JP2004004414A - Dry toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide dry toner of superior fine particle fluidity, transfer, heat resistant storage stability, low-temperature fixing properties and heat resistant off-set, in the case of the small particle diameter toner. <P>SOLUTION: In the dry toner containing modified polyester (i) as at least a toner binder, a volume average particle diameter (Dv) of the toner is 3-10 μm, and a ratio (Dv/Dp) of the volume average particle diameter (Dv) to a number-of-pieces average particle diameter (Dp) is 1.05-1.25. <P>COPYRIGHT: (C)2004,JPO

Description

【００９３】
実施例３
（トナーバインダーの作成）
ウレア変性ポリエステル（１）３０部と変性されていないポリエステル（ａ）９７０部を酢酸エチル／ＭＥＫ（１／１）混合溶剤２０００部に溶解、混合し、トナーバインダー（３）の酢酸エチル／ＭＥＫ溶液を得た。その一部を減圧乾燥し、トナーバインダー（３）を得た。そのピーク分子量は５０００、Ｔｇは６２℃、酸価は１０ｍｇＫＯＨ／ｇであった。
【００９４】
（トナーの作成）
トナーバインダー（１）をトナーバインダー（３）に変える以外は実施例１と同様にし、着色剤をカーボンブラック８部に変える以外は実施例２と同様に本発明のトナー（３）を得た。本トナーの体積平均粒径（Ｄｖ）は５．４μｍ、個数平均粒径（Ｄｐ）は４．６μｍで、Ｄｖ／Ｄｐは１．１７であった。評価結果を表２に示す。
【００９５】
実施例４
（トナーバインダーの合成）
ウレア変性ポリエステル（１）５００部と変性されていないポリエステル（ａ）５００部を酢酸エチル／ＭＥＫ（１／１）混合溶剤２０００部に溶解、混合し、トナーバインダー（４）の酢酸エチル／ＭＥＫ溶液を得た。その一部を減圧乾燥し、トナーバインダー（４）を得た。そのピーク分子量は５０００、Ｔｇは６２℃、酸価は１０ｍｇＫＯＨ／ｇであった。
【００９６】
（トナーの作成）
トナーバインダー（１）をトナーバインダー（４）に変え、カーボンブラック８部をトナー材料として用いる以外は実施例１と同様にし、本発明のトナー（４）を得た。本トナーの体積平均粒径（Ｄｖ）は６．８μｍ、個数平均粒径（Ｄｐ）は５．６μｍで、Ｄｖ／Ｄｐは１．２１であった。評価結果を表２に示す。
【００９７】
比較例２
（トナーバインダーの合成）
冷却管、攪拌機および窒素導入管の付いた反応槽中に、ビスフェノールＡエチレンオキサイド２モル付加物３４３部、イソフタル酸１６６部およびジブチルチンオキサイド２部を入れ、常圧で２３０℃で８時間反応し、さらに１０〜１５ｍｍＨｇの減圧で５時間反応した後、８０℃まで冷却し、トルエン中にてトルエンジイソシアネート１４部を入れ１１０℃で５時間反応を行い、次いで脱溶剤し、重量平均分子量９８０００のウレタン変性ポリエステルを得た。ビスフェノールＡエチレンオキサイド２モル付加物３６３部、イソフタル酸１６６部を実施例１と同様に重縮合し、ピーク分子量３８００、酸価７ｍｇＫＯＨ／ｇの変性されていないポリエステルを得た。上記ウレタン変性ポリエステル３５０部と変性されていないポリエステル６５０部をトルエンに溶解、混合後、脱溶剤し、比較トナーバインダー（２）を得た。
比較トナーバインダー（２）のＴｇは５８℃であった。
【００９８】
（トナーの作成）
比較トナーバインダー（２）１００部、カーボンブラック８部を下記の方法でトナー化した。まず、ヘンシェルミキサーを用いて予備混合した後、連続式混練機）で混練した。ついでジェット粉砕機微粉砕した後、気流分級機で分級し、トナー粒子を得た。ついで、トナー粒子１００部に疎水性シリカ０．５部と、疎水化酸化チタン０．５部をヘンシェルミキサーにて混合して比較トナー（２）を得た。本トナーの体積平均粒径（Ｄｖ）は７．２μｍ、個数平均粒径（Ｄｐ）は６．３μｍで、Ｄｖ／Ｄｐは１．１４であった。評価結果を表２に示す。
【００９９】
【表２】

【０１００】
実施例５
（トナーバインダーの作成）
ウレア変性ポリエステル（１）７５０部と変性されていないポリエステル（ａ）２５０部を酢酸エチル／ＭＥＫ（１／１）混合溶剤２０００部に溶解、混合し、トナーバインダー（５）の酢酸エチル／ＭＥＫ溶液を得た。その一部を減圧乾燥し、トナーバインダー（５）を得た。ピーク分子量は５０００、Ｔｇは６２℃、酸価は１０ｍｇＫＯＨ／ｇであった。
【０１０１】
（トナーの作成）
トナーバインダー（１）をトナーバインダー（５）に変える以外は実施例１と同様にし、本発明のトナー（５）を得た。本トナーの体積平均粒径（Ｄｖ）は４．５μｍ、個数平均粒径（Ｄｐ）は３．７μｍで、Ｄｖ／Ｄｐは１．２２であった。評価結果を表３に示す。
【０１０２】
実施例６
（トナーバインダーの作成）
ウレア変性ポリエステル（１）８５０部と変性されていないポリエステル（ａ）１５０部を酢酸エチル／ＭＥＫ（１／１）混合溶剤２０００部に溶解、混合し、トナーバインダー（６）の酢酸エチル／ＭＥＫ溶液を得た。その一部を減圧乾燥し、トナーバインダー（６）を得た。ピーク分子量は５０００、Ｔｇは６２℃、酸価は１０ｍｇＫＯＨ／ｇであった。
【０１０３】
（トナーの作成）
トナーバインダー（１）をトナーバインダー（６）に変える以外は実施例１と同様にし、本発明のトナー（６）を得た。本トナーの体積平均粒径（Ｄｖ）は５．８μｍ、個数平均粒径（Ｄｐ）は４．９μｍで、Ｄｖ／Ｄｐは１．１８であった。評価結果を表３に示す。
【０１０４】
比較例３
（トナーバインダーの合成）
ビスフェノールＡエチレンオキサイド２モル付加物３５４部およびテレフタル酸１６６部をジブチルチンオキサイド２部を触媒として重縮合し、ピーク分子量１２，０００の比較トナーバインダー（３）を得た。Ｔｇは６２℃、酸価は１０ｍｇＫＯＨ／ｇであった。
【０１０５】
（トナーの製造例）
ビーカー内に前記の比較トナーバインダー（３）１００部、酢酸エチル２００部、銅フタロシアニンブルー顔料４部を入れ、５０℃にてＴＫ式ホモミキサーで１２０００ｒｐｍで攪拌し、均一に溶解、分散させ、比較トナー材料溶液を得た。次いで実施例５と同様にトナー化し、比較トナー（３）を得た。本トナーの体積平均粒径（Ｄｖ）は６．５μｍ、個数平均粒径（Ｄｐ）は４．９μｍで、Ｄｖ／Ｄｐは１．３３であった。評価結果を表３に示す。
【０１０６】
【表３】

【０１０７】
実施例７
（トナーバインダーの合成）
ビスフェノールＡエチレンオキサイド２モル付加物７２４部、テレフタル酸２７６部を常圧下、２３０℃で２時間重縮合し、次いで１０〜１５ｍｍＨｇの減圧で５時間反応して、ピーク分子量８００の変性されていないポリエステル（ｂ）を得た。ウレア変性ポリエステル（１）２００部と変性されていないポリエステル（ｂ）８００部を酢酸エチル／ＭＥＫ（１／１）混合溶剤２０００部に溶解、混合し、トナーバインダー（７）の酢酸エチル／ＭＥＫ溶液を得た。その一部を減圧乾燥し、トナーバインダー（７）を単離した。Ｔｇは４５℃であった。
【０１０８】
（トナーの作成）
トナーバインダー（１）をトナーバインダー（７）に変える以外は実施例１と同様にし、トナー（７）を得た。本トナーの体積平均粒径（Ｄｖ）は６．５μｍ、個数平均粒径（Ｄｐ）は５．６μｍで、Ｄｖ／Ｄｐは１．１６であった。評価結果を表４に示す。
【０１０９】
実施例８
（トナーバインダーの合成）
ビスフェノールＡエチレンオキサイド２モル付加物７２４部、テレフタル酸２７６部を常圧下、２３０℃で４時間重縮合し、次いで１０〜１５ｍｍＨｇの減圧で５時間反応して、ピーク分子量２０００の変性されていないポリエステル（ｃ）を得た。ウレア変性ポリエステル（１）２００部と変性されていないポリエステル（ｃ）８００部を酢酸エチル／ＭＥＫ（１／１）混合溶剤２０００部に溶解、混合し、トナーバインダー（８）の酢酸エチル／ＭＥＫ溶液を得た。その一部を減圧乾燥し、トナーバインダー（８）を単離した。Ｔｇは５２℃であった。
【０１１０】
（トナーの作成）
トナーバインダー（１）をトナーバインダー（８）に変える以外は実施例１と同様にし、トナー（８）を得た。本トナーの体積平均粒径（Ｄｖ）は５．６μｍ、個数平均粒径（Ｄｐ）は４．９μｍで、Ｄｖ／Ｄｐは１．１４であった。評価結果を表４に示す。
【０１１１】
実施例９
（トナーバインダーの合成）
ビスフェノールＡエチレンオキサイド２モル付加物７２４部、テレフタル酸２７６部を常圧下、２３０℃で１０時間重縮合し、次いで１０〜１５ｍｍＨｇの減圧で５時間反応して、ピーク分子量３００００の変性されていないポリエステル（ｄ）を得た。ウレア変性ポリエステル（１）２００部と変性されていないポリエステル（ｄ）８００部を酢酸エチル／ＭＥＫ（１／１）混合溶剤２０００部に溶解、混合し、トナーバインダー（９）の酢酸エチル／ＭＥＫ溶液を得た。その一部を減圧乾燥し、トナーバインダー（９）を得た。Ｔｇは６９℃であった。
【０１１２】
（トナーの作成）
トナーバインダー（１）をトナーバインダー（９）に変える以外は実施例１と同様にし、トナー（９）を得た。本トナーの体積平均粒径（Ｄｖ）は７．７μｍ、個数平均粒径（Ｄｐ）は６．２μｍで、Ｄｖ／Ｄｐは１．２４であった。評価結果を表４に示す。
【０１１３】
実施例１０
（トナーバインダーの合成）
ビスフェノールＡエチレンオキサイド２モル付加物７２４部、テレフタル酸２７６部を常圧下、２３０℃で１２時間重縮合し、次いで１０〜１５ｍｍＨｇの減圧で５時間反応して、ピーク分子量３５０００の変性されていないポリエステル（ｅ）を得た。ウレア変性ポリエステル（１）２００部と変性されていないポリエステル（ｅ）８００部を酢酸エチル／ＭＥＫ（１／１）混合溶剤２０００部に溶解、混合し、トナーバインダー（１０）の酢酸エチル／ＭＥＫ溶液を得た。その一部を減圧乾燥し、トナーバインダー（１０）を得た。酸価は１０ｍｇＫＯＨ／ｇ、Ｔｇは７３℃であった。
【０１１４】
（トナーの作成）
トナーバインダー（１）をトナーバインダー（１０）に変える以外は実施例１と同様にし、トナー（１０）を得た。本トナーの体積平均粒径（Ｄｖ）は８．５μｍ、個数平均粒径（Ｄｐ）は６．９μｍで、Ｄｖ／Ｄｐは１．２３であった。評価結果を表４に示す。
【０１１５】
実施例１１
（トナーバインダーの合成）
ビスフェノールＡエチレンオキサイド２モル付加物９２４部、テレフタル酸２７６部を常圧下、２３０℃で８時間重縮合し、次いで１０〜１５ｍｍＨｇの減圧で５時間反応して、ピーク分子量５０００の変性されていないポリエステル（ｆ）を得た。ウレア変性ポリエステル（１）２００部と変性されていないポリエステル（ｆ）８００部を酢酸エチル／ＭＥＫ（１／１）混合溶剤２０００部に溶解、混合し、トナーバインダー（１１）の酢酸エチル／ＭＥＫ溶液を得た。その一部を減圧乾燥し、トナーバインダー（１１）を得た。Ｔｇは６２℃、酸価は０．５ｍｇＫＯＨ／ｇであった。
【０１１６】
（トナーの作成）
トナーバインダー（１）をトナーバインダー（１１）に変える以外は実施例１と同様にし、トナー（１１）を得た。本トナーの体積平均粒径（Ｄｖ）は６．０μｍ、個数平均粒径（Ｄｐ）は４．９μｍで、Ｄｖ／Ｄｐは１．２２であった。評価結果を表４に示す。
【０１１７】
実施例１２
（トナーバインダーの合成）
ビスフェノールＡエチレンオキサイド２モル付加物８２４部、テレフタル酸２７６部を常圧下、２３０℃で８時間重縮合し、次いで１０〜１５ｍｍＨｇの減圧で５時間反応して、ピーク分子量５０００の変性されていないポリエステル（ｇ）を得た。ウレア変性ポリエステル（１）２００部と変性されていないポリエステル（ｇ）８００部を酢酸エチル／ＭＥＫ（１／１）混合溶剤２０００部に溶解、混合し、トナーバインダー（１２）の酢酸エチル／ＭＥＫ溶液を得た。その一部を減圧乾燥し、トナーバインダー（１２）を得た。Ｔｇは６２℃、酸価は２ｍｇＫＯＨ／ｇであった。
【０１１８】
（トナーの作成）
トナーバインダー（１）をトナーバインダー（１２）に変える以外は実施例１と同様にし、トナー（１２）を得た。本トナーの体積平均粒径（Ｄｖ）は４．７μｍ、個数平均粒径（Ｄｐ）は３．９μｍで、Ｄｖ／Ｄｐは１．２１であった。評価結果を表４に示す。
【０１１９】
実施例１３
（トナーバインダーの合成）
ビスフェノールＡエチレンオキサイド２モル付加物７２４部、テレフタル酸２７６部を常圧下、２３０℃で８時間重縮合し、次いで１０〜１５ｍｍＨｇの減圧で５時間反応した後、１６０℃まで冷却して、これに３２部の無水トリメリット酸を加えて２時間反応し、ピーク分子量５０００の変性されていないポリエステル（ｈ）を得た。ウレア変性ポリエステル（１）２００部と変性されていないポリエステル（ｈ）８００部を酢酸エチル／ＭＥＫ（１／１）混合溶剤２０００部に溶解、混合し、トナーバインダー（１３）の酢酸エチル／ＭＥＫ溶液を得た。その一部を減圧乾燥し、トナーバインダー（１３）を得た。Ｔｇは６２℃、酸価は２５ｍｇＫＯＨ／ｇであった。
【０１２０】
（トナーの作成）
トナーバインダー（１）をトナーバインダー（１３）に変える以外は実施例１と同様にし、トナー（１３）を得た。本トナーの体積平均粒径（Ｄｖ）は６．６μｍ、個数平均粒径（Ｄｐ）は５．４μｍで、Ｄｖ／Ｄｐは１．２２であった。評価結果を表４に示す。
【０１２１】
実施例１４
（トナーバインダーの合成）
ビスフェノールＡエチレンオキサイド２モル付加物７２４部、テレフタル酸２７６部を常圧下、２３０℃で８時間重縮合し、次いで１０〜１５ｍｍＨｇの減圧で５時間反応した後、１６０℃まで冷却して、これに４８部の無水トリメリット酸を加えて２時間反応し、ピーク分子量５０００の変性されていないポリエステル（ｉ）を得た。ウレア変性ポリエステル（１）２００部と変性されていないポリエステル（ｉ）８００部を酢酸エチル／ＭＥＫ（１／１）混合溶剤２０００部に溶解、混合し、トナーバインダー（１４）の酢酸エチル／ＭＥＫ溶液を得た。その一部を減圧乾燥し、トナーバインダー（１４）を得た。Ｔｇは６２℃、酸価は３５ｍｇＫＯＨ／ｇであった。
【０１２２】
（トナーの作成）
トナーバインダー（１）をトナーバインダー（１４）に変える以外は実施例１と同様にし、トナー（１４）を得た。本トナーの体積平均粒径（Ｄｖ）は８．２μｍ、個数平均粒径（Ｄｐ）は６．９μｍで、Ｄｖ／Ｄｐは１．１９であった。評価結果を表４に示す。
【０１２３】
実施例１５
（トナーの作成）
トナーバインダー（１）１００部、銅フタロシアニンブルー顔料４部を下記の方法でトナー化した。まず、ヘンシェルミキサーを用いて予備混合した後、連続式混練機で混練した。ついでジェット粉砕機微粉砕した後、気流分級機で分級した後、ターボミル（ターボ工業製）で処理する事により粒子に球形化を施し、更に気流分級機で分級を行ないトナー粒子を得た。ついで、トナー粒子１００部に疎水性シリカ０．５部と、疎水化酸化チタン０．５部をヘンシェルミキサーにて混合してトナー（１５）を得た。本トナーの体積平均粒径（Ｄｖ）は７．１μｍ、個数平均粒径（Ｄｐ）は５．９μｍで、Ｄｖ／Ｄｐは１．２０であった。評価結果を表４に示す。
【０１２４】
実施例１６
（プレポリマーの製造例）
冷却管、攪拌機および窒素導入管の付いた反応槽中に、ビスフェノールＡエチレンオキサイド２モル付加物７２４部、イソフタル酸２５０部、テレフタル酸２４部、およびジブチルチンオキサイド２部を入れ、常圧で２３０℃で８時間反応し、さらに１０〜１５ｍｍＨｇの減圧で脱水しながら５時間反応した後、１６０℃まで冷却して、これに３２部の無水フタル酸を加えて２時間反応した。次いで、８０℃まで冷却し、酢酸エチル中にてイソホロンジイソシアネート１８８部と２時間反応を行い重量平均分子量１２０００のイソシアネート基含有プレポリマー（１）を得た。
【０１２５】
（ケチミン化合物の製造例）
攪拌棒および温度計のついた反応槽中にイソホロンジアミン３０部とメチルエチルケトン７０部を仕込み、５０℃で５時間反応を行いケチミン化合物（１）を得た。
【０１２６】
（トナーの製造例）
ビーカー内に前記のプレポリマー（１）１５．４部、ポリエステル（ａ）６４部、酢酸エチル７８．６部を入れ、攪拌し溶解した。次いで、ペンタエリスリトールテトラベヘネート２０部、銅フタロシアニンブルー顔料４部を入れ、６０℃にてＴＫ式ホモミキサーで１２０００ｒｐｍで攪拌し、均一に溶解、分散させた。最後に、ケチミン化合物（１）２．７部を加え溶解させた。これをトナー材料溶液（１）とする。ビーカー内にイオン交換水７０６部、ハイドロキシアパタイト１０％懸濁液（日本化学工業（株）製スーパタイト１０）２９４部、ドデシルベンゼンスルホン酸ナトリウム０．２部を入れ均一に溶解した。ついで６０℃に昇温し、ＴＫ式ホモミキサーで１２０００ｒｐｍに攪拌しながら、上記トナー材料溶液（１）を投入し１０分間攪拌した。ついでこの混合液を攪拌棒および温度計付のコルベンに移し、９８℃まで昇温して、ウレア化反応をさせながら溶剤を除去し、濾別、洗浄、乾燥した後、風力分級し、体積平均粒径６μｍのトナー粒子を得た。ついで、トナー粒子１００部に疎水性シリカ０．５部と、疎水化酸化チタン０．５部をヘンシェルミキサーにて混合して、本発明のトナー（１６）を得た。本トナーの体積平均粒径（Ｄｖ）は６．８μｍ、個数平均粒径（Ｄｐ）は５．６μｍで、Ｄｖ／Ｄｐは１．２１であった。評価結果を表４に示す。
【０１２７】
実施例１７
実施例１に使用したウレア変性ポリエステル（１）の代わりに、（ポリスチレン変性ポリエステルの合成例）で示した、ポリスチレングラフト変性ポリエステル（１）を用い、実施例１と同様にトナー（１７）を作成した。本トナーの体積平均粒径（Ｄｖ）は６．２μｍ、個数平均粒径（Ｄｐ）は５．９μｍで、Ｄｖ／Ｄｐは１．０５であった。評価結果を表４に示す。
【０１２８】
【表４】

【０１２９】
［特性評価方法］
トナーの粒径（体積平均粒径、個数平均粒径）は、コールターエレクトロニクス社製のコールターカウンターモデルＴＡ−ＩＩにて測定した。
【０１３０】
（１）粉体流動性
ホソカワミクロン製パウダーテスターを用いてかさ密度を測定した。流動性の良好なトナーほど、かさ密度は大きい。
【０１３１】
（２）光沢発現温度（ＧＬＯＳＳ）（℃）
市販カラー複写機（ＰＲＥＴＥＲ５５０；リコー製）の定着装置を用いて定着評価した。定着画像の６０゜光沢が１０％以上となる定着ロール温度をもって光沢発現温度とした。
【０１３２】
（３）ホットオフセット発生温度（ＨＯＴ）（℃）
上記ＧＬＯＳＳと同様に定着評価し、定着画像へのホットオフセットの有無を目視評価した。ホットオフセットが発生した定着ロール温度をもってホットオフセット発生温度とした。
【０１３３】
（４）定着下限温度（℃）
定着ローラーとしてポリプロピレンテトラフルオロエチレン製ローラーを使用した（株）リコー製複写機　ＭＦ−２００の定着部を改造した装置を用いて、これにリコー製のタイプ６２００紙をセットし複写テストを行った。定着画像をパットで擦った後の画像濃度の残存率が７０％以上となる定着ロール温度をもって定着下限温度とした。
【０１３４】
（５）ホットオフセット発生温度（ＨＯＴ）（℃）
上記定着下限温度と同様に定着評価し、定着画像へのホットオフセットの有無を目視評価した。ホットオフセットが発生した定着ロール温度をもっ定着ロール温度をもってホットオフセット発生温度とした。
【０１３５】
（６）帯電量
作成したカラートナー５重量部と、以下記載のキャリア９５重量部を、ブレンダーで１０分間混合し、現像剤を作成する。
【０１３６】
（キャリア）
芯材（平均粒径５０μｍの球形フェライト粒子）
コート材構成材料（アミノシラン系カップリング材を分散したシリコーン樹脂）　アミノシラン系カップリング材とシリコーン樹脂をトルエンに分散させ、分散液を調整後、加温状態にて芯材にスプレーコートし、焼成、冷却後、平均コート樹脂膜厚み０．２μｍのもの。
現像剤の帯電量は、ブローオフ法により、エレクトロメーターを使用して測定した。本現像剤を、リコー製プリテール６５０機に搭載し、更に、３万枚のプリント後の現像剤の帯電量を測定した。
帯電量の適正値は、トナーの十分な現像性を得る事と逆帯電トナーによる地汚れを防止する為に、絶対値で１５〜２５（μｃ／ｇ）程度である。
【０１３７】
実施例１８
〔トナーバインダーの製造〕
冷却管、攪拌機及び窒素導入管を設けた反応槽中に、ビスフェノールＡエチレンオキサイド２モル付加物７２４部、イソフタル酸２７６部及びジブチルチンオキサイド２部を入れ、常圧、２３０℃で８時間反応させ、さらに１０〜１５ｍｍＨｇの減圧下で５時間反応させた後、１６０℃まで冷却して、これに３２部の無水フタル酸を加えて２時間反応させた。
次いで、８０℃まで冷却し、酢酸エチル中にて、イソフォロンジイソシアネート１８８部と２時間反応させ、イソシアネート含有プレポリマーを得た。
続いて、このプレポリマー２６７部とイソホロンジアミン１４部を５０℃で２時間反応させ、重量平均分子量６４０００のウレア変性ポリエステル（Ａ）を得た。
【０１３８】
上記と同様に、ビスフェノールＡエチレンオキサイド２モル付加物７２４部、テレフタル酸２７６部を常圧下、２３０℃で８時間重縮合し、次いで、１０〜１５ｍｍＨｇの減圧下で５時間反応させて、ピーク分子量５０００の変性されていないポリエステル（Ｂ）を得た。
ウレア変性ポリエステル（Ａ）２００部と変性されていないポリエステル（Ｂ）８００部を酢酸エチル／ＭＥＫ（１／１）混合溶剤２０００部に溶解、混合し、トナーバインダーの酢酸エチル／ＭＥＫ溶液を得た。
一部減圧乾燥し、トナーバインダーを単離した。Ｔｇは６２℃であった。
【０１３９】
〔トナーの製造〕
ビーカー内に上記のトナーバインダーの酢酸エチル／ＭＥＫ溶液２４０部、ペンタエリスリトールテトラベヘネート（融点８１℃、溶融粘度２５ｃｐｓ）２０部、銅フタロシアニンブルー顔料４部を入れ、６０℃にてＴＫ式ホモミキサーで１２０００ｒｐｍで攪拌し、均一に溶解、分散させた。
ビーカー内にイオン交換水７０６部、ハイドロキシアパタイト１０％懸濁液（日本化学工業（株）製スーパタイト１０）２９４部及びドデシルベンゼンスルホン酸ナトリウム０．２部を入れ、均一に溶解した。
次いで、６０℃に昇温し、ＴＫ式ホモミキサーで１２０００ｒｐｍに攪拌しながら、上記トナー材料溶液を投入し、１０分間攪拌した。
続いて、この混合液を攪拌棒及び温度計付のコルベンに移し、８０℃まで昇温して溶剤を除去し、塩酸をｐＨ２まで加え、ハイドロキシアパタイトを溶解除去した。この時点では不定形の粒子が非常に多く含まれていた。その後分散液を攪拌しながら７５℃まで昇温し、そのまま３０分保った後、２０℃まで冷却した。
濾別、洗浄、乾燥した後、風力分級し、トナー粒子を得た。
体積平均粒径（Ｄｖ）は６．２μｍで、平均円形度は０．９６２、円形度０．９５以下の割合は１５．８％であった。
次いで、トナー粒子１００部に疎水性シリカ０．５部と、疎水化酸化チタン０．５部をヘンシェルミキサーにて混合して、トナー（１８）を得た。
評価結果を表５に示す。
【０１４０】
実施例１９
〔トナーバインダーの製造〕
ビスフェノールＡエチレンオキサイド２モル付加物３３４部、ビスフェノールＡプロピレンオキサイド２モル付加物３３４部イソフタル酸２７４部及び無水トリメリット酸２０部を重縮合した後、イソホロンジイソシアネート１５４部を反応させプレポリマーを得た。
次いで、このプレポリマー２１３部とイソホロンジアミン９．５部及びジブチルアミン０．５部を実施例１８と同様に反応させ、重量平均分子量７９０００のウレア変性ポリエステル（Ａ）を得た。
ウレア変性ポリエステル（Ａ）２００部と変性されていないポリエステル（Ｂ）８００部を酢酸エチル／ＭＥＫ（１／１）混合溶剤２０００部に溶解、混合し、トナーバインダーの酢酸エチル溶液を得た。
一部減圧乾燥し、トナーバインダーを単離した。Ｔｇは６５℃であった。
【０１４１】
〔トナーの製造〕
溶解温度及び分散温度を５０℃に変えた以外は、実施例１と同様にして、トナー（１９）を得た。
このトナーの体積平均粒径（Ｄｖ）は５．２μｍ、平均円形度は０．９８５、円形度０．９５以下の割合は５．８％であった。
評価結果を表５に示す。
【０１４２】
比較例４
〔トナーバインダーの製造〕
ビスフェノールＡエチレンオキサイド２モル付加物３５４部及びイソフタル酸１６６部を、ジブチルチンオキサイド２部を触媒として重縮合し、重量平均分子量８，０００のトナーバインダーを得た。
このトナーバインダーのＴｇは５７℃であった。
【０１４３】
〔トナーの製造〕
ビーカー内に前記の上記トナーバインダー１００部、酢酸エチル溶液２００部及び銅フタロシアニンブルー顔料４部を入れ、５０℃にてＴＫ式ホモミキサーで１２０００ｒｐｍで攪拌し、均一に溶解、分散させた。
次いで、実施例１８と同様にしてトナー化し、体積平均粒径６μｍの比較トナー（４）を得た。
ただし、溶剤除去工程を９８℃で行い、８００ｒｐｍで攪拌しながら行った。
光学顕微鏡によれば一部の粒子は凝集し、また、表面の凹凸が激しいものであった。
但し実施例１８における酸処理、球形化処理は行なわなかった。
このトナーの体積平均粒径（Ｄｖ）は６．３μｍ、平均円形度は０．９３５、円形度０．９５以下の割合は３５．２％であった。
【０１４４】
評価結果を表５に示す。
【表５】

【０１４５】
実施例２０
〔トナーの製造〕
着色剤をカーボンブラック８部に代えた以外は、実施例１９と同様にしてトナーバインダーをトナー化し、トナー（２０）を得た。
このトナーの体積平均粒径（Ｄｖ）は５．４μｍ、平均円形度は０．９６５、円形度０．９５以下の割合は２４．９％であった。
評価結果を表６に示す。
【０１４６】
実施例２１
〔トナーバインダーの製造〕
ビスフェノールＡエチレンオキサイド２モル付加物３６３部及びイソフタル酸１６６部を実施例１と同様に重縮合し、ピーク分子量４３００の変性されていないポリエステル（Ｂ）を得た。
ウレア変性ポリエステル（Ａ）３００部と変性されていないポリエステル（Ｂ）７００部を酢酸エチル／ＭＥＫ（１／１）３０００部に溶解、混合し、トナーバインダーの酢酸エチル溶液を得た。
一部減圧乾燥し、トナーバインダーを単離した。Ｔｇは５７℃であった。
【０１４７】
〔トナーの製造〕
トナーバインダーの酢酸エチル／ＭＥＫ溶液３００部及びカーボンブラック８部をトナー材料として用いた以外は、実施例１８と同様にし、トナー（２１）を得た。
このトナーの体積平均粒径（Ｄｖ）は６．８μｍ、平均円形度は０．９８６、円形度０．９５以下の割合は３．２％であった。
評価結果を表６に示す。
【０１４８】
比較例５
〔トナーバインダーの製造〕
冷却管、攪拌機および窒素導入管を設けた反応槽中に、ビスフェノールＡエチレンオキサイド２モル付加物３４３部、イソフタル酸１６６部及びジブチルチンオキサイド２部を入れ、常圧、２３０℃で８時間反応し、さらに、１０〜１５ｍｍＨｇの減圧下で５時間反応した後、８０℃まで冷却し、トルエン中にてトルエンジイソシアネート１４部を入れ、１１０℃で５時間反応を行い、次いで、脱溶剤し、重量平均分子量９８０００のウレタン変性ポリエステルを得た。
ビスフェノールＡエチレンオキサイド２モル付加物３６３部及びイソフタル酸１６６部を実施例１と同様に重縮合し、ピーク分子量３８００、水酸基価２５、酸価７の変性されていないポリエステル（Ｂ）を得た。
このウレタン変性ポリエステル３５０部と変性されていないポリエステル（Ｂ）６５０部をトルエンに溶解、混合後、脱溶剤し、トナーバインダーを得た。
このトナーバインダーのＴｇは５８℃であった。
【０１４９】
〔トナーの製造〕
上記トナーバインダー１００部及びカーボンブラック８部を下記の方法でトナー化した。
先ず、ヘンシェルミキサーを用いて予備混合した後、連続式混練機で混練した。次いで、ジェット粉砕機微粉砕した後、気流分級機で分級し、トナー粒子を得た。
続いて、トナー粒子１００部に疎水性シリカ０．５部と、疎水化酸化チタン０．５部をヘンシェルミキサーにて混合して、比較トナー（５）を得た。
このトナーの体積平均粒径（Ｄｖ）は７．２μｍ、平均円形度は０．９３２、円形度０．９５以下の割合は５４．８％であった。
【０１５０】
評価結果を表６に示す。
【表６】

【０１５１】
実施例２２
〔プレポリマーの製造〕
冷却管、攪拌機および窒素導入管を設けた反応槽中に、ビスフェノールＡエチレンオキサイド２モル付加物７２４部、イソフタル酸２５０部、テレフタル酸２４部及びジブチルチンオキサイド２部を入れ、常圧、２３０℃で８時間反応し、さらに、１０〜１５ｍｍＨｇの減圧下で脱水しながら、５時間反応した後、１６０℃まで冷却して、これに３２部の無水フタル酸を加えて２時間反応させた。
次いで、８０℃まで冷却し、酢酸エチル中にてイソホロンジイソシアネート１８８部と２時間反応を行い、重量平均分子量１２０００のイソシアネート基含有プレポリマーを得た。
【０１５２】
〔ケチミン化合物の製造〕
攪拌棒および温度計設けた反応槽中に、イソホロンジアミン３０部とメチルエチルケトン７０部を仕込み、５０℃で５時間反応を行い、ケチミン化合物を得た。
【０１５３】
〔変性されていないポリエステルの製造〕
上記と同様にビスフェノールＡエチレンオキサイド２モル付加物７２４部及びテレフタル酸２７６部を常圧下、２３０℃で６時間重縮合し、次いで、１０〜１５ｍｍＨｇの減圧下で脱水しながら、５時間反応させて、ピーク分子量６０００の変性されていないポリエステル（Ｂ）を得た。
【０１５４】
〔トナーの製造〕
ビーカー内に上記のプレポリマー１５．４部、ポリエステル（ｃ）６４部及び酢酸エチル７８．６部を入れ、攪拌し溶解した。
続いて、ペンタエリスリトールテトラベヘネート２０部及び銅フタロシアニンブルー顔料４部を入れ、６０℃にて、ＴＫ式ホモミキサーで１２０００ｒｐｍで攪拌し、均一に溶解、分散させた。
終りに、ケチミン化合物２．７部を加え、溶解させた。これをトナー材料溶液とする。
ビーカー内にイオン交換水７０６部、ハイドロキシアパタイト１０％懸濁液（日本化学工業（株）製スーパタイト１０）２９４部及びドデシルベンゼンスルホン酸ナトリウム０．２部を入れ均一に溶解した。
次いで、６０℃に昇温し、ＴＫ式ホモミキサーで１２０００ｒｐｍに攪拌しながら、上記トナー材料溶液を投入し、１０分間攪拌した。
続いて、この混合液を攪拌棒及び温度計付のコルベンに移し、８０℃まで昇温して、ウレア化反応をさせながら溶剤を除去し、濾別、洗浄、乾燥した後、風力分級し、トナー粒子を得た。
塩酸をｐＨ２まで加え、ハイドロキシアパタイトを溶解除去した。この時点では不定形の粒子が非常に多く含まれていた。その後分散液を攪拌しながら７５℃まで昇温し、そのまま３０分保った後、２０℃まで冷却した。
終りに、トナー粒子１００部に疎水性シリカ０．５部と、疎水化酸化チタン０．５部をヘンシェルミキサーにて混合して、トナー（２２）を得た。
このトナーの体積平均粒径（Ｄｖ）は４．５μｍ、平均円形度は０．９９５、円形度０．９５以下の割合は１．２％であった。
評価結果を表７に示す。
【０１５５】
実施例２３
〔プレポリマーの製造〕
実施例１８と同様にして、ビスフェノールＡエチレンオキサイド２モル付加物６６９部、イソフタル酸２７４部及び無水トリメリット酸２０部を重縮合した後、イソホロンジイソシアネート１５４部を反応させ、重量平均分子量１５０００のプレポリマーを得た。
【０１５６】
〔トナーの製造〕
ビーカー内に上記のプレポリマー１５．５部、ポリエステル６４部、酢酸エチル７８．８部を入れ、攪拌し溶解した。
次いで、トリメチロールプロパントリベヘネート２０部及び銅フタロシアニンブルー顔料４部を入れ、５０℃にて、ＴＫ式ホモミキサーで１２０００ｒｐｍで攪拌し、均一に溶解、分散させた。
終りに、ケチミン化合物２．４部及びジブチルアミン０．０３６部を加え、溶解させた。
これをトナー材料溶液とする。
このトナー材料溶液を用い、分散温度を５０℃に変えた以外は、実施例５と同様にしてトナー化し、トナー（２３）を得た。
このトナーの体積平均粒径（Ｄｖ）は５．８μｍ、平均円形度は０．９７６、円形度０．９５以下の割合は８．２％であった。
【０１５７】
評価結果を表７に示す。
比較例６
〔トナーバインダーの製造〕
ビスフェノールＡエチレンオキサイド２モル付加物３５４部及びテレフタル酸１６６部を、ジブチルチンオキサイド２部を触媒として重縮合し、重量平均分子量１２，０００のトナーバインダーを得た。
【０１５８】
〔トナーの製造〕
ビーカー内に上記のトナーバインダー１００部、酢酸エチル２００部及び銅フタロシアニンブルー顔料４部を入れ、５０℃にて、ＴＫ式ホモミキサーで１２０００ｒｐｍで攪拌し、均一に溶解、分散させ、トナー材料溶液を得た。
次いで、実施例５と同様にトナー化し、比較トナー（６）を得た。
このトナーの体積平均粒径（Ｄｖ）は６．５μｍ、平均円形度は０．９７２、円形度０．９５以下の割合は９．６％であった。
【０１５９】
評価結果を表７に示す。
【表７】

【０１６０】
［評価方法］
トナーの粒径（体積平均粒径、個数平均粒径）は、コールターエレクトロニクス社製のコールターカウンターモデルＴＡ−ＩＩにより測定した。
【０１６１】
（１）粉体流動性
ホソカワミクロン製パウダーテスターを用いて、かさ密度を測定した。
流動性の良好なトナーほど、かさ密度は大きい。
【０１６２】
（２）光沢発現温度（ＧＬＯＳＳ）
市販カラー複写機（ＰＲＥＴＥＲ５５０；リコー製）の定着装置を用いて、定着評価した。
定着画像の６０゜光沢が１０％以上となる定着ロール温度をもって光沢発現温度とした。
【０１６３】
（３）ホットオフセット発生温度（ＨＯＴ）
上記ＧＬＯＳＳと同様に定着評価し、定着画像へのホットオフセットの有無を目視評価した。
ホットオフセットが発生した定着ロール温度をもってホットオフセット発生温度とした。
【０１６４】
（４）定着下限温度
定着ローラーとしてポリテトラフルオロエチレン製ローラーを使用した（株）リコー製複写機ＭＦ−２００の定着部を改造した装置を用いて、これにリコー製のタイプ６２００紙をセットし、複写テストを行った。
定着画像をパットで擦った後の画像濃度の残存率が７０％以上となる定着ロール温度をもって定着下限温度とした。
【０１６５】
（５）ホットオフセット発生温度（ＨＯＴ）
上記定着下限温度と同様に定着評価し、定着画像へのホットオフセットの有無を目視評価した。
ホットオフセットが発生した定着ロール温度をもっ定着ロール温度をもってホットオフセット発生温度とした。
【０１６６】
（６）画像濃度
製造したカラートナー５重量部と、以下記載のキャリア９５重量部を、ブレンダーで１０分間混合し、現像剤を製造した。
（キャリア）
芯材（平均粒径５０μｍの球形フェライト粒子）
コート材構成材料（アミノシラン系カップリング材を分散したシリコーン樹脂）　アミノシラン系カップリング材とシリコーン樹脂をトルエンに分散させ、分散液を調整後、加温状態にて芯材にスプレーコートし、焼成、冷却後、平均コート樹脂膜厚み０．２μｍのもの。
帯電量は、トナーの十分な現像性を得ることと逆帯電トナーによる地汚れを防止するために、絶対値で１５〜２５（μｃ／ｇ）程度になるように攪拌時間と速度を調節し、現像剤を製造した。
この現像剤を、市販カラー複写機（ＰＲＥＴＥＲ５５０；リコー製）に入れ、画像占有率７％の印字率で、リコー社製６０００ペーパーを用いてランニングを実施した。
そのときの初期１０枚目の画像と３万枚目の画像のべた部の画像濃度をＸ−Ｒｉｔｅ９３８スペクトロデンシトメーター（Ｘ−Ｒｉｔｅ社製）により測定し、これを４個所で行い、平均を求めた。
また、転写抜けランクは、印字された文字部を光学顕微鏡により１００倍に拡大し、観察して、ラインの抜けの状態を段階見本と比較しながら、５段階で評価した。
【０１６７】
【発明の効果】
本発明によれば、小粒径トナーとした場合の粉体流動性、転写性に優れると共に、良好な耐熱保存性、低温定着性、耐ホットオフセット性を有し、とりわけ、フルカラー複写機等に用いた場合に画像の光沢性及び耐ホットオフセット性に優れ、かつ熱ロールへのオイル塗布を不要とした乾式トナーが提供され、電子写真、静電記録、静電印刷等の分野に寄与するところはきわめて大きいものである。
【図面の簡単な説明】
【図１】フロー式粒子像分析装置の説明図である。
【図２】画像形成装置の１例についての要部断面構成図を示す。
【図３】プロセスカートリッジの１つの例についての構成図を示す。
【符号の説明】
（図２）
１　感光体ドラム
２　帯電器
３　レーザ光
４　現像装置
５　転写装置
６　クリーニング装置
９　除電ランプ
（図３）
４１　感光体
４４　画像露光部
４５　現像ローラ[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a dry toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, a manufacturing method thereof, a process cartridge, an image forming method, and an image forming apparatus. . More particularly, the present invention relates to a dry toner for electrophotography used for a copier, a laser printer, a plain paper fax, etc. using a direct or indirect electrophotographic development system, a method of manufacturing the same, a process cartridge, an image forming method, and an image forming apparatus. . Further, a dry toner for electrophotography used in a full-color copying machine, a full-color laser printer, a full-color plain paper fax, etc. using a direct or indirect electrophotographic multicolor developing system, a method for producing the same, a process cartridge, an image forming method, and an image It relates to a forming apparatus.
[0002]
[Prior art]
In the developing process, for example, the developer used in electrophotography, electrostatic recording, electrostatic printing, etc. is once adhered to an image carrier such as a photoconductor on which an electrostatic image is formed, After being transferred from the photoreceptor to a transfer medium such as transfer paper in the transfer step, it is fixed on the paper surface in the fixing step. At that time, as a developer for developing an electrostatic charge image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner and a one-component developer (a magnetic toner, Non-magnetic toner) is known.
2. Description of the Related Art Conventionally, as a dry toner used for electrophotography, electrostatic recording, electrostatic printing, and the like, a toner obtained by melt-kneading a toner binder such as a styrene-based resin or polyester with a colorant and the like and finely pulverizing the same is used.
[0003]
These dry toners are developed and transferred to paper or the like, and then fixed by heating and melting using a hot roll. At that time, if the temperature of the hot roll is too high, there is a problem that the toner is excessively melted and fused to the hot roll (hot offset). On the other hand, if the temperature of the hot roll is too low, the toner does not melt sufficiently and the fixing becomes insufficient. From the viewpoint of energy saving and miniaturization of apparatuses such as copying machines, toners having a higher hot offset generation temperature (hot offset resistance) and a lower fixing temperature (low temperature fixing property) are required. Further, it is necessary to have heat-resistant storage stability in which the toner does not block during storage and at ambient temperature in the apparatus. Particularly in full-color copying machines and full-color printers, since the gloss and color mixing properties of the images are required, the toner must have a lower melt viscosity, and a sharp-melting polyester toner binder is used. ing. Since hot offset easily occurs in such a toner, silicone oil or the like is conventionally applied to a heat roll in a full-color device. However, the method of applying silicone oil to the heat roll requires an oil tank and an oil application device, and the device becomes complicated and large. It also causes deterioration of the heat roll, and requires maintenance at regular intervals. Further, it is unavoidable that oil adheres to copy paper, OHP (overhead projector) film, and the like. In particular, OHP has a problem of deterioration of color tone due to the adhered oil.
[0004]
In order to obtain high-quality, high-quality images, improvements have been made by reducing the particle size of the toner. Inside, the toner is further pulverized by agitation with the carrier in the developing section, or when used as a one-component developer, due to contact stress between the developing roller and the toner supply roller, a layer thickness regulating blade, a friction charging blade, etc. And the quality of the image is degraded because the fluidizing agent is embedded in the toner surface. In addition, due to its shape, the fluidity of the powder is poor, requiring a large amount of fluidization, and the filling rate in the toner bottle is low, which is an obstacle to compactness.
[0005]
In addition, the process of transferring an image formed from multicolor toner from a photoreceptor to a transfer medium or paper to create a full-color image is becoming more complicated, and the transferability due to irregular shapes such as pulverized toner is increasing. Due to the badness, problems such as missing of the transferred image and a large amount of toner consumption to compensate for it have occurred.
Therefore, there is an increasing demand for further improving the transfer efficiency to reduce the amount of consumed toner to obtain a high-quality image without missing the image and to reduce the running cost. If the transfer efficiency is very good, there is no need for a cleaning unit to remove untransferred toner from the photoreceptor or the transfer medium, so that the equipment can be miniaturized, the cost can be reduced, and the waste toner can be eliminated. Because there is. Various methods for producing spherical toner have been devised in order to compensate for the disadvantages of such irregular shape effects.
[0006]
Among the above problems, (1) a method using a polyester partially crosslinked with a polyfunctional monomer as a toner binder to achieve both heat storage stability, low-temperature fixability and hot offset resistance No. 57-109825) and (2) those using urethane-modified polyester as a toner binder (Japanese Patent Publication No. 7-101318). Further, as a method for reducing the amount of oil applied to a heat roll for full color, (3) a method in which polyester fine particles and wax fine particles are granulated (Japanese Patent Application Laid-Open No. 7-56390) has been proposed.
Further, to improve powder flowability and transferability when the particle size is reduced, (4) after dispersing a vinyl monomer composition containing a colorant, a polar resin and a release agent in water, And (5) a toner obtained by subjecting a toner made of a polyester resin to a spherical shape in water using a solvent (JP-A-9-34167). ing.
Further, (6) Japanese Patent Application Laid-Open No. 11-133666 discloses a substantially spherical dry toner using a polyester resin modified by a urea bond.
[0007]
However, all of the toners disclosed in (1) to (3) have insufficient powder flowability and transferability, and cannot achieve high image quality by reducing the particle size. Further, the toners disclosed in (1) and (2) cannot be used because full compatibility for heat resistance and low-temperature fixability are still insufficient, and glossiness is not developed for full color use. Further, the toner disclosed in (3) has insufficient low-temperature fixability and does not have satisfactory hot offset property in oil-less fixation. The toners disclosed in (4) and (5) have the effect of improving powder fluidity and transferability, but the toners disclosed in (4) have insufficient low-temperature fixability, and The problem is that the required energy increases. In particular, this problem is remarkable in a full-color toner. The toner disclosed in (5) is more excellent in low-temperature fixability, but has insufficient hot offset resistance, and does not make oil application to a heat roll unnecessary for full color use.
[0008]
In the toner disclosed in (6), the viscoelasticity of the toner can be appropriately adjusted by using a polyester extended by urea bonds, and both the glossiness and the releasability as a full-color toner can be achieved. Was excellent. In particular, the so-called electrostatic offset, in which the fixing roller is charged during use and the toner on the unfixed image on the transfer medium is electrostatically scattered or adheres to the fixing roller, is called the positive charging property of the urea binding component. And the neutralization of the weakly negative charge of the polyester resin itself. However, despite the advantages described above, when actually used, the agitation with the carrier in the developing section inside the machine, and when used as a one-component developer, the developing roller and the toner supply roller, the layer thickness The toner is further pulverized by contact stress caused by a regulating blade or a triboelectric charging blade and the like, and a phenomenon that image quality is deteriorated because ultrafine particles are generated or a fluidizing agent is embedded in the toner surface is likely to occur. There remains a problem that the life as a toner is short.
Further, in order to improve the fluidity and transferability of the toner in order to obtain a high-quality image, a toner having a shape represented by Wadell's practical sphericity can only be represented by its average shape, which is not acceptable. It was impossible to prevent the deterioration of the image quality due to the inclusion of the fixed particles.
JP-A-11-133666 states that the average value of practical sphericity should be in the range of 0.9 to 1.00, but the content of circularity less than 0.95 is 30% by weight or less. It is important.
The generation of irregular particles is likely to occur in the step of removing the organic solvent because the particles shrink. This can be prevented by removing the organic solvent after emulsification and then heating at a temperature higher than the softening point of the resin and lower than the melting point of the release agent. This step is desirably performed after dissolving and removing the solid fine particle dispersant.
[0009]
[Problems to be solved by the invention]
The present invention provides a dry toner excellent in both powder fluidity and transferability when a small particle size toner is used and heat resistance storage stability, low-temperature fixability and hot offset resistance, and is particularly suitable for a full-color copying machine and the like. It is an object of the present invention to provide a dry toner having excellent glossiness of an image when used and having a long life as a toner and a method for manufacturing the same, and a process cartridge, an image forming method, and an image forming apparatus using the toner. I do.
[0010]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention.
That is, according to the present invention, a dry toner, a method for manufacturing the same, a process cartridge, an image forming method, and an image forming apparatus described below are provided.
[0011]
(1) In a dry toner containing at least the modified polyester (i) as a toner binder, the toner has a volume average particle diameter (Dv) of 3 to 10 μm and a ratio (Dv) to the number average particle diameter (Dp). / Dp) is 1.05 to 1.25.
(2) The average circularity of the toner is from 0.96 to 1.00, and the content of toner having a circularity of less than 0.95 is 30% or less based on the weight of all toners. The dry toner according to (1) above.
(3) The toner binder contains an unmodified polyester (ii), and the weight ratio (i) / (ii) of the modified polyester (i) to the unmodified polyester (ii) is 5/95 to 80. / 20, the dry toner according to any one of the above (1) and (2).
(4) In a dry toner containing the modified polyester (i) as a toner binder, the average circularity of the toner is 0.96 to 1.00 and the content of the toner having a circularity of less than 0.95 is reduced by weight. A dry toner characterized by being 30% or less of all toners on a standard basis.
(5) The dry toner according to any one of (1) to (4), wherein the modified polyester (i) is a modified polyester having a urea bond.
(6) The modified polyester (i), wherein the modified polyester (i) is a modified polyester having a urea bond obtained by reacting a polyester prepolymer (A) having an isocyanate group with an amine (B). The dry toner according to any one of (1) to (4).
(7) The toner obtained by dissolving / dispersing the toner composition containing the modified polyester (i) in an organic solvent and dispersing in an aqueous medium. The dry toner according to any one of (1) to (6).
(8) A toner obtained through a step of dissolving / dispersing a toner composition containing a prepolymer in an organic solvent and dispersing in an aqueous medium, wherein the prepolymer is modified polyester ( Dry toner according to any one of the above (1) to (7), which is converted into i).
(9) The dry toner according to any one of (1) to (8), wherein the peak molecular weight of the toner binder is 1,000 to 30,000.
(10) The dry toner according to any one of (1) to (9), wherein the toner binder has an acid value of 1 to 30 mgKOH / g.
(11) The dry toner according to any one of (1) to (10), wherein the glass transition point (Tg) of the toner binder is 50 to 70 ° C.
(12) In the method for producing a dry toner according to any one of the above (1) to (11), the toner composition containing the modified polyester (i) is dissolved or dispersed in an organic solvent, and then dissolved in an aqueous medium. And a method for producing a dry toner.
(13) The modified polyester (i) is a modified ester having a urea bond obtained by reacting a polyester prepolymer (A) having an isocyanate group with an amine (B) in a step. The method for producing a dry toner according to the above (12).
(14) In a process cartridge which supports the photosensitive member and the developing means integrally and can be detachably installed in the image forming apparatus, the developing means holds a toner, and the toner is any of the above (1) to (11) A process cartridge comprising the dry toner according to any one of the above.
(15) An image forming method including a transfer step of transferring a toner image carried on a toner image carrier to a transfer material and a cleaning step of cleaning the toner remaining on the surface of the toner image carrier after the transfer using a blade. , Wherein the toner according to any one of (1) to (11) is used.
(16) An image forming apparatus having a transfer unit for transferring a toner image carried on a toner image carrier to a transfer material and a cleaning unit for cleaning toner remaining on the toner image carrier surface after the transfer using a blade , Wherein the toner according to any one of (1) to (11) is used.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention is a dry toner containing the modified polyester (i) at least as a toner binder and having the following properties (I) and / or (II).
(Characteristic I)
The volume average particle diameter (Dv) is 3 to 10 μm, and the ratio (Dv / Dp) to the number average particle diameter (Dp) is 1.05 to 1.25.
(Characteristic II)
The average circularity of the toner is from 0.96 to 1.00, and the content of toner having a circularity of less than 0.95 is 30% or less based on the weight of all toners.
[0013]
Use of the toner of the above-mentioned property (I) is excellent in all of heat resistance storage stability, low-temperature fixability, and hot offset resistance, and particularly excellent in glossiness of an image when used in a full-color copying machine and the like. In the case of the developer, even if the toner balance is performed for a long period of time, the fluctuation of the particle diameter of the toner in the developer is reduced, and the good and stable developability is obtained even in the long-term stirring in the image forming apparatus (developing apparatus). can get. In addition, even when the toner is used as a one-component developer, even when the toner balance is performed, the variation in the particle diameter of the toner is reduced, and the filming of the toner to the developing roller and the thinning of the toner are performed. There was no fusion of the toner to members such as the blade, and good and stable developability and images were obtained even when the developing device was used for a long time (stirring).
[0014]
In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning performance. is there. Further, when the volume average particle diameter (Dv) is smaller than the range of the present invention, in a two-component developer, the toner is fused to the surface of the carrier during long-term stirring in the developing device, and the chargeability of the carrier is reduced. When used as a one-component developer, filming of the toner on the developing roller and fusion of the toner to a member such as a blade for thinning the toner are likely to occur.
Further, these phenomena are the same in the toner having a fine powder content higher than the range of the present invention.
Conversely, if the particle size of the toner is larger than the range of the present invention, it is difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is In many cases, the variation in the particle diameter of the particles becomes large. It was also found that the same applies when the volume average particle diameter / number average particle diameter (Dv / Dp) is larger than 1.25.
When the ratio (volume average particle diameter) / (number average particle diameter) is smaller than 1.05, there is a preferable aspect in terms of stabilizing the behavior of the toner and making the charge amount uniform, but the toner cannot be charged sufficiently. It was clarified that the cleaning performance was sometimes deteriorated.
[0015]
It is important that the toner has a specific shape and shape distribution (Characteristic II), and has an average circularity of less than 0.96 and an irregular shape that is too far from a sphere, that is, the circularity referred to in the present invention. Is less than 0.95 in an amount exceeding 30%, satisfactory transferability and high quality images free of dust cannot be obtained.
[0016]
Here, the average circularity is an average value of the circularity of each particle defined by the following equation.
Circularity = A / 4πB²
A: Projected area of particle
B: Perimeter of projected image of particle
The circularity of each particle was measured using a flow-type particle image analyzer “FPIA-1000” manufactured by Toa Medical Electronics Co., Ltd.
The degree of circularity is a shape index indicating the simplicity or complexity of the shape around a particle, and approaches 1.00 as the shape around the particle is smoother and closer to a circle.
Then, it indicates that the sphericity of the particle increases as the circularity approaches 1.
[0017]
As a specific measuring method, 0.1 to 0.5 ml of a surfactant (alkylbenzenesulfonate) as a dispersant is added to 100 to 150 ml of water from which impurity solids have been removed in advance in a container. About 0.1 to 0.5 g.
The suspension in which the sample is dispersed is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the concentration of the dispersion is set to 3000 to 10,000 / μl, and the shape and distribution of the toner are measured by the above apparatus. .
A toner containing 30% or less of particles having an average circularity of 0.96 or more and less than 0.95 is effective for forming a high-definition image with proper density and reproducibility. A toner having an average circularity of 0.98 to 1.00 and 10% or less of particles having a circularity of less than 0.95 is a preferable toner.
FIG. 1 shows a structural explanatory view of the flow type particle image analyzer.
[0018]
Amorphous particles have many points of contact with a smooth medium on the photoreceptor, etc., and charge is concentrated on the tip of the protrusion, so that particles with a van der Waals force and mirror image force are relatively stronger than particles having a relatively spherical shape. High strength.
For this reason, in the electrostatic transfer step, in the toner in which the irregular particles and the spherical particles are mixed, the spherical particles are selectively moved, and the image of the character portion or the line portion is missing.
In addition, the remaining toner must be removed for the next development step, which causes a problem that a cleaner device is required and a toner yield (a ratio of toner used for image formation) is low. I was
[0019]
As described above, a modified polyester having a urea bond or the like (hereinafter sometimes referred to as a modified polyester) can easily adjust the molecular weight of its high molecular component, and has a fixing property (suitable glossiness, fixing property) of a dry toner, particularly a full-color toner. This is advantageous in ensuring a wide range of releasability without a release oil applying mechanism to the heating medium.
In addition, a modified polyester prepolymer at the terminal can suppress the adhesion to the heating medium for fixing while maintaining the high fluidity and transparency of the unmodified polyester resin itself in the fixing temperature range.
Furthermore, when a toner having a specific circularity and a circularity distribution using a modified polyester as a binder resin is used, the adhesive force with a photoreceptor or an intermediate transfer member can be reduced.
[0020]
Normally, areas where a large amount of developer has adhered, such as characters, lines, and the edges and centers of dots, are compressed by the transfer medium, and the adhesion to the photoreceptor and intermediate transfer body is increased. Will happen.
However, when a toner having a specific circularity and a circularity distribution using a modified polyester as a binder resin is used, the developed toner components are laminated in a structure close to a finely-packed structure, and are compressed by a transfer medium. However, since the change in volume is small, the adhesiveness to the photoreceptor and the intermediate transfer member does not change, and the transfer is uniformly performed by the transfer electric field, so that transfer omission does not occur.
[0021]
Furthermore, since the charge on the toner of the photoreceptor or the intermediate transfer member is almost circular and has no protrusion, it is difficult to aggregate, and the image power can be reduced.
Also, since the number of points of contact with the photoreceptor and the transfer medium is smaller than that of the irregular shaped particles, the adhesive force due to van der Waals force is reduced, and even if the toner layer is less flexible and is strongly compressed by a hard transfer medium, It has been found that omission at the time of transfer does not occur and that the amount of untransferred toner is extremely reduced.
[0022]
However, if particles close to irregular shapes are mixed to some extent in the toner layer, the layered structure of the developed toner is disturbed, so that the transferability reacts sensitively, and satisfactory prevention of transfer omission and transfer residue and transfer residue are prevented. Toner reduction cannot be realized.
In addition to this, usually, in order to prevent transfer omission, a measure is taken to increase the coverage of the toner surface by increasing the amount of external additives and reduce the adhesion to the photoreceptor or the like. At the time of transfer, the developer reacts sensitively to the electrostatic repulsive force of the toners, so that the developer is scattered, resulting in a problem that the image transferred onto the transfer medium is blurred and dust is generated.
[0023]
In the present invention, since the modified polyester is used as the binder resin, the positive resilience of the modified component and the neutralization of the weakly negative charge of the polyester resin itself weaken the electrostatic repulsion between the toners, resulting in a cohesive force. And the toner is not scattered, so that an excellent effect of simultaneously solving the problems of transfer omission, image blur, and dust can be achieved.
Furthermore, using a full-color toner having a specific circularity and circularity distribution using a modified polyester as a binder resin, the image is developed on the photoreceptor many times, and sequentially transferred onto an intermediate transfer body or a transfer medium. It has also been found that when a is formed, transferability, blurring of an image, and dust are effective for uniform reproducibility of a halftone in which the most noticeable.
[0024]
(Modified polyester)
In the present specification, the modified polyester (modified polyester) (i) refers to a polyester resin containing a functional group contained in a monomer unit of an acid or an alcohol and a bonding group other than an ester bond, or a polyester resin. A state in which resin components having different compositions are bonded by a covalent bond, an ionic bond, or the like. For example, a polyester terminal reacted with a bond other than an ester bond, specifically, an acid group, a functional group such as an isocyanate group that reacts with a hydroxyl group is introduced into the terminal, and the terminal is modified by further reacting with an active hydrogen compound. And those subjected to an extension reaction.
[0025]
Furthermore, the use of a compound having a plurality of active hydrogen groups so that polyester terminals are bonded to each other is also included (urea-modified polyester, urethane-modified polyester, etc.).
In addition, a reactive group such as a double bond is introduced into the polyester main chain, radical polymerization is caused therefrom to introduce a carbon-carbon bond graft component to the side chain, or a double bond is cross-linked. (Styrene-modified, acrylic-modified polyester, etc.).
Further, those obtained by copolymerizing resin components having different constitutions in the main chain of the polyester or reacting with a carboxyl group or a hydroxyl group at the terminal, for example, a silicone modified with a carboxyl group, a hydroxyl group, an epoxy group or a mercapto group at the terminal. Those copolymerized with a resin are also included (such as silicone-modified polyester).
Hereinafter, the modified polyester will be described in more detail.
[0026]
(Example of synthesis of polystyrene-modified polyester)
724 parts of bisphenol A ethylene oxide 2 mol adduct, 200 parts of isophthalic acid and 70 parts of fumaric acid, and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introducing pipe, and were placed at 230 ° C. under normal pressure. After further reacting at a reduced pressure of 10 to 15 mmHg for 5 hours, the mixture was cooled to 160 ° C., and 32 parts of phthalic anhydride was added thereto and reacted for 2 hours. Then, the mixture was cooled to 80 ° C., and 200 parts of styrene, 1 part of benzoyl peroxide and 0.5 part of dimethylaniline were added thereto in ethyl acetate, and the mixture was reacted for 2 hours. Ethyl acetate was distilled off to obtain a compound having a weight average molecular weight of 92,000. Polystyrene graft-modified polyester (1) was obtained.
[0027]
(Urea modified polyester)
Examples of the urea-modified polyester include a reaction product of a polyester prepolymer (A) having an isocyanate group and an amine (B). Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2), which is obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate (3). No. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, and a mercapto group. Of these, an alcoholic hydroxyl group is preferable.
[0028]
Examples of the polyol (1) include a diol (1-1) and a polyol having a valence of 3 or more (1-2), and (1-1) alone or a mixture of (1-1) and a small amount of (1-2). Mixtures are preferred.
[0029]
Examples of the diol (1-1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol). , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexane dimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Of these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols, and alkylene glycols having 2 to 12 carbon atoms. Is a combination of
[0030]
Trihydric or higher polyols (1-2) include trihydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Such as trisphenol PA, phenol novolak, and cresol novolak); and the above-mentioned trivalent or higher polyphenols alkylene oxide adducts.
[0031]
Examples of the polycarboxylic acid (2) include a dicarboxylic acid (2-1) and a trivalent or higher polycarboxylic acid (2-2), and (2-1) alone or (2-1) and a small amount of ( The mixture of 2-2) is preferred.
[0032]
Examples of the dicarboxylic acid (2-1) include alkylenedicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid). , Naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
[0033]
Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). The polycarboxylic acid (2) may be reacted with the polyol (1) using the above-mentioned acid anhydride or lower alkyl ester (eg, methyl ester, ethyl ester, isopropyl ester).
[0034]
The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1, as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. It is from 5/1 to 1/1, more preferably from 1.3 / 1 to 1.02 / 1.
[0035]
Examples of the polyisocyanate (3) include aliphatic polyisocyanates (such as tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,6-diisocyanatomethylcaproate); alicyclic polyisocyanates (such as isophorone diisocyanate and cyclohexylmethane diisocyanate); Aromatic diisocyanates (such as tolylene diisocyanate and diphenylmethane diisocyanate); araliphatic diisocyanates (such as α, α, α ′, α′-tetramethylxylylene diisocyanate); isocyanurates; And a combination of two or more of these.
[0036]
The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4/1, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the hydroxyl group-containing polyester. It is 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. If [NCO] / [OH] exceeds 5, the low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester becomes low, and the hot offset resistance deteriorates. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If the content is less than 0.5% by weight, the hot offset resistance is deteriorated and the heat storage stability and the low-temperature fixability are both disadvantageous. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.
[0037]
The isocyanate group contained in one molecule in the prepolymer (A) having an isocyanate group is usually at least 1, preferably 1.5 to 3 on average, and more preferably 1.8 to 2.5 on average. It is. If it is less than one per molecule, the molecular weight of the modified polyester becomes low, and the hot offset resistance deteriorates.
[0038]
Examples of the amines (B) include diamines (B1), triamine or higher polyamines (B2), amino alcohols (B3), aminomercaptans (B4), amino acids (B5), and those obtained by blocking amino groups of B1 to B5. (B6) and the like.
Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4 ′ diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3 ′ dimethyldicyclohexylmethane, diaminecyclohexane, And aliphatic diamines (such as ethylenediamine, tetramethylenediamine, and hexamethylenediamine).
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the aminomercaptan (B4) include aminoethylmercaptan and aminopropylmercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the product obtained by blocking the amino group of B1 to B5 (B6) include ketimine compounds and oxazoline compounds obtained from the amines and ketones (such as acetone, methyl ethyl ketone, and methyl isobutyl ketone) of B1 to B5. Preferred of these amines (B) are B1 and a mixture of B1 and a small amount of B2.
[0039]
Further, if necessary, the molecular weight of the modified polyester can be adjusted by using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine and the like), and those obtained by blocking them (ketimine compounds).
The ratio of the amines (B) is defined as the equivalent ratio [NCO] / [NHx] of the isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and the amino groups [NHx] in the amines (B). , Usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, and more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low, and the hot offset resistance deteriorates.
In the present invention, the modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually from 100/0 to 10/90, preferably from 80/20 to 20/80, and more preferably from 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance deteriorates.
[0040]
The modified polyester (i) of the present invention is produced by a one-shot method or a prepolymer method.
The weight average molecular weight of the modified polyester (i) such as urea-modified polyester is usually 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the modified polyester is not particularly limited when an unmodified polyester (unmodified polyester) (ii) described later is used in combination, and is a number average molecular weight that is easily obtained to obtain the weight average molecular weight. Good.
When the modified polyester (i) is used alone, the number average molecular weight is usually 20,000 or less, preferably 1,000 to 10,000, and more preferably 2,000 to 8,000. If it exceeds 20,000, the low-temperature fixability and the gloss when used in a full-color device deteriorate.
[0041]
(Unmodified polyester)
In the present invention, not only the modified polyester (i) used alone, but also the unmodified polyester (unmodified polyester) (ii) can be contained as a toner binder component together with this (i). The combined use of (ii) improves low-temperature fixability and glossiness when used in a full-color device, and is more preferable than single use.
Examples of the unmodified polyester (ii) include the same polycondensates of the polyol (1) and the polycarboxylic acid (2) as in the polyester component (i), and preferred ones are also the same as (i). . It is preferable that (i) and (ii) are at least partially compatible with each other in view of low-temperature fixability and hot offset resistance. Therefore, the polyester component (i) and the polyester component (ii) preferably have similar compositions. When (ii) is used in combination, the weight ratio of (i) and (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferably, it is 7/93 to 20/80. When the weight ratio of (i) is less than 5%, the hot offset resistance deteriorates, and the heat resistance storage stability and the low-temperature fixability are disadvantageous.
[0042]
The peak molecular weight of the unmodified polyester (ii) is generally from 1,000 to 30,000, preferably from 1500 to 10,000, and more preferably from 2,000 to 8,000. If it is less than 1,000, the heat-resistant preservability deteriorates, and if it exceeds 10,000, the low-temperature fixability deteriorates. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of compatibility between heat-resistant storage stability and low-temperature fixability. The acid value of (ii) is usually 1 to 30 mgKOH / g, preferably 5 to 20 mgKOH / g. By having an acid value, it tends to be negatively chargeable.
[0043]
In the present invention, the glass transition point (Tg) of the toner binder is usually from 50 to 70C, preferably from 55 to 65C. If the temperature is lower than 50 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the presence of the modified polyester resin, the dry toner of the present invention tends to have good heat-resistant storage stability even at a low glass transition point, as compared with known polyester-based toners.
[0044]
The storage elastic modulus of the toner binder was 10,000 dyne / cm at a measurement frequency of 20 Hz.²Is usually 100 ° C. or higher, preferably 110 to 200 ° C. If the temperature is lower than 100 ° C., the hot offset resistance deteriorates.
[0045]
As for the viscosity of the toner binder, the temperature (Tη) at which the viscosity becomes 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or less, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, TG 'is preferably higher than T [eta] from the viewpoint of achieving both low-temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or more. It is more preferably at least 10 ° C, particularly preferably at least 20 ° C. The upper limit of the difference is not particularly limited. The difference between Tη and Tg is preferably from 0 to 100 ° C. from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability. The temperature is more preferably from 10 to 90 ° C, particularly preferably from 20 to 80 ° C.
[0046]
(Colorant)
As the colorant used in the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow Iron oxide, loess, graphite, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), Pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast Yellow (5G, R), Tartrazine lake, Quinoline yellow lake, Anthrazan yellow BGL, Isoindolinone yellow, Bengala, Lead red, Lead red, Cadmium red, Cadmium mercury red, Antimony red, Permanent red 4R , Para-red, phi-sa-red, parac Le orthonitroaniline Red, Lithol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Khan Min BS, permanent red (F2R, F4R, FRL, FRLL, F4RH), and the like.
[0047]
Furthermore, Fast Scarlet VD, Belcan Fast Rubin B, Brilliant Scarlet G, Lisor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Media, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, oil orange, cobalt blue, cerulean blue, alkaline blue lake, peacock blue lake , Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Dark Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc oxide And lithobon.
[0048]
In the present invention, the coloring agents can be used alone or in the form of a mixture. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.
[0049]
The colorant used in the present invention can be used as a masterbatch combined with a resin.
Examples of the binder resin to be manufactured or kneaded with the master batch include, in addition to the above-mentioned modified and unmodified polyester resins, polymers of styrene such as polystyrene, poly p-chlorostyrene, and polyvinyl toluene, and polymers substituted with styrene; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. can be used alone or in combination. You.
[0050]
In the present masterbatch, a masterbatch can be obtained by mixing and kneading the resin for the masterbatch and the colorant with high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. The so-called flushing method is also known as a method of mixing and kneading an aqueous paste containing water of a coloring agent together with a resin and an organic solvent, transferring the coloring agent to the resin side, and removing water and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high-shear dispersion device such as a three-roll mill is preferably used.
[0051]
(Release agent)
The toner of the present invention may contain a wax (release agent) together with a toner binder and a colorant. In the present invention, known waxes can be used, for example, polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long-chain hydrocarbons (paraffin waxes, Sasol wax, etc.); carbonyl group-containing waxes, etc. Is mentioned. Preferred among these are carbonyl group-containing waxes. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18 Polyalkanol esters (such as tristearyl trimellitate and distearyl maleate); polyalkanoic acid amides (such as ethylenediamine dibehenylamide); and polyalkylamides (such as trimellitic acid tristearyl amide). And dialkyl ketones (such as distearyl ketone). Preferred among these carbonyl group-containing waxes are polyalkanoic esters. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, and more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C adversely affects heat-resistant storage stability, and a wax having a melting point of more than 160 ° C tends to cause cold offset during fixing at a low temperature. The melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a value measured at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor improvement effects on hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.
[0052]
(Charge control agent)
The toner of the present invention may optionally contain a charge control agent. As the charge control agent, any known charge control agents can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified) Quaternary ammonium salts), alkyl amides, phosphorus alone or compounds, tungsten alone or compounds, fluorine-based activators, salicylic acid metal salts, and salicylic acid derivative metal salts. Specifically, bontron 03 of a nigrosine dye, bontron P-51 of a quaternary ammonium salt, bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, and E-82 of a salicylic acid metal complex 84, phenolic condensate E-89 (all manufactured by Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (all manufactured by Hodogaya Chemical Industry), quaternary ammonium Copy charge of salt PSY @ VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG @ VP2036, copy charge NX @ VP434 (all from Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinac Don, azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.
[0053]
In the present invention, the amount of the charge control agent used is determined by the type of the binder resin, the presence or absence of additives used as necessary, the toner manufacturing method including the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the binder resin. Preferably, the range is 0.2 to 5 parts by weight. If the amount exceeds 10 parts by weight, the chargeability of the toner is too large, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller increases, the fluidity of the developer decreases, and the image density decreases. Causes a decline. These charge control agents and release agents can be melt-kneaded together with the masterbatch and the resin, or of course, may be added when dissolved and dispersed in an organic solvent.
[0054]
(External additives)
An external additive can be added to the toner of the present invention in order to assist the flowability, developability, and chargeability of the colored particles. As this external additive, inorganic fine particles can be preferably used. The primary particle size of the inorganic fine particles is preferably from 5 μm to 2 μm, and particularly preferably from 5 μm to 500 μm. The specific surface area by the BET method is 20 to 500 m.²/ G. The usage ratio of the inorganic fine particles is preferably from 0.01 to 5% by weight of the toner, and particularly preferably from 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous Examples include earth, chromium oxide, cerium oxide, pengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
[0055]
The toner of the present invention may further include polycondensation of polymer fine particles such as polystyrene, methacrylate and acrylate copolymers obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, silicone, benzoguanamine, and nylon. And polymer particles of a thermosetting resin.
[0056]
Such an external additive can be subjected to a surface treatment to increase its hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. Examples of the surface treatment agent in this case include a silane coupling agent, a silylating agent, a silane coupling agent having an alkyl fluoride group, an organic titanate coupling agent, an aluminum coupling agent, a silicone oil, and a modified silicone. Oil and the like are preferred.
[0057]
A cleaning property improving agent can be used to remove the post-transfer developer remaining on the photoconductor and the primary transfer medium. Examples of the cleaning property improver include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, and polymer fine particles produced by soap-free emulsion polymerization of polymethyl methacrylate fine particles, polystyrene fine particles, and the like. I can do it. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.
[0058]
(Toner manufacturing method)
The manufacturing method of the dry toner of the present invention will be exemplified.
First, the toner binder can be manufactured by the following method.
The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off under reduced pressure if necessary. Thus, a polyester having a hydroxyl group is obtained.
Next, the polyisocyanate (3) is reacted therewith at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group. Further, this (A) is reacted with an amine (B) at 0 to 140 ° C. to obtain a urea-modified polyester modified with a urea group.
When reacting (3) and when reacting (A) and (B), a solvent can be used if necessary. Solvents that can be used include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethyl formamide, dimethyl acetamide, etc.) and ethers And the like (e.g., tetrahydrofuran), which are inert to isocyanate (3).
When a non-urea-modified polyester (ii) not modified with a urea bond is used in combination, (ii) is produced in the same manner as in the case of the polyester having a hydroxyl group, and this is dissolved in the solution after the completion of the reaction of (i). And then mix.
[0059]
The dry toner can be produced by the following method, but is not limited thereto. In the case of the present invention, it is preferable to use the toner production method in an aqueous medium described below.
[0060]
(Melt-kneading pulverization method)
A binder resin containing a modified polyester resin, a charge controlling agent, and a toner component such as a pigment are mechanically mixed. This mixing step may be performed under normal conditions using a normal mixer or the like with rotating blades, and is not particularly limited.
After the completion of the above mixing step, the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used.
[0061]
It is important that the melt-kneading is performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be cut. Specifically, the melt-kneading temperature should be determined with reference to the softening point of the binder resin. If the temperature is lower than the softening point, cutting is severe, and if the temperature is too high, dispersion does not proceed.
After the completion of the above-described melt-kneading process, the kneaded material is then pulverized. In this pulverization step, it is preferable to first perform coarse pulverization and then finely pulverize. At this time, a method of crushing by colliding with a collision plate in a jet stream, or crushing by a narrow gap between a rotor and a stator which rotate mechanically is preferably used.
After the completion of the pulverizing step, the pulverized product is classified in a gas stream by centrifugal force or the like, thereby producing a developer having a predetermined particle size, for example, an average particle size of 5 to 20 μm.
[0062]
Further, when preparing the developer, in order to enhance the fluidity, preservability, developability and transferability of the developer, the hydrophobic silica fine particles mentioned above in the developer produced as described above are further added. Inorganic fine particles such as powder may be added and mixed.
For mixing the external additive, a general powder mixer is used, but it is preferable that the internal temperature can be adjusted by equipping with a jacket or the like. In order to change the history of the load applied to the external additive, the external additive may be added during or gradually. Of course, the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. A strong load may be applied first, and then a relatively weak load may be applied, or vice versa.
[0063]
Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Lodige mixer, a Nauter mixer, and a Henschel mixer.
In order to make the resulting toner spherical, a method of melting and kneading a toner material comprising a toner binder and a colorant, and then mechanically forming the finely pulverized material using a hybridizer, mechanofusion, or the like, or a so-called spray drying method. A method in which a toner material is dissolved and dispersed in a solvent in which a toner binder is soluble, and then the solvent is removed using a spray drying apparatus to obtain a spherical toner. In addition, a method of forming a sphere by heating in an aqueous medium is exemplified, but the method is not limited thereto.
[0064]
(Method of manufacturing toner in aqueous medium)
The toner of the present invention can be produced by a method including a step of dissolving or dispersing a toner composition containing a modified polyester or a polyester prepolymer in an organic solvent and dispersing it in an aqueous medium. In this method, when a polyester prepolymer is used, the prepolymer is converted into a modified polyester during the process.
As the aqueous medium used in the present invention, water alone may be used, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (eg, methanol, isopropanol, ethylene glycol), dimethylformamide, tetrahydrofuran, cellosolves (eg, methylcellosolve), lower ketones (eg, acetone, methylethylketone), and the like.
[0065]
As the prepolymer, a polyester prepolymer (A) having an isocyanate group can be used. This prepolymer is reacted with (B) in an aqueous medium.
As a method for stably forming a dispersion comprising the modified polyester (i) and the prepolymer (A) in an aqueous medium, a toner composition containing the modified polyester (i) and the prepolymer (A) in an aqueous medium is used. In addition, a method of dispersing by a shear force and the like can be mentioned. The prepolymer (A) and another toner composition (hereinafter, referred to as toner raw material) such as a colorant, a colorant masterbatch, a release agent, a charge control agent, and an unmodified polyester resin may be modified polyester or a modified polyester resin in an aqueous medium. The prepolymer (A) may be mixed when it is dispersed to form a dispersion, but it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in an aqueous medium. Further, in the present invention, other toner raw materials such as a coloring agent, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, and after the particles are formed. May be added. For example, after forming particles containing no coloring agent, a coloring agent can be added by a known dyeing method.
[0066]
The dispersing method is not particularly limited, but known equipment such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. The high-speed shearing method is preferable in order to make the particle size of the dispersed particles 2 to 20 μm. When a high-speed shearing disperser is used, the number of revolutions is not particularly limited, but it is usually 1,000 to 30,000 rpm, preferably 5,000 to 20,000 rpm. The dispersion time is not particularly limited, but is usually 0.1 to 5 minutes in the case of a batch system. The temperature at the time of dispersion is usually 0 to 150 ° C (under pressure), preferably 40 to 98 ° C. A higher temperature is preferred because the viscosity of the dispersion containing the modified polyester (i) and the prepolymer (A) is lower and the dispersion is easier.
[0067]
The amount of the aqueous medium to be used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts of the toner composition containing the modified polyester (i) and the prepolymer (A). If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle size cannot be obtained. If it exceeds 20,000 parts by weight, it is not economical. In addition, a dispersant can be used if necessary. The use of a dispersant is preferred because the particle size distribution becomes sharp and the dispersion is stable.
[0068]
A surfactant can be used as a dispersant for emulsifying and dispersing the oily phase in which the toner composition is dispersed in an organic solvent in a liquid containing water. Examples of such surfactants include anionic surfactants such as alkyl benzene sulfonates, α-olefin sulfonates, and phosphate esters; alkyl amine salts; amino alcohol fatty acid derivatives; polyamine fatty acid derivatives; and amine salts such as imidazoline. Type, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, quaternary ammonium salt type cationic surfactant such as benzethonium chloride, fatty acid amide derivative, In addition to nonionic surfactants such as polyhydric alcohol derivatives, amphoteric such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine Surface active agents.
[0069]
Further, by using a surfactant having a fluoroalkyl group, the effect can be improved with a very small amount. Preferred examples of the anionic surfactant having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonylglutamate, and 3- [omega-fluoroalkyl (C6 to C11). ) Sodium] oxy] -1-alkyl (C3-C4) sulfonate, Sodium 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, Fluoroalkyl (C11-C20) carboxy Acid and metal salt, perfluoroalkylcarboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.
[0070]
As trade names, Surflon S-111, S-112, S-113 (manufactured by Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (manufactured by Sumitomo 3M), Unidyne DS-101 , DS-102, (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink and Chemicals), Ektop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204, (manufactured by Tochem Products Inc.), Futagent F-100, F150 (manufactured by Neos), and the like.
[0071]
Examples of the cationic surfactant include an aliphatic quaternary ammonium salt such as an aliphatic primary, secondary or secondary amine acid which pertains to a fluoroalkyl group, and a perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt. Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names are Surflon S-121 (manufactured by Asahi Glass Co., Ltd.), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (manufactured by Daikin Industries, Ltd.) ), Megafac F-150, F-824 (manufactured by Dainippon Ink and Chemicals), Ectop EF-132 (manufactured by Tochem Products), Futagent F-300 (manufactured by Neos) and the like.
[0072]
Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite, and the like can be used as the inorganic compound dispersant that is hardly soluble in water.
Further, the dispersed droplets may be stabilized by a polymer-based protective colloid. For example, an acid such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or a (meth) acrylic monomer containing a hydroxyl group Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylic acid Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin monoacrylate, glycerin monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or esters of vinyl alcohol and compounds containing a carboxyl group, for example, Vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocycle thereof, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl Polyoxyethylenes such as esters and celluloses such as methylcellulose, hydroxyethylcellulose and hydroxypropylcellulose can be used.
[0073]
In order to remove the organic solvent from the obtained emulsified dispersion and obtain a dry toner, a method of gradually elevating the temperature of the entire system and completely evaporating and removing the organic solvent in the droplets can be adopted. Alternatively, it is also possible to spray the emulsified dispersion in a dry atmosphere, completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and collectively evaporate and remove the aqueous dispersant. . As a drying atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide, combustion gas, or the like, particularly various air streams heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Satisfactory target quality can be obtained by short-time treatment such as spray dryer, belt dryer and rotary kiln.
In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. I do. In addition, it can be removed by an operation such as decomposition with an enzyme.
[0074]
When a fine particle dispersant is used, the dispersant can be left on the surface of the toner particles. However, it is preferable to remove the dispersant by washing after elongation and / or crosslinking reaction from the viewpoint of charging the toner.
[0075]
Further, in order to lower the viscosity of the aqueous dispersion of the toner composition, a solvent in which the modified polyester (i) or the prepolymer (A) is soluble can be added. The use of a solvent is preferred in that the particle size distribution becomes sharp. It is preferable that the solvent is volatile having a boiling point of less than 100 ° C. from the viewpoint of easy removal by evaporation. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are preferred.
[0076]
In the case of the aqueous dispersion containing the prepolymer (A), the amount of the solvent to be used relative to 100 parts of the prepolymer (A) is usually 0 to 300 parts, preferably 0 to 100 parts, more preferably 25 to 70 parts. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after the elongation and / or crosslinking reaction. The elongation and / or crosslinking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the combination of the amines (B), and is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. The reaction temperature is generally 0-150C, preferably 40-98C. In addition, a known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.
[0077]
When the obtained toner has a wide particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by cyclone, decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder after drying, but it is preferable to perform the classification operation in a liquid in terms of efficiency. The obtained unnecessary fine particles or coarse particles can be returned to the kneading step again and used for forming particles. At this time, the fine particles or coarse particles may be in a wet state.
[0078]
It is preferable that the used dispersant is removed from the obtained dispersion as much as possible.
By mixing the resulting dried toner powder with different kinds of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by applying a mechanical impact force to the mixed powder. Immobilization and fusion at the surface can prevent the dissociation of foreign particles from the surface of the resulting composite particles.
[0079]
As specific means, there are a method of applying an impact force to the mixture by a blade rotating at a high speed, a method of throwing the mixture into a high-speed air flow, accelerating, and colliding particles or composite particles with an appropriate collision plate. is there. As the equipment, Angular mill (manufactured by Hosokawa Micron), I-type mill (manufactured by Nippon Pneumatic) was modified to reduce the pulverized air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), Kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.
[0080]
In the toner of the present invention, the ratio Dv / Dp (characteristic I) between the volume average particle diameter Dv and the number average diameter (Dn) is mainly determined by, for example, water layer viscosity, oil layer viscosity, characteristics of resin fine particles, and addition amount. It can be controlled by adjusting etc. Further, Dv and Dp can be controlled by adjusting, for example, the characteristics and the amount of addition of the resin fine particles.
[0081]
In order to make the content of the circularity less than 0.95 in the characteristic (II) less than 30% based on the total weight of the toner, it is necessary to remove the organic solvent after emulsification and then release the resin at a temperature higher than the softening point of the resin. The heating can be performed at a temperature lower than the melting point of the agent to prevent the generation of irregular shaped particles. This step is preferably performed after dissolving and removing the solid fine particle dispersant.
[0082]
(Carrier for two components)
When the toner of the present invention is used in a two-component developer, the toner may be used as a mixture with a magnetic carrier. Parts are preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, and magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Also, polyvinyl and polyvinylidene resins, for example, acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins such as polystyrene resins and styrene acrylic copolymer resins, polychlorinated resins Halogenated olefin resin such as vinyl, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. If necessary, a conductive powder or the like may be contained in the coating resin. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide and the like can be used. These conductive powders preferably have an average particle size of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control the electric resistance. Further, the toner of the present invention can be used as a one-component magnetic toner or a non-magnetic toner without using a carrier.
[0083]
Hereinafter, the present invention will be described with reference to the drawings.
FIG. 2 is a cross-sectional configuration diagram of a main part of one example of the image forming apparatus. In this example, an electrophotographic copying machine is illustrated as an image forming apparatus. In FIG. 1, reference numeral 1 denotes a photosensitive drum serving as a latent image carrier, which rotates in the direction of the arrow in the drawing, and around which a charger 2 is disposed, and a laser beam 3 corresponding to an image read from a document. Is irradiated as exposure means. Further, a developing device 4, a paper feeding unit 7, a transfer device 5, a cleaning device 6, and a static elimination lamp 9 are arranged around the photoreceptor 1. The image forming apparatus 4 further includes developing rollers 41 and 42, a paddle-like stirring member 43, a stirring member 44, a doctor 45, a toner supply unit 46, and a supply roller 47. The cleaning means 6 has a cleaning brush 61 and a cleaning blade 62. The members 81 and 82 disposed above and below the apparatus 4 are guide rails for attaching and detaching or supporting the image forming apparatus.
The life of the cleaning blade 61 of the cleaning device can also be detected. The cleaning blade 61 is always in contact with the photoconductor during image formation, and wears as the photoconductor rotates. When the cleaning blade is worn, the function of removing the residual toner on the photoreceptor surface is reduced, and the quality of a copied image is deteriorated. Also, if the toner is close to a true sphere and the fluidity is improved compared to the pulverized toner without abrasion, the transferability is improved, but in cleaning the cleaning toner easily passes through the installed blade and the cleaning failure is likely to occur. Is done. By using the toner according to the present invention, this problem can be favorably cleaned.
[0084]
The image forming apparatus as described above may be fixedly incorporated in a copying apparatus, a facsimile, or a printer, or may be incorporated in the apparatus in the form of a process cartridge. The process cartridge is one device (part) that includes a photoconductor, and further includes a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, and a discharging unit. Although there are many shapes and the like of the process cartridge, a general example is shown in FIG.
[0085]
【Example】
Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto. Hereinafter, "part" indicates "part by weight".
[0086]
Example 1
(Synthesis of toner binder)
724 parts of bisphenol A ethylene oxide 2 mol adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide were put into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, and reacted at 230 ° C. for 8 hours under normal pressure. After further reacting at a reduced pressure of 10 to 15 mmHg for 5 hours, the mixture was cooled to 160 ° C., and 32 parts of phthalic anhydride was added thereto and reacted for 2 hours. Next, the mixture was cooled to 80 ° C. and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate-containing prepolymer (1). Next, 267 parts of the prepolymer (1) and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain a urea-modified polyester (1) having a weight average molecular weight of 64000.
In the same manner as above, 724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid are polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted under reduced pressure of 10 to 15 mmHg for 5 hours to modify the peak molecular weight to 5,000. Untreated polyester (a) was obtained.
200 parts of the urea-modified polyester (1) and 800 parts of the unmodified polyester (a) are dissolved and mixed in 2,000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and a solution of the toner binder (1) in ethyl acetate / MEK is mixed. Got. A part thereof was dried under reduced pressure to obtain a toner binder (1). Its Tg was 62 ° C and the acid value was 10 mgKOH / g.
[0087]
(Create toner)
In a beaker, 240 parts of the above-mentioned ethyl acetate / MEK solution of the toner binder (1), 20 parts of pentaerythritol tetrabehenate (melting point: 81 ° C., melt viscosity: 25 cps), and 4 parts of copper phthalocyanine blue pigment are placed. The mixture was stirred at 12000 rpm with a TK homomixer, and was uniformly dissolved and dispersed. In a beaker, 706 parts of ion-exchanged water, 294 parts of a hydroxyapatite 10% suspension (Supatite 10 manufactured by Nippon Chemical Industry Co., Ltd.), and 0.2 part of sodium dodecylbenzenesulfonate were put and uniformly dissolved. Then, the temperature was raised to 60 ° C., and the above-mentioned toner material solution was charged and stirred for 10 minutes while stirring at 12,000 rpm with a TK homomixer. Then, the mixture was transferred to a kolben equipped with a stirring rod and a thermometer, heated to 98 ° C. to remove the solvent, separated by filtration, washed, dried, and then subjected to air classification to obtain toner particles. The volume average particle diameter (Dv) was 6.2 μm, the number average particle diameter (Dp) was 5.2 μm, and Dv / Dp was 1.19. Then, 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide were mixed with 100 parts of the toner particles using a Henschel mixer to obtain a toner (1) of the present invention. Table 1 shows the evaluation results.
[0088]
Example 2
(Synthesis of toner binder)
In the same manner as in Example 1, 334 parts of bisphenol A ethylene oxide 2 mol adduct, 334 parts of bisphenol A propylene oxide adduct 274 parts of isophthalic acid and 20 parts of trimellitic anhydride are polycondensed, and 154 parts of isophorone diisocyanate Was reacted to obtain a prepolymer (2). Next, 213 parts of the prepolymer (2), 9.5 parts of isophoronediamine and 0.5 part of dibutylamine were reacted in the same manner as in Example 1 to obtain a urea-modified polyester (2) having a weight average molecular weight of 79000. 200 parts of the urea-modified polyester (2) and 800 parts of the unmodified polyester (a) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1) to obtain a solution of the toner binder (2) in ethyl acetate. Was. A part thereof was dried under reduced pressure to obtain a toner binder (2). Its peak molecular weight was 5000, Tg was 62 ° C., and acid value was 10 mgKOH / g.
[0089]
(Create toner)
A toner (2) of the present invention was obtained in the same manner as in Example 1 except that the melting temperature and the dispersion temperature were changed to 50 ° C. The volume average particle diameter (Dv) of this toner was 5.2 μm, the number average particle diameter (Dp) was 4.4 μm, and Dv / Dp was 1.18. Table 1 shows the evaluation results.
[0090]
Comparative Example 1
(Synthesis of toner binder)
354 parts of bisphenol A ethylene oxide 2 mol adduct and 166 parts of isophthalic acid were polycondensed using 2 parts of dibutyltin oxide as a catalyst to obtain a comparative toner binder (1) having a peak molecular weight of 4,000. The Tg of the comparative toner binder (1) was 57 ° C.
[0091]
(Create toner)
100 parts of the comparative toner binder (1), 200 parts of an ethyl acetate solution, and 4 parts of a copper phthalocyanine blue pigment were placed in a beaker, and the mixture was stirred at 50 ° C. with a TK homomixer at 12,000 rpm to be uniformly dissolved and dispersed. . Next, a toner was prepared in the same manner as in Example 1 to obtain a comparative toner (1) having a volume average particle diameter of 6 μm. The volume average particle diameter (Dv) of this toner was 6.3 μm, the number average particle diameter (Dp) was 5.4 μm, and Dv / Dp was 1.17. Table 1 shows the evaluation results.
[0092]
[Table 1]

[0093]
Example 3
(Preparation of toner binder)
30 parts of the urea-modified polyester (1) and 970 parts of the unmodified polyester (a) are dissolved and mixed in 2,000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and the toner binder (3) is dissolved in ethyl acetate / MEK. Got. A part thereof was dried under reduced pressure to obtain a toner binder (3). Its peak molecular weight was 5000, Tg was 62 ° C., and acid value was 10 mgKOH / g.
[0094]
(Create toner)
A toner (3) of the present invention was obtained in the same manner as in Example 1, except that the toner binder (1) was changed to the toner binder (3), and the colorant was changed to 8 parts of carbon black. The volume average particle diameter (Dv) of this toner was 5.4 μm, the number average particle diameter (Dp) was 4.6 μm, and Dv / Dp was 1.17. Table 2 shows the evaluation results.
[0095]
Example 4
(Synthesis of toner binder)
500 parts of the urea-modified polyester (1) and 500 parts of the unmodified polyester (a) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and a solution of the toner binder (4) in ethyl acetate / MEK is mixed. Got. A part thereof was dried under reduced pressure to obtain a toner binder (4). Its peak molecular weight was 5000, Tg was 62 ° C., and acid value was 10 mgKOH / g.
[0096]
(Create toner)
A toner (4) of the present invention was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (4) and 8 parts of carbon black was used as a toner material. The volume average particle diameter (Dv) of the toner was 6.8 μm, the number average particle diameter (Dp) was 5.6 μm, and Dv / Dp was 1.21. Table 2 shows the evaluation results.
[0097]
Comparative Example 2
(Synthesis of toner binder)
343 parts of bisphenol A ethylene oxide 2 mol adduct, 166 parts of isophthalic acid and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 230 ° C. for 8 hours under normal pressure. After further reacting at a reduced pressure of 10 to 15 mmHg for 5 hours, the mixture was cooled to 80 ° C., and 14 parts of toluene diisocyanate was added in toluene and reacted at 110 ° C. for 5 hours. Then, the solvent was removed, and a urethane having a weight average molecular weight of 98,000 was obtained. A modified polyester was obtained. 363 parts of bisphenol A ethylene oxide 2 mol adduct and 166 parts of isophthalic acid were polycondensed in the same manner as in Example 1 to obtain an unmodified polyester having a peak molecular weight of 3,800 and an acid value of 7 mgKOH / g. 350 parts of the urethane-modified polyester and 650 parts of the unmodified polyester were dissolved and mixed in toluene, and then the solvent was removed to obtain a comparative toner binder (2).
The Tg of the comparative toner binder (2) was 58 ° C.
[0098]
(Create toner)
100 parts of the comparative toner binder (2) and 8 parts of carbon black were converted to toner by the following method. First, the mixture was premixed using a Henschel mixer, and then kneaded with a continuous kneader. Then, after finely pulverizing with a jet pulverizer, the particles were classified with an airflow classifier to obtain toner particles. Then, 0.5 parts of hydrophobic silica and 0.5 parts of hydrophobic titanium oxide were mixed with 100 parts of the toner particles using a Henschel mixer to obtain Comparative Toner (2). The volume average particle diameter (Dv) of this toner was 7.2 μm, the number average particle diameter (Dp) was 6.3 μm, and Dv / Dp was 1.14. Table 2 shows the evaluation results.
[0099]
[Table 2]

[0100]
Example 5
(Preparation of toner binder)
750 parts of the urea-modified polyester (1) and 250 parts of the unmodified polyester (a) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and a solution of the toner binder (5) in ethyl acetate / MEK is mixed. Got. A part thereof was dried under reduced pressure to obtain a toner binder (5). The peak molecular weight was 5000, the Tg was 62 ° C., and the acid value was 10 mgKOH / g.
[0101]
(Create toner)
A toner (5) of the present invention was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (5). The volume average particle diameter (Dv) of this toner was 4.5 μm, the number average particle diameter (Dp) was 3.7 μm, and Dv / Dp was 1.22. Table 3 shows the evaluation results.
[0102]
Example 6
(Preparation of toner binder)
850 parts of the urea-modified polyester (1) and 150 parts of the unmodified polyester (a) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and a solution of the toner binder (6) in ethyl acetate / MEK is mixed. Got. A part thereof was dried under reduced pressure to obtain a toner binder (6). The peak molecular weight was 5000, the Tg was 62 ° C., and the acid value was 10 mgKOH / g.
[0103]
(Create toner)
A toner (6) of the present invention was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (6). The volume average particle diameter (Dv) of this toner was 5.8 μm, the number average particle diameter (Dp) was 4.9 μm, and Dv / Dp was 1.18. Table 3 shows the evaluation results.
[0104]
Comparative Example 3
(Synthesis of toner binder)
354 parts of bisphenol A ethylene oxide 2 mol adduct and 166 parts of terephthalic acid were polycondensed using 2 parts of dibutyltin oxide as a catalyst to obtain a comparative toner binder (3) having a peak molecular weight of 12,000. Tg was 62 ° C. and the acid value was 10 mg KOH / g.
[0105]
(Example of toner production)
100 parts of the comparative toner binder (3), 200 parts of ethyl acetate, and 4 parts of copper phthalocyanine blue pigment were placed in a beaker, stirred at 12000 rpm with a TK homomixer at 50 ° C., and uniformly dissolved and dispersed. A toner material solution was obtained. Next, a toner was prepared in the same manner as in Example 5 to obtain a comparative toner (3). The volume average particle diameter (Dv) of the toner was 6.5 μm, the number average particle diameter (Dp) was 4.9 μm, and Dv / Dp was 1.33. Table 3 shows the evaluation results.
[0106]
[Table 3]

[0107]
Example 7
(Synthesis of toner binder)
Polycondensation of 724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid under normal pressure at 230 ° C. for 2 hours, followed by reaction at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain an unmodified polyester having a peak molecular weight of 800. (B) was obtained. 200 parts of the urea-modified polyester (1) and 800 parts of the unmodified polyester (b) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and a solution of the toner binder (7) in ethyl acetate / MEK is mixed. Got. A part thereof was dried under reduced pressure to isolate the toner binder (7). Tg was 45 ° C.
[0108]
(Create toner)
A toner (7) was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (7). The volume average particle diameter (Dv) of the toner was 6.5 μm, the number average particle diameter (Dp) was 5.6 μm, and Dv / Dp was 1.16. Table 4 shows the evaluation results.
[0109]
Example 8
(Synthesis of toner binder)
Polycondensation of 724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid under normal pressure at 230 ° C. for 4 hours, followed by reaction at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain an unmodified polyester having a peak molecular weight of 2,000. (C) was obtained. 200 parts of the urea-modified polyester (1) and 800 parts of the unmodified polyester (c) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and a solution of the toner binder (8) in ethyl acetate / MEK is mixed. Got. A part thereof was dried under reduced pressure to isolate the toner binder (8). Tg was 52 ° C.
[0110]
(Create toner)
A toner (8) was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (8). The volume average particle diameter (Dv) of the toner was 5.6 μm, the number average particle diameter (Dp) was 4.9 μm, and Dv / Dp was 1.14. Table 4 shows the evaluation results.
[0111]
Example 9
(Synthesis of toner binder)
724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid are polycondensed at 230 ° C. for 10 hours under normal pressure, and then reacted at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain an unmodified polyester having a peak molecular weight of 30,000. (D) was obtained. 200 parts of the urea-modified polyester (1) and 800 parts of the unmodified polyester (d) are dissolved and mixed in 2,000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and a solution of the toner binder (9) in ethyl acetate / MEK is mixed. Got. A part thereof was dried under reduced pressure to obtain a toner binder (9). Tg was 69 ° C.
[0112]
(Create toner)
A toner (9) was obtained in the same manner as in Example 1, except that the toner binder (1) was changed to the toner binder (9). The volume average particle diameter (Dv) of this toner was 7.7 μm, the number average particle diameter (Dp) was 6.2 μm, and Dv / Dp was 1.24. Table 4 shows the evaluation results.
[0113]
Example 10
(Synthesis of toner binder)
Polycondensation of 724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid under normal pressure at 230 ° C. for 12 hours, followed by reaction at a reduced pressure of 10 to 15 mmHg for 5 hours to give an unmodified polyester having a peak molecular weight of 35,000. (E) was obtained. 200 parts of the urea-modified polyester (1) and 800 parts of the unmodified polyester (e) are dissolved and mixed in 2,000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and a solution of the toner binder (10) in ethyl acetate / MEK is mixed. Got. A part thereof was dried under reduced pressure to obtain a toner binder (10). The acid value was 10 mgKOH / g, and Tg was 73 ° C.
[0114]
(Create toner)
A toner (10) was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (10). The volume average particle diameter (Dv) of the toner was 8.5 μm, the number average particle diameter (Dp) was 6.9 μm, and Dv / Dp was 1.23. Table 4 shows the evaluation results.
[0115]
Example 11
(Synthesis of toner binder)
924 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid are polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted under reduced pressure of 10 to 15 mmHg for 5 hours to obtain an unmodified polyester having a peak molecular weight of 5,000. (F) was obtained. 200 parts of the urea-modified polyester (1) and 800 parts of the unmodified polyester (f) are dissolved and mixed in 2,000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and a solution of the toner binder (11) in ethyl acetate / MEK is mixed. Got. A part thereof was dried under reduced pressure to obtain a toner binder (11). Tg was 62 ° C. and the acid value was 0.5 mg KOH / g.
[0116]
(Create toner)
A toner (11) was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (11). The volume average particle diameter (Dv) of this toner was 6.0 μm, the number average particle diameter (Dp) was 4.9 μm, and Dv / Dp was 1.22. Table 4 shows the evaluation results.
[0117]
Example 12
(Synthesis of toner binder)
Polycondensation of 824 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid under normal pressure at 230 ° C. for 8 hours, followed by reaction at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain an unmodified polyester having a peak molecular weight of 5,000. (G) was obtained. 200 parts of the urea-modified polyester (1) and 800 parts of the unmodified polyester (g) are dissolved and mixed in 2,000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and a solution of the toner binder (12) in ethyl acetate / MEK is mixed. Got. A part thereof was dried under reduced pressure to obtain a toner binder (12). Tg was 62 ° C., and the acid value was 2 mgKOH / g.
[0118]
(Create toner)
A toner (12) was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (12). The volume average particle diameter (Dv) of this toner was 4.7 μm, the number average particle diameter (Dp) was 3.9 μm, and Dv / Dp was 1.21. Table 4 shows the evaluation results.
[0119]
Example 13
(Synthesis of toner binder)
Bisphenol A ethylene oxide 2 mol adduct 724 parts and terephthalic acid 276 parts are polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted at a reduced pressure of 10 to 15 mmHg for 5 hours, and then cooled to 160 ° C. After adding 32 parts of trimellitic anhydride and reacting for 2 hours, an unmodified polyester (h) having a peak molecular weight of 5000 was obtained. 200 parts of the urea-modified polyester (1) and 800 parts of the unmodified polyester (h) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and a solution of the toner binder (13) in ethyl acetate / MEK is mixed. Got. A part thereof was dried under reduced pressure to obtain a toner binder (13). Tg was 62 ° C. and the acid value was 25 mg KOH / g.
[0120]
(Create toner)
A toner (13) was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (13). The volume average particle diameter (Dv) of this toner was 6.6 μm, the number average particle diameter (Dp) was 5.4 μm, and Dv / Dp was 1.22. Table 4 shows the evaluation results.
[0121]
Example 14
(Synthesis of toner binder)
Bisphenol A ethylene oxide 2 mol adduct 724 parts and terephthalic acid 276 parts are polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted at a reduced pressure of 10 to 15 mmHg for 5 hours, and then cooled to 160 ° C. 48 parts of trimellitic anhydride were added and reacted for 2 hours to obtain an unmodified polyester (i) having a peak molecular weight of 5000. 200 parts of the urea-modified polyester (1) and 800 parts of the unmodified polyester (i) are dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and a toner binder (14) solution in ethyl acetate / MEK is mixed. Got. A part thereof was dried under reduced pressure to obtain a toner binder (14). Tg was 62 ° C., and the acid value was 35 mgKOH / g.
[0122]
(Create toner)
A toner (14) was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (14). The volume average particle diameter (Dv) of this toner was 8.2 μm, the number average particle diameter (Dp) was 6.9 μm, and Dv / Dp was 1.19. Table 4 shows the evaluation results.
[0123]
Example 15
(Create toner)
100 parts of toner binder (1) and 4 parts of copper phthalocyanine blue pigment were converted to toner by the following method. First, the mixture was premixed using a Henschel mixer, and then kneaded with a continuous kneader. Then, after finely pulverizing with a jet pulverizer, the particles were classified by an airflow classifier, and then processed by a turbo mill (manufactured by Turbo Kogyo Co., Ltd.) to make the particles spherical, and further classified by an airflow classifier to obtain toner particles. Then, 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide were mixed with 100 parts of the toner particles using a Henschel mixer to obtain a toner (15). The volume average particle diameter (Dv) of this toner was 7.1 μm, the number average particle diameter (Dp) was 5.9 μm, and Dv / Dp was 1.20. Table 4 shows the evaluation results.
[0124]
Example 16
(Example of prepolymer production)
In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introducing pipe, 724 parts of a 2-mol adduct of bisphenol A ethylene oxide, 250 parts of isophthalic acid, 24 parts of terephthalic acid, and 2 parts of dibutyltin oxide were placed at 230 atmospheric pressure. After reacting for 8 hours at a temperature of 10 ° C. and further dehydrating at a reduced pressure of 10 to 15 mmHg for 5 hours, the mixture was cooled to 160 ° C., and 32 parts of phthalic anhydride was added thereto and reacted for 2 hours. Next, the mixture was cooled to 80 ° C. and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate group-containing prepolymer (1) having a weight average molecular weight of 12,000.
[0125]
(Production example of ketimine compound)
30 parts of isophoronediamine and 70 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stirring rod and a thermometer, and reacted at 50 ° C. for 5 hours to obtain a ketimine compound (1).
[0126]
(Example of toner production)
In a beaker, 15.4 parts of the above prepolymer (1), 64 parts of polyester (a) and 78.6 parts of ethyl acetate were put and dissolved by stirring. Next, 20 parts of pentaerythritol tetrabehenate and 4 parts of copper phthalocyanine blue pigment were added, and the mixture was stirred at 60 ° C. with a TK homomixer at 12,000 rpm to be uniformly dissolved and dispersed. Finally, 2.7 parts of ketimine compound (1) was added and dissolved. This is designated as a toner material solution (1). In a beaker, 706 parts of ion-exchanged water, 294 parts of a hydroxyapatite 10% suspension (Supatite 10 manufactured by Nippon Chemical Industry Co., Ltd.), and 0.2 part of sodium dodecylbenzenesulfonate were put and uniformly dissolved. Then, the temperature was raised to 60 ° C., and the above-mentioned toner material solution (1) was charged and stirred for 10 minutes while stirring at 12,000 rpm with a TK homomixer. Then, the mixed solution was transferred to a kolben equipped with a stir bar and a thermometer, heated to 98 ° C., the solvent was removed while the urea reaction was being performed, filtered, washed, dried, air-classified, and volume-averaged. Thus, toner particles having a particle size of 6 μm were obtained. Then, 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide were mixed with 100 parts of the toner particles using a Henschel mixer to obtain a toner (16) of the present invention. The volume average particle diameter (Dv) of the toner was 6.8 μm, the number average particle diameter (Dp) was 5.6 μm, and Dv / Dp was 1.21. Table 4 shows the evaluation results.
[0127]
Example 17
In place of the urea-modified polyester (1) used in Example 1, a toner (17) was prepared in the same manner as in Example 1 by using the polystyrene-grafted modified polyester (1) shown in (Synthesis example of polystyrene-modified polyester). did. The volume average particle diameter (Dv) of this toner was 6.2 μm, the number average particle diameter (Dp) was 5.9 μm, and Dv / Dp was 1.05. Table 4 shows the evaluation results.
[0128]
[Table 4]

[0129]
[Characteristic evaluation method]
The particle size (volume average particle size, number average particle size) of the toner was measured using a Coulter Counter Model TA-II manufactured by Coulter Electronics.
[0130]
(1) Powder flowability
The bulk density was measured using a Hosokawa Micron powder tester. The higher the flowability of the toner, the greater the bulk density.
[0131]
(2) Gloss development temperature (GLOSS) (° C)
The fixing was evaluated using a fixing device of a commercially available color copying machine (PRETER550; manufactured by Ricoh). The gloss development temperature was defined as the fixing roll temperature at which the 60 ° gloss of the fixed image became 10% or more.
[0132]
(3) Hot offset occurrence temperature (HOT) (° C)
The fixing was evaluated in the same manner as in the above GLOSS, and the presence or absence of hot offset to the fixed image was visually evaluated. The temperature of the fixing roll at which the hot offset occurred was defined as the hot offset occurrence temperature.
[0133]
(4) Minimum fixing temperature (° C)
Ricoh type 6200 paper was set in this machine using a modified apparatus of the fixing unit of Ricoh Co., Ltd. MF-200 using a polypropylene tetrafluoroethylene roller as a fixing roller, and a copying test was performed. The fixing roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad was 70% or more was defined as the fixing lower limit temperature.
[0134]
(5) Hot offset occurrence temperature (HOT) (° C)
The fixing was evaluated in the same manner as the fixing lower limit temperature, and the presence or absence of hot offset to the fixed image was visually evaluated. The fixing roll temperature at which the hot offset occurred was taken as the hot offset occurrence temperature.
[0135]
(6) Charge amount
5 parts by weight of the prepared color toner and 95 parts by weight of a carrier described below are mixed for 10 minutes by a blender to prepare a developer.
[0136]
(Carrier)
Core material (spherical ferrite particles with an average particle size of 50 μm)
Coating material constituent material (silicone resin with aminosilane-based coupling material dispersed) 分散 Disperse the aminosilane-based coupling material and silicone resin in toluene, adjust the dispersion, spray coat the core material in a heated state, bake, After cooling, the average coating resin film thickness is 0.2 μm.
The charge amount of the developer was measured by a blow-off method using an electrometer. This developer was mounted on a Ricoh Pretail 650 machine, and the charge amount of the developer after printing 30,000 sheets was measured.
An appropriate value of the charge amount is about 15 to 25 (μc / g) in absolute value in order to obtain sufficient developability of the toner and to prevent background contamination due to the oppositely charged toner.
[0137]
Example 18
[Production of toner binder]
724 parts of bisphenol A ethylene oxide 2 mol adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide were placed in a reaction vessel provided with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 230 ° C. for 8 hours under normal pressure. After further reacting under reduced pressure of 10 to 15 mmHg for 5 hours, the mixture was cooled to 160 ° C., and 32 parts of phthalic anhydride was added thereto and reacted for 2 hours.
Next, the mixture was cooled to 80 ° C. and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate-containing prepolymer.
Subsequently, 267 parts of this prepolymer and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain a urea-modified polyester (A) having a weight average molecular weight of 64,000.
[0138]
Similarly to the above, 724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid are polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted under reduced pressure of 10 to 15 mmHg for 5 hours to obtain a peak molecular weight. 5000 unmodified polyester (B) were obtained.
200 parts of the urea-modified polyester (A) and 800 parts of the unmodified polyester (B) were dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1) to obtain a solution of a toner binder in ethyl acetate / MEK. .
The toner binder was partially dried under reduced pressure to isolate the toner binder. Tg was 62 ° C.
[0139]
[Production of toner]
In a beaker, 240 parts of the above-mentioned toner binder in ethyl acetate / MEK, 240 parts of pentaerythritol tetrabehenate (melting point: 81 ° C., melt viscosity: 25 cps) and 20 parts of copper phthalocyanine blue pigment were placed. The mixture was stirred at 12000 rpm with a mixer, and was uniformly dissolved and dispersed.
In a beaker, 706 parts of ion-exchanged water, 294 parts of a 10% suspension of hydroxyapatite (Supatite 10 manufactured by Nippon Chemical Industry Co., Ltd.) and 0.2 part of sodium dodecylbenzenesulfonate were uniformly dissolved.
Next, the temperature was raised to 60 ° C., and the above-mentioned toner material solution was charged while stirring at 12,000 rpm with a TK homomixer, followed by stirring for 10 minutes.
Subsequently, the mixed solution was transferred to a kolben equipped with a stirring rod and a thermometer, heated to 80 ° C. to remove the solvent, hydrochloric acid was added to pH 2, and hydroxyapatite was dissolved and removed. At this time, amorphous particles were contained very much. Thereafter, the temperature of the dispersion was raised to 75 ° C. while stirring, kept for 30 minutes, and then cooled to 20 ° C.
After filtration, washing, and drying, the particles were classified by wind to obtain toner particles.
The volume average particle diameter (Dv) was 6.2 μm, the average circularity was 0.962, and the ratio of the circularity of 0.95 or less was 15.8%.
Next, 0.5 parts of hydrophobic silica and 0.5 parts of hydrophobic titanium oxide were mixed with 100 parts of the toner particles using a Henschel mixer to obtain a toner (18).
Table 5 shows the evaluation results.
[0140]
Example 19
[Production of toner binder]
After polycondensation of 334 parts of bisphenol A ethylene oxide 2 mol adduct, 334 parts of bisphenol A propylene oxide 2 mol adduct 274 parts of isophthalic acid and 20 parts of trimellitic anhydride, 154 parts of isophorone diisocyanate were reacted to obtain a prepolymer. .
Next, 213 parts of this prepolymer, 9.5 parts of isophoronediamine and 0.5 part of dibutylamine were reacted in the same manner as in Example 18 to obtain a urea-modified polyester (A) having a weight average molecular weight of 79000.
200 parts of the urea-modified polyester (A) and 800 parts of the unmodified polyester (B) were dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1) to obtain an ethyl acetate solution of a toner binder.
A portion was dried under reduced pressure to isolate the toner binder. Tg was 65 ° C.
[0141]
[Production of toner]
A toner (19) was obtained in the same manner as in Example 1, except that the melting temperature and the dispersion temperature were changed to 50 ° C.
The volume average particle diameter (Dv) of this toner was 5.2 μm, the average circularity was 0.985, and the ratio of the circularity of 0.95 or less was 5.8%.
Table 5 shows the evaluation results.
[0142]
Comparative Example 4
[Production of toner binder]
354 parts of bisphenol A ethylene oxide 2 mol adduct and 166 parts of isophthalic acid were polycondensed using 2 parts of dibutyltin oxide as a catalyst to obtain a toner binder having a weight average molecular weight of 8,000.
The Tg of the toner binder was 57 ° C.
[0143]
[Production of toner]
100 parts of the above toner binder, 200 parts of ethyl acetate solution and 4 parts of copper phthalocyanine blue pigment were placed in a beaker, and the mixture was stirred at 50 ° C. with a TK homomixer at 12,000 rpm to be uniformly dissolved and dispersed.
Next, a toner was prepared in the same manner as in Example 18 to obtain a comparative toner (4) having a volume average particle size of 6 μm.
However, the solvent removal step was performed at 98 ° C. and the stirring was performed at 800 rpm.
According to the optical microscope, some of the particles were agglomerated, and surface irregularities were severe.
However, the acid treatment and the sphering treatment in Example 18 were not performed.
The volume average particle diameter (Dv) of this toner was 6.3 μm, the average circularity was 0.935, and the ratio of the circularity of 0.95 or less was 35.2%.
[0144]
Table 5 shows the evaluation results.
[Table 5]

[0145]
Example 20
[Production of toner]
A toner (20) was obtained by converting a toner binder into a toner in the same manner as in Example 19 except that the colorant was changed to 8 parts of carbon black.
The volume average particle diameter (Dv) of this toner was 5.4 μm, the average circularity was 0.965, and the ratio of the circularity of 0.95 or less was 24.9%.
Table 6 shows the evaluation results.
[0146]
Example 21
[Production of toner binder]
363 parts of bisphenol A ethylene oxide 2 mol adduct and 166 parts of isophthalic acid were polycondensed in the same manner as in Example 1 to obtain an unmodified polyester (B) having a peak molecular weight of 4,300.
300 parts of the urea-modified polyester (A) and 700 parts of the unmodified polyester (B) were dissolved and mixed in 3000 parts of ethyl acetate / MEK (1/1) to obtain a toner binder ethyl acetate solution.
A portion was dried under reduced pressure to isolate the toner binder. Tg was 57 ° C.
[0147]
[Production of toner]
A toner (21) was obtained in the same manner as in Example 18 except that 300 parts of an ethyl acetate / MEK solution of a toner binder and 8 parts of carbon black were used as toner materials.
The volume average particle diameter (Dv) of this toner was 6.8 μm, the average circularity was 0.986, and the ratio of the circularity of 0.95 or less was 3.2%.
Table 6 shows the evaluation results.
[0148]
Comparative Example 5
[Production of toner binder]
343 parts of bisphenol A ethylene oxide 2 mol adduct, 166 parts of isophthalic acid and 2 parts of dibutyltin oxide were put into a reaction vessel provided with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 230 ° C. for 8 hours under normal pressure. After further reacting under reduced pressure of 10 to 15 mmHg for 5 hours, the mixture was cooled to 80 ° C., 14 parts of toluene diisocyanate was added in toluene, and the reaction was carried out at 110 ° C. for 5 hours. A urethane-modified polyester having a molecular weight of 98,000 was obtained.
363 parts of bisphenol A ethylene oxide 2 mol adduct and 166 parts of isophthalic acid were polycondensed in the same manner as in Example 1 to obtain an unmodified polyester (B) having a peak molecular weight of 3,800, a hydroxyl value of 25 and an acid value of 7.
350 parts of the urethane-modified polyester and 650 parts of the unmodified polyester (B) were dissolved and mixed in toluene, and the solvent was removed to obtain a toner binder.
The Tg of this toner binder was 58 ° C.
[0149]
[Production of toner]
100 parts of the toner binder and 8 parts of carbon black were converted into a toner by the following method.
First, the mixture was premixed using a Henschel mixer, and then kneaded with a continuous kneader. Next, after finely pulverizing with a jet pulverizer, the particles were classified with an airflow classifier to obtain toner particles.
Subsequently, 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide were mixed with 100 parts of the toner particles using a Henschel mixer to obtain Comparative Toner (5).
The volume average particle diameter (Dv) of this toner was 7.2 μm, the average circularity was 0.932, and the ratio of the circularity of 0.95 or less was 54.8%.
[0150]
Table 6 shows the evaluation results.
[Table 6]

[0151]
Example 22
[Production of prepolymer]
724 parts of bisphenol A ethylene oxide 2 mol adduct, 250 parts of isophthalic acid, 24 parts of terephthalic acid and 2 parts of dibutyltin oxide were placed in a reaction vessel provided with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and were subjected to normal pressure and 230 ° C. After further reacting for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, the mixture was cooled to 160 ° C., and 32 parts of phthalic anhydride was added thereto and reacted for 2 hours.
Next, the mixture was cooled to 80 ° C. and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate group-containing prepolymer having a weight average molecular weight of 12,000.
[0152]
(Production of ketimine compound)
30 parts of isophoronediamine and 70 parts of methyl ethyl ketone were charged into a reaction tank provided with a stirring rod and a thermometer, and reacted at 50 ° C. for 5 hours to obtain a ketimine compound.
[0153]
(Production of unmodified polyester)
In the same manner as above, 724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid are polycondensed at 230 ° C. for 6 hours under normal pressure, and then reacted for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg. And an unmodified polyester (B) having a peak molecular weight of 6000.
[0154]
[Production of toner]
15.4 parts of the above prepolymer, 64 parts of polyester (c) and 78.6 parts of ethyl acetate were placed in a beaker, and stirred to dissolve.
Subsequently, 20 parts of pentaerythritol tetrabehenate and 4 parts of copper phthalocyanine blue pigment were added, and the mixture was stirred at 60 ° C. with a TK homomixer at 12,000 rpm to uniformly dissolve and disperse.
At the end, 2.7 parts of the ketimine compound was added and dissolved. This is used as a toner material solution.
In a beaker, 706 parts of ion-exchanged water, 294 parts of a 10% suspension of hydroxyapatite (Supatite 10 manufactured by Nippon Chemical Industry Co., Ltd.) and 0.2 part of sodium dodecylbenzenesulfonate were uniformly dissolved.
Next, the temperature was raised to 60 ° C., and the above-mentioned toner material solution was charged while stirring at 12,000 rpm with a TK homomixer, followed by stirring for 10 minutes.
Subsequently, the mixed solution was transferred to a kolben equipped with a stir bar and a thermometer, heated to 80 ° C., the solvent was removed while the urea reaction was being performed, filtered, washed, dried, and air-classified. Toner particles were obtained.
Hydrochloric acid was added to pH 2 to dissolve and remove hydroxyapatite. At this time, amorphous particles were contained very much. Thereafter, the temperature of the dispersion was raised to 75 ° C. while stirring, kept for 30 minutes, and then cooled to 20 ° C.
Finally, 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide were mixed with 100 parts of the toner particles using a Henschel mixer to obtain a toner (22).
The volume average particle diameter (Dv) of this toner was 4.5 μm, the average circularity was 0.995, and the ratio of the circularity of 0.95 or less was 1.2%.
Table 7 shows the evaluation results.
[0155]
Example 23
[Production of prepolymer]
In the same manner as in Example 18, 669 parts of bisphenol A ethylene oxide 2 mol adduct, 274 parts of isophthalic acid and 20 parts of trimellitic anhydride were polycondensed, and 154 parts of isophorone diisocyanate were reacted to obtain a prepolymer having a weight average molecular weight of 15,000. A polymer was obtained.
[0156]
[Production of toner]
15.5 parts of the above prepolymer, 64 parts of polyester, and 78.8 parts of ethyl acetate were placed in a beaker, and stirred to dissolve.
Next, 20 parts of trimethylolpropane tribehenate and 4 parts of copper phthalocyanine blue pigment were added, and the mixture was stirred at 50 ° C. with a TK homomixer at 12,000 rpm to be uniformly dissolved and dispersed.
At the end, 2.4 parts of a ketimine compound and 0.036 parts of dibutylamine were added and dissolved.
This is used as a toner material solution.
Using this toner material solution, a toner (23) was obtained in the same manner as in Example 5, except that the dispersion temperature was changed to 50 ° C.
The volume average particle diameter (Dv) of the toner was 5.8 μm, the average circularity was 0.976, and the ratio of the circularity of 0.95 or less was 8.2%.
[0157]
Table 7 shows the evaluation results.
Comparative Example 6
[Production of toner binder]
354 parts of bisphenol A ethylene oxide 2 mol adduct and 166 parts of terephthalic acid were polycondensed using 2 parts of dibutyltin oxide as a catalyst to obtain a toner binder having a weight average molecular weight of 12,000.
[0158]
[Production of toner]
100 parts of the above toner binder, 200 parts of ethyl acetate and 4 parts of copper phthalocyanine blue pigment are placed in a beaker, and the mixture is stirred at 50 ° C. with a TK homomixer at 12000 rpm to uniformly dissolve and disperse. Obtained.
Next, a toner was prepared in the same manner as in Example 5 to obtain a comparative toner (6).
The volume average particle diameter (Dv) of the toner was 6.5 μm, the average circularity was 0.972, and the ratio of the circularity of 0.95 or less was 9.6%.
[0159]
Table 7 shows the evaluation results.
[Table 7]

[0160]
[Evaluation method]
The particle size (volume average particle size, number average particle size) of the toner was measured using a Coulter Counter Model TA-II manufactured by Coulter Electronics.
[0161]
(1) Powder flowability
The bulk density was measured using a Hosokawa Micron powder tester.
The higher the flowability of the toner, the greater the bulk density.
[0162]
(2) Gloss development temperature (GLOSS)
The fixing was evaluated using a fixing device of a commercially available color copying machine (PRETER550; manufactured by Ricoh).
The gloss development temperature was defined as the fixing roll temperature at which the 60 ° gloss of the fixed image became 10% or more.
[0163]
(3) Hot offset occurrence temperature (HOT)
The fixing was evaluated in the same manner as in the above GLOSS, and the presence or absence of hot offset to the fixed image was visually evaluated.
The temperature of the fixing roll at which the hot offset occurred was defined as the hot offset occurrence temperature.
[0164]
(4) Minimum fixing temperature
Ricoh type 6200 paper was set in a modified apparatus of the copier MF-200 manufactured by Ricoh Co., Ltd. using a polytetrafluoroethylene roller as a fixing roller, and a copying test was performed. .
The fixing roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad was 70% or more was defined as the fixing lower limit temperature.
[0165]
(5) Hot offset occurrence temperature (HOT)
The fixing was evaluated in the same manner as the fixing lower limit temperature, and the presence or absence of hot offset to the fixed image was visually evaluated.
The fixing roll temperature at which the hot offset occurred was taken as the hot offset occurrence temperature.
[0166]
(6) Image density
5 parts by weight of the produced color toner and 95 parts by weight of a carrier described below were mixed for 10 minutes by a blender to prepare a developer.
(Carrier)
Core material (spherical ferrite particles with an average particle size of 50 μm)
Coating material constituent material (silicone resin with aminosilane-based coupling material dispersed) 分散 Disperse the aminosilane-based coupling material and silicone resin in toluene, adjust the dispersion, spray coat the core material in a heated state, bake, After cooling, the average coating resin film thickness is 0.2 μm.
The stirring time and speed are adjusted so that the charge amount is about 15 to 25 (μc / g) in absolute value in order to obtain a sufficient developing property of the toner and prevent background contamination due to the oppositely charged toner. A developer was manufactured.
The developer was placed in a commercially available color copying machine (PRETER 550; manufactured by Ricoh), and running was performed using 6000 paper manufactured by Ricoh at a printing rate of 7% image occupancy.
At this time, the image densities of the solid portions of the initial 10th image and the 30,000th image were measured with an X-Rite 938 spectrodensitometer (manufactured by X-Rite), and the measurement was carried out at four locations. I asked.
The transfer missing rank was evaluated on a scale of 5 while enlarging the printed character portion by 100 times with an optical microscope and observing it, and comparing the state of the line missing with a step sample.
[0167]
【The invention's effect】
According to the present invention, the powder fluidity when a small particle diameter toner, excellent transferability, good heat storage stability, low-temperature fixability, hot offset resistance, especially, full-color copier and the like A dry toner which is excellent in glossiness and hot offset resistance of an image when used and does not require oil application to a hot roll is provided, and contributes to fields such as electrophotography, electrostatic recording and electrostatic printing. Is extremely large.
[Brief description of the drawings]
FIG. 1 is an explanatory view of a flow type particle image analyzer.
FIG. 2 is a cross-sectional view illustrating a main part of an example of an image forming apparatus.
FIG. 3 is a configuration diagram illustrating one example of a process cartridge.
[Explanation of symbols]
(Fig. 2)
1 photoconductor drum
2 charger
3 laser light
4 developing device
5 Transfer device
6 Cleaning device
9 Static elimination lamp
(Fig. 3)
41 photoconductor
44 ° image exposure unit
45 ° developing roller

Claims (16)

In a dry toner containing at least the modified polyester (i) as a toner binder, the toner has a volume average particle diameter (Dv) of 3 to 10 μm and a ratio (Dv / Dp) to a number average particle diameter (Dp). Is from 1.05 to 1.25. The average circularity of the toner is from 0.96 to 1.00, and the content of the toner having a circularity of less than 0.95 is 30% or less based on the weight of the total toner. 2. The dry toner according to item 1. The toner binder contains an unmodified polyester (ii), and the weight ratio (i) / (ii) of the modified polyester (i) to the unmodified polyester (ii) is 5/95 to 80/20. 3. The dry toner according to claim 1, wherein the dry toner is provided. In a dry toner containing the modified polyester (i) as a toner binder, the average circularity of the toner is 0.96 to 1.00, and the content of the toner having a circularity of less than 0.95 is based on the weight. A dry toner characterized by being 30% or less of the toner. The dry toner according to any one of claims 1 to 4, wherein the modified polyester (i) is a modified polyester having a urea bond. The modified polyester (i) is a modified polyester having a urea bond obtained by reacting a polyester prepolymer (A) having an isocyanate group with an amine (B). A dry toner according to any one of the above. 4. A toner obtained by dissolving / dispersing a toner composition containing the modified polyester (i) in an organic solvent and dispersing in an aqueous medium. 6. The dry toner according to any one of 6. A toner obtained by dissolving / dispersing a toner composition containing a prepolymer in an organic solvent and dispersing in an aqueous medium, wherein the prepolymer is added to the modified polyester (i) during the step. The dry toner according to claim 1, wherein the dry toner is converted. The dry toner according to any one of claims 1 to 8, wherein the peak molecular weight of the toner binder is 1,000 to 30,000. The dry toner according to any one of claims 1 to 9, wherein the toner binder has an acid value of 1 to 30 mgKOH / g. The dry toner according to any one of claims 1 to 10, wherein the glass transition point (Tg) of the toner binder is 50 to 70 ° C. The method for producing a dry toner according to any one of claims 1 to 11, wherein the toner composition containing the modified polyester (i) is dissolved or dispersed in an organic solvent, and then dispersed in an aqueous medium. A method for producing a dry toner. The modified polyester (i) is a modified ester having a urea bond obtained by reacting a polyester prepolymer (A) having an isocyanate group with an amine (B) in a step. 13. The method for producing a dry toner according to item 12. 12. A process cartridge which integrally supports a photosensitive member and a developing unit and is detachably installed in an image forming apparatus, wherein the developing unit holds a toner, and the toner is any one of claims 1 to 11. A process cartridge characterized by being a dry toner. An image forming method comprising: a transfer step of transferring a toner image carried on a toner image carrier to a transfer material; and a cleaning step of cleaning the toner remaining on the toner image carrier surface after the transfer using a blade. Item 12. An image forming method using the toner according to any one of Items 1 to 11. An image forming apparatus comprising: a transfer unit that transfers a toner image carried on a toner image carrier to a transfer material; and a cleaning unit that uses a blade to clean toner remaining on the surface of the toner image carrier after the transfer. Item 12. An image forming apparatus using the toner according to any one of Items 1 to 11.

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