JP3933567B2 - Electrophotographic carrier, developer, container and image forming method - Google Patents

Description

を仕込み、４００回転／分で１５分間攪拌したところ、白色の乳濁液が得られた。加熱して、系内温度７５℃まで昇温し５時間反応させた。さらに、１％過硫酸アンモニウム水溶液３０部加え、７５℃で５時間熟成してビニル系樹脂（スチレン−メタクリル酸−メタクリル酸エテレンオキサイド付加物硫酸エステルのナトリウム塩の共重合体）の水性分散液［微粒子分散液１］を得た。
［微粒子分散液１］をＬＡ−９２０で測定した体積平均粒径は、０．１４μｍであった。［微粒子分散液１］の一部を乾燥して樹脂分を単離した。該樹脂分のＴｇは１５２℃であった。
【００７２】

を混合攪拌し、乳白色の液体を得た。これを［水相１］とする。
【００７３】
（低分子ポリエステルの合成）
製造例３
冷却管、攪拌機および窒素導入管の付いた反応容器中に、
ビスフェノールＡエチレンオキサイド２モル付加物 ２２０部
ビスフェノールＡプロピレンオキサイド３モル付加物 ５６１部
テレフタル酸 ２１８部
アジピン酸 ４８部
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の減圧で５時間反応した後、反応容器に無水トリメリット酸４５部を入れ、１８０℃、常圧で２時間反応し、［低分子ポリエステル１］を得た。［低分子ポリエステル１］は、数平均分子量２５００、重量平均分子量６７００、Ｔｇ４３℃、酸価２５であった。
【００７４】
（プレポリマーの合成）
製造例４
冷却管、攪拌機および窒索導入管の付いた反応容器中に、
ビスフェノールＡエチレンオキサイド２モル付加物 ６８２部
ビスフェノールＡプロピレンオキサイド２モル付加物 ８１部
テレフタル酸 ２８３部
無水トリメリツト酸 ２２部
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の減圧で５時間反応した［中間体ポリエステル１］を得た。［中間体ポリエステル１］は、数平均分子量２１００、重量平均分子量９５００、Ｔｇ５５℃、酸価０．５、水酸基価４９であった。
次に、冷却管、攪拌機および窒素導入管の付いた反応容器中に、
［中間体ポリエステル１］ ４１１部
イソホロンジイソシアネート ８９部
酢酸エチル ５００部
を入れ１００℃で５時間反応し、［プレポリマー１］を得た。［プレポリマー１］の遊離イソシアネート重量％は、１．５３％であった。
【００７５】
（ケチミンの合成）
製造例５
攪拌棒および温度計をセットした反応容器に、
イソホロンジアミン １７０部
メチルエチルケトン ７５部
を仕込み、５０℃で５時間反応を行ない、［ケチミン化合物１］を得た。［ケチミン化合物１］のアミン価は４１８であった。
【００７６】
（マスターバッチの合成）
製造例６
顔料カーボンブラック（キャボット社性リーガル４００Ｒ） ４０部
結着樹脂：ポリエステル樹脂 ６０部
（三洋化成ＲＳ−８０１酸価１０、Ｍｗ２００００Ｔｇ、６４℃）
水 ３０部
上記原材料をヘンシェルミキサーにて混合し、顔料凝集体中に水が染み込んだ混合物を得た。これをロール表面温度１３０℃に設定した２本ロールにより４５分間混練を行ない、パルベライザーで１ｍｍφの大きさに粉砕し、［マスターバッチ１］を得た。次に、このマスターバッチ顔料を用いて、以下の方法により、トナーとした。
【００７７】
（油相の作成）
製造例７
攪拌棒および温度計をセットした容器に、
［低分子ポリエステル１］ ３７８部
カルナバＷＡＸ １１０部
ＣＣＡ（サリチル酸金属錯体Ｅ−８４：オリエント化学工業） ２２部
酢酸エチル ９４７部
を仕込み、攪拌下８０℃に昇温し、８０℃のまま５時間保持した後、１時間で３０℃に冷却した。次いで容器に
［マスターバッチ１］ ５００部
酢酸エチル ５００部
を仕込み、１時間混合し［原料溶解液１］を得た。［原料溶解液１］：１３２４部を容器に移し、ビーズミル（ウルトラビスコミル、アイメックス社製）を用いて、送液速度１ｋｇ／ｈｒ、ディスク周速度６ｍ／秒、０．５ｍｍジルコニアビーズを８０体積％充填、３パスの条件で、カーボンブラック、ＷＡＸの分散を行なった。次いで、［低分子ポリエステル１］の６５％酢酸エチル溶液：１３２４部を加え、上記条件のビーズミルで１パスし、［顔料・ＷＡＸ分散液１］を得た。［顔料・ＷＡＸ分散液１］の固形分濃度（１３０℃、３０分）は５０％であった。
【００７８】
（乳化⇒脱溶剤）
トナーは、
［顔料・ＷＡＸ分散液１］ ６４８部
［プレポリマー１］ １５４部
［ケチミン化合物１］ ６．６部
を容器に入れ、ＴＫホモミキサー（特殊機化製）で５，０００ｒｐｍで１分間混合した後、容器に［水相１］１２００部を加え、ＴＫホモミキサーで、回転数１３，０００ｒｐｍで２０分間混合し［乳化スラリー１］を得た。
攪拌機および温度計をセットした容器に、［乳化スラリー１］を投入し、３０℃で８時間脱溶剤した後、４５℃で４時間熟成を行ない、［分散スラリー１］を得た。［分散スラリー１］は、体積平均粒径５．９５μｍ、個数平均粒径５．４５μｍ（マルチサイザーで測定）であった。
【００７９】
（洗浄⇒乾燥）
［乳化スラリー１］１００部を減圧濾過した後、
▲１▼：濾過ケーキにイオン交換水１００部を加え、ＴＫホモミキサーで混合（回転数１２，０００ｒｐｍで１０分間）した後濾過した。
▲２▼：▲１▼の濾過ケーキに１０％水酸化ナトリウム水溶液１００部を加え、超音波振動を付与してＴＫホモミキサーで混合（回転数１２，０００ｒｐｍで３０分間）した後、減圧濾過した。この超音波アルカリ洗浄を再度行なった（超音波アルカリ洗浄２回）。
▲３▼：▲２▼の濾過ケーキに１０％塩酸１００部を加え、ＴＫホモミキサーで混合（回転数１２，０００ｒｐｍで１０分間）した後濾過した。
▲４▼：▲３▼の濾過ケーキにイオン交換水３００部を加え、ＴＫホモミキサーで混合（回転数１２，０００ｒｐｍで１０分間）した後濾過する操作を２回行ない［濾過ケーキ１］を得た。
［濾過ケーキ１］を循風乾燥機にて４５℃で４８時間乾燥し、目開き７５μｍメッシュで篩い、体積平均粒径Ｄｖ６．０５μｍ、個数平均粒径Ｄｎ５．５８μｍ、Ｄｖ／Ｄｎ１．０８（マルチサイザーＩＩで測定）、樹脂微粒子残存率０．１ｗｔ％の［トナー１］を得た。
【００８０】
こうして得た［トナー１］、［キャリア１］及びその現像剤を、以下の項目について評価を行なった。但し、トナーについてはトナー１００部に疎水性シリカ０．７部と、疎水化酸化チタン０．３部をヘンシェルミキサーにて混合したものを用いた。
【００８１】
＜各種評価方法について＞
（ａ）トナー粒径
トナーの粒径は、コールターエレクトロニクス社製の粒度測定器「コールターカウンターＴＡII」を用い、アパーチャー径１００μｍで測定した。体積平均粒径および個数平均粒径は上記粒度測定器により求めた。結果は表１に記す。
（ｂ）帯電量
［キャリア１］９５ｗｔ％に対し［トナー１］５ｗｔ％の割合で混合し摩擦帯電させた現像剤を、一般的なブローオフ法［東芝ケミカル（株）製：ＴＢ−２００］にて測定した帯電量。結果は表１に記す。
（ｃ）トナー円形度
フロー式粒子像分析装置ＦＰＩＡ−１０００（東亜医用電子株式会社製）により平均円形度として計測できる。具体的な測定方法としては、容器中の予め不純固形物を除去した水１００〜１５０ｍｌ中に分散剤として界面活性剤、好ましくはアルキルベンゼンスルフォン酸塩を０．１〜０．５ｍｌ加え、更に測定試料を０．１〜０．５ｇ程度加える。試料を分散した懸濁液は超音波分散器で約１〜３分間分散処理を行ない、分散液濃度を３０００〜１万個／μｌとして前記装置によりトナーの形状及び分布を測定することによって得られる。結果は表１に記す。
（ｄ）樹脂微粒子残存率の測定方法
トナー中のスチレンアクリル樹脂微粒子の熱分解生成物であるスチレンモノマーを指紋成分として、下記条件で、トナー粒子へスチレンアクリル樹脂微粒子を０．０１ｗｔ％、０．１０ｗｔ％、１．００ｗｔ％、３．００ｗｔ％、１０．０ｗｔ％添加する標準添加法を用いて、トナー表面に偏在する樹脂微粒子をスチレンモノマーのピーク面積で算出し測定した。
分析機器：熱分解ガスクロマトグラフ（質量分析）計装置；島津製作所ＱＲ−５０００日本分析工業ＪＨＰ−３Ｓ熱分解温度；５９０℃×１２秒
カラム；ＤＢ−１Ｌ＝３０ｍ
Ｉ．Ｄ＝０．２５ｍｍ
Ｆｉｌｍ＝０．２５μｍ
カラム温度；４０℃（保持２分）〜（１０℃／分昇温）３００℃
気化室温度；３００℃
いずれの項目も５％画像面積の画像チャートを５００００枚まで連続でランニングした後、以下に述べる評価を行なった。結果は表１に記す。
（ｅ）定着性
毎分Ａ４サイズの用紙を４５枚印刷できるリコー社製ｉｍａｇｉｏＮｅｏ４５０改造機を用いて、［キャリア１］９５ｗｔ％、［トナー１］５ｗｔ％の割合で混合し摩擦帯電させた現像剤により、普通紙及び厚紙の転写紙（リコー製タイプ６２００及びＮＢＳリコー製複写印刷用紙＜１３５＞）にベタ画像で、１．０±０．１ｍｇ／ｃｍ^２単位のトナーが現像される様に調整を行ない、定着ベルトの温度が可変となる様に調整を行なって、普通紙でオフセットの発生しない温度を、厚紙で定着下限温度を測定した。定着下限温度は、得られ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。結果は表２に記す。
（ｆ）画像濃度
ベタ画像出力後、画像濃度をＸ−Ｒｉｔｅ（Ｘ−Ｒｉｔｅ社製）により測定。これを各色単独に５点測定し各色ごとに平均を求めた。結果は表２に記す。
（ｇ）地肌汚れ
白紙画像を現像中に停止させ、現像後の感光体上の現像剤をテープ転写し、未転写のテープの画像濃度との差を９３８スペクトロデンシトメーター（Ｘ−Ｒｉｔｅ社製）により測定。結果は表２に記す。
（ｈ）クリーニング性
清掃工程を通過した感光体上の転写残トナーをスコッチテープ（住友スリーエム（株）製）で白紙に移し、それをマクベス反射濃度計ＲＤ５１４型で測定し、ブランクとの差が０．０１以下のものを○（良好）、それを越えるものを×（不良）として評価した。結果は表２に記す。
（ｉ）フィルミング
現像ローラまたは感光体上のトナーフィルミング発生状況の有無を観察した。○がフィルミングがなく、△はスジ上のフィルミングが見られ、×は全体的にフィルミングがある。結果は表２に記す。
（ｊ）帯電量低下量
（ｂ）に記した初期の帯電量（Ｑ１）から、リコー社製ｉｍａｇｉｏＮｅｏ４５０改造機を用いて、［キャリア１］９５ｗｔ％、［トナー１］５ｗｔ％の割合で混合し摩擦帯電させた現像剤を用い、３００，０００枚のランニング評価を行なった後の現像剤中のトナーを、前記ブローオフ装置にて除去し得たキャリアを同様の方法で測定した帯電量（Ｑ２）を差し引いた量のことを言い、目標値は５．０以下である。また、帯電量低下の原因はキャリア表面へのトナースペントであるため、このトナースペントを減らすことで、帯電量低下を抑えることができる。結果は表２に記す。
（ｋ）抵抗変化量
初期のキャリアを抵抗計測平行電極：ギャップ２ｍｍの電極間に投入し、ＤＣ２５０Ｖを印加し３０ｓｅｃ後の抵抗値をハイレジスト計で計測した値を体積抵抗率に変換した値（Ｒ１）から、リコー社製ｉｍａｇｉｏＮｅｏ４５０改造機を用いて、［キャリア１］９５ｗｔ％、［トナー１］５ｗｔ％の割合で混合し摩擦帯電させた現像剤を用い、３００，０００枚のランニング評価を行なった後の現像剤中のトナーを前記ブローオフ装置にて除去し得たキャリアを、前記抵抗測定方法と同様の方法で測定した値（Ｒ２）を差し引いた量のことをいい、目標値は絶対値で２．０［Ｌｏｇ（Ω・ｃｍ）］以内である。また、抵抗値変化の原因は、キャリアの結着樹脂の膜削れ、トナー成分のスペント、キャリア被覆膜中の大粒子の脱離などであるため、これらを減らすことで、抵抗変化量を抑えることができる。結果は表２に記す。
（ｌ）地汚れ
リコー社製ｉｍａｇｉｏＮｅｏ４５０改造機を用いて、［キャリア１］９５ｗｔ％、［トナー１］５ｗｔ％の割合で混合し摩擦帯電させた現像剤を用い、３０００枚のランニングにおける地汚れを、［◎：非常に良い、○：良い、△：悪い、×：非常に悪い］の４段階で評価した。評価の可否については、◎及び○が可で、△及び×を否とする。この地汚れの原因は、現像剤中への補給トナーの混ざりが不充分である場合に、トナーの帯電が充分に立ち上がらないため、現像ローラ上の現像剤からトナーが飛び出すことによるものである。結果は表２に示す。
（ｍ）トナー飛散
リコー社製ｉｍａｇｉｏＮｅｏ４５０改造機を用いて、［キャリア１］９５ｗｔ％、［トナー１］５ｗｔ％の割合で混合し摩擦帯電させた現像剤を用い、５０，０００枚のランニング後の、装置内現像部周りのトナーの飛散程度を、［◎：非常に良い、○：良い、△：悪い、×：非常に悪い］の４段階で評価した。評価の可否については、◎及び○が可で、△及び×を否とする。このトナー飛散の原因は、現像剤中への補給トナーの混ざりが不充分である場合に、トナーの帯電が充分に立ち上がらないため、現像ローラ上の現像剤からトナーが飛び出すことによるものである。
（ｎ）磁化
キャリアの磁化測定は、東英工業株式会社製 多試料回転式磁化測定装置 Ｍｏｄｅｌ ＲＥＭ−１によって測定し、１ｋＯｅにおける磁化を用いた。
（ｏ）キャリア粒径
キャリアの粒径測定は、Ｍｉｃｒｏｔｒａｃ社製 ＭＩＣＲＯＴＲＡＣ Ｍｏｄｅｌ ９３２０−Ｘ１００によって測定した。また、本発明で言う平均粒径Ｄｖとは、体積分布により得られた値である。
（ｐ）キャリア付着
キャリア付着の測定は、リコー社製ｉｍａｇｉｏＮｅｏ４５０改造機を用いて、白紙画像を現像中に停止させ、現像後の感光体上の現像剤をテープ転写し、面積５０ｃｍ^２中のキャリア付着個数をもってキャリア付着量とする。キャリア付着量の目標値は１００個／５０ｃｍ^２以下。
【００８２】
＜実施例２＞…参考例
実施例１において、芯材として焼成フェライト粉［平均粒径；５０μｍ、磁化（１ｋＯｅ）；７０ｅｍｕ／ｇ、Ｄｖの６３％径以下含有量；０．９ｗｔ％］を用いたこと以外は同様である［キャリア２］を製造した。こうして得た［キャリア２］について実施例１と同様の評価を行なった。
【００８３】
＜実施例３＞…参考例
アクリル樹脂溶液（固形分５０ｗｔ％） ２１．０部
グアナミン溶液（固形分７０ｗｔ％） ６．４部
アルミナ粒子［０．３μｍ、固有抵抗１０^１４（Ω・ｃｍ）］ ７．６部
シリコン樹脂溶液［固形分２３ｗｔ％
（ＳＲ２４１０：東レ・ダウコーニング・シリコーン社製）］６５．０部
アミノシラン［固形分１００ｗｔ％
（ＳＨ６０２０：東レ・ダウコーニング・シリコーン社製）］ ０．３部
トルエン ６０部
ブチルセロソルブ ６０部
をホモミキサーで１０分間分散し、アクリル樹脂及びシリコン樹脂のブレンド被覆膜形成溶液を得、実施例２と同様の方法でキャリア化し［キャリア３］を得た。こうして得た［キャリア３］について実施例１と同様の評価を行なった。
【００８４】
＜実施例４＞…参考例
アクリル樹脂溶液（固形分５０ｗｔ％） ２１．０部
グアナミン溶液（固形分７０ｗｔ％） ６．４部
アルミナ粒子［０．３μｍ、固有抵抗１０^１４（Ω・ｃｍ）］ ７．６部
トルエン ６０部
ブチルセロソルブ ６０部
をホモミキサーで１０分間分散し、アクリル樹脂被覆膜形成溶液を得た。実施例２と同様の方法にて芯材表面に膜厚０．０８μｍになるようにスピラコーター（岡田精工社製）により塗布し乾燥した後、
シリコン樹脂溶液［固形分２３ｗｔ％
（ＳＲ２４１０：東レ・ダウコーニング・シリコーン社製）］６５．０部
アミノシラン［固形分１００ｗｔ％
（ＳＨ６０２０：東レ・ダウコーニング・シリコーン社製）］ ０．３部
トルエン ６０部
ブチルセロソルブ ６０部
を容器内でアジテーターにより５分間分散し、シリコン樹脂被覆膜形成溶液を得、この溶液を上記アクリル樹脂被覆層が形成されているキャリア表面へ、アクリル樹脂層とシリコン樹脂層の総膜厚が０．１５μｍとなるように塗布し乾燥した。その後は、実施例１と同様の方法によりキャリアを得、［キャリア４］とした。これにより、被覆膜は下層がアクリル樹脂、上層がシリコン樹脂と二層構造を形成する。こうして得た［キャリア４］について実施例１と同様の評価を行なった。
【００８５】
＜実施例５＞
アクリル樹脂溶液（固形分５０ｗｔ％） ２１．０部
グアナミン溶液（固形分７０ｗｔ％） ６．４部
アルミナ粒子［０．３μｍ、固有抵抗１０^１４（Ω・ｃｍ）］１２１．０部
シリコン樹脂溶液［固形分２３ｗｔ％
（ＳＲ２４１０：東レ・ダウコーニング・シリコーン社製）］６５．０部
アミノシラン［固形分１００ｗｔ％
（ＳＨ６０２０：東レ・ダウコーニング・シリコーン社製）］ ０．３部
トルエン ３００部
ブチルセロソルブ ３００部
をホモミキサーで１０分間分散し、アルミナ粒子を含むアクリル樹脂及びシリコン樹脂のブレンド被覆膜形成溶液を得、実施例２と同様の方法でキャリア化し、［キャリア５］を得た。こうして得た［キャリア５］について実施例１と同様の評価を行なった。
【００８６】
＜実施例６＞
実施例５において、アルミナの代わりに、酸化チタン粒子［０．３μｍ、固有抵抗１０^７（Ω・ｃｍ）］１２１．０部を用いた以外は同様である［キャリア６］を製造した。こうして得た［キャリア６］について実施例１と同様の評価を行なった。
【００８７】
＜実施例７＞
実施例５において、アルミナの代わりに、酸化亜鉛粒子［０．３μｍ、固有抵抗１０^７（Ω・ｃｍ）］１２１．０部を用いた以外は同様である［キャリア７］を製造した。こうして得た［キャリア７］について実施例１と同様の評価を行なった。
【００８８】
＜実施例８＞…参考例
アクリル樹脂溶液（固形分５０ｗｔ％） ２．２部
グアナミン溶液（固形分７０ｗｔ％） ０．７部
アルミナ粒子［０．３μｍ、固有抵抗１０^１４（Ω・ｃｍ）］１２１．０部
シリコン樹脂溶液［固形分２３ｗｔ％
（ＳＲ２４１０：東レ・ダウコーニング・シリコーン社製）］１２６．０部
アミノシラン［固形分１００ｗｔ％
（ＳＨ６０２０：東レ・ダウコーニング・シリコーン社製）］ ０．６３部
トルエン ６０部
ブチルセロソルブ ６０部
をホモミキサーで１０分間分散し、アクリル樹脂及びシリコン樹脂のブレンド被覆膜形成溶液を得、実施例２と同様の方法でキャリア化し、［キャリア８］を得た。こうして得た［キャリア８］について実施例１と同様の評価を行なった。
【００８９】
＜比較例１＞
実施例１において、芯材として焼成フェライト粉［平均粒径；１９μｍ、磁化（１ｋＯｅ）；５８ｅｍｕ／ｇ、Ｄｖの６３％径以下含有量；１．２ｗｔ％］を用いたこと以外は同様である［キャリア９］を製造した。こうして得た［キャリア９］について実施例１と同様の評価を行なった。
【００９０】
＜比較例２＞
実施例１において、芯材として焼成フェライト粉［平均粒径；８１μｍ、磁化（１ｋＯｅ）；７３ｅｍｕ／ｇ、Ｄｖの６３％径以下含有量；１．０ｗｔ％］を用いたこと以外は同様である［キャリア１０］を製造した。こうして得た［キャリア１０］について実施例１と同様の評価を行なった。
【００９１】
＜比較例３＞
実施例５において、アルミナの粒径が２．３μｍのものを用いたことによりＤ／ｈが１５．３となり、それ以外は同様である［キャリア１１］を製造した。こうして得た［キャリア１１］について実施例１と同様の評価を行なった。
【００９２】
＜実施例９＞…参考例
シリコン樹脂溶液［固形分２３ｗｔ％
（ＳＲ２４１０：東レ・ダウコーニング・シリコーン社製）］１３２．２部
アミノシラン［固形分１００ｗｔ％
（ＳＨ６０２０：東レ・ダウコーニング・シリコーン社製）］ ０．６６部
アルミナ粒子［０．３μｍ、固有抵抗１０^１４（Ω・ｃｍ）］１２１．０部
トルエン ３００部
ブチルセロソルブ ３００部
をホモミキサーで１０分間分散し、アルミナ粒子を含有するシリコン樹脂被覆膜形成溶液を得、実施例２と同様の方法で［キャリア１２］を製造した。こうして得た［キャリア１２］について実施例１と同様の評価を行なった。
【００９３】
＜比較例４＞
実施例５において、アルミナの粒径が０．１２μｍのものを用いたことによりＤ／ｈが０．８となり、それ以外は同様である［キャリア１３］を製造した。こうして得た［キャリア１３］について実施例１と同様の評価を行なった。
【００９４】
＜比較例５＞
実施例５において、芯材を１ｋＯｅにおける磁化が３５ｅｍｕ／ｇのものに変えた以外は同様である［キャリア１４］を製造した。こうして得た［キャリア１４］について実施例１と同様の評価を行なった。
【００９５】
＜比較例６＞
実施例５において、芯材を１ｋＯｅにおける磁化が８４ｅｍｕ／ｇのものに変えた以外は同様である［キャリア１５］を製造した。こうして得た［キャリア１５］について実施例１と同様の評価を行なった。
【００９６】
＜実施例１０＞
実施例２での超音波アルカリ洗浄を１回にした以外は実施例２と同様にして体積平均粒径Ｄｖ６．１０μｍ、個数平均粒径Ｄｎ５．５４μｍ、Ｄｖ／Ｄｎ１．１０、樹脂微粒子残存率０．５ｗｔ％の［トナー２］を得た。こうして得た［トナー２］を実施例１と同様の方法により評価を行なった。
【００９７】
＜実施例１１＞
実施例２での油相の作成時にＣＣＡを２２部加えない以外は実施例２と同様にしてトナーを得た。このトナー１００部にＣＣＡ（サリチル酸金属錯体Ｅ−８４：オリエント化学工業）０．５部を添加し、Ｑミキサー（三井鉱山製）にてＣＣＡ打ち込み処理を施し、体積平均粒径Ｄｖ５．８２μｍ、個数平均粒径Ｄｎ５．２０μｍ、Ｄｖ／Ｄｎ１．１２、樹脂微粒子残存率０．３ｗｔ％の［トナー３］を得た。こうして得た［トナー３］を実施例１と同様の方法により評価を行なった。
【００９８】
（低分子ポリエステルの合成）
製造例８
冷却管、攪拌機および窒素導入管の付いた反応容器中に、
ビスフェノールＡエチレンオキサイド２モル付加物 ２６２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 ２０２部
ビスフェノールＡプロピレンオキサイド３モル付加物 ２３６部
テレフタル酸 ２６６部
アジピン酸 ４８部
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の減圧で５時間反応した後、反応容器に無水トリメリット酸３４部を入れ、１８０℃、常圧で２時間反応し、［低分子ポリエステル２］を得た。［低分子ポリエステル２］は、数平均分子量２３９０、重量平均分子量６０１０、Ｔｇ６２℃、酸価２０．７であった。
【００９９】
（油相の作成）
製造例９
攪拌棒および温度計をセットした容器に、
［低分子ポリエステル２］ ３７８部
カルナバＷＡＸ １１０部
ＣＣＡ（サリチル酸金属錯体Ｅ−８４：オリエント化学工業） ２２部
酢酸エチル ９４７部
を仕込み、攪拌下８０℃に昇温し、８０℃のまま５時間保持した後、１時問で３０℃に冷却した。次いで容盤に［マスターバッチ１］５００部、酢酸エチル５００部を仕込み、１時間混合し［原料溶解液２］を得た。［原料溶解液２］１３２４部を容器に移し、ビーズミル（ウルトラビスコミル、アイメックス社製）を用いて、送液速度１ｋｇ／ｈｒ、ディスク周速度６ｍ／秒、０．５ｍｍジルコニアビーズを８０体積％充填、３パスの条件で、カーボンブラック、ＷＡＸの分散を行なった。次いで、［低分子ポリエステル２］の６５％酢酸エチル溶液１３２４部加え、上記条件のビーズミルで１パスし、［顔料・ＷＡＸ分散液２］を得た。［顔料・ＷＡＸ分散液２］の固形分濃度（１３０℃、３０分）は５２％であった。
【０１００】
＜実施例１２＞
実施例２での［顔料・ＷＡＸ分散液１］の代わりに［顔料・ＷＡＸ分散液２］を使用し、超音波を印加せずアルカリ洗浄２回した以外は実施例２と同様にして体積平均粒径Ｄｖ６．３１μｍ、個数平均粒径Ｄｎ５．６７μｍ、Ｄｖ／Ｄｎ１．１１、樹脂微粒子残存率１．５ｗｔ％の［トナー４］を得た。こうして得た［トナー４］を実施例１と同様の方法により評価を行なった。
【０１０１】
＜実施例１３＞
実施例１２での超音波を印可せずアルカリ洗浄１回した以外は実施例２と同様にして体積平均粒径Ｄｖ６．４５μｍ、個数平均粒径Ｄｎ５．４６μｍ、Ｄｖ／Ｄｎ１．１８、樹脂微粒子残存率２．４ｗｔ％の［トナー５］を得た。こうして得た［トナー５］を実施例１と同様の方法により評価を行なった。
【０１０２】
（低分子ポリエステルの合成）
製造例１０
冷却管、攪拌機および窒素導入管の付いた反応容器中に、
ビスフェノールＡプロピレンオキサイド２モル付加物 ７１９部
テレフタル酸 ２７４部
アジピン酸４８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、反応容器に無水トリメリット酸７部を入れ、１８０℃、常圧で２時間反応し、［低分子ポリエステル３］を得た。［低分子ポリエステル３］は、数平均分子量２２９０、重量平均分子量５７５０、Ｔｇ６５℃、酸価４．９であった。
【０１０３】
（油相の作成）
製造例１１
攪拌棒および温度計をセットした容器に、
［低分子ポリエステル３］ ３７８部
カルナバＷＡＸ １１０部
ＣＣＡ（サリチル酸金属錯体Ｅ−８４：オリエント化学工業） ２２部
酢酸エチル ９４７部
を仕込み、攪拌下８０℃に昇温し、８０℃のまま５時間保持した後、１時問で３０℃に冷却した。次いで容盤に［マスターバッチ１］５００部、酢酸エチル５００部を仕込み、１時間混合し［原料溶解液３］を得た。［原料溶解液３］１３２４部を容器に移し、ビーズミル（ウルトラビスコミル、アイメックス社製）を用いて、送液速度１ｋｇ／ｈｒ、ディスク周速度６ｍ／秒、０．５ｍｍジルコニアビーズを８０体積％充填、３パスの条件で、カーボンブラック、ＷＡＸの分散を行なった。次いで、［低分子ポリエステル３］の６５％酢酸エチル溶液１３２４部加え、上記条件のビーズミルで１パスし、［顔料・ＷＡＸ分散液３］を得た。［顔料・ＷＡＸ分散液３］の固形分濃度（１３０℃、３０分）は４９％であった。
【０１０４】
＜実施例１４＞
実施例２での［顔料・ＷＡＸ分散液１］の代わりに［顔料・ＷＡＸ分散液３］を使用し、超音波を印可せずアルカリ洗浄４回した以外は実施例２と同様にして体積平均粒径Ｄｖ７．０４μｍ、個数平均粒径Ｄｎ５．６４μｍ、Ｄｖ／Ｄｎ１．２５、樹脂微粒子残存率１．５ｗｔ％の［トナー６］を得た。こうして得た［トナー６］を実施例１と同様の方法により評価を行なった。
【０１０５】
＜実施例１５＞
実施例２での［顔料・ＷＡＸ分散液１］の代わりに［顔料・ＷＡＸ分散液３］を使用し、超音波を印可せずアルカリ洗浄２回した以外は実施例２と同様にして体積平均粒径Ｄｖ７．０２μｍ、個数平均粒径Ｄｎ５．６３μｍ、Ｄｖ／Ｄｎ１．２５、樹脂微粒子残存率２．３ｗｔ％の［トナー７］を得た。こうして得た［トナー７］を実施例１と同様の方法により評価を行なった。
【０１０６】
（低分子ポリエステルの合成）
製造例１２
冷却管、攪拌機および窒素導入管の付いた反応容器中に、
ビスフェノールＡエチレンオキサイド２モル付加物 １２１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 ６４部
ビスフェノールＡプロピレンオキサイド３モル付加物 ５２７部
テレフタル酸 ２４６部
アジピン酸 ４８部
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の減圧で５時間反応した後、反応容器に無水トリメリット酸４２部を入れ、１８０℃、常圧で２時間反応し、［低分子ポリエステル４］を得た。［低分子ポリエステル４］は、数平均分子量２５００、重量平均分子量６１９０、Ｔｇ４８℃、酸価２５．２であった。
【０１０７】
（油相の作成）
製造例１３
攪拌棒および温度計をセットした容器に、
［低分子ポリエステル４］ ３７８部
カルナバＷＡＸ １１０部
ＣＣＡ（サリチル酸金属錯体Ｅ−８４：オリエント化学工業） ２２部
酢酸エチル ９４７部
を仕込み、攪拌下８０℃に昇温し、８０℃のまま５時間保持した後、１時問で３０℃に冷却した。次いで容器に［マスターバッチ１］５００部、酢酸エチル５００部を仕込み、１時間混合し［原料溶解液４］を得た。
［原料溶解液４］１３２４部を容器に移し、ビーズミル（ウルトラビスコミル、アイメックス社製）を用いて、送液速度１ｋｇ／ｈｒ、ディスク周速度６ｍ／秒、０．５ｍｍジルコニアビーズを８０体積％充填、３パスの条件で、カーボンブラック、ＷＡＸの分散を行なった。次いで、［低分子ポリエステル４］の６５％酢酸エチル溶液１３２４部加え、上記条件のビーズミルで１パスし、［顔料・ＷＡＸ分散液４］を得た。［顔料・ＷＡＸ分散液４］の固形分濃度（１３０℃、３０分）は４９％であった。
【０１０８】
＜実施例１６＞
実施例２での［顔料・ＷＡＸ分散液１］の代わりに［顔料・ＷＡＸ分散液４］を使用した以外は実施例２と同様にして体積平均粒径Ｄｖ４．８４μｍ、個数平均粒径Ｄｎ４．０２μｍ、Ｄｖ／Ｄｎ１．２０、樹脂微粒子残存率０．３ｗｔ％の［トナー８］を得た。こうして得た［トナー８］を実施例１と同様の方法により評価を行なった。
【０１０９】
＜実施例１７＞
実施例２での［顔料・ＷＡＸ分散液１］の代わりに［顔料・ＷＡＸ分散液４］を使用し、超音波アルカリ洗浄を１回にした以外は実施例２と同様にして体積平均粒径Ｄｖ５．１３μｍ、個数平均粒径Ｄｎ４．２４μｍ、Ｄｖ／Ｄｎ１．２１、樹脂微粒子残存率０．８ｗｔ％の［トナー９］を得た。こうして得た［トナー９］を実施例１と同様の方法により評価を行なった。
【０１１０】
＜比較例７＞
イオン交換水７０９ｇに０．１Ｍ−Ｎａ_３ＰＯ_４水溶液４５１ｇを投入し６０℃に加温した後、ＴＫホモミキサーを用いて１２，０００ｒｐｍにて攪拌した。これに１．０Ｍ−ＣａＣｌ２水溶液６８ｇを徐々に添加し、Ｃａ_３（ＰＯ_４）２を含む水系媒体を得た。

をＴＫ式ホモミキサーに投入、６０℃に加温し、１２，０００ｒｐｍにて均一に溶解、分散した。これに、重合開始剤、２，２’−アゾビス（２，４−ジメチルバレロニトリル）１０ｇを溶解し、重合性単量体系を調製した。前記水系媒体中に上記重合性単量体系を投入し、６０℃、Ｎ_２雰囲気下において、ＴＫホモミキサーにて１０，０００ｒｐｍで２０分間攪拌し、重合性単量体系を造粒した。その後、パドル攪拌翼で攪拌しつつ、６０℃で３時間反応させた後、液温を８０℃とし、１０時間反応させた。
重合反応終了後冷却し、塩酸を加えリン酸カルシウムを溶解させた後、濾過、水洗、乾燥をして、体積平均粒径Ｄｖ６．３３μｍ、個数平均粒径Ｄｎ５．６４μｍ、Ｄｖ／Ｄｎ１．１２の［トナー１０］を得た。
キャリアは、
シリコーン樹脂溶液［固形分１５重量％
（ＳＲ２４１１：東レダウコーニング社製）］ ２２７部
γ−（２−アミノエチル）アミノプロピルトリメトキシシラン ６部
カーボンブラック［０．０４μｍ（＃２５：三菱化学）］ ２．６部
トルエン １９２部
ブチルセロソルブ １９２部
をホモミキサーで１０分間分散してシリコン樹脂被覆形成液を得、実施例２と同様の方法でキャリア化し、［キャリア１６］を得た。こうして得た［トナー１０］と［キャリア１６］を実施例１と同様の方法により評価を行なった。
【０１１１】
＜比較例８＞
（ワックス粒子水性分散液の調製）
１０００ｍｌの攪拌装置、温度センサー、窒素導入管及び冷却管付き４頭コルベンに脱気した蒸留水５００ｍｌにニューコール５６５Ｃ（日本乳化剤社製）２８．５ｇ、キャンデリアワックスＮｏ．１（野田ワックス社製）１８５．５ｇを添加し窒素気流下攪拌を行ないつつ、温度を昇温した。内温８５℃の時点で５Ｎ−水酸化ナトリウム水溶液を添加しそのまま７５℃まで昇温した後、そのまま１時間加熱攪拌を続け、室温まで冷却し［ワックス粒子水性分散液１］を得た。
【０１１２】
（着色剤水性分散液の調製）
カーボンブラック（商品名：モーガルＬ、キャボット社製）１００ｇ、ドデシル硫酸ナトリウム２５ｇを蒸留水５４０ｍｌに添加し、充分攪拌を行なった後、加圧型分散機（ＭＩＮＩ−ＬＡＢ：ラーニー社製）を用い、分散を行ない［着色剤分散液Ｉ］を得た。
【０１１３】
（バインダー微粒子水性分散液の合成）
攪拌装置、冷却管、温度センサー及び窒素導入管を装着した１Ｌの４頭コルベンに
蒸留水 ４８０ｍｌ
ドデシル硫酸ナトリウム ０．６ｇ
スチレン １０６．４ｇ
ｎ−ブチルアクリレート ４３．２ｇ
メタクリル酸 １０．４ｇ
を添加し攪拌を行ないながら窒素気流下７０℃まで昇温した。ここで過硫酸カリウム２．１ｇを１２０ｍｌの蒸留水に溶解した開始剤水溶液を添加し、窒素気流下７０℃、３時間攪拌を行ない、重合を完結させた後室温まで冷却し、［高分子量バインダー微粒子分散液１］を得た。
攪拌装置、冷却管、温度センサー及び窒素導入管を装着した５Ｌの４頭コルベンに
蒸留水 ２４００ｍｌ
ドデシル硫酸ナトリウム ２．８ｇ
スチレン ６２０ｇ
ｎ−ブチルアクリレート １２８ｇ
メタクリル酸 ５２ｇ
ｔｅｒｔ−ドデシルメルカプタン ２７．４ｇ
を添加し攪拌を行ないながら窒素気流下７０℃まで昇温した。ここで過硫酸カリウム１１．２ｇを６００ｍｌの蒸留水に溶解した開始剤水溶液を添加し、窒素気流下７０℃、３時間攪拌を行ない、重合を完結させた後室温まで冷却し、［低分子量バインダー微粒子分散液２］を得た。
【０１１４】
（トナーの合成）
攪拌装置、冷却管、温度センサーを備えた１Ｌセパラブルフラスコに、
［高分子量バインダー微粒子分散液１］ ４７．６ｇ
［低分子量バインダー微粒子分散液２］ １９０．５ｇ
［ワックス粒子水性分散液１］ ７．７ｇ
［着色剤分散液Ｉ］ ２６．７ｇ
蒸留水 ２５２．５ｍｌ
を加え混合攪拌した後、５Ｎ−水酸化ナトリウム水溶液を用いｐＨ＝９．５に調節を行なった。更に攪拌下、塩化ナトリウム５０ｇを蒸留水６００ｍｌに溶解した塩化ナトリウム水溶液、イソプロパノール７７ｍｌ及びフルオラードＦＣ−１７０Ｃ（住友３Ｍ社製：フッ素系ノニオン界面活性剤）１０ｍｇを１０ｍｌの蒸留水に溶解した界面活性剤水溶液を順次添加し、内温を８５℃まで上昇させ６時間反応を行なった後、室温まで冷却した。この反応液を５Ｎ−水酸化ナトリウム水溶液を用いｐＨ＝１３に調整した後、濾過を行ない、更に蒸留水に再懸濁を行ない濾過、再懸濁を繰り返し、洗浄を行なった後乾燥し、体積平均粒径Ｄｖ６．５８μｍ、個数平均粒径Ｄｎ５．３３μｍ、Ｄｖ／Ｄｎ１．２３の［トナー１１］を得た。こうして得た［トナー１１］と［キャリア１６］を実施例１と同様の方法により評価を行なった。
【０１１５】
＜比較例９＞
（顔料の分散液の調製）
ｎ−ドデシル硫酸ナトリウム：０．９重量部と、イオン交換水：１０重量部とを樹脂容器に仕込み、攪拌してｎ−ドデシル硫酸ナトリウムの水溶液を調製した。この水溶液を攪拌しながら、カーボンブラック：リーガル４００Ｒ（キャボット社製）１．２重量部を徐々に添加した。添加後１時間攪拌し、次いで、サンドグラインダーを用い、カーボンブラックの分散処理を２０時間にわたり連続して行なうことにより、［顔料分散液（Ｃ−１）］を得た。
【０１１６】
（界面活性剤の水溶液の調製）
アニオン系の界面活性剤であるドデシルベンゼンスルホン酸ナトリウム０．０５５重量部と、イオン交換水４重量部とをステンレスポットに仕込み、この系を室温で攪拌することにより［調製例（Ｓ−１）］を得た。また、ノニオン系の界面活性剤「ニューコール５６５Ｃ」（日本乳化剤社製）０．０１４重量部と、イオン交換水４重量部とをステンレスポットに仕込み、この系を室温で攪拌することにより、［調製例（Ｓ−２）］を得た。さらに、ノニオン系の界面活性剤「ＦＣ−１７０Ｃ」（住友スリーエム社製）１重量部と、イオン交換水１０００重量部とをガラスビーカーに仕込み、この系を室温で攪拌することにより、［調製例（Ｓ−３）］を得た。
【０１１７】
（重合開始剤の水溶液の調製）
重合開始剤である過硫酸カリウム（関東化学社製）２００．７重量部と、イオン交換水１２０００重量部とをホウロウポットに仕込み、この系を室温で攪拌することにより、［調製例（Ｐ−１）］を得た。また、重合開始剤である過硫酸カリウム（関東化学社製）２２３．８重量部と、イオン交換水１２０００重量部とをホウロウポットに仕込み、この系を室温で攪拌することにより、［調製例（Ｐ−２）］を得た。
【０１１８】
（塩化ナトリウムの水溶液の調製）
塩析剤である塩化ナトリウム（和光純薬社製）５．３６重量部と、イオン交換水２０重量部とをステンレスポットに仕込み、この系を室温で攪拌することにより、［塩化ナトリウム溶液（Ｎ）］を得た。
【０１１９】
（トナー粒子の製造）
温度センサ、冷却管、窒素導入装置および攪拌翼を備え、ガラスライニング処理が内面に施された内容積１００Ｌの反応釜に、［調製例（Ｓ−１）］４Ｌと、［調製例（Ｓ−２）］４Ｌとを仕込み、この系を室温で攪拌しながら、イオン交換水４４Ｌを添加し、この系を加熱した。系の温度が７０℃になったところで、［調製例（Ｐ−１）］１２Ｌを添加し、系の温度を７２℃±１℃に制御しながら、スチレン１２．１ｋｇとアクリル酸ｎ−ブチル２．８８ｋｇとメタクリル酸１．０４ｋｇとｔ−ドデシルメルカプタン９．０２ｇとからなる単量体混合物（Ｉ）を添加し、この系の温度を８０℃±１℃に制御しながら６時間にわたり攪拌を行なった。系の温度が４０℃以下となるまで冷却した後、この系に、［調製例（Ｓ−１）］４Ｌと、［調製例（Ｓ−２）］４Ｌとを添加し、この系を加熱した。系の温度が７０℃になったところで、［調製例（Ｐ−２）］１２Ｌを添加し、さらに、スチレン１１ｋｇとアクリル酸ｎ−ブチル４ｋｇとメタクリル酸１．０４ｋｇとｔ−ドデシルメルカプタン５４８ｇとからなる単量体混合物（II）を添加し、この系の温度を７５℃±２℃に制御しながら６時間にわたり攪拌を行ない、さらに、この系の温度を８０℃±２℃に制御しながら１２時間にわたり攪拌を行なった。系の温度が４０℃以下となるまで冷却して攪拌を停止した。ポールフィルターによりスケール（異物）を濾別除去することにより、高分子量樹脂を核とし、低分子量樹脂を殻とする複合樹脂微粒子（Ａ）の分散液［複合ラテックス（１−Ａ）］を得た。該複合樹脂微粒子（Ａ）の高分子量樹脂（核）のピーク分子量は２９，０００、低分子量樹脂（殻）のピーク分子量は１２，０００、複合樹脂微粒子（Ａ）の重量平均分子量は３４，０００であった。また、この複合樹脂微粒子（Ａ）の重量平均粒径は１５０ｎｍ、ガラス転移温度（Ｔｇ）は５８℃、軟化点は１２１℃であった。
温度センサ、冷却管、窒素導入装置、櫛形バッフルおよび攪拌翼（ファウドラー翼）を備え、ガラスライニング処理が内面に施された内容積１００Ｌの反応釜に、［調製例（Ｓ−１）］４Ｌと、［調製例（Ｓ−２）］とを仕込み、この系を室温で攪拌しながら、イオン交換水４４Ｌを添加し、この系を加熱した。系の温度が７０℃になったところで、［調製例（Ｐ−１）］１２Ｌを添加し、さらに、スチレン１１ｋｇとアクリル酸ｎ−ブチル４ｋｇとメタクリル酸１．０４ｋｇとｔ−ドデシルメルカプタン９．０２ｇとからなる単量体混合物を添加し、この系の温度を７２℃±２℃に制御しながら６時間にわたり攪拌を行ない、さらに、この系の温度を８０℃±２℃に制御しながら１２時間にわたり攪拌を行なった。系の温度が４０℃以下となるまで冷却して攪拌を停止した。ポールフィルターによりスケール（異物）を濾別除去することにより、樹脂微粒子（Ｂ）の分散液［ラテックス（１−Ｂ）］を得た。このラテックス（１−Ｂ）を構成する樹脂微粒子（Ｂ）のピーク分子量は３１０，０００、重量平均分子量は１９０，０００であった。また、この樹脂微粒子（Ｂ）の重量平均粒径は１３８ｎｍ、ガラス転移温度（Ｔｇ）は５８℃、軟化点は１２６℃であった。
温度センサ、冷却管、窒素導入装置、櫛形バッフルおよび攪拌翼（アンカー翼）を備えた内容積１００Ｌのステンレス製の反応釜に、［複合ラテックス（１−Ａ）］２０ｋｇと、［顔料分散液（Ｃ−１）］０．４ｋｇと、イオン交換水２０ｋｇとを仕込み、この系を室温で攪拌した。系の温度を４０℃まで加温し、塩化ナトリウム溶液（Ｎ）２０Ｌと、イソプロピルアルコール（関東化学社製）６ｋｇと、ノニオン系の界面活性剤「ＦＣ−１７０Ｃ」（住友スリーエム社製）１重量部と、イオン交換水１０００重量部とをガラスビーカーに仕込み、この系を室温で攪拌することにより、［調製例（Ｓ−３）］を得た。［調製例（Ｓ−３）］１Ｌとを、この順に添加した。この系を１０分間放置した後加熱を開始し、６０分間かけて８５℃まで昇温させ、８５℃±２℃で１時間にわたり攪拌を行なうことにより、複合樹脂微粒子（Ａ）と着色剤微粒子とを塩析／融着させて着色粒子（コア粒子）を形成した。次いで、８５℃±２℃の温度条件下で、［ラテックス（１−Ｂ）］５．２ｋｇと、ワックスエマルジョン（数平均分子量３，０００のポリプロピレンエマルジョン、数平均一次粒子径：１２０ｎｍ、固形分濃度：２９．９重量％）３．４１ｋｇとを添加し、さらに、８５℃±２℃で４．０時間にわたり攪拌を行なうことにより、着色粒子（コア粒子）の表面に、樹脂微粒子（Ｂ）およびポリプロピレン微粒子を塩析／融着させることによって付着させた。系の温度が４０℃以下となるまで冷却して攪拌を停止した後、目開き４５μｍのフィルターで凝集物を濾別除去することにより、トナー粒子の分散液を得た。次いで、この分散液を減圧濾過してウエットケーキ（トナー粒子の集合物）を得、これをイオン交換水で洗浄処理した。洗浄処理されたウエットケーキをヌッチェより取り出し、４０℃の送風乾燥機で１００時間かけて乾燥することにより、ブロック状のトナー粒子の集合物を得た。次いで、この集合物をヘンシェル粉砕機で解砕処理することにより、体積平均粒径Ｄｖ６．４５μｍ、個数平均粒径Ｄｎ５．３１μｍ、Ｄｖ／Ｄｎ１．２１の［トナー１２］を得た。こうして得た［トナー１２］と［キャリア１６］を実施例１と同様の方法により評価を行なった。
【０１２０】
＜比較例１０＞
ポリビニルアルコール（「ＰＶＡ−２３５」、（株）クラレ製）１部を水１００部に溶解した。これを［水相２］とする。実施例１において、［水相１］の代わりに［水相２］を使用した以外は、実施例１と同様にして［トナー１３］を得た。こうして得た［トナー１３］と［キャリア１６］を実施例１と同様の方法により評価を行なった。
【０１２１】
＜比較例１１＞
実施例１の超音波アルカリ洗浄回数を０回にした以外は実施例１と同様にして体積平均粒径Ｄｖ６．２１μｍ、個数平均粒径Ｄｎ５．３０μｍ、Ｄｖ／Ｄｎ１．１７、樹脂微粒子残存率３．５ｗｔ％の［トナー１４］を得た。こうして得た［トナー１４］と［キャリア１６］を実施例１と同様の方法により評価を行なった。
【０１２２】
【表１】

注）実施例１〜４、８及び９は参考例である。
【０１２３】
【表２】

注）実施例１〜４、８及び９は参考例である。
【０１２４】
トナー１０、１４については定着不良により連続印刷することができず、中止した。トナー１１、１２については微量な定着不良を発生していたが、１万枚後では帯電低下による地汚れの悪化により実用上使用できないレベルであったので、評価を中止した。トナー１３については粒径制御ができず、初期から地汚れが悪く、実用上使用できないレベルであったので、評価を中止した。キャリア９については、初期からキャリア付着が目標値を超え、実用上使用できないレベルであったので、評価を中止した。キャリア１０について、初期から地汚れが悪く、実用上使用できないレベルであったので、評価を中止した。キャリア１１、１３については、８０００枚時点で帯電量低下量及び抵抗変化量共に大きく、実用上使用できないレベルであったので、評価を中止した。キャリア１４、１５については、補給トナーの現像剤への分散が悪く、評価開始してまもなく地汚れ、トナー飛散が発生し、実用上使用できないレベルであったので、評価を中止した。
【０１２５】
【発明の効果】
以上、詳細かつ具体的な説明より明らかなように、本発明の現像剤は、地汚れ、トナー飛散、キャリア付着がなく、キャリア表面へのトナースペントの蓄積が少なく、長期にわたり安定した帯電量を得られるとともに、キャリア結着樹脂の大幅な膜削れが発生しないため、長期にわたり安定した電気抵抗が得られ、画像悪化が発生しない。更に、初期の印字品質が良好で、連続印字での画質の安定性にも優れ、安定したクリーニング性を有し、感光体、現像ローラ等に対するフィルミング汚染が防止された低温定着トナーが得られる。したがって、コピー枚数が増加するにつれ発生する複写画像の画質劣化が大幅に改善され、長期にわたり良好な画像を維持することができるという優れた効果を奏するものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrostatic charge image developing developer and a color developer for visualizing an electrostatic charge image formed on the surface of a photoreceptor in electrophotography and electrostatic recording, and an image forming method loaded with the developer. About.
[0002]
[Prior art]
Conventionally, in an electrophotographic apparatus, an electrostatic recording apparatus, or the like, an electric or magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a transfer material such as paper and then fixed by a method such as heating. Toner used for electrostatic image development is generally colored particles in which a binder, a colorant, a charge control agent, and other additives are contained in a binder resin. There is a suspension polymerization method. In the pulverization method, a colorant, a charge control agent, an offset preventing agent and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner. According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment. From this requirement, the melt-mixed composition must be made sufficiently brittle. Therefore, when the above composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, the particle size Fine powders of 5 μm or less and coarse powders of 20 μm or more must be removed by classification, which has the disadvantage that the toner yield becomes very low. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. The uneven dispersion of the compounding agent adversely affects the fluidity, developability, durability, image quality and the like of the toner.
[0003]
In recent years, in order to overcome these problems in the pulverization method, a toner production method by a suspension polymerization method has been proposed and implemented. A technique for producing a toner for developing an electrostatic latent image by a polymerization method is known. For example, toner particles are obtained by a suspension polymerization method. However, the toner particles obtained by the suspension polymerization method are spherical and have a drawback of poor cleaning properties. Development / transfer with a low image area ratio results in a small amount of residual toner, and poor cleaning does not pose a problem. However, images with a high image area ratio, such as photographic images, and untransferred images formed due to poor paper feed, etc. Toner may be generated on the photoconductor as untransferred toner, and if accumulated, the image may be soiled. In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. For this reason, a method is disclosed in which resin fine particles obtained by an emulsion polymerization method are associated to obtain amorphous toner particles (see, for example, Patent Document 1).
However, in the toner particles obtained by the emulsion polymerization method, a large amount of the surfactant remains not only on the surface but also inside the particles even after the water washing step, and the environmental stability of the toner charging is impaired. The amount distribution is widened, and the background stain of the obtained image becomes poor. Further, the remaining surfactant contaminates the photoreceptor, the charging roller, the developing roller, etc., and the original charging ability cannot be exhibited.
[0004]
On the other hand, in a fixing process by a contact heating method performed using a heating member such as a heat roller, the toner particles are required to release from the heating member (hereinafter referred to as “offset resistance”). Here, the offset resistance can be improved by the presence of a release agent on the toner particle surface. On the other hand, a method is disclosed in which not only the resin fine particles are contained in the toner particles but also the resin fine particles are unevenly distributed on the surface of the toner particles, thereby improving the offset resistance (for example, Patent Documents). 2 and 3). However, the minimum fixing temperature increases, and the low temperature fixing property, that is, the energy saving fixing property is not sufficient.
[0005]
In the method of obtaining irregularly shaped toner particles by associating resin fine particles obtained by the emulsion polymerization method, the following problems occur.
When the release agent fine particles are associated with each other in order to improve the offset resistance, the release agent fine particles are taken into the toner particles, and as a result, the offset resistance cannot be sufficiently improved. . Resin fine particles, release agent fine particles, colorant fine particles, etc. are randomly fused to constitute toner particles, so there is a variation in composition (content ratio of constituent components) and molecular weight of constituent resins among the obtained toner particles. As a result, the toner particles have different surface characteristics, and a stable image cannot be formed over a long period of time. Furthermore, in a low-temperature fixing system that requires low-temperature fixing, fixing inhibition occurs due to resin fine particles unevenly distributed on the toner surface, and a fixing temperature range cannot be secured.
[0006]
On the other hand, with respect to the carrier, toner component filming prevention on the carrier surface, formation of a uniform carrier surface, prevention of surface oxidation, prevention of moisture sensitivity deterioration, extension of developer life, prevention of carrier adhesion to the photoreceptor surface, photosensitivity For the purpose of protecting the body from scratches or abrasion by the carrier, controlling the polarity of the charge, or adjusting the amount of charge, a hard and high-strength coating layer is usually provided by coating with an appropriate resin material. For example, those coated with a specific resin material (for example, see Patent Document 4), those in which various additives are added to the coating layer (for example, see Patent Documents 5 to 11), and the carrier surface. Using additives with additives attached to them (for example, see Patent Document 12), and using a coating film containing conductive particles larger than the coating film thickness For example, see Patent Document 13.) And the like have been disclosed.
Patent Document 14 describes that a benzoguanamine-n-butyl alcohol-formaldehyde copolymer is used as a main component for a carrier coating material, and Patent Document 15 describes a carrier-coated cross-linked product of a melamine resin and an acrylic resin. Patent Document 16 describes that the carrier scattering and carrier adhesion to the surface of the photosensitive member are prevented, and that the spikes that do not easily collapse are formed, and the photosensitivity by rubbing with a hard magnetic brush is described. In order to prevent scratches on the body surface, a core material having a volume average particle diameter of 25 to 45 μm is coated with a silicon resin or polystyrene resin, and an average void diameter is 10 to 20 μm and a small particle diameter particle having a volume average particle diameter of 22 μm or less is contained. The rate is less than 1%, the magnetization in a magnetic field of 1 KOe is 67 to 88 emu / g, and the difference in magnetization between the flying object and the main body is 10 emu at 1 KOe. g or less of the magnetic carrier is described.
[0007]
However, the carrier described in Patent Document 11 has a magnetic carrier core material having an average particle diameter of 20 to 100 μm (for example, 50 μm (Examples 1, 2, and 3), and inorganic fine particles in an amount of 0.001 to 1 wt% with respect to the carrier core material. Preferably coated with 0.01 to 0.5 wt% styrene-acrylic resin, the magnetic properties of the magnetic carrier core material are unknown, the particle size of the inorganic fine particles, and the ratio of the amount to the coating resin is unknown The thickness of the coating layer of styrene-acrylic resin is also unclear.The carrier described in Patent Document 12 has an average particle size of 40 μm or more (for example, 48 μm (Example 1), 46 μm (Example 2), 43 μm (implemented). Example 3)) magnetic carrier particles-resin dispersion type (magnetic fine particles; binder resin ratio 30; 70-95; 5), preferably coercive force in a magnetic field of 5000 Oe is 30 O. Or more, and the volume resistivity of 10¹²Covered with a styrene-n-butyl methacrylate resin containing conductive fine particles of Ωcm or less in an amount of 0.01 to 10 wt%, preferably 5% or less, based on the coating resin (the particle diameter of the conductive fine particles is preferably 0.1 μm or less). The carrier described in Patent Document 13 is coated with a magnetic carrier particle-resin dispersion type core material having a particle size of preferably 30 to 150 μm, for example 50 μm, and conductive fine particles. 0.01 to 50 wt%, preferably around 25% of the resin (the particle diameter of the conductive fine particles is the same as or larger than the film thickness of the resin coating layer within 3 μm) In addition, the layer thickness is preferably only 0.1 to 10 μm coated with styrene-methacrylate resin, and the degree of magnetization of the carrier core material is unknown, and the carrier described in Patent Document 14 has a particle size of Preferably, 7.3 parts of acrylic resin per 1000 parts of Cu-Zn ferrite particle core of 20 to 120 μm, for example 50 μm, and 16 parts of benzoguanamine-n-butyl alcohol / formaldehyde cocondensate for cross-linking this (Examples) 1, 2), for example, 7.3 parts of acrylic resin and 5.0 parts of MMA / perfluorooctyl methacrylate copolymer per 1000 parts of 50 μm Cu—Zn ferrite particle core and benzoguanamine-n— for crosslinking them 16 parts of butyl alcohol / formaldehyde cocondensate (Example 3), for example, 20 parts of acrylic resin per 1000 parts of 50 μm Cu—Zn ferrite particle core material (unknown magnetizing force) and benzoguanamine-n-butyl for crosslinking this 9.0 parts of alcohol-formaldehyde cocondensate (Example 4) is merely coated with each, and the magnetizing force of the Cu-Zn ferrite particle core is unknown, and the carrier described in Patent Document 15 is disclosed in JP-A-60-57352 and JP-A-60-57352. In order to improve the developer blocking and insufficient durability and moisture resistance in resin-coated carriers as described in JP-A-62-262057, the saturation magnetization is preferably 35 to 70 emu / g, and the particle size is preferably Although a ferrite particle core material of 30 to 150 μm, for example 80 μm, is only obtained by baking and crosslinking an acrylic resin and a melamine resin, the benzoguanamine monomer and formaldehyde copolymer film used in the carrier described in Patent Document 16 have high hardness. It has poor elasticity and the polystyrene resin film is highly brittle.
[0008]
In this case, the carrier particles can be smoothly cleaned with the toner surface, including a good mixing property and charge imparting to the toner, and a charge imparting and adhesion resistance to the surface of the photoreceptor. Achieved, if it is a magnetic carrier, satisfies the smooth conveyance with the developing sleeve and the soft spike that does not damage the photoconductor surface on the other side, with the rich spike that can supply the required amount of toner sufficiently. Therefore, it is desirable that the resin has an appropriate particle size distribution and a certain range of average particle diameter, and also has an appropriate magnetization, and the coating resin has high adhesiveness and low brittleness so that it can be easily peeled off from the carrier core material. However, it is necessary to have a hardness that does not damage the surface of the photoreceptor, and on the other hand, the toner component film does not form a strong adhesion (filming) on the surface. It is desirable to satisfy two contradictory properties of having a low degree of poor adhesion at the same time, and these properties are preferably maintained for a long period of time. In the case of high cohesion and adhesiveness at normal temperature), it is increasingly difficult to obtain a developer and carrier that simultaneously satisfy these multiple properties. Both of the above conventional techniques have advantages and disadvantages. What is satisfactory is not achieved.
[0009]
Furthermore, there are many needs for space saving of devices, and in recent years, many devices that have been miniaturized have been put on the market. In the case of such an apparatus, since the developing device is also downsized, the developing device has a simple stirring structure and has a small stirring margin. As a result, the stirring of the developer is lowered, particularly the dispersion (mixing) speed of the replenishing toner is lowered, and the uniform dispersion (mixing) property is deteriorated, resulting in problems such as toner scattering from the developing roller and ground contamination. Furthermore, although it is not necessarily the toner obtained by the polymerization method, the spherical toner is caused by its shape, which causes a problem that it is difficult to mix with the carrier.
[0010]
From the above, durability and carrier adhesion suppression are still insufficient. Concerning durability, there are problems such as spent toner on the carrier surface, destabilization of the charge amount, and reduction of the coating layer due to film removal of the coating resin and accompanying resistance reduction. Although it can be obtained, the image quality of the copy image decreases as the number of copies increases, which is a problem. Further, toner scattering and background contamination due to difficulty in mixing the carrier and the toner are also problems, and improvement is necessary.
[0011]
[Patent Document 1]
Japanese Patent No. 2537503 (Claims on the first page, first column, first line to second column, sixth line)
[Patent Document 2]
Japanese Patent Laid-Open No. 2000-292773 (claims on page 2, column 1, line 1 to column 2, line 30)
[Patent Document 3]
JP 2000-292978 A (Claims on page 2, column 1, line 1 to page 2, column 3, line 22)
[Patent Document 4]
Japanese Patent Application Laid-Open No. 58-108548 (Claim 1st page, lower left column, lines 4 to 6)
[Patent Document 5]
Japanese Patent Application Laid-Open No. 54-1555048 (Claim 1st page, lower left column, lines 4 to 10)
[Patent Document 6]
Japanese Patent Application Laid-Open No. 57-40267 (Claim 1 on page 1, lower left column, lines 4 to 8)
[Patent Document 7]
Japanese Patent Application Laid-Open No. 58-108549 (the first page, lower left column, claims 4 to 7)
[Patent Document 8]
Japanese Patent Application Laid-Open No. 59-166968 (Claim 1st page, lower left column, lines 4 to 7)
[Patent Document 9]
Japanese Examined Patent Publication No. 1-19584 (claims on page 1, column 1, lines 1 to 7)
[Patent Document 10]
Japanese Examined Patent Publication No. 3-628 (Claim 1 on page 1, column 1, lines 1 to 6)
[Patent Document 11]
Japanese Patent Laid-Open No. 6-202381 (Claim 2 on page 2, column 1, lines 1 to 12)
[Patent Document 12]
Japanese Patent Application Laid-Open No. 5-273789 (Claim 2 on page 1, column 1, lines 1 to 9)
[Patent Document 13]
JP-A-9-160304 (Claim 2 on page 2, column 1, lines 1 to 45)
[Patent Document 14]
JP-A-8-6307 (Claim 2 on page 2, column 1, lines 1 to 12)
[Patent Document 15]
Japanese Patent No. 2683624 (Claim 1 on page 1, column 1, lines 1 to 7)
[Patent Document 16]
Japanese Patent Laid-Open No. 2002-296846 (page 2, column 1, line 1 to line 12 claims, paragraph [0030])
[0012]
[Problems to be solved by the invention]
The present invention has been made in view of the above problems, and an object of the present invention is to cope with a low-temperature fixing system, maintain good cleaning properties, have good offset resistance, and contaminate a fixing device and an image. It is to provide a developer for developing an electrostatic charge image and a developer for color. Another object of the present invention is to provide a developer for developing an electrostatic charge image and a developer for color which can form a visible image having a sharp charge amount distribution and good sharpness over a long period of time. Another object of the present invention is to provide a carrier and a developer with less toner scattering, background contamination, and carrier adhesion.
[0013]
[Means for Solving the Problems]
  The above problem is that (1) “in a carrier having a coating layer composed of at least a binder resin and particles, the particle diameter (D) and the film thickness (h) of the binder resin layer are 1 <[D / h] <10, the magnetization of the carrier at 1 kOe is in the range of 40 to 80 emu / g, and the average particle diameter Dv of the carrier is in the range of 20 to 70 μm.In addition, the binder resin of the carrier coating layer contains at least an acrylic resin and a silicon resin, the ratio of the acrylic resin is 10 to 90 wt%, and the total content of particles contained in the coating layer is 40-95 wt% of coating film composition componentA carrier for developing an electrostatic charge image ”, (2)“ a content of 63% or less of the average particle diameter Dv is 1 wt%Less thanThe electrostatic charge image developing carrier according to item (1), wherein:(3)“The at least each resin in the coating layer made of an acrylic resin and a silicon resin has a layer structure.(1)Term or number(2)The carrier for developing an electrostatic image according to the item ",(4)“The particles contained in the coating layer are one or more of alumina, titanium oxide, zinc oxide, or those obtained by subjecting them to surface treatment.(3)The electrostatic charge image developing carrier according to any one of the items is solved.
  In addition, the above problem is(5)“A solution or dispersion formed by dissolving or dispersing a toner composition containing a toner binder composed of a modified polyester resin capable of reacting with active hydrogen in an organic solvent is used as a crosslinking agent in an aqueous medium containing resin fine particles. And / or a toner obtained by reacting with an extender, removing the solvent from the obtained dispersion, and washing and desorbing the resin fine particles adhering to the toner surface. A toner for developing an electrostatic charge image in which the residual ratio of the resin fine particles remaining on the toner particle surface measured by a meter to the toner particles is 5 wt% or less with respect to the toner particles, and the items (1) to (1) First(4)An electrostatic charge image developing developer, comprising the carrier according to any one of Items 1 to 3,(6)“The developer toner is a full-color toner.(5)The developer for developing an electrostatic image according to the item ",(7)“The toner binder contains an unmodified polyester resin together with a modified polyester resin, and the weight ratio of the modified polyester resin to the unmodified polyester resin is 5/95 to 80/20. Said first(5)Term or number(6)The developer for developing an electrostatic image according to the item ",(8)“The toner binder has an acid value of 1 to 30 mg KOH / g.(5)Item to No.(7)The developer for developing an electrostatic image according to any one of the items ",(9)“The toner binder has a glass transition point (Tg) of 50 to 70 ° C.(5)Item to No.(8)The developer for developing an electrostatic image according to any one of the items ",(10)“The resin fine particles are made of at least one resin selected from vinyl resins, polyurethane resins, epoxy resins, and polyester resins.(5)Item to No.(9)The developer for developing an electrostatic image according to any one of the items ",(11)“The resin fine particles have an average particle diameter of 5 to 2000 nm.(5)Item to No.(10)The developer for developing an electrostatic image according to any one of the items ",(12)“The toner particles have a volume average particle diameter of 4 to 8 μm.(5)Item to No.(11)The developer for developing an electrostatic image according to any one of the items ",(13)“The ratio Dv / Dn of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner particles is 1.25 or less.(5)Item to No.(12)The developer for developing an electrostatic image according to any one of the items ",(14)“The average circularity of the toner particles is 0.94 to 0.99.(5)Item to No.(13)The developer for developing an electrostatic image according to any one of the items ",(15)“The step of removing the solvent from the dispersion is performed under reduced pressure and / or heating conditions.(5)Item to No.(14)The developer for developing an electrostatic image according to any one of the items ",(16)“The step of removing the solvent from the dispersion is performed by filtration.(5)Item to No.(15)The electrostatic charge image developing developer according to any one of the items above.
  In addition, the above problem is(17)"The first(5)Item to No.(16)This is solved by a container containing the developer for developing an electrostatic image according to any one of the items.
  In addition, the above problem is(18)"The first(5)Item to No.(16)An image forming method characterized in that the developer for developing an electrostatic charge image according to any one of the items is used.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, the present invention will be described in more detail.
  As a result of continuous studies to solve the above-described problems of the prior art, the present inventors have determined that the particle diameter (D) and the binder resin in a carrier having a coating film composed of at least a binder resin and particles. The film thickness (h) is 1 <[D / h] <10, the magnetization of the carrier at 1 kOe is in the range of 40 to 80 emu / g, and the average particle diameter Dv of the carrier is in the range of 20 to 70 μm.In addition, the binder resin of the carrier coating layer contains at least an acrylic resin and a silicon resin, the ratio of the acrylic resin is 10 to 90 wt%, and the total content of particles contained in the coating layer is 40-95 wt% of coating film composition componentIt has been found that the improvement effect is remarkable by using the electrostatic charge image developing carrier.
[0015]
Specifically, by setting [D / h] within the above range, the carrier surface becomes uneven, the biting between the carrier and the toner increases, and the magnetization at 1 kOe is in the range of 40 to 80 emu / g. Thus, the holding force between the carrier particles is properly maintained, so that the toner is quickly dispersed (mixed) in the carrier or developer. When [D / h] is 1 or less, since the particles are buried in the binder resin, the carrier surface does not have an uneven shape, and the effect cannot be obtained sufficiently. Further, when [D / h] is 10 or more, the contact area between the particles and the binder resin is small, so that a sufficient binding force cannot be obtained and the particles are easily detached, which is not preferable. On the other hand, when the magnetization is less than 40 emu / g, since the coercive force between the carrier particles is small, the dispersion (mixing) of the toner in the carrier or the developer cannot be obtained quickly, which is not preferable. On the other hand, if it exceeds 80 emu / g, the retention force between the carrier particles becomes too large, so that it becomes difficult for the toner to intervene between the carrier particles, and the effect cannot be obtained efficiently.
[0016]
When the average carrier particle diameter Dv exceeds 70 μm, the ears formed by the developer become thick, so that the reproducibility of sharp images is lowered, and the specific surface area is small, so the ability to impart charge to the toner is poor. This is not preferable because defects due to poor charging such as background fogging occur. On the other hand, when the particle size is less than 20 μm, the magnetization of one carrier of fine particles in the particle size distribution becomes very small, which is not preferable because the carrier adheres to the surface of the photoreceptor.
In addition, the carrier core material referred to in the present invention may be a known one as a two-component carrier for electrophotography, for example, appropriately selected according to the use and purpose of use of the carrier such as ferrite, magnetite, iron and nickel. Use it.
[0017]
Furthermore, the effects obtained by setting [D / h] in the above range may be as follows.
By setting [D / h] within the above range, the particles are more convex than the coating film. Therefore, by stirring to triboelectrically charge the developer, friction with toner or friction between carriers is achieved. Contact with strong impact on the binder resin can be relaxed. As a result, it is possible to prevent spent toner on the carrier, and to suppress film abrasion of the binder resin, which is a place where charging occurs.
[0018]
  Further, the content of 63% or less of the average particle diameter Dv is 1 wt%.Less thanTherefore, the effect is remarkable. First, the 63% diameter will be described. The 63% diameter means a value obtained by multiplying Dv by 0.63. Further, when the content of the 63% diameter or less is 1 wt% or more, there is a large amount of fine powder in the particle size distribution, which is not preferable because carrier adhesion tends to occur.
[0019]
Furthermore, the improvement effect is remarkable because the binder resin of the carrier coating layer contains at least an acrylic resin. This is because acrylic resin has a strong adhesive property and low brittleness, so it has a very excellent property of wear resistance, and it is difficult for deterioration such as coating film scraping and film peeling to occur. 1 <[D / h] < 10 can be maintained stably.
[0020]
The acrylic resin here refers to a resin having an acrylic component and is not particularly limited. In addition, it is possible to use the acrylic resin alone, but it is also possible to use at least one other component that undergoes a crosslinking reaction at the same time. Examples of the other component that undergoes a crosslinking reaction include an amino resin and an acidic catalyst, but are not limited thereto. The amino resin here refers to guanamine, melamine resin and the like, but is not limited thereto. Moreover, what has a catalytic action can be used with the acidic catalyst said here. For example, it has a reactive group such as a fully alkylated type, a methylol group type, an imino group type, and a methylol / imino group type, but is not limited thereto.
[0021]
  Silicone resin has poor compatibility with other resins, but its compatibility with acrylic resin is relatively good.In the present invention,Use a mixture of bothTheHowever, at least in the coating layer made of acrylic resin and silicon resin, each resin has a layer structure, and the improvement effect is remarkable (relatively good adhesion at the interface between the two layers is acrylic resin). This is also attributed to the relatively good compatibility between the resin and silicon resin). This is because, as mentioned above, acrylic resin has a very excellent property of abrasion resistance because of its strong adhesiveness and low brittleness, but on the other hand, since it has a high surface energy, in combination with a toner that is easy to spend, Problems such as a decrease in charge amount due to accumulation of toner component spent may occur. In this case, this problem can be solved by using together a silicon resin that has an effect that it is difficult to spend the toner component due to the low surface energy and the accumulation of the spent component is difficult to progress due to film scraping. However, since silicon resin has weak adhesiveness and high brittleness, it also has a weak point of poor wear resistance. Therefore, it is important to obtain a good balance between the properties of these two resins. It is possible to obtain a coating film having the property.
[0022]
The term “silicon resin” as used herein refers to a generally known silicone resin, and examples include straight silicone consisting only of organosilosan bonds, and silicone resins modified with alkyd, polyester, epoxy, acrylic, urethane, and the like. However, it is not limited to this. Examples of commercially available straight silicon resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical, SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicon. In this case, it is possible to use the silicon resin alone, but it is also possible to simultaneously use other components that undergo a crosslinking reaction, charge amount adjusting components, and the like. Further, as modified silicone resin, KR206 (alkyd modified), KR5208 (acryl modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical, SR2115 (epoxy modified) manufactured by Toray Dow Corning Silicon Co., Ltd. , SR2110 (alkyd modified) and the like.
[0023]
  Furthermore,In the present invention,In the coating layer made of at least acrylic resin and silicon resin, the acrylic resin ratio is 10 to 90 wt%.ThisThus, the improvement effect is remarkable. This is not preferable when the ratio of the acrylic resin is less than 10 wt%, because most of the coating layer occupies the silicon resin component, resulting in deterioration of wear resistance due to the high brittleness that is a defect of the silicon resin. On the other hand, when the ratio of the acrylic resin exceeds 90 wt%, most of the coating layer occupies the acrylic resin component. Therefore, the toner component spent due to the high surface energy and the difficulty of film scraping, which are disadvantages of the acrylic resin, are caused. Is unfavorable as it accumulates.
[0024]
Further, in the coating layer made of at least an acrylic resin and a silicon resin, each resin has a layer structure, so that the improvement effect is remarkable. There are several functions required for the coating film of the carrier, such as the spent resistance function, the wear resistance function, and the adhesive function. However, there is no material that can satisfy these functions with one material. There is something with a good function. Therefore, it is possible to form a coating film having an excellent function by combining several kinds of materials having an excellent function. Specifically, by using an acrylic resin for the adhesive layer with the core material, the adhesion between the core material and the coating film is strengthened, and a silicon resin layer is provided on the acrylic resin to provide a resistance to toner components. Although it exhibits good spent properties, it is not limited to this.
[0025]
  Furthermore,In the present invention,The total content of particles contained in the coating layer is 40 to 95 wt% of the coating film composition componentThisThus, the improvement effect is remarkable. This is because when the amount is less than 40 wt%, since the proportion of the particles is smaller than the proportion of the binder resin on the surface of the carrier particles, the effect of relieving contact with a strong impact on the binder resin is achieved. This is not preferable because it is small and sufficient durability cannot be obtained. On the other hand, when the amount is more than 95 wt%, the proportion of the particles is excessive as compared with the proportion of the binder resin on the carrier surface, so that the proportion of the binder resin that is a charging occurrence point is insufficient. , Can not demonstrate sufficient charging ability. In addition, since the amount of particles is too large compared to the amount of binder resin, the ability to hold particles by the binder resin becomes insufficient, and the particles are easily detached, which is not preferable because sufficient durability cannot be obtained.
[0026]
Moreover, although it is Unexamined-Japanese-Patent No. 9-160304 similar to this invention mentioned previously, it differs from this invention about the content rate range of particle | grains, "0.01-50 wt% of coat resin", ie, this When converted to the content calculation method of the present invention, it is “0.01 to 33.33 wt% of the coating film composition component”. In this case, the durability is improved as compared with the conventional case. Since the proportion of the particles is smaller than the proportion of the binder resin on the surface, the effect of alleviating contact with a strong impact on the binder resin is small, and sufficient durability cannot be obtained.
[0027]
Furthermore, the improvement effect is remarkable when the particle | grains contained in a coating layer are any one of alumina, titanium oxide, zinc oxide, or those which surface-treated them, or one or more. Since the effect is obtained by keeping the carrier surface in an uneven shape, if the particles are easily crushed or worn by the external force applied to the carrier surface, this effect cannot be maintained over a long period of time and is stable. It is not preferable because quality cannot be obtained. Since the particles mentioned here have tough properties, they are strong against this external force, do not cause crack wear, and can maintain the coating layer protecting effect over a long period of time. Further, the particle size is preferably 5 μm or less, and the location of the particles in the coating film is preferably present in the acrylic resin. The reason is that the particles can be held for a long time due to the strong adhesiveness of the acrylic resin, but it is not always necessary to be present in the acrylic resin.
[0028]
It is also effective to contain carbon black in the coating resin as necessary. The effect is remarkable, and it can be used as a regulator that lowers the resistance when the resistance is high in the case of a coating film composed of only the coating resin or the coating resin and particles. In general, when a carrier having a high resistance is used as a developer, on the image surface of a large area of a copy image, the image density at the center is very thin and only the edges are expressed deeply, so-called edge effect is sharply used. It becomes the image that was. In addition, when the image is a character or a thin line, the image is clear due to the edge effect. However, when the image is halftone, there is a defect that the image is very reproducible. Therefore, it is possible to obtain an excellent image by appropriately using the carbon book.
[0029]
Furthermore, it can also be used for a color carrier. In the case of a carrier for a color developer, a scraped film is mixed in the image, and if the scraped film has a dark color due to reasons such as containing carbon black, it becomes a defective image because it clearly stands out in the image, In the present invention, the coating resin has an acrylic resin, and as described above, since the acrylic resin has a property of being highly adhesive and difficult to scrape, the carbon black can be firmly held in the coating resin, and the resin This is because the carbon black is hardly detached from the carrier because it is difficult to scrape itself. In particular, the effect is great by dispersing carbon black in an acrylic resin. In the layer structure coating film, the effect is great by forming an acrylic resin film in which carbon black is dispersed in the lower layer and a silicon resin layer not containing carbon black in the upper layer. The carbon black mentioned here can be any of those commonly used for carriers or toners. On the other hand, in the case of a highly brittle resin such as silicon resin that can be easily scraped, if carbon black is contained in the coating resin, a scraped black film appears in the image, which becomes a defective image and cannot be used.
[0030]
Further, a solution or a dispersion formed by dissolving or dispersing a toner composition containing a carrier of the present invention and a toner binder composed of a modified polyester resin capable of reacting with active hydrogen in an organic solvent is formed into resin fine particles. In a toner obtained by reacting with a crosslinking agent and / or an extender in an aqueous medium containing the solvent, removing the solvent from the obtained dispersion, and washing and desorbing the resin fine particles adhering to the toner surface A static charge image developing toner having a residual ratio of the resin fine particles remaining on the surface of the toner particles measured by a gas chromatograph (mass spectrometry) to the toner particles of 5 wt% or less with respect to the toner particles. The improvement effect is remarkable by the developer for charge image development. By adopting such a configuration, it is possible to obtain cleaning performance, compatibility with a low-temperature fixing system, anti-offset properties, sharpness of charge amount distribution, and maintainability of a sharp image over a long period of time. The characteristics of the carrier and the toner are established by this combination, and will be described in detail below.
Further, since the developer toner is a full color toner, the improvement effect is remarkable.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.
[0031]
(Residual rate of resin fine particles)
The resin fine particles in the toner of the present invention are added in the production process in order to control the toner shape (circularity, particle size distribution, etc.) described later, but the residual ratio of the resin fine particles unevenly distributed on the toner surface to the toner particles is 5 wt. It is important that the residual ratio of resin fine particles is 5 wt% or more. If the resin fine particle residual ratio is 5 wt% or more, the resin fine particles inhibit the adhesiveness to the fixing paper, and the minimum fixing temperature increases. Therefore, since a sufficient fixing temperature range cannot be secured, there is a problem that fixing cannot be performed by a copying machine of a low-temperature fixing system, or the fixed image is peeled off when rubbed. In addition, the resin fine particles inhibit the triboelectric chargeability, resulting in poor charging of the toner, resulting in background smearing of the obtained image and toner scattering at the developing portion, causing toner contamination of each member / part.
[0032]
The residual ratio of the resin fine particles can be measured by analyzing a substance caused by the resin fine particles without using the toner particles with a pyrolysis gas chromatograph (mass spectrometry), and calculating from the peak area. The residual ratio of the resin fine particles is expressed by the following formula.
[Expression 1]
R = A / B × 100
R: Residual rate of resin fine particles
A: Weight of resin fine particles on toner particles
B: Toner particle weight
[0033]
(Circularity and circularity distribution)
It is important that the toner in the present invention has a specific shape and shape distribution. An toner having an average circularity of 0.94 or less and an irregular shape that is too far from a spherical shape has satisfactory transferability and dust. A high-quality image with no image cannot be obtained. As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. . Toner having an average circularity of 0.94 to 0.99, which is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle, has high reproducibility with an appropriate density reproducibility. It was found to be effective for forming a clear image. More preferably, particles having an average circularity of 0.945 to 0.985 and a circularity of less than 0.94 are 10% or less. In addition, when the average circularity is 0.99 or more, in a system employing blade cleaning or the like, a cleaning failure occurs on the photosensitive member or the transfer belt, causing stain on the image. For example, development / transfer with a low image area ratio results in a small amount of residual toner and poor cleaning does not pose a problem, but images with a high image area ratio such as photographic images, and untransferred images due to poor paper feed, etc. The formed toner may be generated as a transfer residual toner on the photoconductor, and if accumulated, the image may be soiled. In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. This value can be measured as an average circularity by a flow type particle image analyzer FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .
[0034]
[Dv / Dn (ratio of volume average particle diameter / number average particle diameter)]
The toner has a volume average particle diameter (Dv) of 4 to 8 μm and a ratio (Dv / Dn) to the number average particle diameter (Dn) of 1.25 or less, preferably 1.10 to 1.25. The toner has excellent heat resistance, low-temperature fixability, and hot offset resistance, particularly excellent image gloss when used in full-color copiers, etc. Even if the balance is performed, the fluctuation of the toner particle diameter in the developer is reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. Even when used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner is filmed on the developing roller and the toner is thinned. The toner was not fused to a member such as a blade, and good and stable developability and images were obtained even when the developing device was used (stirred) for a long time. 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 properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced, or the one-component development is performed. When used as an agent, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur. Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention.
On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large.
It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25. Further, when the volume average particle size / number average particle size is smaller than 1.10, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and uniformizing the charge amount, but the toner cannot be sufficiently charged. As a result, it became clear that the cleaning property may be deteriorated.
[0035]
[Modified polyester resin capable of reacting with active hydrogen (MPE)]
Examples of the reactive modified polyester resin (RMPE) capable of reacting with active hydrogen include a polyester prepolymer (A) having an isocyanate group. Examples of the prepolymer (A) include a polycondensate of a polyol (PO) and a polycarboxylic acid (PC) and a polyisocyanate (PIC) reacted with a polyester having active hydrogen. Examples of the group containing active hydrogen in the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.
Modified polyester (MPE) such as urea-modified polyester is easy to adjust the molecular weight of its polymer component, and is a dry toner, especially oil-less low-temperature fixing characteristics (extensive releasability without a mechanism for applying a release oil to a fixing heating medium) And fixing property). Particularly, a polyester prepolymer whose end is modified with urea can suppress adhesion to a heating medium for fixing while maintaining high fluidity and transparency in the fixing temperature range of the unmodified polyester resin itself.
[0036]
Examples of the polyol (PO) include diol (DIO) and trivalent or higher polyol (TO), and DIO alone or a mixture of DIO and a small amount of TO is preferable.
Examples of the diol 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-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) ); Adducts of alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) of the above alicyclic diols; Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, 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. It is a combined use.
[0037]
Examples of the trivalent or higher polyol (TO) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or higher phenols (Tris) Phenol PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or more polyphenols.
Examples of the polycarboxylic acid (PC) include dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC), and DIC alone or a mixture of DIC and a small amount of TC is preferable.
Dicarboxylic acids include alkylene dicarboxylic 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.) ) And the like. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher valent polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
In addition, as polycarboxylic acid, you may make it react with a polyol using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.
The ratio of the polyol (PO) and the polycarboxylic acid (PC) is usually 2/1 to 1/1, as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH], preferably 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.
[0038]
As polyisocyanate (PIC), aliphatic polyisocyanate (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanate (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactams, etc. And a combination of two or more of these.
The ratio of the polyisocyanate (PIC) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1.
When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, in the case of a urea-modified polyester, the urea content in the polyester becomes low and the hot offset resistance deteriorates. The content of the polyisocyanate (PIC) component in the polyester 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. %. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. If it is less than 1 per molecule, the molecular weight of the modified polyester will be low, and the hot offset resistance will deteriorate.
[0039]
In the present invention, a urea-modified polyester that is preferably used as a toner binder can be obtained by a reaction between a polyester prepolymer (A) having an isocyanate group and an amine (B).
As amines (B), diamine (B1), triamine or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and amino groups of (B1) to (B5) (B6) etc. that are blocked.
Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diamines). Cyclohexane, isophoronediamine, etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. As (B6) which blocked the amino group of (B1) to (B5), ketimine compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of (B1) to (B5), And oxazolyzone compounds. Among these amines (B), preferred are (B1) and a mixture of (B1) and a small amount of (B2).
[0040]
Furthermore, the molecular weight of a modified polyester such as urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).
The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of a modified polyester such as urea-modified polyester (UMPE) becomes low, and the hot offset resistance deteriorates. In the present invention, the polyester modified with urea bonds (UMPE) may contain urethane bonds as well as urea bonds. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.
As a crosslinking agent or an extender for the modified polyester used in the present invention, an active hydrogen compound capable of reacting with a reactive group such as an isocyanate group, preferably the amines (B) can be used.
[0041]
The modified polyester such as urea-modified polyester (UMPE) used as a toner binder in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester 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 such as urea-modified polyester is not particularly limited when the unmodified polyester (PE) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. . In the case of the modified polyester alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.
[0042]
[Unmodified polyester (PE)]
In the present invention, the modified polyester (MPE) can be used not only alone, but also with the MPE, unmodified polyester (PE) can be contained as a toner binder component. The combined use of PE improves low-temperature fixability and gloss when used in a full-color device, and is preferable to single use. Examples of PE include polycondensates of polyol (PO) and polycarboxylic acid (PC) similar to those used in the modified polyester such as UMPE, and preferred ones are the same as in the case of modified polyester. . In addition, PE may be modified not only with unmodified polyester but also with a chemical bond other than a urea bond, for example, with a urethane bond. It is preferable that MPE and PE are at least partially compatible in terms of low-temperature fixability and hot offset resistance. Therefore, a similar composition is preferable for the polyester component of MPE and PE. When PE is contained, the weight ratio of MPE to PE is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, and particularly preferably 7/93. ~ 20/80. If the weight ratio of MPE is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The peak molecular weight of PE is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 30000, low-temperature fixability will deteriorate. The hydroxyl value of PE 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 both heat-resistant storage stability and low-temperature fixability. The acid value of PE is usually 1-30, preferably 5-20. By having an acid value, it tends to be negatively charged.
[0043]
In the present invention, the glass transition point (Tg) of the toner binder is usually 50 to 70 ° C., preferably 55 to 65 ° C. If the temperature is less 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 coexistence of the modified polyester resin, the dry toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester toners. The storage elastic modulus of the toner binder is 10,000 dyne / cm at a measurement frequency of 20 Hz.²The temperature (TG ′) at which is reached is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the toner binder, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or lower, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, TG ′ is preferably higher than Tη 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. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.
[0044]
(Coloring agent)
As the colorant used in the present invention, known dyes and pigments can be used. Examples of such materials include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, poly Azo 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, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faucet Red, Parachlor Ortho Nitroaniline Red, risor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome -Million, 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, Bituminous Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Ant Laquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.
[0045]
The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin kneaded with the master batch production or the master batch, in addition to the modified and unmodified polyester resins listed above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substitution products thereof. Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Polymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α -Methyl chloromethacrylate copolymer Styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein 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. wear.
[0046]
This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet cake of a colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture 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.
[0047]
(Release agent)
Further, the toner of the present invention may contain a wax together with a toner binder and a colorant. As the wax used in the present invention, known waxes can be used. Examples of such materials include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbons (paraffin wax, sazol wax, etc.); carbonyl group-containing waxes, and the like. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18 -Octadecanediol distearate, etc.); polyalkanol esters (trimellitic acid tristearyl, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). Of these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving 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.
[0048]
(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. Known charge control agents can be used. Examples of such dyes include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified quaternary ammonium salts). ), Alkylamide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, metal salt of salicylic acid derivative, and the like. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSYVP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge NEGVP2036 of quaternary ammonium salt, copy charge NXVP434 (above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) ), Copper phthalocyanine, perylene, quinacridone, a System pigment, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.
[0049]
In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they can be added directly when dissolved and dispersed in an organic solvent. May be.
[0050]
(Resin fine particles)
As the resin fine particles used in the present invention, any resin can be used as long as it can form an aqueous dispersion, and it may be a thermoplastic resin or a thermosetting resin. Examples of such resins include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. Is mentioned. The resin fine particles may be a combination of two or more of the above resins. Among these, those made of a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, and a resin using a combination thereof are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained.
[0051]
The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, such as a styrene- (meth) acrylate resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylate polymer, Examples include styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.
The average particle diameter of the resin fine particles is 5 to 2000 nm, preferably 20 to 300 nm.
[0052]
(External additive)
As the external additive for assisting the fluidity, developability and chargeability of the colored resin particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 500 nm. The specific surface area according to the BET method is 20 to 500 m.²/ G is preferable. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 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, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
[0053]
In addition, polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine and nylon, thermosetting resin And polymer particles.
Such external additives can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
[0054]
Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.
[0055]
(Production method)
The toner binder can be produced by the following method. Polyol (PO) and polycarboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc., and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (PIC) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group. Further, this (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester modified with a urea bond. When reacting (PIC) and when reacting (A) and (B), a solvent may be used if necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to isocyanates such as tetrahydrofuran (such as tetrahydrofuran). When using polyester (PE) that is not modified with urea bonds, (PE) is produced in the same manner as polyester having a hydroxyl group, and this is dissolved in the solution after completion of the reaction of (UMPE) and mixed. To do.
[0056]
The dry toner of the present invention can be produced by the following method, but is not limited thereto.
(Toner production method in aqueous medium)
The aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.
The toner particles may be formed by reacting a dispersion made of a polyester prepolymer (A) having an isocyanate group in an aqueous medium with amines (B), or a modified polyester such as a urea-modified polyester manufactured in advance. It may be formed by reacting with. As a method for stably forming a dispersion comprising a modified polyester such as urea-modified polyester or prepolymer (A) in an aqueous medium, the composition of the toner raw material comprising the modified polyester or prepolymer (A) in the aqueous medium And a method of dispersing by shearing force. The prepolymer (A) and other toner components (hereinafter referred to as toner raw materials), a colorant, a colorant masterbatch, a release agent, a charge control agent, an unmodified polyester resin, etc. are dispersed in an aqueous medium. It may be mixed at the time of formation, but it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.
[0057]
The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion of the modified polyester or prepolymer (A) has a low viscosity and is easily dispersed.
[0058]
The amount of the aqueous medium 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 a modified polyester such as urea-modified polyester 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 diameter cannot be obtained. If it exceeds 2000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.
[0059]
In the step of synthesizing a modified polyester such as urea-modified polyester from the polyester prepolymer (A), the amine (B) may be added and reacted before dispersing the toner composition in the aqueous medium. After the dispersion, an amine (B) may be added to cause a reaction from the particle interface. In this case, the modified polyester is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided inside the particles.
[0060]
As a dispersant for emulsifying and dispersing the oily phase in which the toner composition is dispersed in a liquid containing water, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, and phosphate esters, alkyls Amine salt type such as amine salt, amino alcohol fatty acid derivative, polyamine fatty acid derivative, imidazoline, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, etc. Quaternary ammonium salt type cationic surfactants, nonionic surfactants such as fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl -N, amphoteric surfactants such as N- dimethyl ammonium betaine and the like.
[0061]
Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkyl carboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, 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.
[0062]
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).
[0063]
In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C 6 -C 10) sulfonamidopropyltrimethylammonium salt which right the fluoroalkyl group, Benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (manufactured by Daikin Industries) ), Megafuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.
[0064]
Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant that is hardly soluble in water.
Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxy Propyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Rylic acid esters, 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 compounds containing vinyl alcohol and a carboxyl group Esters such as pinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinyl pyridine, vinyl pyrrolidone, vinyl imidazole , Homopolymers or copolymers such as those having a nitrogen atom such as ethyleneimine or its heterocyclic ring, polyoxyethylene, Cypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.
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. To do. It can also be removed by operations such as enzymatic degradation.
[0065]
When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.
Furthermore, in order to lower the viscosity of the liquid containing the toner composition, a modified polyester such as urea-modified polyester or a solvent in which the prepolymer (A) is soluble can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal.
[0066]
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 preferable. The usage-amount of the solvent with respect to 100 parts of prepolymers (A) is 0-300 parts normally, Preferably it is 0-100 parts, More preferably, it is 25-70 parts. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after elongation and / or crosslinking reaction.
[0067]
The elongation and / or crosslinking reaction time is selected depending on the reactivity of the prepolymer having active hydrogen such as the polyester prepolymer (A) and the combination of the crosslinking agent and the amine (B) as the elongation agent. 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.
In order to remove the organic solvent from the obtained emulsified dispersion (dispersion), a method of gradually raising the temperature of the entire system and completely removing the organic solvent in the droplets by evaporation can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained by short-time treatment such as spray dryer, belt dryer, rotary kiln.
[0068]
When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the 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 a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder after drying, but it is preferably performed in a liquid in terms of efficiency. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.
[0069]
By mixing the resulting dried toner powder with dissimilar particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by giving mechanical impact force to the mixed powder By immobilizing and fusing on the surface, it is possible to prevent detachment of the foreign particles from the surface of the resulting composite particle.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron Examples include a system (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic mortar.
[0070]
【Example】
  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In addition, the part in an Example shows a weight part.
<Example 1>... Reference examples
  Career
    Acrylic resin solution (solid content 50 wt%) 42.0 parts
    Guanamin solution (solid content 70wt%) 13.0 parts
    Alumina particles [0.3 μm, specific resistance 10¹⁴(Ω · cm)] 7.6 parts
    60 parts of toluene
    60 parts of Butyl cellosolve
Was dispersed with a homomixer for 10 minutes to obtain an acrylic resin coating film forming solution. A sintered ferrite powder [average particle size: 50 μm, magnetization (1 kOe); 70 emu / g, content of 63% or less of Dv; 2.5 wt%] as the core material is used, and the coating film forming solution is applied to the surface of the core material. The film was applied by a Spira coater (Okada Seiko Co., Ltd.) so as to have a film thickness of 0.15 μm and dried. The obtained carrier was baked by standing in an electric furnace at 150 ° C. for 1 hour. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 106 μm to obtain [Carrier 1]. The measurement of the binder resin film thickness was performed by observing the cross section of the carrier with a transmission electron microscope so that the coating film covering the carrier surface could be observed.
[0071]
(Synthesis of organic fine particle emulsion)
Production Example 1
In a reaction vessel with a stir bar and thermometer set,

And stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous dispersion of a vinyl resin (styrene-methacrylic acid-methacrylic acid etherene oxide adduct sulfate sodium salt copolymer) [ A fine particle dispersion 1] was obtained.
The volume average particle diameter of the [fine particle dispersion 1] measured by LA-920 was 0.14 μm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The resin content Tg was 152 ° C.
[0072]

Were mixed and stirred to obtain a milky white liquid. This is designated as [Aqueous Phase 1].
[0073]
(Synthesis of low molecular weight polyester)
Production Example 3
In a reaction vessel with a condenser, stirrer and nitrogen inlet,
220 parts of bisphenol A ethylene oxide 2-mole adduct
Bisphenol A propylene oxide 3 mol adduct 561 parts
218 parts terephthalic acid
48 parts of adipic acid
Dibutyltin oxide 2 parts
And reacted for 8 hours at 230 ° C. under normal pressure and further for 5 hours under reduced pressure of 10 to 15 mmHg. Then, 45 parts of trimellitic anhydride was added to the reaction vessel and reacted for 2 hours at 180 ° C. and normal pressure. Low molecular polyester 1] was obtained. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25.
[0074]
(Prepolymer synthesis)
Production Example 4
In a reaction vessel with a condenser, stirrer, and nitrogen introduction pipe,
Bisphenol A ethylene oxide 2-mole adduct 682 parts
Bisphenol A propylene oxide 2-mole adduct 81 parts
283 parts of terephthalic acid
22 parts trimellitic anhydride
Dibutyltin oxide 2 parts
Was added and reacted at 230 ° C. under normal pressure for 8 hours, and further reacted for 5 hours under reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe,
[Intermediate polyester 1] 411 parts
89 parts of isophorone diisocyanate
500 parts of ethyl acetate
And reacted at 100 ° C. for 5 hours to obtain [Prepolymer 1]. [Prepolymer 1] had a free isocyanate weight% of 1.53%.
[0075]
(Synthesis of ketimine)
Production Example 5
In a reaction vessel with a stir bar and thermometer set,
170 parts of isophoronediamine
75 parts of methyl ethyl ketone
And reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.
[0076]
(Synthesis of master batch)
Production Example 6
40 parts of pigment carbon black (Cabot Company Legal 400R)
Binder resin: 60 parts of polyester resin
(Sanyo Kasei RS-801 acid value 10, Mw 20000 Tg, 64 ° C.)
30 parts of water
The raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 1]. Next, using this master batch pigment, a toner was prepared by the following method.
[0077]
(Create oil phase)
Production Example 7
In a container with a stir bar and thermometer set,
[Low molecular weight polyester 1] 378 parts
Carnauba WAX 110 parts
CCA (salicylic acid metal complex E-84: Orient Chemical Industries) 22 parts
947 parts ethyl acetate
Was heated to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Then in the container
[Masterbatch 1] 500 parts
500 parts of ethyl acetate
Were mixed for 1 hour to obtain [Raw material solution 1]. [Raw material solution 1]: Transfer 1324 parts to a container, and use a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed 1 kg / hr, disk peripheral speed 6 m / sec, 0.5 volume of 0.5 mm zirconia beads. Carbon black and WAX were dispersed under the conditions of% filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.
[0078]
(Emulsification ⇒ Solvent removal)
Toner
[Pigment / WAX dispersion 1] 648 parts
[Prepolymer 1] 154 parts
[Ketimine Compound 1] 6.6 parts
Is mixed in a container with TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute, and then 1200 parts of [Aqueous phase 1] is added to the container. By mixing, [Emulsified slurry 1] was obtained.
[Emulsified slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was performed at 45 ° C. for 4 hours to obtain [Dispersed slurry 1]. [Dispersion Slurry 1] had a volume average particle size of 5.95 μm and a number average particle size of 5.45 μm (measured with a multisizer).
[0079]
(Washing ⇒ drying)
[Emulsified slurry 1] After 100 parts were filtered under reduced pressure,
{Circle around (1)} 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2): Add 100 parts of 10% aqueous sodium hydroxide to the filter cake of (1), apply ultrasonic vibration, mix with TK homomixer (30 minutes at 12,000 rpm), and then filter under reduced pressure. . This ultrasonic alkali cleaning was performed again (two ultrasonic alkali cleanings).
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm), and filter twice to obtain [Filter cake 1]. It was.
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, sieved with a mesh of 75 μm, volume average particle diameter Dv 6.05 μm, number average particle diameter Dn 5.58 μm, Dv / Dn 1.08 (multiple [Toner 1] having a resin fine particle residual ratio of 0.1 wt% was obtained.
[0080]
[Toner 1], [Carrier 1] and the developer thus obtained were evaluated for the following items. However, the toner used was 100 parts of toner mixed with 0.7 part of hydrophobic silica and 0.3 part of hydrophobic titanium oxide using a Henschel mixer.
[0081]
<About various evaluation methods>
(A) Toner particle size
The particle size of the toner was measured using a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. The volume average particle diameter and the number average particle diameter were determined by the particle size measuring instrument. The results are shown in Table 1.
(B) Charge amount
[Carrier 1] Charge amount measured by a general blow-off method [Toshiba Chemical Co., Ltd .: TB-200] for a developer obtained by mixing and charging at 95 wt% with [Toner 1] at a ratio of 5 wt% . The results are shown in Table 1.
(C) Toner circularity
The average circularity can be measured by a flow type particle image analyzer FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance. About 0.1 to 0.5 g. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. . The results are shown in Table 1.
(D) Measuring method of resin fine particle residual ratio
2. Using styrene monomer, which is a thermal decomposition product of styrene acrylic resin fine particles in the toner, as a fingerprint component, 0.01 wt%, 0.10 wt%, 1.00 wt% of styrene acrylic resin fine particles are added to the toner particles under the following conditions. Using the standard addition method of adding 00 wt% and 10.0 wt%, resin fine particles unevenly distributed on the toner surface were calculated and measured by the peak area of the styrene monomer.
Analytical instrument: pyrolysis gas chromatograph (mass spectrometry) meter device; Shimadzu QR-5000 Japan Analytical Industrial JHP-3S pyrolysis temperature; 590 ° C. × 12 seconds
Column; DB-1L = 30m
I. D = 0.25mm
Film = 0.25 μm
Column temperature: 40 ° C. (holding 2 minutes) to (10 ° C./minute temperature increase) 300 ° C.
Vaporization chamber temperature: 300 ° C
In each item, an image chart having a 5% image area was continuously run up to 50000 sheets, and then the evaluation described below was performed. The results are shown in Table 1.
(E) Fixability
Using a modified imgioNeo450 made by Ricoh that can print 45 sheets of A4 size paper per minute, the developer is mixed with a carrier charged with 95 wt% [toner 1] 5 wt% and triboelectrically charged with plain paper and 1.0 ± 0.1 mg / cm as a solid image on cardboard transfer paper (Ricoh Type 6200 and NBS Ricoh Copy Printing Paper <135>)²Adjustment was performed so that the toner of the unit was developed, and the temperature of the fixing belt was adjusted to be variable, and the temperature at which no offset occurred on plain paper and the fixing lower limit temperature on thick paper were measured. The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more. The results are shown in Table 2.
(F) Image density
After outputting a solid image, the image density was measured by X-Rite (manufactured by X-Rite). This was measured at five points for each color alone, and the average was obtained for each color. The results are shown in Table 2.
(G) Background dirt
The blank image was stopped during development, the developer on the developed photoreceptor was tape transferred, and the difference from the image density of the untransferred tape was measured with a 938 spectrocytometer (manufactured by X-Rite). The results are shown in Table 2.
(H) Cleanability
The transfer residual toner on the photosensitive member that has passed the cleaning process is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Co., Ltd.), measured with a Macbeth reflection densitometer RD514, and the difference from the blank is 0.01 or less. A product was evaluated as ○ (good), and a product exceeding it was evaluated as × (defect). The results are shown in Table 2.
(I) Filming
The presence or absence of toner filming on the developing roller or the photoreceptor was observed. ○ indicates no filming, Δ indicates filming on streaks, and × indicates filming as a whole. The results are shown in Table 2.
(J) Charge reduction amount
From the initial charge amount (Q1) described in (b), using a remodeled imagio Neo450 manufactured by Ricoh Co., Ltd., a carrier charged with 95% by weight of [Carrier 1] and 5% by weight of [Toner 1] was friction-charged. The amount obtained by subtracting the amount of charge (Q2) measured by the same method for the carrier obtained by removing the toner in the developer after performing the running evaluation of 300,000 sheets by the blow-off device. In other words, the target value is 5.0 or less. Further, since the cause of the decrease in the charge amount is the toner spent on the carrier surface, the decrease in the charge amount can be suppressed by reducing the toner spent. The results are shown in Table 2.
(K) Resistance change amount
Ricoh Corporation from the value (R1) obtained by converting the initial carrier into a resistance measurement parallel electrode: the electrode having a gap of 2 mm, applying a DC 250V and measuring the resistance value after 30 sec with a high resist meter into a volume resistivity In a developer after running evaluation of 300,000 sheets using a developer made by mixing and triboelectrically charged with 95% by weight of [Carrier 1] and 5% by weight of [Toner 1] using a modified imgioNeo450 machine Is the amount obtained by subtracting the value (R2) measured by the same method as the resistance measuring method, and the target value is 2.0 [Log] in absolute value. (Ω · cm)]. In addition, the cause of the change in resistance value is scraping of the binder resin film of the carrier, spent spent on the toner component, detachment of large particles in the carrier coating film, etc., and reducing these changes suppresses the resistance change amount. be able to. The results are shown in Table 2.
(L) Dirt
Using a remodeled imgioNeo450 manufactured by Ricoh Co., Ltd., using a developer that was mixed and frictionally charged at a ratio of [Carrier 1] 95 wt% and [Toner 1] 5 wt%, the background stains of 3000 sheets running were It was evaluated in 4 grades, “good”, “good”, “△”, “bad”, “×: very bad”. As for the applicability of evaluation, ◎ and ○ are acceptable, and Δ and × are disqualified. The cause of the background contamination is that the toner does not rise sufficiently when the replenishment toner is not sufficiently mixed into the developer, and the toner is ejected from the developer on the developing roller. The results are shown in Table 2.
(M) Toner scattering
Using a remodeled imgioNeo450 manufactured by Ricoh Co., using a developer that was mixed and frictionally charged at a ratio of [Carrier 1] of 95 wt% and [Toner 1] of 5 wt%, the developing unit in the apparatus after running 50,000 sheets The degree of scattering of the surrounding toner was evaluated in four grades: [［: very good, ○: good, Δ: bad, ×: very bad]. As for the applicability of evaluation, ◎ and ○ are acceptable, and Δ and × are disqualified. The cause of the toner scattering is that the toner does not rise sufficiently when the replenishment toner is not sufficiently mixed into the developer, and the toner is ejected from the developer on the developing roller.
(N) Magnetization
The magnetization of the carrier was measured with a multi-sample rotary magnetization measuring device Model REM-1 manufactured by Toei Kogyo Co., Ltd., and the magnetization at 1 kOe was used.
(O) Carrier particle size
The particle size of the carrier was measured by MICROTRAC Model 9320-X100 manufactured by Microtrac. Further, the average particle diameter Dv referred to in the present invention is a value obtained by volume distribution.
(P) Carrier adhesion
The carrier adhesion is measured by using a modified Ricoh imgio Neo450 machine, stopping a blank paper image during development, and transferring the developer on the photoconductor after development to a tape with an area of 50 cm.²The number of carriers attached inside is defined as the amount of carriers attached. The target value of the carrier adhesion amount is 100/50 cm.²Less than.
[0082]
<Example 2>... Reference examples
  In Example 1, it is the same except that the sintered ferrite powder [average particle size: 50 μm, magnetization (1 kOe); 70 emu / g, 63% diameter or less content of Dv; 0.9 wt%] is used as the core material. [Carrier 2] was produced. [Carrier 2] thus obtained was evaluated in the same manner as in Example 1.
[0083]
<Example 3>... Reference examples
    Acrylic resin solution (solid content 50 wt%) 21.0 parts
    6.4 parts of guanamine solution (solid content 70 wt%)
    Alumina particles [0.3 μm, specific resistance 10¹⁴(Ω · cm)] 7.6 parts
    Silicone resin solution [solid content 23wt%
    (SR2410: manufactured by Toray Dow Corning Silicone)] 65.0 parts
    Aminosilane [Solid content 100wt%
    (SH6020: manufactured by Toray Dow Corning Silicone Co.)] 0.3 parts
    60 parts of toluene
    60 parts of Butyl cellosolve
Was dispersed with a homomixer for 10 minutes to obtain a blend coating film forming solution of an acrylic resin and a silicon resin, which was converted into a carrier in the same manner as in Example 2 to obtain [Carrier 3]. [Carrier 3] thus obtained was evaluated in the same manner as in Example 1.
[0084]
<Example 4>... Reference examples
    Acrylic resin solution (solid content 50 wt%) 21.0 parts
    6.4 parts of guanamine solution (solid content 70 wt%)
    Alumina particles [0.3 μm, specific resistance 10¹⁴(Ω · cm)] 7.6 parts
    60 parts of toluene
    60 parts of Butyl cellosolve
Was dispersed with a homomixer for 10 minutes to obtain an acrylic resin coating film forming solution. After applying and drying with a Spira coater (manufactured by Okada Seiko Co., Ltd.) so as to have a film thickness of 0.08 μm on the core material surface in the same manner as in Example 2,
    Silicone resin solution [solid content 23wt%
    (SR2410: manufactured by Toray Dow Corning Silicone)] 65.0 parts
    Aminosilane [Solid content 100wt%
    (SH6020: manufactured by Toray Dow Corning Silicone Co.)] 0.3 parts
    60 parts of toluene
    60 parts of Butyl cellosolve
In a container for 5 minutes with an agitator to obtain a silicone resin coating film forming solution, and this solution is applied to the carrier surface on which the acrylic resin coating layer is formed. It apply | coated so that it might become 0.15 micrometer, and dried. Thereafter, a carrier was obtained in the same manner as in Example 1, and designated as [Carrier 4]. As a result, the coating film forms a two-layer structure with the acrylic resin in the lower layer and the silicon resin in the upper layer. [Carrier 4] thus obtained was evaluated in the same manner as in Example 1.
[0085]
<Example 5>
Acrylic resin solution (solid content 50 wt%) 21.0 parts
6.4 parts of guanamine solution (solid content 70 wt%)
Alumina particles [0.3 μm, specific resistance 10¹⁴(Ω · cm)] 121.0 parts
Silicone resin solution [solid content 23wt%
(SR2410: manufactured by Toray Dow Corning Silicone)] 65.0 parts
Aminosilane [Solid content 100wt%
(SH6020: manufactured by Toray Dow Corning Silicone Co.)] 0.3 parts
300 parts of toluene
Butyl cellosolve 300 parts
Was dispersed with a homomixer for 10 minutes to obtain a blend coating film forming solution of an acrylic resin and a silicon resin containing alumina particles, and converted into a carrier in the same manner as in Example 2 to obtain [Carrier 5]. [Carrier 5] thus obtained was evaluated in the same manner as in Example 1.
[0086]
<Example 6>
In Example 5, instead of alumina, titanium oxide particles [0.3 μm, specific resistance 10⁷[Omega cm]] [Carrier 6] was produced in the same manner except that 121.0 parts were used. [Carrier 6] thus obtained was evaluated in the same manner as in Example 1.
[0087]
<Example 7>
In Example 5, instead of alumina, zinc oxide particles [0.3 μm, specific resistance 10⁷[Carrier 7] was produced in the same manner except that 121.0 parts of (Ω · cm) was used. [Carrier 7] thus obtained was evaluated in the same manner as in Example 1.
[0088]
<Example 8>... Reference examples
    Acrylic resin solution (solid content 50 wt%) 2.2 parts
    Guanamin solution (solid content 70wt%) 0.7 parts
    Alumina particles [0.3 μm, specific resistance 10¹⁴(Ω · cm)] 121.0 parts
    Silicone resin solution [solid content 23wt%
    (SR2410: manufactured by Toray Dow Corning Silicone)] 126.0 parts
    Aminosilane [Solid content 100wt%
    (SH6020: manufactured by Toray Dow Corning Silicone)] 0.63 parts
    60 parts of toluene
    60 parts of Butyl cellosolve
Was dispersed with a homomixer for 10 minutes to obtain a blend coating film forming solution of an acrylic resin and a silicon resin, which was converted into a carrier in the same manner as in Example 2 to obtain [Carrier 8]. [Carrier 8] thus obtained was evaluated in the same manner as in Example 1.
[0089]
<Comparative Example 1>
In Example 1, it is the same except that the sintered ferrite powder [average particle size: 19 μm, magnetization (1 kOe); 58 emu / g, 63% diameter content or less of Dv; 1.2 wt%] is used as the core material. [Carrier 9] was produced. [Carrier 9] thus obtained was evaluated in the same manner as in Example 1.
[0090]
<Comparative example 2>
In Example 1, it is the same except that the sintered ferrite powder [average particle size: 81 μm, magnetization (1 kOe); 73 emu / g, 63% diameter content or less of Dv; 1.0 wt%] is used as the core material. [Carrier 10] was produced. [Carrier 10] thus obtained was evaluated in the same manner as in Example 1.
[0091]
<Comparative Example 3>
In Example 5, D / h was 15.3 by using alumina having a particle diameter of 2.3 μm, and the same [Carrier 11] was produced. [Carrier 11] thus obtained was evaluated in the same manner as in Example 1.
[0092]
<Example 9>... Reference examples
    Silicone resin solution [solid content 23wt%
    (SR2410: manufactured by Toray Dow Corning Silicone)] 132.2 parts
    Aminosilane [solid content 100wt%
    (SH6020: manufactured by Toray Dow Corning Silicone)] 0.66 parts
    Alumina particles [0.3 μm, specific resistance 10¹⁴(Ω · cm)] 121.0 parts
    300 parts of toluene
    Butyl cellosolve 300 parts
Was dispersed with a homomixer for 10 minutes to obtain a silicon resin coating film forming solution containing alumina particles, and [Carrier 12] was produced in the same manner as in Example 2. [Carrier 12] thus obtained was evaluated in the same manner as in Example 1.
[0093]
<Comparative example 4>
In Example 5, D / h was 0.8 by using alumina having a particle size of 0.12 μm, and otherwise [Carrier 13] was produced. [Carrier 13] thus obtained was evaluated in the same manner as in Example 1.
[0094]
<Comparative Example 5>
In Example 5, [Carrier 14] was produced in the same manner except that the core material was changed to one having a magnetization of 35 emu / g at 1 kOe. [Carrier 14] thus obtained was evaluated in the same manner as in Example 1.
[0095]
<Comparative Example 6>
In Example 5, [Carrier 15] was produced in the same manner except that the core material was changed to one having a magnetization of 84 emu / g at 1 kOe. [Carrier 15] thus obtained was evaluated in the same manner as in Example 1.
[0096]
<Example 10>
The volume average particle diameter Dv 6.10 μm, the number average particle diameter Dn 5.54 μm, Dv / Dn 1.10, and the resin fine particle residual ratio 0, except that the ultrasonic alkaline cleaning in Example 2 was performed once. 5 wt% of [Toner 2] was obtained. [Toner 2] thus obtained was evaluated in the same manner as in Example 1.
[0097]
<Example 11>
A toner was obtained in the same manner as in Example 2 except that 22 parts of CCA was not added when the oil phase was prepared in Example 2. To 100 parts of this toner, 0.5 part of CCA (salicylic acid metal complex E-84: Orient Chemical Co., Ltd.) was added and subjected to CCA injection treatment with a Q mixer (Mitsui Mine). [Toner 3] having an average particle diameter Dn of 5.20 μm, Dv / Dn of 1.12, and a resin fine particle residual ratio of 0.3 wt% was obtained. [Toner 3] thus obtained was evaluated in the same manner as in Example 1.
[0098]
(Synthesis of low molecular weight polyester)
Production Example 8
In a reaction vessel with a condenser, stirrer and nitrogen inlet,
262 parts of bisphenol A ethylene oxide 2-mol adduct
202 parts of bisphenol A propylene oxide 2 mol adduct
236 parts of bisphenol A propylene oxide 3 mol adduct
Terephthalic acid 266 parts
48 parts of adipic acid
Dibutyltin oxide 2 parts
The reaction was continued for 8 hours at 230 ° C. under normal pressure, and further 5 hours under reduced pressure of 10-15 mmHg. Then, 34 parts of trimellitic anhydride was added to the reaction vessel and reacted for 2 hours at 180 ° C. under normal pressure. Low molecular polyester 2] was obtained. [Low molecular polyester 2] had a number average molecular weight of 2390, a weight average molecular weight of 6010, Tg of 62 ° C., and an acid value of 20.7.
[0099]
(Create oil phase)
Production Example 9
In a container with a stir bar and thermometer set,
[Low molecular polyester 2] 378 parts
Carnauba WAX 110 parts
CCA (salicylic acid metal complex E-84: Orient Chemical Industries) 22 parts
947 parts ethyl acetate
Was heated to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were added to the container, and mixed for 1 hour to obtain [Raw material solution 2]. [Raw material solution 2] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 2] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 2]. The solid content concentration of [Pigment / WAX Dispersion 2] (130 ° C., 30 minutes) was 52%.
[0100]
<Example 12>
Volume average was obtained in the same manner as in Example 2 except that [Pigment / WAX Dispersion 1] was used instead of [Pigment / WAX Dispersion 1] in Example 2, and ultrasonic washing was not applied twice, and the alkali was washed twice. [Toner 4] having a particle diameter Dv of 6.31 μm, a number average particle diameter Dn of 5.67 μm, Dv / Dn of 1.11 and a resin fine particle residual ratio of 1.5 wt% was obtained. [Toner 4] thus obtained was evaluated in the same manner as in Example 1.
[0101]
<Example 13>
The volume average particle diameter Dv 6.45 μm, the number average particle diameter Dn 5.46 μm, Dv / Dn 1.18, and the resin fine particles remained, except that the ultrasonic wave in Example 12 was not applied and the alkali cleaning was performed once. [Toner 5] having a rate of 2.4 wt% was obtained. [Toner 5] thus obtained was evaluated in the same manner as in Example 1.
[0102]
(Synthesis of low molecular weight polyester)
Production Example 10
In a reaction vessel with a condenser, stirrer and nitrogen inlet,
Bisphenol A propylene oxide 2-mole adduct 719 parts
274 parts of terephthalic acid
48 parts adipic acid and 2 parts dibutyltin oxide
The reaction was carried out at 230 ° C. for 8 hours at normal pressure and further for 5 hours under reduced pressure of 10 to 15 mmHg. Then, 7 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours at normal pressure. [Low molecular polyester 3] was obtained. [Low molecular polyester 3] had a number average molecular weight of 2290, a weight average molecular weight of 5750, a Tg of 65 ° C., and an acid value of 4.9.
[0103]
(Create oil phase)
Production Example 11
In a container with a stir bar and thermometer set,
[Low molecular weight polyester 3] 378 parts
Carnauba WAX 110 parts
CCA (salicylic acid metal complex E-84: Orient Chemical Industries) 22 parts
947 parts ethyl acetate
Was heated to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were added to the container and mixed for 1 hour to obtain [Raw material solution 3]. [Raw Material Solution 3] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed 1 kg / hr, disk peripheral speed 6 m / sec, 0.5 mm zirconia beads 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 3] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 3]. The solid content concentration of [Pigment / WAX Dispersion 3] (130 ° C., 30 minutes) was 49%.
[0104]
<Example 14>
Volume average was obtained in the same manner as in Example 2, except that [Pigment / WAX Dispersion 3] was used instead of [Pigment / WAX Dispersion 1] in Example 2, and ultrasonic washing was not applied, and alkali washing was performed 4 times. [Toner 6] having a particle diameter Dv of 7.04 μm, a number average particle diameter Dn of 5.64 μm, Dv / Dn of 1.25, and a resin fine particle residual ratio of 1.5 wt% was obtained. [Toner 6] thus obtained was evaluated in the same manner as in Example 1.
[0105]
<Example 15>
Volume average was obtained in the same manner as in Example 2 except that [Pigment / WAX Dispersion 1] was used instead of [Pigment / WAX Dispersion 1] in Example 2, and ultrasonic washing was not applied twice and alkali washing was performed twice. [Toner 7] having a particle diameter Dv of 7.02 μm, a number average particle diameter Dn of 5.63 μm, a Dv / Dn of 1.25, and a resin fine particle residual ratio of 2.3 wt% was obtained. [Toner 7] thus obtained was evaluated in the same manner as in Example 1.
[0106]
(Synthesis of low molecular weight polyester)
Production Example 12
In a reaction vessel with a condenser, stirrer and nitrogen inlet,
121 parts of bisphenol A ethylene oxide 2-mole adduct
Bisphenol A propylene oxide 2-mole adduct 64 parts
Bisphenol A propylene oxide 3 mol adduct 527 parts
246 parts of terephthalic acid
48 parts of adipic acid
Dibutyltin oxide 2 parts
And then reacted for 8 hours at 230 ° C. under normal pressure and further for 5 hours under reduced pressure of 10 to 15 mmHg. Then, 42 parts of trimellitic anhydride was added to the reaction vessel and reacted for 2 hours at 180 ° C. under normal pressure. Low molecular polyester 4] was obtained. [Low molecular polyester 4] had a number average molecular weight of 2500, a weight average molecular weight of 6190, Tg of 48 ° C., and an acid value of 25.2.
[0107]
(Create oil phase)
Production Example 13
In a container with a stir bar and thermometer set,
[Low molecular polyester 4] 378 parts
Carnauba WAX 110 parts
CCA (salicylic acid metal complex E-84: Orient Chemical Industries) 22 parts
947 parts ethyl acetate
Was heated to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 4].
[Raw Material Solution 4] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed 1 kg / hr, disk peripheral speed 6 m / sec, 0.5 mm zirconia beads 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 4] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 4]. The solid content concentration of [Pigment / WAX Dispersion 4] (130 ° C., 30 minutes) was 49%.
[0108]
<Example 16>
The volume average particle diameter Dv was 4.84 μm and the number average particle diameter Dn4.4 was the same as in Example 2 except that [Pigment / WAX Dispersion 4] was used instead of [Pigment / WAX Dispersion 1] in Example 2. [Toner 8] having 02 μm, Dv / Dn of 1.20, and resin fine particle residual ratio of 0.3 wt% was obtained. [Toner 8] thus obtained was evaluated in the same manner as in Example 1.
[0109]
<Example 17>
The volume average particle diameter was the same as in Example 2 except that [Pigment / WAX Dispersion 4] was used instead of [Pigment / WAX Dispersion 1] in Example 2, and ultrasonic cleaning was performed once. [Toner 9] having a Dv of 5.13 μm, a number average particle diameter Dn of 4.24 μm, a Dv / Dn of 1.21, and a resin fine particle residual ratio of 0.8 wt% was obtained. [Toner 9] thus obtained was evaluated in the same manner as in Example 1.
[0110]
<Comparative Example 7>
0.1M-Na in 709g of ion-exchanged water₃PO₄After adding 451 g of the aqueous solution and heating to 60 ° C., the mixture was stirred at 12,000 rpm using a TK homomixer. To this, 68 g of 1.0 M CaCl 2 aqueous solution was gradually added, and Ca₃(PO₄An aqueous medium containing 2) was obtained.

Was placed in a TK homomixer, heated to 60 ° C., and uniformly dissolved and dispersed at 12,000 rpm. Into this, 10 g of a polymerization initiator, 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer system. The polymerizable monomer system is charged into the aqueous medium, 60 ° C., N₂Under an atmosphere, the mixture was stirred at 10,000 rpm for 20 minutes with a TK homomixer to granulate the polymerizable monomer system. Thereafter, the mixture was reacted at 60 ° C. for 3 hours while stirring with a paddle stirring blade, and then the liquid temperature was set at 80 ° C. and the reaction was carried out for 10 hours.
After completion of the polymerization reaction, the mixture was cooled, and hydrochloric acid was added to dissolve calcium phosphate, followed by filtration, washing with water, and drying to obtain a toner having a volume average particle diameter Dv of 6.33 μm, a number average particle diameter Dn of 5.64 μm, and Dv / Dn of 1.12. 10] was obtained.
Career
Silicone resin solution [solid content 15% by weight
(SR2411: manufactured by Toray Dow Corning)] 227 parts
γ- (2-aminoethyl) aminopropyltrimethoxysilane 6 parts
Carbon black [0.04 μm (# 25: Mitsubishi Chemical)] 2.6 parts
192 parts of toluene
Butyl cellosolve 192 parts
Was dispersed with a homomixer for 10 minutes to obtain a silicone resin coating forming liquid, which was converted into a carrier in the same manner as in Example 2 to obtain [Carrier 16]. [Toner 10] and [Carrier 16] thus obtained were evaluated in the same manner as in Example 1.
[0111]
<Comparative Example 8>
(Preparation of aqueous dispersion of wax particles)
1000 ml of distilled water degassed into a 4-head Kolben with a stirrer, temperature sensor, nitrogen inlet tube and cooling tube, 28.5 g of New Coal 565C (manufactured by Nippon Emulsifier Co., Ltd.), 1 (manufactured by Noda Wax) 185.5 g was added, and the temperature was raised while stirring under a nitrogen stream. When the internal temperature was 85 ° C., a 5N sodium hydroxide aqueous solution was added and the temperature was raised to 75 ° C. as it was, followed by continuing heating and stirring as it was for 1 hour and cooling to room temperature to obtain [Wax Particle Aqueous Dispersion 1].
[0112]
(Preparation of aqueous colorant dispersion)
Carbon black (trade name: Mogal L, manufactured by Cabot) 100 g, sodium dodecyl sulfate 25 g was added to 540 ml of distilled water, and after sufficient stirring, a pressure disperser (MINI-LAB: manufactured by Lani) was used. Dispersion was performed to obtain [Colorant Dispersion Liquid I].
[0113]
(Synthesis of aqueous binder fine particle dispersion)
To a 1L four-headed Kolben equipped with a stirrer, cooling pipe, temperature sensor and nitrogen introduction pipe
480ml of distilled water
Sodium dodecyl sulfate 0.6g
Styrene 106.4g
n-Butyl acrylate 43.2g
Methacrylic acid 10.4g
The mixture was heated to 70 ° C. under a nitrogen stream while stirring. Here, an initiator aqueous solution in which 2.1 g of potassium persulfate was dissolved in 120 ml of distilled water was added, and the mixture was stirred at 70 ° C. for 3 hours under a nitrogen stream to complete the polymerization, and then cooled to room temperature. A fine particle dispersion 1] was obtained.
5L 4-head Kolben equipped with a stirrer, cooling pipe, temperature sensor and nitrogen inlet pipe
Distilled water 2400ml
Sodium dodecyl sulfate 2.8g
620 g of styrene
n-Butyl acrylate 128g
Methacrylic acid 52g
27.4 g of tert-dodecyl mercaptan
The mixture was heated to 70 ° C. under a nitrogen stream while stirring. Here, an initiator aqueous solution prepared by dissolving 11.2 g of potassium persulfate in 600 ml of distilled water was added, and the mixture was stirred at 70 ° C. for 3 hours in a nitrogen stream to complete the polymerization, and then cooled to room temperature. A fine particle dispersion 2] was obtained.
[0114]
(Toner synthesis)
In a 1 L separable flask equipped with a stirrer, a condenser, and a temperature sensor,
[High molecular weight binder fine particle dispersion 1] 47.6 g
[Low molecular weight binder fine particle dispersion 2] 190.5 g
[Wax particle aqueous dispersion 1] 7.7 g
[Colorant dispersion I] 26.7 g
252.5 ml of distilled water
Was added and mixed and stirred, and the pH was adjusted to 9.5 using a 5N aqueous sodium hydroxide solution. Further, with stirring, a surfactant in which 50 g of sodium chloride is dissolved in 600 ml of distilled water, 77 ml of isopropanol, and Fluorard FC-170C (manufactured by Sumitomo 3M: Fluoro-based nonionic surfactant) 10 mg in 10 ml of distilled water. Aqueous solutions were sequentially added, the internal temperature was raised to 85 ° C., the reaction was performed for 6 hours, and then cooled to room temperature. The reaction solution is adjusted to pH = 13 using 5N aqueous sodium hydroxide solution, filtered, resuspended in distilled water, repeatedly filtered and resuspended, washed, dried and [Toner 11] having an average particle diameter Dv of 6.58 μm, a number average particle diameter Dn of 5.33 μm, and Dv / Dn of 1.23 was obtained. [Toner 11] and [Carrier 16] thus obtained were evaluated in the same manner as in Example 1.
[0115]
<Comparative Example 9>
(Preparation of pigment dispersion)
A resin container was charged with 0.9 parts by weight of sodium n-dodecyl sulfate and 10 parts by weight of ion-exchanged water, and stirred to prepare an aqueous solution of sodium n-dodecyl sulfate. While stirring this aqueous solution, 1.2 parts by weight of carbon black: Legal 400R (manufactured by Cabot) was gradually added. After the addition, the mixture was stirred for 1 hour, and then a carbon black dispersion treatment was continuously performed for 20 hours using a sand grinder to obtain [Pigment dispersion liquid (C-1)].
[0116]
(Preparation of aqueous solution of surfactant)
By preparing 0.055 parts by weight of sodium anhydrophobic sodium dodecylbenzenesulfonate and 4 parts by weight of ion-exchanged water in a stainless steel pot and stirring the system at room temperature [Preparation Example (S-1) ] Was obtained. In addition, 0.014 parts by weight of a nonionic surfactant “New Coal 565C” (manufactured by Nippon Emulsifier Co., Ltd.) and 4 parts by weight of ion-exchanged water are charged in a stainless steel pot, and this system is stirred at room temperature, Preparation Example (S-2)] was obtained. Furthermore, 1 part by weight of a nonionic surfactant “FC-170C” (manufactured by Sumitomo 3M) and 1000 parts by weight of ion-exchanged water were charged into a glass beaker, and this system was stirred at room temperature, thereby preparing [Preparation Example] (S-3)] was obtained.
[0117]
(Preparation of aqueous solution of polymerization initiator)
200.7 parts by weight of potassium persulfate (manufactured by Kanto Chemical Co., Ltd.) as a polymerization initiator and 12000 parts by weight of ion-exchanged water were charged in a enamel pot, and this system was stirred at room temperature to obtain [Preparation Example (P- 1)] was obtained. Further, 223.8 parts by weight of potassium persulfate (manufactured by Kanto Chemical Co., Ltd.), which is a polymerization initiator, and 12,000 parts by weight of ion-exchanged water are charged into a enamel pot, and this system is stirred at room temperature, thereby preparing [Preparation Example ( P-2)] was obtained.
[0118]
(Preparation of aqueous solution of sodium chloride)
A salting-out agent sodium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) 5.36 parts by weight and ion-exchanged water 20 parts by weight were charged in a stainless steel pot, and this system was stirred at room temperature to obtain a [sodium chloride solution (N )].
[0119]
(Manufacture of toner particles)
In a reaction vessel having an internal volume of 100 L, which is provided with a temperature sensor, a cooling pipe, a nitrogen introducing device and a stirring blade, and whose inner surface is subjected to glass lining treatment, [Preparation Example (S-1)] 4 L and [Preparation Example (S- 2)] 4 L was charged, and 44 L of ion-exchanged water was added while stirring the system at room temperature, and the system was heated. When the temperature of the system reached 70 ° C., [Preparation Example (P-1)] 12 L was added, and the system temperature was controlled at 72 ° C. ± 1 ° C., while 12.1 kg of styrene and n-butyl acrylate 2 A monomer mixture (I) consisting of .88 kg, 1.04 kg of methacrylic acid and 9.02 g of t-dodecyl mercaptan was added, and stirring was performed for 6 hours while controlling the temperature of this system at 80 ° C. ± 1 ° C. It was. After cooling until the temperature of the system was 40 ° C. or lower, 4 L of [Preparation Example (S-1)] and 4 L of [Preparation Example (S-2)] were added to this system, and this system was heated. . When the temperature of the system reached 70 ° C., [Preparation Example (P-2)] 12 L was added, and further from 11 kg of styrene, 4 kg of n-butyl acrylate, 1.04 kg of methacrylic acid, and 548 g of t-dodecyl mercaptan. The monomer mixture (II) was added and stirred for 6 hours while controlling the temperature of the system at 75 ° C. ± 2 ° C., and further, 12% while controlling the temperature of the system at 80 ° C. ± 2 ° C. Stirring was performed over time. Stirring was stopped by cooling until the temperature of the system was 40 ° C or lower. A dispersion (composite latex (1-A)) of composite resin fine particles (A) having a high molecular weight resin as a core and a low molecular weight resin as a shell was obtained by filtering and removing scale (foreign matter) using a pole filter. . The peak molecular weight of the high molecular weight resin (core) of the composite resin fine particles (A) is 29,000, the peak molecular weight of the low molecular weight resin (shell) is 12,000, and the weight average molecular weight of the composite resin fine particles (A) is 34,000. Met. The composite resin fine particles (A) had a weight average particle diameter of 150 nm, a glass transition temperature (Tg) of 58 ° C., and a softening point of 121 ° C.
[Preparation Example (S-1)] 4 L was added to a reaction vessel having an internal volume of 100 L equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, a comb baffle and a stirring blade (Faudler blade), and the inner surface of which was subjected to glass lining treatment. [Preparation Example (S-2)] was charged, and 44 L of ion-exchanged water was added while the system was stirred at room temperature, and the system was heated. When the temperature of the system reached 70 ° C., [Preparation Example (P-1)] 12 L was added, and further 11 kg of styrene, 4 kg of n-butyl acrylate, 1.04 kg of methacrylic acid, and 9.02 g of t-dodecyl mercaptan. The monomer mixture was added and stirred for 6 hours while controlling the temperature of the system at 72 ° C. ± 2 ° C., and further for 12 hours while controlling the temperature of the system at 80 ° C. ± 2 ° C. Stirring was performed over a period of time. Stirring was stopped by cooling until the temperature of the system was 40 ° C or lower. The scale (foreign matter) was removed by filtration using a pole filter to obtain a dispersion [latex (1-B)] of resin fine particles (B). The resin fine particles (B) constituting the latex (1-B) had a peak molecular weight of 310,000 and a weight average molecular weight of 190,000. The resin fine particles (B) had a weight average particle diameter of 138 nm, a glass transition temperature (Tg) of 58 ° C., and a softening point of 126 ° C.
In a stainless steel reaction vessel having an internal volume of 100 L equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, a comb baffle and a stirring blade (anchor blade), 20 kg of [Composite Latex (1-A)] and [Pigment Dispersion Liquid ( C-1)] 0.4 kg and ion-exchanged water 20 kg were charged, and the system was stirred at room temperature. The temperature of the system is heated to 40 ° C., 20 L of a sodium chloride solution (N), 6 kg of isopropyl alcohol (manufactured by Kanto Chemical Co., Ltd.), 1 wt. Of a nonionic surfactant “FC-170C” (manufactured by Sumitomo 3M) Part and 1000 parts by weight of ion-exchanged water were charged into a glass beaker, and this system was stirred at room temperature to obtain [Preparation Example (S-3)]. [Preparation Example (S-3)] 1 L was added in this order. The system is allowed to stand for 10 minutes and then heated, heated to 85 ° C. over 60 minutes, and stirred at 85 ° C. ± 2 ° C. for 1 hour, whereby composite resin fine particles (A) and colorant fine particles Was salted out / fused to form colored particles (core particles). Next, under a temperature condition of 85 ° C. ± 2 ° C., 5.2 kg of [Latex (1-B)] and a wax emulsion (a polypropylene emulsion having a number average molecular weight of 3,000, a number average primary particle size: 120 nm, a solid content concentration) : 29.9 wt%) and 3.41 kg were added, and the mixture was further stirred at 85 ° C. ± 2 ° C. for 4.0 hours, whereby resin fine particles (B) and The polypropylene microparticles were deposited by salting out / fusion. After cooling until the temperature of the system reached 40 ° C. or less and stirring was stopped, aggregates were removed by filtration with a filter having an opening of 45 μm to obtain a dispersion of toner particles. The dispersion was then filtered under reduced pressure to obtain a wet cake (aggregate of toner particles), which was washed with ion-exchanged water. The washed wet cake was taken out from Nutsche and dried for 100 hours with a blow dryer at 40 ° C. to obtain an aggregate of block-like toner particles. Next, this aggregate was pulverized with a Henschel pulverizer to obtain [Toner 12] having a volume average particle diameter Dv of 6.45 μm, a number average particle diameter Dn of 5.31 μm, and Dv / Dn of 1.21. [Toner 12] and [Carrier 16] thus obtained were evaluated in the same manner as in Example 1.
[0120]
<Comparative Example 10>
One part of polyvinyl alcohol ("PVA-235", manufactured by Kuraray Co., Ltd.) was dissolved in 100 parts of water. This is designated as [Aqueous Phase 2]. In Example 1, [Toner 13] was obtained in the same manner as in Example 1 except that [Water phase 2] was used instead of [Water phase 1]. [Toner 13] and [Carrier 16] thus obtained were evaluated in the same manner as in Example 1.
[0121]
<Comparative Example 11>
The volume average particle diameter Dv6.21 μm, the number average particle diameter Dn5.30 μm, Dv / Dn1.17, the resin fine particle residual ratio 3 except that the number of ultrasonic alkaline washings in Example 1 was 0. 5 wt% of [Toner 14] was obtained. [Toner 14] and [Carrier 16] thus obtained were evaluated in the same manner as in Example 1.
[0122]
[Table 1]

      Note) Examples 1-4, 8 and 9 are reference examples.
[0123]
[Table 2]

      Note) Examples 1-4, 8 and 9 are reference examples.
[0124]
The toners 10 and 14 were stopped because continuous printing could not be performed due to poor fixing. For toners 11 and 12, a very small amount of fixing failure occurred. However, after 10,000 sheets, the evaluation was stopped because the level was not practically usable due to deterioration of the background stain due to a decrease in charge. Since the particle size of the toner 13 could not be controlled, the background was bad from the beginning, and the level was not practically usable, the evaluation was stopped. Regarding carrier 9, since the carrier adhesion exceeded the target value from the beginning and was at a level that could not be used practically, the evaluation was stopped. About carrier 10, since background dirt was bad and it was a level which cannot be used practically, evaluation was stopped. Regarding the carriers 11 and 13, since the amount of decrease in charge amount and the amount of resistance change were large at the time of 8000 sheets and were at levels that could not be used practically, the evaluation was stopped. Regarding the carriers 14 and 15, since the replenishment toner was poorly dispersed in the developer, the background contamination and the toner scattering occurred soon after the start of the evaluation, and the levels were not practically usable.
[0125]
【The invention's effect】
As described above, as is clear from the detailed and specific description, the developer of the present invention has no background stain, toner scattering, carrier adhesion, little toner spent accumulation on the carrier surface, and a stable charge amount over a long period of time. In addition to being obtained, the carrier binder resin does not undergo significant film scraping, so that stable electrical resistance can be obtained over a long period of time, and image deterioration does not occur. Furthermore, a low-temperature fixing toner having good initial printing quality, excellent image quality stability in continuous printing, stable cleaning properties, and preventing filming contamination on the photoreceptor, developing roller, etc. can be obtained. . Therefore, the image quality deterioration of the copy image that occurs as the number of copies increases is greatly improved, and an excellent effect is achieved that a good image can be maintained over a long period of time.

Claims (18)

In a carrier having a coating layer composed of at least a binder resin and particles, the particle diameter (D) and the film thickness (h) of the binder resin layer are 1 <[D / h] <10, and 1 kOe of the carrier in the magnetization is in a range of 40~80emu / g, an average particle diameter Dv of the carriers Ri range der of 20 to 70 m, yet the binder resin of the carrier coating layer comprises at least an acrylic resin and silicone resin, and the ratio of the acrylic resin is 10 to 90 wt%, further total content of the particles contained in the coating layer, an electrostatic charge image, characterized in 40～95Wt% der Rukoto covering layer composition component development For carrier. 2. The carrier for developing an electrostatic charge image according to claim 1, wherein a content of the average particle diameter Dv of 63% or less is less than 1 wt%. Wherein at least an acrylic resin and claim 1 or 2 electrostatic image developing carrier according to each of the resin in the coating layer is characterized in that it forms a layer structure comprising a silicone resin. The particle | grains contained in the said coating layer are one of alumina, titanium oxide, zinc oxide, or those which surface-treated them, or one or more, The particle | grains in any one of Claim 1 thru | or 3 characterized by the above-mentioned. A carrier for developing electrostatic images. A solution or dispersion formed by dissolving or dispersing a toner composition containing a toner binder composed of a modified polyester resin capable of reacting with active hydrogen in an organic solvent is used to form a solution or dispersion in an aqueous medium containing resin fine particles. A toner obtained by reacting with an extender, removing the solvent from the obtained dispersion, and washing and desorbing the resin fine particles adhering to the toner surface, which is a pyrolysis gas chromatograph (mass spectrometry) residual rate of the toner particles of the resin particles remaining on the toner particle surfaces as measured by meter comprises a toner for developing an electrostatic image is less than 5 wt% of the toner particles, any one of claims 1 to 4 A developer for developing an electrostatic charge image, comprising the carrier described in 1 above. 6. The electrostatic charge image developing developer according to claim 5 , wherein the developer toner is a full color toner. The toner binder contains an unmodified polyester resin together with a modified polyester resin, and the weight ratio of the modified polyester resin to the unmodified polyester resin is 5/95 to 80/20. The developer for developing an electrostatic charge image according to claim 5 or 6 . The acid value of the toner binder, an electrostatic charge image developer according to any one of claims 5 to 7, characterized in that a 1~30mgKOH / g. The developer for electrostatic image development according to any one of claims 5 to 8 , wherein the toner binder has a glass transition point (Tg) of 50 to 70 ° C. The fine resin particles, a vinyl resin, for developing an electrostatic charge image according to any one of claims 5 to 9, characterized in that it consists of at least one resin selected from polyurethane resins, epoxy resins and polyester resins Developer. The average particle diameter of the resin fine particles, electrostatic image developer according to any one of claims 5 to 10, characterized in that a 5～2000Nm. The volume average particle diameter of the toner particles, an electrostatic charge image developer according to any one of claims 5 to 11 characterized in that it is a 4-8 [mu] m. The ratio Dv / Dn of the volume average particle diameter to the number-average particle size (Dn) of the toner particles (Dv) are electrostatic charge according to any one of claims 5 to 12, characterized in that 1.25 or less Developer for image development. Average circularity, electrostatic image developer according to any one of claims 5 to 13, characterized in that a 0.94 to 0.99 of the toner particles. Removing the solvent from the dispersion, electrostatic image developer according to any one of claims 5 to 14, characterized in that is carried out under conditions of reduced pressure and / or heat. 16. The developer for developing an electrostatic charge image according to claim 5, wherein the step of removing the solvent from the dispersion is performed by filtration. A container containing the developer for developing an electrostatic charge image according to any one of claims 5 to 16 . Image forming method characterized by using an electrostatic charge image developer according to any one of claims 5 to 16.