contains 60 to 90% by weight of a polyester resin component (Gp). 76. The image forming apparatus according to claim 73, wherein the component (W3) dissolved in ethyl acetate contains 25 to 85% by weight of the polyester resin component (Sp). 76. The image forming apparatus according to claim 73, wherein the component (W3) dissolved in ethyl acetate contains 30 to 80% by weight of a polyester resin component (Sp). The ratio (Sp / Gp) between the content of the polyester resin component (Gp) contained in the component (W4) insoluble in ethyl acetate and the polyester resin component (Sp) contained in the component (W3) dissolved in ethyl acetate is 78. The image forming apparatus according to claim 73, wherein the image forming apparatus is 0.60 to 0.95. The ratio (Sp / Gp) between the content of the polyester resin component (Gp) contained in the component (W4) insoluble in ethyl acetate and the polyester resin component (Sp) contained in the component (W3) dissolved in ethyl acetate is 78. The image forming apparatus according to claim 73, wherein the image forming apparatus is 0.65 to 0.90. 80. The image forming apparatus according to claim 54, wherein the total binder resin of the toner has an acid value (AV1) of 7 to 40 mg KOH / g. 80. The image forming apparatus according to claim 54, wherein the total binder resin of the toner has an acid value (AV1) of 10 to 37 mg KOH / g. The image forming apparatus according to any one of claims 54 to 81, wherein the ethyl acetate soluble component (W3) of the toner has an acid value (AV2) of 10 to 45 mgKOH / g. 82. The image forming apparatus according to claim 54, wherein the ethyl acetate-soluble component (W3) of the toner has an acid value (AV2) of 15 to 45 mg KOH / g. The ratio (AV1 / AV2) of the acid value (AV1) of the total binder resin of the toner to the acid value (AV2) of the ethyl acetate soluble component (W3) of the toner is 0.7 to 2.0. 84. The image forming apparatus according to any one of claims 54 to 83, wherein: The ratio (AV1 / AV2) of the acid value (AV1) of the total binder resin of the toner to the acid value (AV2) of the ethyl acetate soluble component (W3) of the toner is 1.0 to 1.5. 84. The image forming apparatus according to any one of claims 54 to 83, wherein: 86. The melting point defined by the endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the wax is 70 to 140 ° C. 86. Image forming apparatus. 86. The melting point defined by the endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the wax is 80 to 135 ° C. 86. Image forming apparatus. 86. The wax according to any one of claims 54 to 85, wherein the wax has a melting point defined by an endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC) of 90 to 130 ° C. Image forming apparatus. The image forming apparatus according to any one of claims 54 to 87, wherein the toner contains a binder resin containing a wax, which is produced in the presence of the wax when the binder resin is produced. . 90. The image forming apparatus according to claim 54, wherein the inorganic fine powder has composite oxide (A) particles represented by the following formula (1).
[M ₁ ] _a [M ₂ ] _b O _c (1)
(Wherein M ₁ represents a metal element selected from the group consisting of Sr, Mg, Zn, Co, Mn, Ca and Ce, M ₂ represents a metal element selected from Ti or Si, and a is 1 ) Represents an integer of ˜9, b represents an integer of 1 to 9, and c represents an integer of 3 to 9.) The image forming apparatus according to any one of claims 54 to 90, wherein 0.10 to 10 parts by weight of composite oxide (A) particles are externally added to 100 parts by weight of toner particles. The image forming apparatus according to claim 54, wherein 0.20 to 5 parts by weight of composite oxide (A) particles are externally added to 100 parts by weight of toner particles. (M ₁₎ is an image forming apparatus according to any one of claims 54 to 92, characterized in that a Sr. (M ₂₎ is an image forming apparatus according to any one of claims 54 to 93, characterized in that a Ti. 95. The image forming apparatus according to claim 54, wherein the composite oxide (A) is strontium titanate (SrTiO ₃ ). (M ₂₎ is an image forming apparatus according to any one of claims 54 to 93, characterized in that is Si. The image forming apparatus according to claim 96, wherein the composite oxide (A) is strontium silicate (SrSiO ₃ ). The image forming apparatus according to claim 54, wherein the composite oxide (A) particles are generated by a sintering method. The image forming apparatus according to claim 54, wherein the composite oxide (A) particles have a weight average diameter of 0.1 to 5.0 μm. 99. The image forming apparatus according to claim 54, wherein the composite oxide (A) particles have a weight average diameter of 0.3 to 3.0 [mu] m. 99. The image forming apparatus according to claim 54, wherein the composite oxide (A) particles have a weight average diameter of 0.5 to 2.5 [mu] m. The image forming apparatus according to claim 54, wherein the colorant is a magnetic material. The image forming apparatus according to claim 54, wherein the toner particles have a weight average diameter larger than that of the composite oxide (A) particles. 104. The image forming apparatus according to claim 103, wherein the toner particles have a weight average diameter of 3 to 12 [mu] m. 104. The image forming apparatus according to claim 103, wherein the toner particles have a weight average diameter of 3 to 9 [mu] m. The cleaning blade
(A) At a temperature of 40 to 80 ° C., the storage elastic modulus (G′B) is 1 × 10 ^{6 to} 5 × 10 ⁶ Pa,
106. The image forming apparatus according to claim 54, wherein the loss elastic modulus (G ″ B) is 1 × 10 ^{4 to} 5 × 10 ⁵ Pa at a temperature of 40 to 80 ° C. .

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