JP2004085850A - Electrostatic charge image developing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner giving a high quality image with good dot reproducibility. <P>SOLUTION: The toner has an additive stuck or fixed on the surface of a powder consisting essentially of a resin and a pigment in such a way that when the surface shape of the powder with the stuck or fixed additive is measured by SPM, a fine ruggedness cycle of 50-150 nm and a coarse ruggedness cycle of 400-800 nm exist in an X direction. In order to achieve the cycles, spherical particles are surface-treated with an inorganic fine powder or fine particles of a charge controlling agent or the like. The surface shape at this time can be controlled according to the kind, amount and particle diameter of the fine powder, mixing conditions and sticking and implanting conditions. <P>COPYRIGHT: (C)2004,JPO

Description

上記原材料をミキサーで十分に混合した後、２軸押出し機によりバレル温度１００℃、混練機回転数１２０ｒｐｍで溶融混練した。混練物を圧延冷却後カッターミルで粗粉砕し、ジェット気流を用いた微粉砕機で粉砕後、旋回式風力分級装置を用いて、平均粒径が６μｍの粒度分布に分級した。
【００６２】
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。
添加剤　シリカ微粉末（粒径３０ｎｍ）　１部
混合回転数　　　　　　　　　　　　　　１１００ｒｐｍ
混合時間　　　　　　　　　　　　　　　１２０ｓ
混合機　　　　　　　　　　　　　　　　スーパーミキサー
本実施例のトナーを作製した後、ＳＰＭ法による評価法によりトナー表面形状を測定した結果、後掲の表１のようになった。
【００６３】
上記作製法で得られたトナーとキャリアをキャリア９７．５部に対し、２．５部の割合で混合し、２成分現像剤を作製した。得られた現像剤を潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験を行なった。その結果、画像のドット再現性は５段階評価でランク５であった。評価結果は後掲の表１に示す。
【００６４】
―実施例２―
実施例１と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６．１μｍの粒度分布に分級した。さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。
添加剤　シリカ微粉末（粒径３０ｎｍ）　１．５部
混合回転数　　　　　　　　　　　　　　１１００ｒｐｍ
混合時間　　　　　　　　　　　　　　　１２０ｓ
混合機　　　　　　　　　　　　　　　　スーパーミキサー
本実施例のトナーを作製した後、ＳＰＭ法による評価法によりトナー表面形状を測定した結果、後掲の表１のようになった。
【００６５】
上記作製法で得られたトナーとキャリアをキャリア９７．５部に対し、２．５部の割合で混合し、２成分現像剤を作製した。得られた現像剤を潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験を行なった。その結果、画像のドット再現性は５段階評価でランク５であった。評価結果は後掲の表１に示す。
【００６６】
―実施例３―
実施例１と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６．１μｍの粒度分布に分級した。さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。
添加剤　シリカ微粉末（粒径３０ｎｍ）　２部
混合回転数　　　　　　　　　　　　　　１１００ｒｐｍ
混合時間　　　　　　　　　　　　　　　１２０ｓ
混合機　　　　　　　　　　　　　　　　スーパーミキサー
本実施例のトナーを作製した後、ＳＰＭ法を用いた評価法によりトナー表面形状を測定した結果、後掲の表１のようになった。
【００６７】
上記作製法で得られたトナーとキャリアをキャリア９７．５部に対し、２．５部の割合で混合し、２成分現像剤を作製した。得られた現像剤を潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験を行なった。その結果、画像のドット再現性は５段階評価でランク５であった。評価結果は後掲の表１に示す。
【００６８】
―実施例４―
実施例１と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６μｍの粒度分布に分級した。さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。
添加剤　シリカ微粉末（粒径３０ｎｍ）　２．５部
混合回転数　　　　　　　　　　　　　　１１００ｒｐｍ
混合時間　　　　　　　　　　　　　　　１２０ｓ
混合機　　　　　　　　　　　　　　　　スーパーミキサー
本実施例のトナーを作製した後、ＳＰＭ法による評価法によりトナー表面形状を測定した結果、後掲の表１のようになった。
【００６９】
上記作製法で得られたトナーとキャリアをキャリア９７．５部に対し、２．５部の割合で混合し、２成分現像剤を作製した。得られた現像剤を潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験を行なった。その結果、画像のドット再現性は５段階評価でランク５であった。評価結果は後掲の表１に示す。
【００７０】
―実施例５―
実施例１と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６．２μｍの粒度分布に分級した。さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。
添加剤　シリカ微粉末（粒径３０ｎｍ）　　３部
混合回転数　　　　　　　　　　　　　　　１１００ｒｐｍ
混合時間　　　　　　　　　　　　　　　　１２０ｓ
混合機　　　　　　　　　　　　　　　　　スーパーミキサー
本実施例のトナーを作製した後、ＳＰＭ法による評価法によりトナー表面形状を測定した結果、後掲の表１のようになった。
【００７１】
上記作製法で得られたトナーとキャリアをキャリア９７．５部に対し、２．５部の割合で混合し、２成分現像剤を作製した。得られた現像剤を潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験を行なった。その結果、画像のドット再現性は５段階評価でランク５であった。評価結果は後掲の表１に示す。
【００７２】
―実施例６―
トナーバインダー（樹脂）の合成
冷却管、攪拌機及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時間反応させる。さらに１０〜１５ｍｍＨｇに減圧して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時間反応した。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時間反応を行い、イソシアネート含有プレポリマーＩを得た。次いでプレポリマーＩ２６７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Ｉを得た。
【００７３】
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に減圧して５時間反応させ、ピーク分子量５０００の変性されていないポリエステルＡを得た。ウレア変性ポリエステルＩ２００部と変性されていないポリエステルＡ８００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Ｉ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Ｉを単離した。分析の結果Ｔｇは６２℃であった。
【００７４】
トナーの作製
トナーバインダーＩ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（溶融粘度２５ｃｐｓ）　２０部
銅フタロシアニンブルー顔料
（Ｃ．Ｉ．ピグメントブルー１５：３）　　　　　　　　　　　　４部
上記原材料をビーカー内で、６０℃にてＴＫ式ホモミキサーで１２０００ｒｐｍで攪拌し、均一に溶解、分散させてトナー材料溶液を作製した。
【００７５】
イオン交換水　　　　　　　　　　　　　　　　　　　　　　　７０６部
ハイドロキシアパタイト１０％懸濁液
（日本化学工業社製スーパタイト１０）　　　　　　　　　　２９４部
ドデシルベンゼンスルホン酸ナトリウム　　　　　　　　　　　０．２部
ビーカー内に上記原材料を入れ均一に溶解した。その後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。ついでこの混合液を攪拌棒及び温度計付のフラスコに移し、３０℃まで昇温して減圧下で溶剤を除去し、濾別、洗浄、乾燥した後、風力分級し、トナー粒子を得た。体積平均粒径は６．２μｍであった。
【００７６】
このトナー粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを得た。
添加剤　シリカ微粉末（粒径３０ｎｍ）　　１部
混合回転数　　　　　　　　　　　　　　　１０００ｒｐｍ
混合時間　　　　　　　　　　　　　　　　１２０ｓ
混合機　　　　　　　　　　　　　　　　　Ｑミキサー
本実施例のトナーを作製した後、ＳＰＭ法による評価法によりトナー表面形状を測定した結果、後掲の表１のようになった。
【００７７】
上記作製法で得られたトナーとキャリアをキャリア９７．５部に対し、２．５部の割合で混合し、２成分現像剤を作製した。得られた現像剤を潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験を行なった。その結果、画像のドット再現性は５段階評価でランク５であった。評価結果は後掲の表１に示す。
【００７８】
―実施例７―
実施例６と同様の原材料、作製方法で粉体の作製、分級を行ない、平均粒径が６．１μｍの粒度分布に分級した。さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。
添加剤　シリカ微粉末（粒径３０ｎｍ）　　１部
混合回転数　　　　　　　　　　　　　　　３０００ｒｐｍ
混合時間　　　　　　　　　　　　　　　　１２０ｓ
混合機　　　　　　　　　　　　　　　　　Ｑミキサー
本実施例のトナーを作製した後、ＳＰＭ法による評価法によりトナー表面形状を測定した結果、後掲の表１のようになった。
【００７９】
上記作製法で得られたトナーとキャリアをキャリア９７．５部に対し、２．５部の割合で混合し、２成分現像剤を作製した。得られた現像剤を潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験を行なった。その結果、画像のドット再現性は５段階評価でランク５であった。評価結果は後掲の表１に示す。
【００８０】
―実施例８―
実施例６と同様の原材料、作製方法で粉体の作製、分級を行ない、平均粒径が６．２μｍの粒度分布に分級した。さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。
添加剤　シリカ微粉末（粒径３０ｎｍ）　　１部
混合回転数　　　　　　　　　　　　　　　５０００ｒｐｍ
混合時間　　　　　　　　　　　　　　　　１２０ｓ
混合機　　　　　　　　　　　　　　　　　Ｑミキサー
本実施例のトナーを作製した後、ＳＰＭ法による評価法によりトナー表面形状を測定した結果、後掲の表１のようになった。
【００８１】
上記作製法で得られたトナーとキャリアをキャリア９７．５部に対し、２．５部の割合で混合し、２成分現像剤を作製した。得られた現像剤を潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験を行なった。その結果、画像のドット再現性は５段階評価でランク５であった。評価結果は後掲の表１に示す。
【００８２】
―実施例９―
実施例６と同様の原材料、作製方法で粉体の作製、分級を行ない、平均粒径が６．０μｍの粒度分布に分級した。さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。
添加剤　シリカ微粉末（粒径３０ｎｍ）　　１部
混合回転数　　　　　　　　　　　　　　　７０００ｒｐｍ
混合時間　　　　　　　　　　　　　　　　１２０ｓ
混合機　　　　　　　　　　　　　　　　　Ｑミキサー
本実施例のトナーを作製した後、ＳＰＭ法による評価法によりトナー表面形状を測定した結果、後掲の表１のようになった。
【００８３】
上記作製法で得られたトナーとキャリアをキャリア９７．５部に対し、２．５部の割合で混合し、２成分現像剤を作製した。得られた現像剤を潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験を行なった。その結果、画像のドット再現性は５段階評価でランク３であった。評価結果は後掲の表１に示す。
【００８４】
―比較例１―
実施例１と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６μｍの粒度分布に分級した。さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。シリカ微粉末は、実施例１と同一のものを用いた。
添加剤　　シリカ微粉末（粒径３０ｎｍ）　０．５部
混合回転数　　　　　　　　　　　　　　　１１００ｒｐｍ
混合時間　　　　　　　　　　　　　　　　１２０ｓ
混合機　　　　　　　　　　　　　　　　　スーパーミキサー
本実施例のトナーを作製した後、ＳＰＭ法による評価法によりトナー表面形状を測定した結果、後掲の表１のようになった。
【００８５】
上記作製法で得られたトナーと、キャリアを、キャリア９７．５部に対し２．５部の割合で混合し、２成分現像剤を作製した。得られた現像剤を潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験を行なった。その結果、画像のドット再現性は５段階評価でランク３であった。評価結果は後掲の表１に示す。
【００８６】
―比較例２―
樹脂　　　　ポリエステル樹脂　　　　　　　　　　　　　　　１００部
着色剤　　　マゼンタ顔料（Ｃ．Ｉ．ピグメントレッド５７）　３．５部
帯電制御剤　サリチル酸亜鉛塩　　　　　　　　　　　　　　　　　５部
上記原材料をミキサーで十分に混合した後、２軸押出し機によりバレル温度１００℃、混練機回転数１２０ｒｐｍで溶融混練した。混練物を圧延冷却後カッターミルで粗粉砕し、ジェット気流を用いた微粉砕機で粉砕後、旋回式風力分級装置を用いて、平均粒径が６μｍの粒度分布に分級した。
【００８７】
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。シリカ微粉末は、実施例１と同一のものを用いた。
添加剤　シリカ微粉末（粒径３０ｎｍ）　　０．１部
混合回転数　　　　　　　　　　　　　　　１１００ｒｐｍ
混合時間　　　　　　　　　　　　　　　　１２０ｓ
混合機　　　　　　　　　　　　　　　　　スーパーミキサー
トナーを作製した後、ＳＰＭ法による評価法によりトナー表面形状を測定した結果、後掲の表１のようになった。
【００８８】
上記作製法で得られたトナーとキャリアをキャリア９７．５部に対し、２．５部の割合で混合し、２成分現像剤を作製した。得られた現像剤を潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験を行なった。その結果、画像のドット再現性は５段階評価でランク１であった。評価結果は後掲の表１に示す。
【００８９】
―比較例３―
実施例６と同様の原材料、作製方法で粉体の作製、分級を行ない、平均粒径が６．３μｍの粒度分布に分級した。さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。シリカ微粉末は、実施例１と同一のものを用いた。
添加剤　シリカ微粉末（粒径３０ｎｍ）　０．５部
混合回転数　　　　　　　　　　　　　　１０００ｒｐｍ
混合時間　　　　　　　　　　　　　　　１２０ｓ
混合機　　　　　　　　　　　　　　　　Ｑミキサー
トナーを作製した後、ＳＰＭ法による評価法によりトナー表面形状を測定した結果、後掲の表１のようになった。
【００９０】
上記作製法で得られたトナーとキャリアをキャリア９７．５部に対し、２．５部の割合で混合し、２成分現像剤を作製した。得られた現像剤を潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験を行なった。その結果、画像のドット再現性は５段階評価でランク３であった。評価結果は後掲の表１に示す。
【００９１】
―比較例４―
実施例６と同様にしてトナーバインダーＩを合成し、次のようにトナーを作製した。
トナーバインダーＩ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（溶融粘度２５ｃｐｓ）　２０部
マゼンタ顔料（Ｃ．Ｉ．ピグメントレッド５７）　　　　　　　　　４部
上記原材料をビーカー内で、６０℃にてＴＫ式ホモミキサーで１２０００ｒｐｍで攪拌し、均一に溶解、分散させてトナー材料溶液を作製した。
【００９２】
イオン交換水　　　　　　　　　　　　　　　　　　　　　　７０６部
ハイドロキシアパタイト１０％懸濁液
（日本化学工業社製スーパタイト１０）　　　　　　　　　２９４部
ドデシルベンゼンスルホン酸ナトリウム　　　　　　　　　　０．２部
ビーカー内に上記原材料を入れ均一に溶解した。その後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。ついでこの混合液を攪拌棒及び温度計付のフラスコに移し、３０℃まで昇温して減圧下で溶剤を除去し、濾別、洗浄、乾燥した後、風力分級し、トナー粒子を得た。体積平均粒径は６．３μｍであった。
【００９３】
このトナー粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを得た。シリカ微粉末は、実施例１と同一のものを用いた。
添加剤　シリカ微粉末（粒径３０ｎｍ）　　０．１部
混合回転数　　　　　　　　　　　　　　　１０００ｒｐｍ
混合時間　　　　　　　　　　　　　　　　１２０ｓ
混合機　　　　　　　　　　　　　　　　　Ｑミキサー
トナーを作製した後、ＳＰＭ法による評価法によりトナー表面形状を測定した結果、後掲の表１のようになった。
【００９４】
上記作製法で得られたトナーと、キャリアを、キャリア９７．５部に対し２．５部の割合で混合し、２成分現像剤を作製した。得られた現像剤を、潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験を行なった。その結果、画像のドット再現性は５段階評価でランク１であった。評価結果は以下の表１に示す。
【００９５】
【表１】

（注）表中の―印は周期性が無いことを示す。
【００９６】
【発明の効果】
本発明のトナーは、特定の表面形状を有しているために流動性に優れ、そのため、本発明のトナーを用いて形成した画像は、ドット再現性に優れている。さらに、本発明のトナーを製造する際に用いたＳＰＭ法による計測の評価は、ドット再現性のよいトナーの指標値となり、有用である。
【図面の簡単な説明】
【図１】添加剤処理をした後のトナー粒子表面のＳＰＭ観察像である。
【図２】トナー粒子表面の添加剤処理をした後の形状測定の一例を示す図である。
【図３】添加剤処理をする前のトナー粒子表面のＳＰＭ観察像である。
【図４】トナー表面の微粉体層の層構成を説明するための模式図である。
【図５】本発明の現像装置を模式的に示した断面図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a toner used in a one-component developing device or a two-component developing device.
[0002]
[Prior art]
Image quality of electrophotographs created by copying machines, printers, and the like has been improved, and recently, reproducibility of fine dots has become very important. The dot reproducibility is greatly affected by the fluidity in addition to the charge amount of the toner and the developer, and it is necessary to stably supply a uniform toner layer or a developer layer to a fine latent image portion. Are coming.
[0003]
Further, as the image quality is improved, the particle size and the function of the toner used for the toner are advanced. For this reason, the structure of the toner has become more complicated, and it is necessary to perform finer control at the time of production than before. In particular, since the fluidity of the toner affects various image qualities in addition to the dot reproducibility, controlling the fluidity is considered to be a very important technique.
[0004]
Japanese Patent Application Laid-Open No. 05-341573 is a conventional technique that focuses on the above-described problems. The technique disclosed in this publication is to provide a polymerized toner with appropriate irregularities on the surface by a resin separation structure. Even when an additive is added to the spherical toner, its characteristics are apt to deteriorate, and there is a problem in durability. As a means for solving the problem, the unevenness of the toner surface is changed by a temperature change during the polymerization to control the surface shape. However, in the present invention, the periodicity of the toner surface shape is not specified, and a random surface property may be used, which is not suitable for high image quality.
[0005]
Further, Japanese Patent Application Laid-Open No. H11-295989 discloses a method of performing development by applying an oscillating electric field between an electrostatic latent image carrier and a developer carrier, and using a D / d50 (D: When the shape of the toner is assumed to be a sphere, it is represented by a numerical value of a converted particle diameter from the BET specific surface area, d50 (a particle diameter corresponding to 50% of a relative weight distribution by particle diameter), and the numerical value is defined. This aims at improving the mobility of the toner in the developing area. However, in this method of defining the surface shape, the periodicity of the surface shape is not described, so that variations occur between toners, and it is difficult to realize high image quality.
[0006]
[Problems to be solved by the invention]
Furthermore, in addition to ensuring the dot reproducibility and toner fluidity described above, when the toner production method changes from a pulverization method to another method such as a polymerization method, the change in the flow characteristics with respect to the manufacturing conditions is large, Compared with the pulverization method, finer control and evaluation at the time of production are required.
[0007]
Accordingly, the present invention provides a toner for developing an electrostatic image capable of obtaining high image quality with good dot reproducibility by evaluating the surface shape of toner particles capable of obtaining stable fluidity and defining such a surface shape. The purpose is to do.
[0008]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that the object of the present invention can be achieved by measuring the surface shape of toner particles using SPM. That is, the present invention relates to a toner for electrostatic charge development, in which an additive is attached or fixed to the surface of a powder comprising at least a resin and a pigment, and the surface shape of the powder to which the additive is attached or fixed Is measured by SPM, and has a small uneven period of 50 to 150 nm and a large uneven period of 400 to 800 nm in the X direction.
[0009]
The present inventors have found that the periodicity of the irregularities on the toner particle surface is very important for the fluidity by directly measuring the surface shape of the toner. In the present invention, the periodicity of the unevenness on the surface of the toner particles is defined by the direct measurement. As a result, the fluidity of the toner in the developing area can be improved, a uniform toner brush can be realized, and high image quality with excellent dot reproducibility can be obtained.
[0010]
The SPM (Scanning Probe Microscope) method used in the present invention scans a probe having a tip with a diameter of about 10 nm, detects an interatomic force acting between the probe and atoms on the sample surface, and detects the shape of the sample surface. Is a method of measuring The resolution is very high, and the unevenness in the Z direction with respect to the scanning direction (X direction) of the probe can be measured. In the present invention, the shape of the toner particle surface was measured by scanning the surface of the toner particle with an SPM probe. As a result, it was found that the toner particles having good fluidity had a three-dimensional surface profile as shown in FIG. Further, the surface shape profile in the XZ plane of a part at that time was as shown in FIG. In other words, it has been found that small-period irregularities and large-period irregularities exist on the surface of the toner particles having good fluidity. The small uneven period was 50 to 150 nm, and the large uneven period was 400 to 800 nm. Further, at this time, it was found that when the unevenness in the Z direction (amplitude of the curve of the profile) was 10 to 200 nm, the fluidity of the toner was good. It is thought that the irregularity of the large cycle is effective for the fluidity, but the irregularity of the small cycle is also very important, and it is thought that pollen etc. has very good fluidity because of the small irregularity Have been. If there are irregularities having a large period together with regular irregularities having a small period as described above, even if an adsorbate is present on the surface, the influence on mobility is reduced.
[0011]
When measuring the toner surface by SPM, the vicinity of the top of a certain toner particle is scanned with a TIP of about 1 μm square along the surface. The vertical displacement at this time is defined as information in the Z-axis direction. This measurement is performed 3 to 10 times while changing the measurement location and the toner particles of the sample, and the state of the whole particles is grasped. First, it is practical to evaluate the surface state with an observation image by SPM, confirm the surface to which the additive is attached, and then perform quantitative unevenness analysis. The unevenness (amplitude) defined in the present invention is obtained by calculating the difference between the concave and convex portions in the Z direction between the small-period irregularities and the large-period irregularities in the profile obtained by the SPM measurement. In the toner of the present invention, the presence of irregularities of 10 to 200 nm in the Z direction defines both large and small period irregularities.
[0012]
It has been difficult to form such a repetitive structure of irregularities by a pulverization method having a rough particle shape. However, even in the pulverization method, a method of producing a spherical uniform particle shape with little unevenness, or in a method of producing powder by a method other than pulverization, surface treatment of the spherical particle surface with fine particles as an additive As a result, a structure having a very small periodic unevenness and a structure having a large periodicity have become possible. In the pulverization method, it is possible to optimize the pulverization conditions so as to have a spherical uniform particle shape with little unevenness, or to include a step of modifying the particle surface after the pulverization step. Even in the pulverization method, it is sufficient that particles can be produced that are spherical and have irregularities (amplitude) in the Z direction on the surface as small as 10 to 50 nm.
[0013]
As shown in FIG. 3, the powder before the surface treatment by adding the fine particles, that is, the powder (base) composed of at least a resin and a pigment, has a small surface irregularity (amplitude) in the Z direction of 10 to 50 nm as shown in FIG. Irregularities are preferred. If the surface of the powder (base) before adding the fine particles has a rough or rough surface, the shape of the surface cannot be controlled even with the addition of the fine particles, and an optimal structure is created. Can not. Further, although the addition processing of the fine particles is affected by the shape of the powder (base) before adding the fine particles, the average circularity of the powder (base) before adding the fine particles is 0.9 to 0.99. When the shape is close to a certain spherical shape, the effect of the fine particle addition processing is excellent, and high image quality with excellent dot reproducibility can be realized. When the circularity is less than 0.9, the effect of the optimum structure of the present invention is small.
[0014]
The shape of the surface of the toner particles can be controlled by the type, the particle size, the amount of the fine particles of the additive, the mixing conditions at the time of the addition, and the fixing and injection conditions. In particular, the amount of the additive is important, and as described below, the composition of the fine powder layer is 1.2 layers ≦ fine powder layer ≦ 1.8 layers, 2.2 layers <fine powder layer <2.8 layers, The amount of the fine powder that satisfies the condition of 3.2 layers <fine powder layer <3.8 layers and 4.2 layers <fine powder layer <4.8 layers is charged, and the fine powder is prepared. The surface structure defined in the present invention can be realized by mixing under such mixing conditions that the deposited structure is not smoothed out and averaged. In Examples and Comparative Examples described below, toners of the present invention and toners outside the range of the present invention were produced mainly by changing the amounts of additives. The type of the fine particles to be added is optimally an inorganic fine powder, and the average particle size is optimally a small particle size of 30 to 200 nm. When the particle size is smaller than 30 nm, it is difficult to create large-period irregularities. When the particle size is larger than 200 nm, it is difficult to create small-period irregularities. The following materials are selected as the inorganic fine powder.
[0015]
The inorganic fine powder used for the toner of the present invention includes Si, Ti, Al, Mg, Ca, Sr, Ba, In, Ga, Ni, Mn, W, Fe, Co, Zn, Cr, Mo, Cu, Ag, Oxides such as V and Zr and composite oxides are exemplified. Among them, fine particles of silicon dioxide (silica), titanium dioxide (titania), and alumina are preferably used. Further, it is effective to subject these fine particles to a surface modification treatment with a hydrophobizing agent or the like.
[0016]
The following are typical examples of the hydrophobizing agent. Dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, p-chloroethyltrichlorosilane, Chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, hexaphenyldisilazane, hexatolydisilazane and the like.
[0017]
The addition amount of the inorganic fine powder is preferably 0.1 to 5% by weight based on the toner. If the amount is less than 0.1% by weight, the effect of improving the fluidity of the toner is poor. If the amount is more than 5% by weight, problems such as scattering of toner between fine lines, contamination inside the apparatus, scratches and abrasion of the photoreceptor tend to occur. There is.
[0018]
Alternatively, a charge control agent may be attached or fixed to the surface of a powder (base) composed of at least a resin and a pigment so that the powder surface has a small cycle and a large cycle. The average particle size is optimally a small particle size of 30 to 200 nm. When the particle size is smaller than 30 nm, it is difficult to create large-period irregularities. When the particle size is larger than 200 nm, it is difficult to create small-period irregularities. Examples of the charge control agent include nigrosine and quaternary ammonium salts, triphenylmethane dyes, imidazole metal complexes and salts, salicylic acid metal complexes and salts, organic boron salts, calixarene compounds, and the like, and two or more kinds may be used in combination. .
[0019]
The mixing or fixation injection conditions for adding the charge control agent are mainly controlled by the number of rotations of the mixture to control the shape of the toner particle surface. That is, the mixing rotation speed can control the force for attaching the fine powder to the powder surface. The mixing speed is optimally 1000 rpm to 6000 rpm, and when the mixing speed is lower than 1000 rpm, the fine powder adheres to the powder (base) surface with a very weak force, and the surface shape is increased. Of the toner, and toner scattering, contamination inside the apparatus, and the like are likely to occur. If the mixing rotation speed is higher than 6000 rpm, the added fine powder will dig into the inside of the base body surface, and the unevenness of the surface will be smoothed, the unevenness will be reduced, and the fluidity will be worse. These mixing conditions vary depending on the type of mixer. In particular, in the case of a mixer capable of being injected, the energy acting between the base material and the fine powder is easily added to the fine powder, so that it is necessary to finely adjust the optimum conditions.
[0020]
Next, a structure having a small period and a large period will be described with reference to a model shown in FIG. As shown in FIG. 4- (2), this structure cannot be realized when the powder is completely or almost completely adhered to the powder surface of one or two layers. That is, at this time, although a period due to the fine powder exists, a large period cannot be realized. Further, as shown in FIG. 4- (1), if the surface of the powder (base) is less than one layer, there are portions with and without a period due to fine fine powder, so that an optimal structure cannot be realized. . In order to realize this structure, one or more layers of fine powder are not formed on the surface of the powder (base) and are not an integer number of layers, but 1.2 layers ≦ fine powder layer ≦ It can be seen that it can be realized in the case of 1.8 layers. However, as shown in FIGS. 4- (3) and (7), in the case of the 1.1 layer or the 1.9 layer, although there is a small cycle, a large cycle cannot be provided. That is, in order to realize a structure having a small period and a large period, it is desirable that the condition of 1.2 layers ≦ fine powder layer ≦ 1.8 layers be satisfied. Similarly, any of 2.2 layers <fine powder layer <2.8 layers, 3.2 layers <fine powder layer <3.8 layers, and 4.2 layers <fine powder layer <4.8 layers When the condition (1) is satisfied, a structure having a small period and a large period can be realized. That is, a small cycle and a large cycle are provided by the structure of the fine powder deposited on the powder (base) surface before the fine powder is added.
[0021]
Therefore, the periodic structure of the surface shape of the toner of the present invention is schematically described as follows: 1.2 layers ≦ fine powder layer ≦ 1.8 layers, 2.2 layers <fine powder layers <2.8 layers, 3.2 Layer <fine powder layer <3.8 layers and 4.2 layer <fine powder layer <4.8 layers. This structure can be realized by mixing under mixing conditions that are not averaged out. In addition, the mixing conditions are insufficient, and cannot be realized under the mixing conditions in which the fine powder is not uniformly covered on the powder (base) surface (= the mixing condition in which the fine powder is unevenly covered). In other words, the mixing is performed under the optimum mixing condition of 1000 rpm to 6000 rpm. If the number of the fine powder layers is five or more, the fine powder layers are not suitable because the fine powder layers are partially peeled off, scattered or the like, and a problem occurs in stability.
[0022]
The toner having the structure defined in the present invention preferably has a weight average particle size of 4 to 10 μm, more preferably 5 to 7 μm, in order to realize a high quality image. If the weight average particle diameter is less than 4 μm, problems such as contamination inside the apparatus due to toner scattering during long-term use, a decrease in image density in a low-humidity environment, poor photoconductor cleaning, and the like are likely to occur, and there is a concern about the effect on the human body. When the weight average particle size exceeds 10 μm, the resolution of the fine spots of 100 μm or less is not sufficient, and the fine spots tend to be scattered to non-image portions, resulting in poor image quality.
[0023]
In the developer using the toner of the present invention, the carrier preferably has an average particle diameter of 20 to 100 μm in order to realize a high quality image. When the average particle size of the carrier is in the range of 20 to 100 μm, the charge amount of the toner can be made more uniform when the toner concentration in the developing device is in the range of 2 to 10% by weight. If it is less than 20 μm, the carrier particles are likely to adhere to the photoreceptor, and the stirring efficiency with the toner is deteriorated, so that it is difficult to obtain a uniform charge amount of the toner. Conversely, when the average particle size of the carrier exceeds 100 μm, fine image reproducibility deteriorates, and high image quality cannot be obtained.
[0024]
Details of the toner and the developer are shown below.
As the resin contained in the toner of the present invention, polystyrene resin, epoxy resin, polyester resin, polyamide resin, styrene acrylic resin, styrene methacrylate resin, polyurethane resin, vinyl resin, polyolefin resin, styrene butadiene resin, phenol resin, polyethylene resin, There are a silicone resin, a butyral resin, a terpene resin, a polyol resin and the like.
[0025]
As the vinyl resin, a homopolymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and a substituted product thereof: styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer Polymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methacryl Methyl acrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer Coalescence, styrene-vinyl ethyl ether Copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Styrenic copolymers such as polymers: polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate and the like.
[0026]
The polyester resin is composed of a dihydric alcohol as shown in Group A below and a dibasic acid salt as shown in Group B, and a trivalent or higher alcohol as shown in Group C or A carboxylic acid may be added as a third component.
[0027]
Group A: ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4 butanediol, neopentyl glycol, 1,4 butenediol, 1,4-bis (hydroxymethyl) cyclohexane , Bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropylene (2,2) -2,2'-bis (4-hydroxyphenyl) propane, polyoxypropylene (3,3) -2, 2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2,0) -2,2′-bis (4 -Hydroxyphenyl) propane and the like.
[0028]
Group B: maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, malonic acid, linoleic acid, or Esters of these acid anhydrides or lower alcohols.
[0029]
Group C: trihydric or higher alcohol such as glycerin, trimethylolpropane, pentaerythritol and the like, and trivalent or higher carboxylic acid such as trimellitic acid and pyromellitic acid.
[0030]
As the polyol resin, an epoxy resin and an alkylene oxide adduct of a dihydric phenol, or a compound having one active hydrogen in the molecule that reacts with the glycidyl ether and the epoxy group, and an active hydrogen that reacts with the epoxy resin in the molecule. Examples include those obtained by reacting two or more compounds.
[0031]
The following are used as the pigment used in the present invention.
Examples of black pigments include azine dyes such as carbon black, oil furnace black, channel black, lamp black, acetylene black, and aniline black, metal salt azo dyes, metal oxides, and composite metal oxides.
[0032]
Examples of the yellow pigment include cadmium yellow, mineral fast yellow, nickel titanium yellow, navels yellow, naphthol yellow S, Hanza yellow G, Hanza yellow 10G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake. .
[0033]
Examples of orange pigments include molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, indanthrene brilliant orange RK, benzidine orange G, and indanthrene brilliant orange GK.
[0034]
Examples of the red pigment include bengara, cadmium red, permanent red 4R, lithol red, pyrazolone red, watching red calcium salt, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake B, alizarin lake, and brilliant carmine 3B.
[0035]
Examples of purple pigments include Fast Violet B and Methyl Violet Lake.
Examples of the blue pigment include cobalt blue, alkali blue, Victoria Blue Lake, phthalocyanine blue, metal-free phthalocyanine blue, partially chlorinated phthalocyanine blue, fast sky blue, and indanthrene blue BC.
Green pigments include chrome green, chromium oxide, pigment green B, malachite green lake, and the like.
These can be used alone or in combination of two or more.
[0036]
Particularly in color toners, good uniform dispersion of pigments is important, and instead of directly injecting the pigment into a large amount of resin, a master batch in which the pigment is once dispersed at a high concentration is prepared and diluted. The method of putting in the form is used. In this case, a solvent is generally used to help dispersibility, but there are environmental problems and the like, and in the present invention, water is used to disperse. When water is used, temperature control is important so that residual moisture in the masterbatch does not matter.
[0037]
In the toner of the present invention, a charge control agent may be blended (internally added) inside the toner particles, or may be used as a mixture (externally added) with the toner particles. The charge control agent makes it possible to control the charge amount optimally according to the development system. In particular, in the present invention, the balance between the particle size distribution and the charge amount can be further stabilized.
[0038]
Nigrosine and quaternary ammonium salts, triphenylmethane-based dyes, imidazole metal complexes and salts can be used alone or in combination of two or more as charge control agents for controlling the toner to have positive charge. Further, a metal salicylate complex, salts, organic boron salts, calixarene-based compounds, and the like are used to control the toner to have a negative charge.
[0039]
Further, a release agent can be internally added to the toner of the present invention in order to prevent offset during fixing. Release agents include natural waxes such as candelilla wax, carnauba wax, and rice wax, montan wax and its derivatives, paraffin wax and its derivatives, polyolefin wax and its derivatives, sasol wax, low molecular weight polyethylene, and low molecular weight polypropylene. And alkyl phosphate esters. The melting point of these release agents is preferably from 65 to 90 ° C. If the temperature is lower than this range, blocking during storage of the toner tends to occur. If the temperature is higher than this range, offset may easily occur in a region where the temperature of the fixing roller is low.
[0040]
A dispersant may be added for the purpose of improving the dispersibility of the release agent and the like. As dispersants, styrene acrylic resin, polyethylene resin, polystyrene resin, epoxy resin, polyester resin, polyamide resin, styrene methacrylate resin, polyurethane resin, vinyl resin, polyolefin resin, styrene butadiene resin, phenol resin, butyral resin, terpene resin, There are polyol resins and the like, and a mixture of two or more of each resin may be used. A suitable amount of the dispersant is 10 parts or less based on 100 parts of the resin. Even if the amount is more than 10 parts, the effect of acidity of the wax is not observed, and conversely, the fixability and the image reproducibility are deteriorated.
[0041]
Examples of a method for producing the toner according to the present invention include a pulverization method and a polymerization method (suspension polymerization, emulsion polymerization / dispersion polymerization, emulsion aggregation, emulsion association, and the like), but are not limited thereto. As an example of the pulverization method, first, the above-described resin, a pigment or dye as a colorant, a charge control agent, a release agent, other additives, and the like are sufficiently mixed by a mixer such as a Henschel mixer, and then a batch type is used. The components are well kneaded using a hot kneader such as a two-roll mill, a Banbury mixer, a continuous twin screw extruder, or a continuous single screw kneader, and after rolling and cooling, cutting is performed. The kneaded toner after cutting is crushed, coarsely crushed using a hammer mill or the like, further finely crushed using a fine crusher or a mechanical crusher using a jet stream, and a classifier using a swirling air stream or a Coanda effect. Is classified to a predetermined particle size by a classifier using Thereafter, an additive composed of inorganic fine particles or the like is attached or fixed to the particle surface by a mixer under the above-described optimum mixing conditions.
[0042]
After this mixing step, the surface shape of the toner particles is evaluated using the SPM method in order to evaluate whether or not the toner particles have a predetermined particle structure. As a result of the evaluation by the SPM method, when the numerical value is within the predetermined setting range, the sample is transferred to a wind sieving process, passed through a sieve of 250 mesh or more to remove coarse particles and agglomerated particles, and then filled with a sample. To obtain the toner of the present invention.
[0043]
A method other than the pulverization method is considered as a method for producing the toner according to the present invention. As an example of the polymerization method, a monomer composition obtained by adding a colorant and a charge control agent to a monomer is suspended in an aqueous medium. The toner particles are obtained by turbidity and polymerization. The granulation method is not particularly limited.
[0044]
For example, the toner of the present invention may be prepared by dissolving at least an isocyanate group-containing polyester prepolymer in an organic solvent, dispersing a pigment colorant, and dissolving or dispersing a release agent in an aqueous medium. In the dispersion in the presence of inorganic fine particles and / or polymer fine particles, the prepolymer is reacted with a polyamine and / or a monoamine having an active hydrogen-containing group in this dispersion to form a urea-modified polyester resin having a urea group. It is also obtained by removing the liquid medium contained therein from the dispersion containing the urea-modified polyester resin.
[0045]
The urea-modified polyester resin has a Tg of 40 to 65 ° C, preferably 45 to 60 ° C. Its number average molecular weight Mn is 2,500 to 50,000, preferably 2,500 to 30,000. Its weight average molecular weight Mw is 10,000 to 500,000, preferably 30,000 to 100,000.
[0046]
This toner contains, as a binder resin, a urea-modified polyester resin having a urea bond, which has a high molecular weight by a reaction between a prepolymer and an amine. The coloring agent is highly dispersed in the binder resin.
[0047]
The obtained dried toner powder is subjected to air classification, and an additive composed of inorganic fine particles or the like is adhered or fixed to the particle surface by a mixer under the above-described optimum mixing conditions. Alternatively, the charge control agent may be injected into the dried toner powder surface and fixedly injected. Thereafter, an additive composed of inorganic fine particles or the like may be adhered or fixed to the particle surface. By driving the charge control agent onto the surface, the charge amount of the toner can be easily controlled.
[0048]
As a specific means for mixing or fixing and adding the additive, a method of applying an impact force to the powder mixture by a high-speed rotating blade, charging the powder mixture into a high-speed air stream, accelerating, and Alternatively, there is a method of causing the composite particles to collide with an appropriate collision plate. As the equipment, Angmill (manufactured by Hosokawa Micron), I-type mill (manufactured by Nippon Pneumatic) was modified to reduce the pulverizing air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), Kryptron system (Manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.
[0049]
After this mixing step, the surface shape of the toner particles is evaluated using the SPM method in order to evaluate whether or not the toner particles have a predetermined particle structure. As a result of the evaluation, when the numerical value is within a predetermined setting range, it is passed to a wind sieving process, passed through a sieve of 250 mesh or more, coarse particles and aggregated particles are removed, and then the sample is passed to a filling process. The toner of the present invention is obtained. The toner of the present invention can be used as a one-component developer, and when used as a two-component developer as described later, it is further mixed with a magnetic carrier at a predetermined mixing ratio to form a two-component developer. .
[0050]
In addition, this evaluation using the SPM method was performed after the granulation, after the air classification, after the treatment of the charge control agent, after the mixing process of the additive, and after the wind sieving process after the mixing process. Applicable to inspection, inspection before filling, etc.
[0051]
The toner of the present invention can be used as a one-component developer used in a contact or non-contact developing system. Various known contact or non-contact development systems are used. For example, there are a contact developing method using an aluminum sleeve, a contact developing method using a conductive rubber belt, and a non-contact developing method using a developing sleeve in which a conductive resin layer containing carbon black or the like is formed on the surface of an aluminum tube. .
[0052]
Further, the toner of the present invention has excellent fluidity both as a one-component developer and a two-component developer described later. Therefore, when developing using an AC bias voltage component at the time of development, the image vibrates faithfully according to the electric field, and faithful development can be performed for a fine latent image, and development with good dot reproducibility becomes possible.
[0053]
The one-component developing method is characterized in that the present toner is used in a developing method in which a roller-shaped blade for making a toner layer uniform is provided at an outlet of a toner supply unit as shown in FIG. In such a system, not only filming on the photosensitive member but also filming on the doctor roller occurs. For this reason, not only can the toner layer not be formed uniformly, but also the toner charging becomes non-uniform, and the toner charge becomes small. For this reason, defective development occurs. However, when the toner of the present invention is used, filming to the doctor roller does not occur, stable development is performed, and a system having excellent durability characteristics is obtained.
[0054]
Further, when the toner of the present invention is a magnetic toner, fine particles of a magnetic substance may be internally added to the toner particles. As the magnetic material, a ferromagnetic material such as ferrite, magnetite, iron, nickel, cobalt, or an alloy thereof can be considered. The average particle size of the magnetic material is preferably 0.1 to 1 μm. The content of the magnetic substance is preferably from 10 to 70 parts by weight based on 100 parts by weight of the toner.
[0055]
The toner of the present invention can be mixed with a magnetic carrier and used as a two-component developer. As the carrier used for the two-component developer, known carriers can be used. For example, magnetic particles such as iron powder, ferrite powder, nickel powder, and magnetite powder, or the surface of these magnetic particles is coated with a fluorine resin or vinyl resin And those treated with a silicone resin or the like, or magnetic particle-dispersed resin particles in which magnetic particles are dispersed in a resin. The average particle size of these magnetic carriers is preferably 20 to 100 μm. Preferably, it is 20 to 70 μm.
[0056]
Examples of the coating material on the carrier surface include amino resins, for example, urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, epoxy resin and the like. In addition, 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, polyhexafluoropropylene resin , Copolymers of vinylidene fluoride and acrylic monomers, copolymers of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinyl fluoride Fluoro such as terpolymers of isopropylidene and a non-fluorinated monomer, and silicone resins.
[0057]
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 fine particles preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control the electric resistance. Further, the two-component developer of the present invention can be used by adding an inorganic fine powder to a toner as a fluidity improver.
[0058]
In the developer of the present invention, other additives such as lubricant powders such as Teflon (registered trademark) powder, zinc stearate powder, polyvinylidene fluoride powder, or oxidized powder may be added within a range that does not substantially adversely affect the developer. An abrasive such as cerium powder, silicon carbide powder, strontium titanate powder, or a conductivity imparting agent such as carbon black powder, zinc oxide powder, or tin oxide powder may be used in a small amount as a developability improver.
[0059]
As described above, the method for evaluating whether the toner has the structure specified in the present invention by using the SPM method includes a polymerization method and a spray drying method which are manufactured without using a kneading step or a pulverizing step. It can also be used for the toner and capsule toner prepared in the above.
[0060]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described specifically with reference to Examples. However, the present invention is not limited to the following examples. In the following examples, a toner in which the mixing conditions were changed was prepared, the surface shape of the toner particles was evaluated using the SPM method, and the dot reproducibility was evaluated on a five-point scale as roughness of the image (rank 1: bad → rank 5). : Good). The circularity of the powder (base) before treatment with the additive was measured as an average circularity using a flow-type particle image analyzer FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.). All parts in the following formulations are parts by weight.
[0061]
-Example 1-

After sufficiently mixing the above raw materials with a mixer, the mixture was melt-kneaded with a twin-screw extruder at a barrel temperature of 100 ° C. and a kneader rotation speed of 120 rpm. The kneaded product was rolled and cooled, coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and then classified into a particle size distribution having an average particle size of 6 μm using a revolving air classifier.
[0062]
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additive Silica fine powder (particle size 30nm) 1 part
Mixing speed 1100rpm
Mixing time 120s
Mixer Super Mixer
After the toner of this example was manufactured, the surface shape of the toner was measured by the evaluation method using the SPM method, and the results are as shown in Table 1 below.
[0063]
The toner and carrier obtained by the above method were mixed in a ratio of 2.5 parts to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was ranked 5 on a five-point scale. The evaluation results are shown in Table 1 below.
[0064]
-Example 2-
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 1, and the particles were classified into a particle size distribution having an average particle size of 6.1 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder (particle size 30nm) 1.5 parts
Mixing speed 1100rpm
Mixing time 120s
Mixer Super Mixer
After the toner of this example was manufactured, the surface shape of the toner was measured by the evaluation method using the SPM method, and the results are as shown in Table 1 below.
[0065]
The toner and carrier obtained by the above method were mixed in a ratio of 2.5 parts to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was ranked 5 on a five-point scale. The evaluation results are shown in Table 1 below.
[0066]
-Example 3-
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 1, and the particles were classified into a particle size distribution having an average particle size of 6.1 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder (particle size 30nm) 2 parts
Mixing speed 1100rpm
Mixing time 120s
Mixer Super Mixer
After the toner of this example was manufactured, the surface shape of the toner was measured by an evaluation method using the SPM method, and the results are as shown in Table 1 below.
[0067]
The toner and carrier obtained by the above method were mixed in a ratio of 2.5 parts to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was ranked 5 on a five-point scale. The evaluation results are shown in Table 1 below.
[0068]
-Example 4-
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 1, and the particles were classified into a particle size distribution having an average particle diameter of 6 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder (particle size 30nm) 2.5 parts
Mixing speed 1100rpm
Mixing time 120s
Mixer Super Mixer
After the toner of this example was manufactured, the surface shape of the toner was measured by the evaluation method using the SPM method, and the results are as shown in Table 1 below.
[0069]
The toner and carrier obtained by the above method were mixed in a ratio of 2.5 parts to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was ranked 5 on a five-point scale. The evaluation results are shown in Table 1 below.
[0070]
-Example 5-
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 1, and classified into a particle size distribution with an average particle size of 6.2 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder (particle size 30nm) 3 parts
Mixing speed 1100rpm
Mixing time 120s
Mixer Super Mixer
After the toner of this example was manufactured, the surface shape of the toner was measured by the evaluation method using the SPM method, and the results are as shown in Table 1 below.
[0071]
The toner and carrier obtained by the above method were mixed in a ratio of 2.5 parts to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was ranked 5 on a five-point scale. The evaluation results are shown in Table 1 below.
[0072]
-Example 6-
Synthesis of toner binder (resin)
724 parts of bisphenol A ethylene oxide 2 mol adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide are put in 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 reducing the pressure to 10 to 15 mmHg and reacting 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 I. Next, 267 parts of Prepolymer I and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain a urea-modified polyester I having a weight average molecular weight of 64000.
[0073]
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 of 5,000. An unmodified polyester A was obtained. 200 parts of urea-modified polyester I and 800 parts of unmodified polyester A were dissolved and mixed in 2000 parts of a mixed solvent of ethyl acetate / MEK (1/1) to obtain a solution of toner binder I in ethyl acetate / MEK. A part of the mixture was dried under reduced pressure to isolate the toner binder I. As a result of analysis, Tg was 62 ° C.
[0074]
Preparation of toner
240 parts of an ethyl acetate / MEK solution of toner binder I
Pentaerythritol tetrabehenate (melt viscosity 25 cps) 20 parts
Copper phthalocyanine blue pigment
(CI Pigment Blue 15: 3) 4 parts
The above raw materials were stirred in a beaker at 60 ° C. with a TK homomixer at 12,000 rpm, and were uniformly dissolved and dispersed to prepare a toner material solution.
[0075]
706 parts of ion exchange water
Hydroxyapatite 10% suspension
(Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.) 294 parts
Sodium dodecylbenzenesulfonate 0.2 parts
The above raw materials were put into a beaker and uniformly dissolved. Thereafter, 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 flask equipped with a stir bar and a thermometer, heated to 30 ° C., the solvent was removed under reduced pressure, filtered, washed and dried, and then subjected to air classification to obtain toner particles. The volume average particle size was 6.2 μm.
[0076]
An additive was mixed with 100 parts of the toner particles under the following mixing conditions to obtain a toner.
Additive Silica fine powder (particle size 30nm) 1 part
Mixing speed 1000rpm
Mixing time 120s
Mixer Q mixer
After the toner of this example was manufactured, the surface shape of the toner was measured by the evaluation method using the SPM method, and the results are as shown in Table 1 below.
[0077]
The toner and carrier obtained by the above method were mixed in a ratio of 2.5 parts to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was ranked 5 on a five-point scale. The evaluation results are shown in Table 1 below.
[0078]
-Example 7-
Powder was prepared and classified using the same raw materials and preparation method as in Example 6, and classified into a particle size distribution having an average particle size of 6.1 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additive Silica fine powder (particle size 30nm) 1 part
Mixing speed 3000rpm
Mixing time 120s
Mixer Q mixer
After the toner of this example was manufactured, the surface shape of the toner was measured by the evaluation method using the SPM method, and the results are as shown in Table 1 below.
[0079]
The toner and carrier obtained by the above method were mixed in a ratio of 2.5 parts to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was ranked 5 on a five-point scale. The evaluation results are shown in Table 1 below.
[0080]
-Example 8-
Powder was prepared and classified using the same raw materials and preparation method as in Example 6, and classified into a particle size distribution having an average particle size of 6.2 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additive Silica fine powder (particle size 30nm) 1 part
Mixing speed 5000rpm
Mixing time 120s
Mixer Q mixer
After the toner of this example was manufactured, the surface shape of the toner was measured by the evaluation method using the SPM method, and the results are as shown in Table 1 below.
[0081]
The toner and carrier obtained by the above method were mixed in a ratio of 2.5 parts to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was ranked 5 on a five-point scale. The evaluation results are shown in Table 1 below.
[0082]
-Example 9-
Powder was prepared and classified using the same raw materials and preparation method as in Example 6, and classified into a particle size distribution having an average particle size of 6.0 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additive Silica fine powder (particle size 30nm) 1 part
Mixing speed 7000rpm
Mixing time 120s
Mixer Q mixer
After the toner of this example was manufactured, the surface shape of the toner was measured by the evaluation method using the SPM method, and the results are as shown in Table 1 below.
[0083]
The toner and carrier obtained by the above method were mixed in a ratio of 2.5 parts to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was ranked 3 on a five-point scale. The evaluation results are shown in Table 1 below.
[0084]
-Comparative Example 1-
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 1, and the particles were classified into a particle size distribution having an average particle diameter of 6 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner. The same silica fine powder as in Example 1 was used.
Additives Silica fine powder (particle size 30nm) 0.5 parts
Mixing speed 1100rpm
Mixing time 120s
Mixer Super Mixer
After the toner of this example was manufactured, the surface shape of the toner was measured by the evaluation method using the SPM method, and the results are as shown in Table 1 below.
[0085]
The toner obtained by the above method and a carrier were mixed at a ratio of 2.5 parts to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was ranked 3 on a five-point scale. The evaluation results are shown in Table 1 below.
[0086]
-Comparative Example 2-
100% polyester resin
Colorant Magenta pigment (CI Pigment Red 57) 3.5 parts
Charge control agent zinc salicylate 5 parts
After sufficiently mixing the above raw materials with a mixer, the mixture was melt-kneaded with a twin-screw extruder at a barrel temperature of 100 ° C. and a kneader rotation speed of 120 rpm. The kneaded product was rolled and cooled, coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and then classified into a particle size distribution having an average particle size of 6 μm using a revolving air classifier.
[0087]
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner. The same silica fine powder as in Example 1 was used.
Additives Silica fine powder (particle size 30nm) 0.1 part
Mixing speed 1100rpm
Mixing time 120s
Mixer Super Mixer
After preparing the toner, the surface shape of the toner was measured by an evaluation method based on the SPM method. As a result, the results are as shown in Table 1 below.
[0088]
The toner and carrier obtained by the above method were mixed in a ratio of 2.5 parts to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was ranked 1 on a five-point scale. The evaluation results are shown in Table 1 below.
[0089]
-Comparative Example 3-
Powder was prepared and classified using the same raw materials and preparation method as in Example 6, and classified into a particle size distribution having an average particle size of 6.3 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner. The same silica fine powder as in Example 1 was used.
Additives Silica fine powder (particle size 30nm) 0.5 parts
Mixing speed 1000rpm
Mixing time 120s
Mixer Q mixer
After preparing the toner, the surface shape of the toner was measured by an evaluation method based on the SPM method. As a result, the results are as shown in Table 1 below.
[0090]
The toner and carrier obtained by the above method were mixed in a ratio of 2.5 parts to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was ranked 3 on a five-point scale. The evaluation results are shown in Table 1 below.
[0091]
-Comparative Example 4-
A toner binder I was synthesized in the same manner as in Example 6, and a toner was produced as follows.
240 parts of an ethyl acetate / MEK solution of toner binder I
Pentaerythritol tetrabehenate (melt viscosity 25 cps) 20 parts
Magenta pigment (CI Pigment Red 57) 4 parts
The above raw materials were stirred in a beaker at 60 ° C. with a TK homomixer at 12,000 rpm, and were uniformly dissolved and dispersed to prepare a toner material solution.
[0092]
706 parts of ion exchange water
Hydroxyapatite 10% suspension
(Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.) 294 parts
Sodium dodecylbenzenesulfonate 0.2 parts
The above raw materials were put into a beaker and uniformly dissolved. Thereafter, 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 flask equipped with a stir bar and a thermometer, heated to 30 ° C., the solvent was removed under reduced pressure, filtered, washed and dried, and then subjected to air classification to obtain toner particles. The volume average particle size was 6.3 μm.
[0093]
An additive was mixed with 100 parts of the toner particles under the following mixing conditions to obtain a toner. The same silica fine powder as in Example 1 was used.
Additives Silica fine powder (particle size 30nm) 0.1 part
Mixing speed 1000rpm
Mixing time 120s
Mixer Q mixer
After preparing the toner, the surface shape of the toner was measured by an evaluation method based on the SPM method. As a result, the results are as shown in Table 1 below.
[0094]
The toner obtained by the above method and a carrier were mixed at a ratio of 2.5 parts to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was ranked 1 on a five-point scale. The evaluation results are shown in Table 1 below.
[0095]
[Table 1]

(Note) The-mark in the table indicates that there is no periodicity.
[0096]
【The invention's effect】
The toner of the present invention has excellent fluidity due to having a specific surface shape, and therefore, an image formed using the toner of the present invention has excellent dot reproducibility. Further, the evaluation of the measurement by the SPM method used when manufacturing the toner of the present invention is useful as an index value of the toner having good dot reproducibility.
[Brief description of the drawings]
FIG. 1 is an SPM observation image of a toner particle surface after an additive treatment.
FIG. 2 is a diagram illustrating an example of shape measurement after an additive treatment of toner particle surfaces is performed.
FIG. 3 is an SPM observation image of a toner particle surface before an additive treatment.
FIG. 4 is a schematic diagram for explaining a layer configuration of a fine powder layer on a toner surface.
FIG. 5 is a cross-sectional view schematically showing a developing device of the present invention.

Claims (18)

An electrostatic charge developing toner in which an additive is attached or fixed to the surface of a powder composed of at least a resin and a pigment, and the surface shape of the powder to which the additive is attached or fixed is measured by SPM. A toner having a small uneven period of 50 to 150 nm and a large uneven period of 400 to 800 nm in the X direction. 2. The electrostatic image development according to claim 1, wherein when the surface shape of the powder to which the additive is attached or fixed is measured by SPM, unevenness of 10 to 200 nm exists in the Z direction. 3. For toner. 3. The electrostatic image development according to claim 1, wherein when the surface shape of the powder comprising at least the resin and the pigment is measured by SPM, irregularities of 10 to 50 nm exist in the Z direction. For toner. The toner according to any one of claims 1 to 3, wherein the powder comprising at least the resin and the pigment has an average circularity of 0.9 to 0.99. . The toner according to any one of claims 1 to 4, wherein the powder comprising at least the resin and the pigment is prepared by a method other than a pulverization method. The toner according to any one of claims 1 to 5, wherein the additive is an inorganic fine powder having an average particle diameter of 30 to 200 nm. The toner according to any one of claims 1 to 5, wherein the additive is a charge control agent having an average particle diameter of 30 to 200 nm. The toner according to any one of claims 1 to 7, wherein the powder comprising at least the resin and the pigment further contains a charge control agent. The toner according to any one of claims 1 to 8, wherein the powder comprising at least the resin and the pigment further contains a release agent. 10. The toner according to claim 9, wherein the powder comprising at least the resin and the pigment further contains a dispersant for a release agent. The toner according to any one of claims 1 to 10, wherein the powder comprising at least the resin and the pigment is prepared using a composition in which the resin and the pigment are kneaded in advance. Development toner. The toner according to claim 1, wherein the toner has a volume average particle diameter of 4 to 10 μm. A one-component developing method comprising performing contact or non-contact development using the toner according to any one of claims 1 to 12. 14. The one-component developing method according to claim 13, wherein a doctor roller is used. A two-component developing method, comprising developing using the toner according to claim 1 and a carrier having a particle size of 20 to 100 μm. The one-component developing method or the two-component developing method according to claim 13, wherein the developing is performed by applying an AC bias voltage component. A powder comprising at least a resin and a pigment is produced, an additive is attached or fixed to the surface of the powder, and the powder having the additive attached or fixed to the surface is evaluated using SPM. A method for producing a toner for developing an electrostatic image, comprising obtaining the toner according to any one of claims 1 to 12. A toner evaluation device for developing an electrostatic charge image, wherein the toner surface shape is evaluated by using an SPM method to obtain the toner according to claim 1.

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