JP4161656B2 - Toner for developing electrostatic image, method for producing toner for developing electrostatic image, image forming method and image forming apparatus using the same - Google Patents

Description

【０１３５】
【化２】

【０１３６】
上記化合物の添加量は、トナー全体に対し１〜３０質量％、好ましくは２〜２０質量％、さらに好ましくは３〜１５質量％である。
【０１３７】
本発明に係るトナーでは、ミニエマルジョン重合法により樹脂粒子中に上記離型剤を内包させ、トナー粒子とともに塩析、融着させて調製することが好ましい。
【０１３８】
（荷電制御剤）
トナーは、着色剤、離型剤以外にトナー用材料として種々の機能を付与することのできる材料を添加することができる。具体的には、荷電制御剤等が挙げられる。これらの成分は前述の塩析／融着段階で樹脂粒子と着色剤微粒子と同時に添加し、トナー中に包含する方法、樹脂粒子自体に添加する方法等種々の方法で添加することができる。
【０１３９】
荷電制御剤は、種々の公知のもので、且つ水中に分散することができるものを使用することができる。具体的には、ニグロシン系染料、ナフテン酸または高級脂肪酸の金属塩、アルコキシル化アミン、第４級アンモニウム塩化合物、アゾ系金属錯体、サリチル酸金属塩あるいはその金属錯体等が挙げられる。
【０１４０】
（外添剤）
本発明に係るトナーには、流動性の改良やクリーニング性の向上などの目的で、いわゆる外添剤を添加して使用することができる。これら外添剤としては特に限定されるものでは無く、種々の無機微粒子、有機微粒子及び滑剤を使用することができる。
【０１４１】
外添剤として使用できる無機微粒子としては、従来公知のものを挙げることができる。具体的には、シリカ微粒子、チタン微粒子、アルミナ微粒子等を好ましく用いることができる。これら無機微粒子は疎水性であることが好ましい。
【０１４２】
シリカ微粒子の具体例としては、日本アエロジル株式会社製の市販品Ｒ−８０５、Ｒ−９７６、Ｒ−９７４、Ｒ−９７２、Ｒ−８１２、Ｒ−８０９、ヘキスト株式会社製のＨＶＫ−２１５０、Ｈ−２００、キャボット株式会社製の市販品ＴＳ−７２０、ＴＳ−５３０、ＴＳ−６１０、Ｈ−５、ＭＳ−５等が挙げられる。
【０１４３】
チタン微粒子の具体例としては、例えば、日本アエロジル株式会社製の市販品Ｔ−８０５、Ｔ−６０４、テイカ株式会社製の市販品ＭＴ−１００Ｓ、ＭＴ−１００Ｂ、ＭＴ−５００ＢＳ、ＭＴ−６００、ＭＴ−６００ＳＳ、ＪＡ−１、富士チタン株式会社製の市販品ＴＡ−３００ＳＩ、ＴＡ−５００、ＴＡＦ−１３０、ＴＡＦ−５１０、ＴＡＦ−５１０Ｔ、出光興産株式会社製の市販品ＩＴ−Ｓ、ＩＴ−ＯＡ、ＩＴ−ＯＢ、ＩＴ−ＯＣ等が挙げられる。
【０１４４】
アルミナ微粒子の具体例としては、例えば、日本アエロジル株式会社製の市販品ＲＦＹ−Ｃ、Ｃ−６０４、石原産業株式会社製の市販品ＴＴＯ−５５等が挙げられる。
【０１４５】
外添剤として使用できる有機微粒子としては、数平均一次粒子径が１０〜２０００ｎｍ程度の球形の微粒子を挙げることができる。かかる有機微粒子の構成材料としては、ポリスチレン、ポリメチルメタクリレート、スチレン−メチルメタクリレート共重合体などのを挙げることができる。
【０１４６】
外添剤として使用できる滑剤としては、高級脂肪酸の金属塩を挙げることができる。かかる高級脂肪酸の金属塩の具体例としては、ステアリン酸亜鉛、ステアリン酸アルミニウム、ステアリン酸銅、ステアリン酸マグネシウム、ステアリン酸カルシウム等のステアリン酸金属塩；オレイン酸亜鉛、オレイン酸マンガン、オレイン酸鉄、オレイン酸銅、オレイン酸マグネシウム等のオレイン酸金属塩；パルミチン酸亜鉛、パルミチン酸銅、パルミチン酸マグネシウム、パルミチン酸カルシウム等のパルミチン酸金属塩；リノール酸亜鉛、リノール酸カルシウム等のリノール酸金属塩；リシノール酸亜鉛、リシノール酸カルシウムなどのリシノール酸金属塩等が挙げられる。
【０１４７】
外添剤の添加量としては、トナーに対して０．１〜５質量％程度であることが好ましい。
【０１４８】
〈外添剤の添加工程〉
この工程は、乾燥処理されたトナー粒子に外添剤を添加する工程である。
【０１４９】
外添剤を添加するために使用される装置としては、タービュラーミキサー、ヘンシエルミキサー、ナウターミキサー、Ｖ型混合機などの種々の公知の混合装置を挙げることができる。
【０１５０】
（トナー粒子）
本発明に係るトナーの粒径は、個数平均粒径で３〜１０μｍが好ましく、更に好ましくは３〜８μｍである。この粒径は、トナーの製造方法において、凝集剤（塩析剤）の濃度や有機溶媒の添加量、融着時間、重合体の組成によって制御することができる。
【０１５１】
個数平均粒径が３〜１０μｍであることにより、定着工程において、飛翔して加熱部材に付着しオフセットを発生させる付着力の大きいトナー微粒子が少なくなり、また、転写効率が高くなってハーフトーンの画質が向上し、細線やドット等の画質が向上する。
【０１５２】
トナーの個数平均粒径は、レーザー回折式粒径測定装置「コールターカウンターＴＡ−II」、「コールターマルチサイザー、ＳＬＡＤ１１００」（島津製作所株式会社製レーザー回折式粒径測定装置）等を用いて測定することができる。
【０１５３】
本発明においては、「コールターマルチサイザー」を用い、粒度分布を出力するインターフェース（日科機株式会社製）、パーソナルコンピューターを接続して使用した。前記コールターマルチサイザーにおけるアパーチャーとしては、１００μｍのものを用いて、２μｍ以上（例えば２〜４０μｍ）のトナーの体積分布を測定して粒度分布および平均粒径を算出した。
【０１５４】
（現像剤）
本発明に係るトナーは、一成分現像剤でも二成分現像剤として用いてもよい。
【０１５５】
一成分現像剤として用いる場合は、非磁性一成分現像剤、あるいはトナー中に０．１〜０．５μｍ程度の磁性粒子を含有させ磁性一成分現像剤としたものがあげられ、いずれも使用することができる。
【０１５６】
また、キャリアと混合して二成分現像剤として用いることができる。この場合は、キャリアの磁性粒子として、鉄、フェライト、マグネタイト等の金属、それらの金属とアルミニウム、鉛等の金属との合金等の従来から公知の材料を用いることが出来る。特にフェライト粒子が好ましい。上記磁性粒子は、その体積平均粒径としては１５〜１００μｍ、より好ましくは２５〜８０μｍのものがよい。
【０１５７】
キャリアの体積平均粒径の測定は、代表的には湿式分散機を備えたレーザ回折式粒度分布測定装置「ヘロス（ＨＥＬＯＳ）」（シンパティック株式会社製）により測定することができる。
【０１５８】
キャリアは、磁性粒子が更に樹脂により被覆されているもの、あるいは樹脂中に磁性粒子を分散させたいわゆる樹脂分散型キャリアが好ましい。コーティング用の樹脂組成としては、特に限定は無いが、例えば、オレフィン系樹脂、スチレン系樹脂、スチレン−アクリル系樹脂、シリコーン系樹脂、エステル系樹脂或いはフッ素含有重合体系樹脂等が用いられる。また、樹脂分散型キャリアを構成するための樹脂としては、特に限定されず公知のものを使用することができ、例えば、スチレン−アクリル系樹脂、ポリエステル樹脂、フッ素系樹脂、フェノール樹脂等を使用することができる。
【０１５９】
（画像形成方法）
次に、本発明のトナーを用いる画像形成方法及び画像形成装置について説明する。
【０１６０】
図２は、本発明のトナーを用いる画像形成方法の一例を示す画像形成装置の断面構成図である。
【０１６１】
図２に示す画像形成装置は、デジタル方式による画像形成装置であって、画像読取り部Ａ、画像処理部Ｂ（図示省略）、画像形成部Ｃ、転写紙搬送手段としての転写紙搬送部Ｄから構成されている。
【０１６２】
画像読取り部Ａの上部には原稿を自動搬送する自動原稿送り手段が設けられていて、原稿載置台１１１上に載置された原稿は原稿搬送ローラ１１２によって１枚宛分離搬送され読み取り位置１１３ａにて画像の読み取りが行われる。原稿読み取りが終了した原稿は原稿搬送ローラ１１２によって原稿排紙皿１１４上に排出される。
【０１６３】
一方、プラテンガラス１１３上に置かれた場合の原稿の画像は走査光学系を構成する照明ランプ及び第１ミラーから成る第１ミラーユニット１１５の速度ｖによる読み取り動作と、Ｖ字状に位置した第２ミラー及び第３ミラーから成る第２ミラーユニット１１６の同方向への速度ｖ／２による移動によって読み取られる。
【０１６４】
読み取られた画像は、投影レンズ１１７を通してラインセンサである撮像素子ＣＣＤの受光面に結像される。撮像素子ＣＣＤ上に結像されたライン状の光学像は順次電気信号（輝度信号）に光電変換されたのちＡ／Ｄ変換を行い、画像処理部Ｂにおいて濃度変換、フィルタ処理などの処理が施された後、画像データは一旦メモリに記憶される。
【０１６５】
画像形成部Ｃでは、画像形成ユニットとして、像担持体であるドラム状の感光体（以下、感光体ドラムとも云う）１２１と、その外周に、帯電手段である帯電器１２２、現像手段である現像装置１２３、転写手段である転写器１２４、分離手段である分離器１２５、クリーニング装置（ブレードクリーニング）１２６及びＰＣＬ（プレチャージランプ）１２７が各々動作順に配置されている。感光体１２１は、光導電性化合物をドラム基体上に塗布形成したもので、例えば有機感光体（ＯＰＣ）が好ましく使用され、図示の時計方向に駆動回転される。
【０１６６】
回転する感光体１２１へは帯電器１２２による一様帯電がなされた後、露光光学系１３０により画像処理部Ｂのメモリから呼び出された画像信号に基づいた像露光が行われる。書き込み手段である露光光学系１３０は図示しないレーザーダイオードを発光光源とし、回転するポリゴンミラー１３１、ｆθレンズ（符号なし）、シリンドリカルレンズ（符号なし）を経て反射ミラー１３２により光路が曲げられ主走査がなされるもので、感光体１２１に対してＡｏの位置において像露光が行われ、感光体１２１の回転（副走査）によって潜像が形成される。本実施の形態の一例では文字部に対して露光を行い潜像を形成する。
【０１６７】
感光体１２１上の潜像は現像装置１２３によって反転現像が行われ、感光体１２１の表面に可視像のトナー像が形成される。転写紙搬送部Ｄでは、画像形成ユニットの下方に異なるサイズの転写紙Ｐが収納された転写紙収納手段としての給紙ユニット１４１（Ａ）、１４１（Ｂ）、１４１（Ｃ）が設けられ、また側方には手差し給紙を行う手差し給紙ユニット１４２が設けられていて、それらの何れかから選択された転写紙Ｐは案内ローラ１４３によって搬送路１４０に沿って給紙され、給紙される転写紙の傾きと偏りの修正を行うレジストローラ対１４４によって転写紙Ｐは一時停止を行ったのち再給紙が行われ、搬送路１４０、転写前ローラ１４３ａ及び転写進入ガイド板１４６に案内され、感光体１２１上のトナー画像が転写位置Ｂｏにおいて転写器１２４によって転写紙Ｐに転写され、次いで分離器１２５によって除電されて転写紙Ｐは感光体１２１面より分離し、搬送装置１４５により定着器１５０に搬送される。
【０１６８】
定着器１５０は定着ローラ１５１と加圧ローラ１５２とを有しており、転写紙Ｐを定着ローラ１５１と加圧ローラ１５２との間を通過させることにより、加熱、加圧によってトナーを熔着させる。トナー画像の定着を終えた転写紙Ｐは、排紙トレイ１６４上に排出される。
【０１６９】
【実施例】
以下に、実施例を挙げて具体的に説明するが、本発明の実施態様はこれらに限定されるものではない。
【０１７０】
《前処理着色剤の調製》
下記表１に示す３種の着色剤を、窒素気流中で２００℃に各処理時間加熱し、「前処理着色剤２、３、５、７」を調製した。尚「前処理着色剤１、４、６」は窒素気流中での加熱処理を行わなかったものである。
【０１７１】
前処理着色剤中の芳香族アミン量は、ヘッドスペースガスクロマトグラフにより測定した。尚、芳香族アミンは全てｏ−アニシジン化合物であった。
【０１７２】
表１に、用いた着色剤、処理時間、着色剤中の芳香族アミン量を示す。
【０１７３】
【表１】

【０１７４】
《ウェット状着色剤の調製》
前記「前処理着色剤１〜７」を、表２に示した水分量になるように、それぞれイオン交換水を添加し、２軸混練装置で着色剤を分散し、「ウェット状着色剤１〜７−２」の１３種を調製した。
【０１７５】
表２に、前処理着色剤とウェット状着色剤中の水分量を示す。
【０１７６】
【表２】

【０１７７】
《着色剤分散液の調製》
〔着色剤分散液１の調製〕
ドデシル硫酸ナトリウム９０ｇをイオン交換水１６００ｍｌに撹拌溶解して界面活性剤水溶液（水系媒体）を調製した。この水溶液に、着色剤の量が４０ｇになるよう「ウェット状着色剤１」を、撹拌しながら徐々に添加して着色剤含有溶液を調製した。次いで、撹拌装置「クレアミックス」（エム・テクニック株式会社製）を用いて溶液中の着色剤を水系媒体中に分散し、「着色剤分散液１」を調製した。
【０１７８】
尚、「着色剤分散液１」中の着色剤の質量平均粒子径（分散粒子径）及び粒度分布は、電気泳動光散乱光度計「ＥＬＳ−８００」（大塚電子株式会社製）を用いて測定した値である。
【０１７９】
〔着色剤分散液２−１の調製〕
「着色剤分散液１」で用いた「ウェット状着色剤１」を、「ウェット状着色剤２−１」に変更した以外は、「着色剤分散液１」と同じ条件で「着色剤分散液２−１」を調製した。
【０１８０】
〔着色剤分散液２−２の調製〕
「着色剤分散液１」で用いた「ウェット状着色剤１」を、「ウェット状着色剤２−２」に変更した以外は、「着色剤分散液１」と同じ条件で「着色剤分散液２−２」を調製した。
【０１８１】
〔着色剤分散液２−３の調製〕
「着色剤分散液１」で用いた「ウェット状着色剤１」を、「ウェット状着色剤２−３」に変更した以外は、「着色剤分散液１」と同じ条件で「着色剤分散液２−３」を調製した。
【０１８２】
〔着色剤分散液２−４の調製〕
「着色剤分散液１」で用いた「ウェット状着色剤１」を、「ウェット状着色剤２−４」に変更した以外は、「着色剤分散液１」と同じ条件で「着色剤分散液２−４」を調製した。
【０１８３】
〔着色剤分散液２−５の調製〕
「着色剤分散液１」で用いた「ウェット状着色剤１」を、「ウェット状着色剤２−５」に変更した以外は、「着色剤分散液１」と同じ条件で「着色剤分散液２−５」を調製した。
【０１８４】
〔着色剤分散液３の調製〕
「着色剤分散液１」で用いた「ウェット状着色剤１」を、「ウェット状着色剤３」に変更した以外は、「着色剤分散液１」と同じ条件で「着色剤分散液３」を調製した。
【０１８５】
〔着色剤分散液４の調製〕
「着色剤分散液１」で用いた「ウェット状着色剤１」を、「ウェット状着色剤４」に変更した以外は、「着色剤分散液１」と同じ条件で「着色剤分散液４」を調製した。
【０１８６】
〔着色剤分散液５の調製〕
「着色剤分散液１」で用いた「ウェット状着色剤１」を、「ウェット状着色剤５」に変更した以外は、「着色剤分散液１」と同じ条件で「着色剤分散液５」を調製した。
【０１８７】
〔着色剤分散液６−１の調製〕
「着色剤分散液１」で用いた「ウェット状着色剤１」を、「ウェット状着色剤６−１」に変更した以外は、「着色剤分散液１」と同じ条件で「着色剤分散液６−１」を調製した。
【０１８８】
〔着色剤分散液６−２の調製〕
「着色剤分散液１」で用いた「ウェット状着色剤１」を、「ウェット状着色剤６−２」に変更した以外は、「着色剤分散液１」と同じ条件で「着色剤分散液６−２」を調製した。
【０１８９】
〔着色剤分散液７−１の調製〕
「着色剤分散液１」で用いた「ウェット状着色剤１」を、「ウェット状着色剤７−１」に変更した以外は、「着色剤分散液１」と同じ条件で「着色剤分散液７−１」を調製した。
【０１９０】
〔着色剤分散液７−２の調製〕
「着色剤分散液１」で用いた「ウェット状着色剤１」を、「ウェット状着色剤７−２」に変更した以外は、「着色剤分散液１」と同じ条件で「着色剤分散液７−２」を調製した。
【０１９１】
《着色粒子の調製》
〔着色粒子１の調製〕
（ラテックス（１ＨＭＬ）の調製）
〈１：核粒子の調製（第１段重合）〉
攪拌装置、温度センサー、冷却管、窒素導入装置を取り付けた５０００ｍｌのセパラブルフラスコに、アニオン系界面活性剤Ａ（Ｃ₁₀Ｈ₂₁（ＯＣＨ₂ＣＨ₂）₂ＯＳＯ₃Ｎａ）４．０ｇをイオン交換水３０４０ｇに溶解した界面活性剤溶液（水系媒体）を仕込み、窒素気流下２３０ｒｐｍの攪拌速度で攪拌しながら、内温を８０℃に昇温した。
【０１９２】
この界面活性剤溶液に、重合開始剤（過硫酸カリウム：ＫＰＳ）１０．０ｇをイオン交換水４００ｇに溶解した開始剤溶液を添加し、温度を７５℃とした後、スチレン５２８ｇ、ｎ−ブチルアクリレート２０４ｇ、メタクリル酸６８．０ｇ、ｎ−オクチル−３−メルカプトプロピオン酸エステル２４．４ｇからなる単量体混合液を１時間かけて滴下し、この系を７５℃にて２時間にわたり加熱、攪拌することにより重合（第１段重合）を行い、ラテックス（高分子量樹脂からなる樹脂粒子の分散液）を調製した。これを「ラテックス（１Ｈ）」とする。
【０１９３】
〈２：中間層の形成（第２段重合）〉
攪拌装置を取り付けたフラスコ内において、スチレン９５．０ｇ、ｎ−ブチルアクリレート３６．０ｇ、メタクリル酸９．０ｇ、ｎ−オクチル−３−メルカプトプロピオン酸エステル０．５９ｇからなる単量体混合液に、離型剤として前記例示化合物１９）の７０ｇを添加し、９０℃で加温、溶解して単量体溶液１を調製した。
【０１９４】
次いで、上記アニオン系界面活性剤Ａの１．０ｇを、イオン交換水１５６０ｍｌに溶解した界面活性剤溶液を９８℃に加熱し、この界面活性剤溶液に、核粒子の分散液である前記ラテックス（１Ｈ）を固形分換算で２８ｇ添加した後、循環経路を有する機械式分散機「クレアミックス（ＣＬＥＡＲＭＩＸ）」（エム・テクニック株式会社製）により、上記調製した単量体溶液１を８時間混合分散し、均一な分散粒子径（２８４ｎｍ）を有する乳化粒子（油滴）を含む乳化液を調製した。
【０１９５】
次いで、この乳化液に重合開始剤（ＫＰＳ）５．０ｇをイオン交換水２００ｍｌに溶解した開始剤溶液とイオン交換水７５０ｍｌとを添加し、この系を９８℃にて１２時間にわたり加熱攪拌することにより重合（第２段重合）を行い、ラテックス（高分子量樹脂からなる樹脂粒子の表面が中間分子量樹脂により被覆された構造の複合樹脂粒子の分散液）を得た。これを「ラテックス（１ＨＭ）」とする。
【０１９６】
上記「ラテックス（１ＨＭ）」を乾燥し、走査型電子顕微鏡で観察したところ、ラテックスに取り囲まれなかった例示化合物１９）を主成分とする粒子（４００〜１０００ｎｍ）が観察された。
【０１９７】
〈３：外層の形成（第３段重合）〉
上記調製した「ラテックス（１ＨＭ）」に、重合開始剤（ＫＰＳ）６．８ｇをイオン交換水２６５ｍｌに溶解した開始剤溶液を添加し、８０℃の温度条件下で、スチレン２４９ｇ、ｎ−ブチルアクリレート８８．２ｇ、メタクリル酸１９．４ｇ、ｎ−オクチル−３−メルカプトプロピオン酸エステル７．４５ｇからなる単量体混合液を１時間かけて滴下した。滴下終了後、２時間にわたり加熱攪拌することにより重合（第３段重合）を行った後、２８℃まで冷却し、ラテックス（高分子量樹脂からなる中心部と、中間分子量樹脂からなる中間層と、低分子量樹脂からなる外層とを有し、中間層に離型剤として例示化合物１９）が含有されている複合樹脂粒子の分散液）を得た。このラテックスを「ラテックス（１ＨＭＬ）」とする。
【０１９８】
〈ラテックス（２Ｌ）の調製〉
攪拌装置を取り付けたフラスコ内に、重合開始剤（ＫＰＳ）１４．８ｇをイオン交換水４００ｍｌに溶解した開始剤溶液を添加し、８０℃の温度条件下で、スチレン６００ｇ、ｎ−ブチルアクリレート１９０ｇ、メタクリル酸３０．０ｇ、ｎ−オクチル−３−メルカプトプロピオン酸エステル２０．８ｇからなる単量体混合液を１時間かけて滴下した。滴下終了後、２時間にわたり加熱攪拌することにより重合を行った後、２８℃まで冷却し、ラテックス（低分子量樹脂からなる樹脂粒子の分散液）を得た。このラテックスを「ラテックス（２Ｌ）」とする。
【０１９９】
このラテックス（２Ｌ）を構成する樹脂粒子は、１１，０００に分子量ピークを有するものであり、またこの樹脂粒子の質量平均粒径は１２８ｎｍであった。
【０２００】
（凝集・融着工程）
前記調製した「ラテックス（１ＨＭＬ）」４２０．７ｇ（固形分換算）と、イオン交換水９００ｇと、上記調製した「着色剤分散液１」２００ｇとを、温度センサー、冷却管、窒素導入装置、攪拌装置を取り付けた反応容器（四つ口フラスコ）に入れ攪拌した。容器内の温度を３０℃に調整した後、この溶液に５モル／Ｌの水酸化ナトリウム水溶液を加えてｐＨを９．０に調整した。
【０２０１】
次いで、塩化マグネシウム・６水和物の１２．１ｇをイオン交換水１０００ｍｌに溶解した水溶液を、攪拌下で３０℃にて１０分間かけて添加した。３分間放置した後に昇温を開始し、この水溶液を６０分間かけて９０℃まで昇温し、粒子の成長を開始した。その状態で、「コールターカウンターＴＡ−II」にて会合粒子の粒径を測定し、体積平均粒径が５．０μｍになった時点で、停止剤として塩化ナトリウムの４０．２ｇをイオン交換水１０００ｍｌに溶解した水溶液を添加して粒子成長を停止させた。さらに、熟成処理として、液温度９８℃にて２時間にわたり加熱攪拌することにより融着を継続させた。その後、８℃／分の条件で３０℃まで冷却した。
【０２０２】
（シェリング工程）
上記により、凝集・融着を行った粒子に、前記調製した「ラテックス（２Ｌ）」９６ｇを添加し、３時間に亘り加熱、攪拌を継続し、「ラテックス（１ＨＭＬ）」の凝集粒子表面に「ラテックス（２Ｌ）」をシェリングさせた。次いで、塩化ナトリウム４０．２ｇを添加し、８℃／分の降温条件で３０℃まで冷却し、次いで、塩酸を添加してｐＨを２．０に調整して、攪拌を停止した。
【０２０３】
以上のようにしてシェリングした融着粒子を濾過し、４５℃のイオン交換水で繰り返し洗浄し、その後、４０℃の温風で乾燥することにより、「着色粒子１」を調製した。
【０２０４】
〔着色粒子２〜１３の調製〕
上記「着色粒子１」の調製において、着色剤分散液として用いた「着色剤分散液１」を「着色剤分散液２−１〜７−２」に変更した以外は同様にして、「着色粒子２〜１３」を調製した。
【０２０５】
《トナー、現像剤の調製》
上記調製した「着色粒子１〜１３」に、それぞれ疎水性シリカ（数平均一次粒径＝１２ｎｍ、疎水化度＝６８）を１．０質量％及び疎水性酸化チタン（数平均一次粒径＝２０ｎｍ、疎水化度＝６３）を１．２質量％添加し、ヘンシェルミキサーにより混合して、「トナー１〜１３」を調製した。
【０２０６】
次いで、上記調製した各トナーに対して、シリコーン樹脂を被覆した体積平均粒径６０μｍのフェライトキャリアを混合し、それぞれトナー濃度が６％の「現像剤１〜１３」を調製した。
【０２０７】
尚、トナーの粒子径は、「コールターマルチサイザー」（コールター株式会社製）を使用して測定した値である。
【０２０８】
表３に、トナー調製に用いた前処理着色剤番号、ウェット着色剤番号、着色剤分散液中の着色剤の粒子径及び粒度分布、トナーの粒子径、トナー中の芳香族アミン量を示す。
【０２０９】
【表３】

【０２１０】
《評価結果》
（臭気）
床が５ｍ×５ｍ、高さが２ｍの密閉された部屋の中で、デジタル複写機「コニカ７０６５」（コニカ株式会社製）を改造して、定着器の定着ロール表面温度を１７０℃に設定した評価機を用い、上記で調製した「トナー１〜１３」と「現像剤１〜１３」で、画素率が７％のＡ４版画像を連続して１０００枚プリントを行った。
【０２１１】
臭気の評価は、１０００枚のプリント終了時に２０名の評価員により、臭気を感じた人数で行った。
【０２１２】
評価基準
◎：１名の評価員も臭気を感じなかった
○：３名以下の評価員が臭気を感じた
×：４名以上の評価員が臭気を感じた。
【０２１３】
（機内部材の着色汚染）
デジタル複写機「コニカ７０６５」（コニカ株式会社製）を改造して、定着器の定着ロール表面温度を１７０℃に設定した評価機を用い、トナー及び着色剤が飛散しやすい高温高湿の環境（３３℃、８０％ＲＨ）下、上記で調製した「トナー１〜１３」と「現像剤１〜１３」で、画素率が７％のＡ４版画像を連続して５０，０００枚プリントを行った。
【０２１４】
プリント終了後、評価機内を観察し、着色汚染された部材の汚染がどの程度で落ちるかを評価した。
【０２１５】
評価基準
○：着色汚染された部材を指で触ると、汚染が落ちるレベル
×：着色汚染された部材を指でこすっても、汚染が落ちないレベル
評価結果を、表４に示す。
【０２１６】
【表４】

【０２１７】
表４より明らかなように、本発明のトナー（トナー番号１、３、４、５、７、８、９、１３）を用いると、比較例のトナー（トナー番号２、６、１０、１１、１２）に比較して、機内部材の着色汚染が落としやすく、熱定着時に発生する臭気が少ないことが判る。
【０２１８】
【発明の効果】
実施例で実証した如く、本発明のトナー、該トナーの製造方法、それを用いた画像形成方法及び画像形装置は、機内部材の着色汚染、熱定着時の臭気発生が低減されており優れた効果を有する。
【図面の簡単な説明】
【図１】着色剤分散液を調製するための分散装置の一例を示す。
【図２】本発明のトナーを用いる画像形成方法の一例を示す画像形成装置の断面構成図である。
【符号の説明】
１０１ スクリーン
１０２ ロータ
Ｍ 攪拌室
１０３ 加圧真空アタッチメント
１０４ 予備分散液入口
１０５ 分散液出口
１０７ 冷却ジャケット
１０８ 冷却コイル
１２１ 感光体
１２２ 帯電器
１２３ 現像装置
１２４ 転写器
１２５ 分離器
１２６ クリーニング装置
１２７ ＰＣＬ（プレチャージランプ）
１３０ 露光光学系
１５１ 定着器
Ｐ 転写紙[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a toner for developing an electrostatic image in which coloring contamination of in-machine members and generation of odor during heat fixing are reduced, a method for producing the toner for developing an electrostatic image, an image forming method and an image forming apparatus using the same. It is.
[0002]
[Prior art]
In digital copiers and laser printers, high-quality images can be continuously obtained even when large quantities of printing are performed. It is important that the colorant is uniformly incorporated into the toner particles by the diameter, that there is no free colorant, and that the colorant used does not contain a compound that generates odor.
[0003]
Generally, the colorant is used by dispersing it in toner particles after uniformly dispersing the powdery colorant by applying energy such as mechanical dispersion or ultrasonic dispersion. However, in this method, since the energy applied to disperse the colorant tends to be non-uniform, the dispersed particle size of the colorant is difficult to be uniform, and the distribution of the dispersed particle size tends to be broad. As a result, a phenomenon occurs in which the colorant is not uniformly dispersed in the formed toner particles, or there is a free colorant that cannot enter the toner particles. When printing using this toner, the charge amount of the toner decreases with the print, and a high-quality image cannot be obtained, or the in-machine member enters the toner or toner particles that are easily scattered due to the decrease in the charge amount. It becomes easy to be colored and contaminated with a free colorant that cannot be contained.
[0004]
Further, many colorants contain compounds having an odor, and when these are used as raw materials for the colorant, an odor is generated by heating during fixing.
[0005]
As a prior application patent according to the present invention, there is one that pays attention to dispersion of a colorant (for example, see Patent Document 1).
[0006]
There is a problem that the in-machine member is colored and contaminated due to scattering of the toner whose charge amount is reduced due to the colorant not being uniformly dispersed in the toner particles, or scattering of the liberated colorant, and odor is added to the raw colorant. The problem with the generated compounds is remarkable in the yellow colorant, and it has not been solved yet.
[0007]
[Patent Document 1]
JP 2001-08736 A
[0008]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION The present invention has been proposed in view of the above-mentioned problems, and the object of the present invention is to prevent electrostatic staining of an in-machine member and to generate an electrostatic charge image developing toner (hereinafter simply referred to as toner) that generates less odor during heat fixing. Another object is to provide a method for producing the toner, an image forming method using the toner, and an image forming apparatus.
[0009]
[Means for Solving the Problems]
The object of the present invention is achieved by adopting the following configuration.
[0010]
  1. In the toner for developing an electrostatic charge image containing at least a resin and a colorant, the colorant is a yellow colorant, and the yellow colorant is a wet colorant having a water content of 40 to 80% by mass.Polymerization method dispersed in water systemAnd a toner for developing an electrostatic image, wherein the content of the o-anisidine compound is 0.1 to 50 ppm.
[0011]
  2. In the toner for developing an electrostatic charge image containing at least a resin and a colorant, the colorant is a yellow colorant, and the yellow colorant is a wet colorant having a water content of 40 to 80% by mass.Polymerization method dispersed in water systemAnd a toner for developing an electrostatic image, wherein the content of the o-anisidine compound is 0.1 to 20 ppm.
[0012]
3. 3. The method for producing a toner for developing an electrostatic charge image according to 1 or 2, wherein the toner component is produced through a drying step after the toner component is dispersed in a solvent. Manufacturing method.
[0013]
4). 3. A method for producing a toner for developing an electrostatic charge image according to item 1 or 2, wherein the toner is produced through a step of dispersing a wet colorant in an aqueous system.
[0016]
  As a result of intensive studies, the present inventors have found that a toner having a water content of 40 to 80% by mass is easy to obtain uniformly dispersed particles close to primary fine particles instead of a dry powder colorant that is difficult to uniformly disperse during toner production. Uses wet colorant and causes odoro-anisidine compound (hereinafter referred to as aromatic amine)It has been found that the use of a small amount of colorant can reduce the occurrence of odor at the time of color contamination of the in-machine member and heat fixing, and as a result, the present invention has been achieved.
[0017]
In the present invention, the toner contains at least a resin and a colorant, and the colorant is a yellow colorant, and the yellow colorant has a moisture content of 40 to 80% by mass with which uniform dispersed particles are easily obtained. And a colorant in which the amount of the aromatic amine is adjusted so that the amount of the aromatic amine in the toner is 0.1 to 50 ppm is used.
[0018]
Hereinafter, the present invention will be described in detail.
The colorant used in the toner of the present invention is a yellow colorant.
[0019]
Examples of the yellow colorant include a monoazo yellow colorant and a disazo yellow colorant. Among these, a monoazo yellow colorant is preferable.
[0020]
Examples of the yellow colorant include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 156, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, and the like, but are not limited thereto.
[0021]
The colorant used as a raw material in the present invention is in a wet state having a water content of 40 to 80% by mass.
[0022]
A wet colorant having a water content of 40 to 80% by mass is originally familiar with water, so when dispersed in water, it easily disperses uniformly to near the primary particle diameter. When the toner is produced, the colorant can be uniformly dispersed in the toner particles, and the amount of the colorant released from the toner particles can be reduced as much as possible.
[0023]
When the water content is less than 40% by mass, it is difficult to make the colorant evenly blended with water since the water content is small. On the other hand, if the amount of water exceeds 80% by mass, the amount of water increases so that it is difficult to keep the colorant stably dispersed in water.
[0024]
The wet colorant can be prepared by a method of finishing in a wet state at the time of producing the colorant, or a method of adding an appropriate amount of ion exchange water to a once dried colorant fine powder and then redispersing using a dispersing device. The preparation method is not particularly limited as long as it can be uniformly blended with water.
[0025]
Examples of the apparatus capable of preparing the wet colorant include a uniaxial kneading apparatus, a biaxial kneading apparatus, a two-roll kneading apparatus, a three-roll kneading apparatus, a ball mill, and a sand mill. Among these, a biaxial kneader is preferable.
[0026]
The colorant dispersion used for obtaining the toner of the present invention can be prepared by dispersing the wet colorant in an aqueous medium containing a surfactant using the following dispersing device.
[0027]
The surfactant for dispersing the wet colorant in the aqueous medium is dissolved at a concentration equal to or higher than the critical micelle concentration (CMC), and the surfactant used is the toner polymerization described below. The same one used in the process can be used.
[0028]
The mass average particle diameter (dispersion particle diameter) of the colorant fine particles in the colorant dispersion is preferably 10 to 200 nm. When the mass average particle size of the colorant fine particles is less than 10 nm, the colorant fine particles are suspended in the aqueous system, and when the mass average particle size exceeds 200 nm, the colorant fine particles are appropriately dispersed in the aqueous system. Since it becomes easy to settle without being dispersed, it becomes difficult to introduce the colorant into the toner particles, and the colorant is not preferred because it remains free in the aqueous system without being taken into the toner particles.
[0029]
The particle size distribution of the colorant fine particles in the colorant dispersion is preferably 20 to 60 nm with a standard deviation.
[0030]
The mass average particle diameter (dispersed particle diameter) and particle size distribution of the colorant fine particles can be measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.).
[0031]
The dispersion device for obtaining a colorant dispersion by dispersing a wet colorant in an aqueous medium is not particularly limited, and a stirring device “CLEARMIX” (M Technique) equipped with a rotor that rotates at high speed. Co., Ltd.), ultrasonic dispersers, mechanical homogenizers, manton gourins, pressure dispersers such as pressure homogenizers, and medium dispersers such as Getzmann mills and diamond fine mills. “Mix” is preferred.
[0032]
This “Clearmix” has a rotor (stirring blade) that rotates at a high speed and a fixed screen (fixed ring) that surrounds the rotor, and a shearing force, collision force, pressure fluctuation, cavitation and It has a structure that imparts the action of a potential core, and these actions function synergistically to effectively emulsify and disperse the liquid to be treated.
[0033]
FIG. 1 shows an example of a dispersing device for preparing a colorant dispersion.
That is, the dispersing apparatus shown in FIG. 1 generates a shearing force by a screen that forms a stirring chamber and a rotor that rotates at a high speed in the stirring chamber, and the action of the shearing force (in addition, collision force, pressure fluctuation, cavitation). By the action of the potential core, the wet colorant is uniformly dispersed in the aqueous medium containing the surfactant to obtain a stable colorant dispersion.
[0034]
FIG. 1A is a schematic diagram showing a rotor that rotates at a high speed and a fixed screen that surrounds the rotor. In FIG. 1, 101 is a screen, M is an agitation chamber partitioned by the screen 101, 102. Indicates a rotor rotating at high speed in the stirring chamber M.
[0035]
The rotor 102 is a stirring blade that rotates at a high speed, and its rotation speed is usually 4,500 to 22,000 rpm, preferably 10,000 to 21,500 rpm. The tip peripheral speed of the rotor 102 is usually 10 to 40 m / sec, preferably 15 to 30 m / sec.
[0036]
The screen 101 arranged so as to surround the rotor 102 is formed of a fixed ring composed of a large number of slits (not shown). The width of the slit is 0.5 to 5 mm, preferably 0.8 to 2 mm. Moreover, the number of slits is 10-50, Preferably it is 15-30. The gap (clearance) between the rotor 102 and the screen 101 is usually 0.1 to 1.5 mm, preferably 0.2 to 1.0 mm.
[0037]
The average particle size and particle size distribution of the colorant fine particles are adjusted by controlling the number of revolutions of the rotor 102, and can be adjusted by selecting the shapes of the screen 101 and the rotor 102. Specifically, the screen (S1.0-24, S1.5-24, S1.5-18, S2.0-18, S3.0-9) and the rotor (R1), which are standard equipment in “CLEARMIX”, are provided. Although a preferable dispersion state is obtained by combination with ~ R4), it may be produced in-house to obtain a more preferable dispersion state.
[0038]
FIG.1 (b) is a schematic diagram which shows the continuous processing apparatus (Clear mix) provided with the rotor and the screen. The predispersed dispersion liquid (preliminary dispersion liquid) is supplied to the stirring chamber between the screen 101 and the rotor from the preliminary dispersion liquid inlet 104 shown in FIG. The screen 101 and the rotor are surrounded by a pressurized vacuum attachment 103, and a temperature sensor, a cooling jacket 107, and a cooling coil 108 are disposed. The colorant in the preliminary dispersion is dispersed in the aqueous medium by applying a shearing force generated by the rotor rotating at high speed and the screen 101.
[0039]
That is, the colorant in the preliminary dispersion supplied to the band-shaped stirring chamber between the screen 101 and the rotor receives a shearing force (mechanical energy) generated by high-speed rotation of the screen 101 and the rotor, Further, in addition to the shearing force, it is stably dispersed in the aqueous medium by the action of collision force, pressure fluctuation, cavitation, and potentio core, and becomes a colorant dispersion. The dispersion liquid of the colorant fine particles is ejected from the slit of the screen 101 into the pressurized vacuum attachment 103, and a dispersion liquid of the colorant fine particles having the same average particle size and particle size distribution as the wet colorant is obtained. The dispersion liquid containing the colorant fine particles is sent to the next process from the dispersion liquid outlet 105.
[0040]
The amount of aromatic amine in the toner of the present invention is 0.1 to 50 ppm.
When the amount of the aromatic amine exceeds 50 ppm, the odor due to the aromatic amine volatilized at the time of heat fixing becomes so bad that it is not preferable.
[0041]
The amount of aromatic amine in the toner can be adjusted to 0.1 to 50 ppm by limiting the amount of aromatic amine in the colorant used as a raw material to a specified range.
[0042]
Examples of a method for keeping the amount of aromatic amine in the colorant within a specified range include heating the colorant in a nitrogen stream or reducing the pressure at room temperature. Among these, heating is performed in a nitrogen stream. The method is preferred.
[0043]
In the present invention, the amount of the aromatic amine in the colorant and toner can be measured by a head space type gas chromatograph using a detection method used in a normal gas chromatograph such as an internal standard method. In this method, a colorant or toner is sealed in an open / close container, heated to a temperature at the time of heat fixing of a copying machine or the like, and the gas in the container is quickly gas chromatographed in a state where the container is filled with volatile components. In addition to measuring the amount of volatile components by injecting into the gas, MS (mass spectrometry) is also performed.
[0044]
Below, the measuring method by a head space gas chromatograph is demonstrated in detail.
<Headspace gas chromatograph measurement method>
1. Sample collection
Take 0.8 g of sample in a 20 ml headspace vial. The sample amount is weighed to 0.01 g (necessary for calculating the area per unit mass). Seal the vial with a septum using a dedicated crimper.
[0045]
2. Sample heating
The sample is put in a 170 ° C. constant temperature bath and heated for 30 minutes.
[0046]
3. Setting gas chromatographic separation conditions
A separation column is prepared by packing a carrier coated with silicon oil SE-30 to a mass ratio of 15% into a column having an inner diameter of 3 mm and a length of 3 m. The separation column is attached to a gas chromatograph, and He is used as a carrier to flow at 50 ml / min. The temperature of the separation column is set to 40 ° C., and measurement is performed while the temperature is increased to 260 ° C. at 15 ° C./min. Hold for 5 minutes after reaching 260 ° C.
[0047]
4). Sample introduction
The vial bottle is taken out from the thermostat, and 1 ml of gas generated from the sample is immediately collected with a gas tight syringe and injected into the separation column.
[0048]
5. Calculation
A calibration curve is prepared in advance using the aromatic hydrocarbon compound used as the internal reference material, and the concentration of each component is determined.
[0049]
6). equipment
(1) Headspace conditions
Headspace equipment
HP 7694 manufactured by Hewlett-Packard Co., Ltd.
Temperature conditions
Transfer line: 200 ° C
Loop temperature: 200 ° C
Sample volume: 0.8g / 20ml vial
(2) GC / MS conditions
GC: HP5890 manufactured by Hewlett-Packard Co., Ltd.
MS: HP5971 manufactured by Hewlett-Packard Co., Ltd.
Column: HP-624 30m x 0.25mm
Oven temperature: 40 ° C (3min) -15 ° C / min-260 ° C
Measurement mode: SIM
Next, the toner of the present invention and the method for producing the toner will be described.
[0050]
The toner of the present invention is characterized by being manufactured through a drying process after the toner component is dispersed in a solvent, and manufactured through a process of dispersing the wet colorant in an aqueous system.
[0051]
As a specific production method, a polymerizable monomer (monomer) as a starting material, for example, a production method by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, a dispersion polymerization method, or a solvent in advance Examples of the production method include dispersing and suspending a solution of the toner component dissolved or dispersed in the aqueous medium in an aqueous medium. Among these, a production method for polymerizing a polymerizable monomer in an aqueous medium is mentioned. preferable.
[0052]
In this production method, a polymerizable monomer is polymerized by a suspension polymerization method to prepare resin particles, or a polymerizable monomer in a liquid (in an aqueous medium) to which an emulsion of a necessary additive is added. The body is subjected to emulsion polymerization or mini-emulsion polymerization to prepare fine resin particles. If necessary, charge controllable resin particles are added, and then an organic solvent, a flocculant such as a salt is added, and the resin particles are added. Is produced by a method of agglomerating and fusing.
[0053]
<Suspension polymerization method>
As an example of a method for producing the toner of the present invention, a charge control resin is dissolved in a polymerizable monomer, and various constituent materials such as a colorant, a mold release agent, and a polymerization initiator are added. Then, various constituent materials are dissolved or dispersed in the polymerizable monomer using a homogenizer, a sand mill, a sand grinder, an ultrasonic disperser or the like. The polymerizable monomer in which these various constituent materials are dissolved or dispersed is dispersed in oil droplets of a desired size as a toner in an aqueous medium containing a dispersion stabilizer using a homomixer or a homogenizer. Thereafter, the stirring mechanism is transferred to a reaction device (stirring device) which is a stirring blade described later, and the polymerization reaction is advanced by heating. After completion of the reaction, the dispersion stabilizer is removed, filtered, washed, and dried to prepare the toner of the present invention. The “aqueous medium” here refers to a medium containing at least 50% by mass of water.
[0054]
<Emulsion polymerization method>
As another method for producing the toner of the present invention, a method in which resin particles are prepared by aggregation / fusion in an aqueous medium is preferable. The method is not particularly limited, and examples thereof include methods disclosed in JP-A Nos. 5-265252, 6-329947, and 9-15904. That is, a method of salting out, agglomerating, and fusing a plurality of fine particles composed of resin particles and colorants, or a constituent material such as resin particles and a colorant, particularly in water using an emulsifier Then, a coagulant with a critical coagulation concentration or higher is added for salting out, and at the same time, the formed polymer is heated and fused at a temperature higher than the glass transition temperature of the polymer itself to gradually grow the particle size while forming fused particles. When the desired particle size is reached, a large amount of water is added to stop particle size growth, and the shape is controlled by smoothing the particle surface while heating and stirring, and the particles are heated in a fluidized state while containing water. By drying, the toner of the present invention can be formed. Here, a solvent that is infinitely soluble in water, such as alcohol, may be added simultaneously with the flocculant.
[0055]
In the toner production method of the present invention, the crystalline resin is dissolved in the polymerizable monomer, and then the composite resin fine particles and the colorant fine particles formed through the step of polymerizing the polymerizable monomer are salted out / fused. A method of wearing is preferably used. When the crystalline substance is dissolved in the polymerizable monomer, the crystalline substance may be dissolved and dissolved, or may be melted and dissolved.
[0056]
In addition, as a method for producing the toner of the present invention, a step of salting out / fusion of composite resin fine particles and colorant fine particles obtained by a multistage polymerization method is preferably used. Here, the multistage polymerization method will be described below.
[0057]
(Method for producing composite resin particles obtained by multistage polymerization method)
When the multistage polymerization method is used, the toner production method of the present invention is preferably composed of the following steps.
[0058]
1: Multistage polymerization process
2: A salting out / fusing step for obtaining toner particles by salting out / fusing the composite resin particles and the colorant fine particles.
3: Filtration / washing step of separating the toner particles from the toner particle dispersion and removing the surfactant from the toner particles.
4: Drying step of drying the washed toner particles
5: Step of adding an external additive to the dried toner particles
Consists of
[0059]
Hereinafter, each step will be described in detail.
[Multistage polymerization process]
The multi-stage polymerization step is a polymerization method performed for expanding the molecular weight distribution of the resin particles so as to obtain a toner in which offset generation is prevented. That is, in order to form phases having different molecular weight distribution in one resin particle, the polymerization reaction is performed in multiple stages, and the obtained resin particle has a molecular weight gradient from the center of the particle toward the surface layer. It is intended to be formed. For example, a method of forming a low molecular weight surface layer by first obtaining a high molecular weight resin particle dispersion and then newly adding a polymerizable monomer and a chain transfer agent is employed.
[0060]
In the present invention, it is preferable to employ a multi-stage polymerization method of three-stage polymerization or more from the viewpoint of production stability and crushing strength of the resulting toner. Hereinafter, the two-stage polymerization method and the three-stage polymerization method, which are representative examples of the multistage polymerization method, will be described. The toner obtained by such a multistage polymerization reaction preferably has a lower molecular weight as the surface layer from the viewpoint of crushing strength.
[0061]
<Two-stage polymerization method>
The two-stage polymerization method is a method for producing composite resin particles composed of a central portion (core) formed from a high molecular weight resin containing a crystalline substance and an outer layer (shell) formed from a low molecular weight resin. is there.
[0062]
This method will be described in detail. First, a crystalline substance is dissolved in a monomer to prepare a monomer solution, and the monomer solution is added to oil droplets in an aqueous medium (for example, a surfactant aqueous solution). After the dispersion, this system is polymerized (first stage polymerization) to prepare a dispersion of high molecular weight resin particles containing a crystalline substance.
[0063]
Next, a polymerization initiator and a monomer for obtaining a low molecular weight resin are added to the dispersion of the resin particles, and the monomer is polymerized in the presence of the resin particles (second-stage polymerization). Thus, a coating layer made of a low molecular weight resin (monomer polymer) is formed on the surface of the resin particles.
[0064]
<Three-stage polymerization method>
The three-stage polymerization method produces composite resin particles composed of a central part (core) formed from a high molecular weight resin, an intermediate layer containing a crystalline substance, and an outer layer (shell) formed from a low molecular weight resin. Is the method. The toner of the present invention exists as the composite resin particles as described above.
[0065]
This method will be specifically described. First, a dispersion of resin particles obtained by a polymerization process (first-stage polymerization) according to a conventional method is added to an aqueous medium (for example, an aqueous solution of a surfactant). In the aqueous medium, a monomer solution obtained by dissolving a crystalline substance in a monomer is dispersed in oil droplets, and then this system is polymerized (second-stage polymerization) to obtain resin particles (cores). A coating layer (intermediate layer) made of a resin (monomer polymer) containing a crystalline substance is formed on the surface of the particles, and a dispersion of composite resin particles (high molecular weight resin-intermediate molecular weight resin) is prepared. Prepare.
[0066]
Next, a polymerization initiator and a monomer for obtaining a low molecular weight resin are added to the obtained dispersion of composite resin particles, and the monomer is polymerized in the presence of the composite resin particles (third-stage polymerization). ), A coating layer made of a low molecular weight resin (monomer polymer) is formed on the surface of the composite resin particles. In the above method, the incorporation of the intermediate layer is preferable because the crystalline substance can be finely and uniformly dispersed.
[0067]
One aspect of the toner production method of the present invention is that the polymerizable monomer is polymerized in an aqueous medium. That is, when forming resin particles (core particles) or a coating layer (intermediate layer) containing a crystalline substance, the crystalline substance is dissolved in the monomer, and the resulting monomer solution is oiled in an aqueous medium. It is a method of obtaining latex particles by dispersing in drops and adding a polymerization initiator to this system for polymerization treatment.
[0068]
The aqueous medium used here refers to a medium comprising 50 to 100% by mass of water and 0 to 50% by mass of a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, tetrahydrofuran, and the like, and an alcohol-based organic solvent that does not dissolve the obtained resin is preferable.
[0069]
As a suitable polymerization method for forming resin particles or a coating layer containing a crystalline substance, the crystalline substance is a monomer in an aqueous medium in which a surfactant having a concentration equal to or lower than the critical micelle concentration is dissolved. The monomer solution dissolved in is dispersed in oil droplets using mechanical energy to prepare a dispersion, and a water-soluble polymerization initiator is added to the resulting dispersion to cause radical polymerization in the oil droplets. A method (hereinafter referred to as “mini-emulsion method” in the present invention), and the effects of the present invention can be exhibited more preferably. In the above method, an oil-soluble polymerization initiator may be used instead of or together with the water-soluble polymerization initiator.
[0070]
According to the mini-emulsion method that mechanically forms oil droplets, unlike the usual emulsion polymerization method, the crystalline substance dissolved in the oil phase has little detachment and is sufficient in the formed resin particles or coating layer. Any amount of crystalline material can be introduced.
[0071]
Here, the dispersing machine for dispersing oil droplets by mechanical energy is not particularly limited. For example, a stirring device “CLEARMIX” (M Technique Co., Ltd.) equipped with a rotor that rotates at high speed. Company-made), ultrasonic disperser, mechanical homogenizer, manton gourin and pressure homogenizer. Further, the dispersed particle diameter is preferably 10 to 1000 nm, more preferably 50 to 1000 nm, and particularly preferably 30 to 300 nm.
[0072]
By giving a distribution to the dispersed particle diameter, the phase separation structure of the crystalline substance in the toner particles, that is, the ferret horizontal diameter, the shape factor, and the coefficient of variation thereof may be controlled.
[0073]
In addition, as other polymerization methods for forming resin particles or a coating layer containing a crystalline substance, known methods such as an emulsion polymerization method, a suspension polymerization method, and a seed polymerization method can be employed. These polymerization methods can also be employed to obtain resin particles (core particles) or coating layers constituting the composite resin particles that do not contain a crystalline substance.
[0074]
The particle diameter of the composite resin particles obtained in this polymerization step is in the range of 10 to 1000 nm in terms of mass average particle diameter measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.). It is preferable.
[0075]
Moreover, it is preferable that the glass transition temperature (Tg) of a composite resin particle exists in the range of 48-74 degreeC, More preferably, it is 52-64 degreeC.
[0076]
The softening point of the composite resin particles is preferably in the range of 95 to 140 ° C.
The toner of the present invention is obtained by fusing resin particles on the surface of the resin and colored particles by a salting-out / fusing method to form a resin layer. This will be described below.
[0077]
[Salting out / fusion process]
This salting-out / fusion process is carried out by salting out / bonding the composite resin particles and the colorant fine particles obtained in the multistage polymerization process (to cause salting-out and fusion at the same time). This is a step of obtaining non-spherical toner particles.
[0078]
In the present invention, salting out / fusion means that salting out (aggregation of particles) and fusion (disappearance of the interface between particles) occur simultaneously or salting out and fusion occur simultaneously. . In order to perform salting-out and fusion at the same time, it is preferable to agglomerate particles (composite resin particles, colorant fine particles) under a temperature condition equal to or higher than the glass transition temperature (Tg) of the resin constituting the composite resin particles. .
[0079]
In this salting-out / fusion step, internal additive particles such as a charge control agent (fine particles having a number average primary particle size of about 10 to 1000 nm) may be salted out / fused together with the composite resin particles and the colorant fine particles. Good. Further, the colorant fine particles may be surface-modified, and conventionally known ones can be used as the surface modifier.
[0080]
[Aging process]
The aging step is a step subsequent to the salting-out / fusion step, and after the resin particles are fused, the temperature is kept near the melting point of the crystalline substance, preferably the melting point ± 20 ° C., and stirring is continued at a constant strength. This is a step of phase-separating the crystalline substance. In this step, it is possible to control the ferret horizontal diameter, shape factor, and variation coefficient of the crystalline material.
[0081]
Moreover, in this invention, it is preferable that the total value of the bivalent (trivalent) metal element used for a coagulant | flocculant and the monovalent | monohydric metal element added as an aggregation terminator mentioned later is 350-35000 ppm. The measurement of the residual amount of metal ions in the toner is performed using a fluorescent X-ray analyzer “System 3270 type” (manufactured by Rigaku Denki Kogyo Co., Ltd.) and a metal species of a metal salt used as a flocculant (for example, calcium chloride It can be determined by measuring the intensity of the fluorescent X-ray emitted from the calcium. As a specific measurement method, a plurality of toners having a known content ratio of the flocculant metal salt are prepared, each toner 5g is pelletized, the content ratio (mass ppm) of the flocculant metal salt, and the metal species of the metal salt The relationship (calibration curve) with the fluorescent X-ray intensity (peak intensity) is measured. Next, the toner (sample) whose content of the flocculant metal salt is to be measured is similarly pelletized, and the fluorescent X-ray intensity from the metal species of the flocculant metal salt is measured. Amount "can be determined.
[0082]
[Filtering and washing process]
In this filtration / washing step, a filtration treatment for filtering the toner particles from the toner particle dispersion obtained in the above step, and a surfactant or salt from the filtered toner particles (cake-like aggregate). A cleaning process for removing deposits such as a depositing agent is performed. Here, the filtration method is not particularly limited, such as a centrifugal separation method, a vacuum filtration method using Nutsche or the like, a filtration method using a filter press or the like.
[0083]
[Drying process]
This step is a step of drying the washed toner particles.
[0084]
Examples of dryers used in this process include spray dryers, vacuum freeze dryers, vacuum dryers, etc., stationary shelf dryers, mobile shelf dryers, fluidized bed dryers, rotary dryers It is preferable to use a stirring dryer or the like.
[0085]
The water content of the dried toner particles is preferably 5% by mass or less, and more preferably 2% by mass or less.
[0086]
In addition, when the toner particles that have been dried are aggregated due to weak interparticle attraction, the aggregate may be crushed. Here, as the crushing treatment apparatus, a mechanical crushing apparatus such as a jet mill, a Henschel mixer, a coffee mill, or a food processor can be used.
[0087]
The toner of the present invention forms composite resin particles in the absence of a colorant, adds a dispersion of colorant fine particles to the dispersion of the composite resin particles, and saltes out the composite resin particles and the colorant fine particles. It is preferably prepared by fusing.
[0088]
Thus, the polymerization reaction for obtaining the composite resin particles is not inhibited by preparing the composite resin particles in a system in which no colorant is present. For this reason, according to the toner of the present invention, excellent offset resistance is not impaired, and coloring contamination and image staining of the in-machine member due to the toner and the colorant are not caused.
[0089]
Further, as a result of the polymerization reaction for obtaining the composite resin particles being reliably performed, no monomer or oligomer remains in the obtained toner particles, and the heat fixing step of the image forming method using the toner No odor of monomer or oligomer is generated.
[0090]
Furthermore, since the surface characteristics of the obtained toner particles are uniform and the charge amount distribution is sharp, an image with excellent sharpness can be formed over a long period of time. According to such a toner having a uniform composition, molecular weight, and surface characteristics between toner particles, an image forming method including a fixing process using a contact heating method maintains good adhesion (high fixing strength) to an image support. However, it is possible to improve the offset resistance and the anti-winding property, and an image having an appropriate gloss can be obtained.
[0091]
Next, each component used in the toner manufacturing process will be described in detail.
(Polymerizable monomer)
As a polymerizable monomer for producing the resin (binder) used in the present invention, a hydrophobic monomer is an essential constituent, and a crosslinkable monomer is used as necessary. Moreover, it is desirable to contain at least one monomer having an acidic polar group or a monomer having a basic polar group as described below.
[0092]
(1) Hydrophobic monomer
The hydrophobic monomer constituting the monomer component is not particularly limited, and conventionally known monomers can be used. Moreover, it can be used combining 1 type (s) or 2 or more types so that the required characteristic may be satisfy | filled.
[0093]
Specifically, monovinyl aromatic monomers, (meth) acrylic acid ester monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, diolefin monomers , Halogenated olefin monomers and the like can be used.
[0094]
Examples of vinyl aromatic monomers include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, p-ethyl styrene, p. -N-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, 2, Examples thereof include styrene monomers such as 4-dimethylstyrene and 3,4-dichlorostyrene and derivatives thereof.
[0095]
Examples of acrylic monomers include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, methyl methacrylate, methacrylic acid. Examples include butyl acid, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.
[0096]
Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl benzoate.
[0097]
Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like.
[0098]
Examples of the monoolefin monomer include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene and the like.
[0099]
Examples of the diolefin monomer include butadiene, isoprene, chloroprene and the like.
[0100]
(2) Crosslinkable monomer
In order to improve the characteristics of the resin particles, a crosslinkable monomer may be added. Examples of the crosslinkable monomer include those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diallyl phthalate.
[0101]
(3) Monomers having acidic polar groups
Examples of the monomer having an acidic polar group include (a) an α, β-ethylenically unsaturated compound having a carboxyl group (—COOH) and (b) a sulfone group (—SOOH)._ThreeMention may be made of α, β-ethylenically unsaturated compounds having H).
[0102]
Examples of the α, β-ethylenically unsaturated compound (a) having a —COO group include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, maleic acid monobutyl ester, maleic acid. Examples thereof include acid monooctyl esters, and metal salts thereof such as Na and Zn.
[0103]
-SO of (b)_ThreeExamples of the α, β-ethylenically unsaturated compound having an H group include sulfonated styrene, its Na salt, allylsulfosuccinic acid, octyl allylsulfosuccinate, and its Na salt.
[0104]
(4) Monomers having basic polar groups
As the monomer having a basic polar group, (i) a (meth) acrylic acid ester of an aliphatic alcohol having 1 to 12, preferably 2 to 8, particularly preferably 2, an amine group or a quaternary ammonium group. , (Ii) (meth) acrylic acid amide or (meth) acrylic acid amide mono- or disubstituted optionally with an alkyl group having 1 to 18 carbon atoms on N, (iii) a heterocyclic group having N as a ring member And (iv) N, N-diallyl-alkylamine or a quaternary ammonium salt thereof. Among them, (i) aliphatic alcohol (meth) acrylic acid ester having an amine group or quaternary ammonium group is preferable as a monomer having a basic polar group.
[0105]
Examples of (meth) acrylic acid esters of aliphatic alcohols having an amine group or quaternary ammonium group (i) include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the above four compounds. A quaternary ammonium salt, 3-dimethylaminophenyl acrylate, 2-hydroxy-3-methacryloxypropyltrimethylammonium salt, etc. can be mentioned.
[0106]
(Ii) (Meth) acrylic acid amide or optionally mono- or dialkyl-substituted (meth) acrylic acid amide on N includes acrylamide, N-butylacrylamide, N, N-dibutylacrylamide, piperidylacrylamide, methacrylamide, N-butylmethacrylamide, N, N-dimethylacrylamide, N-octadecylacrylamide and the like can be mentioned.
[0107]
Examples of the vinyl compound substituted with a heterocyclic group having N as a ring member in (iii) include vinylpyridine, vinylpyrrolidone, vinyl-N-methylpyridinium chloride, vinyl-N-ethylpyridinium chloride and the like.
[0108]
Examples of (iv) N, N-diallyl-alkylamine include N, N-diallylmethylammonium chloride and N, N-diallylethylammonium chloride.
[0109]
(Polymerization initiator)
The radical polymerization initiator used in the present invention can be appropriately used as long as it is water-soluble. For example, persulfates (for example, potassium persulfate, ammonium persulfate, etc.), azo compounds (for example, 4,4′-azobis-4-cyanovaleric acid and its salts, 2,2′-azobis (2-amidinopropane) Salt), peroxide compounds and the like. Furthermore, the radical polymerization initiator can be combined with a reducing agent as necessary to form a redox initiator. Use of a redox initiator is preferred because the polymerization activity is increased, the polymerization temperature can be lowered, and the polymerization time can be shortened.
[0110]
The polymerization temperature may be any temperature as long as it is equal to or higher than the lowest radical generation temperature of the polymerization initiator, but for example, a range of 50 ° C. to 90 ° C. is used. However, it is possible to perform polymerization at room temperature or higher by using a polymerization initiator that starts at room temperature, for example, a combination of hydrogen peroxide and a reducing agent (ascorbic acid or the like).
[0111]
(Surfactant)
In particular, in order to perform miniemulsion polymerization using the above-described polymerizable monomer, it is preferable to disperse oil droplets in an aqueous medium using a surfactant. The surfactant that can be used in this case is not particularly limited, and the following ionic surfactants can be given as examples of suitable compounds.
[0112]
Examples of the ionic surfactant include sulfonate (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol- 6-sulfonate sodium, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sulfonate sodium, etc.) , Sulfate salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, stearyl Potassium, calcium oleate and the like).
[0113]
Nonionic surfactants can also be used. Specifically, for example, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, Examples include sorbitan esters.
[0114]
In the present invention, these surfactants are mainly used as an emulsifier during emulsion polymerization, but may be used for other steps or for other purposes.
[0115]
(Molecular weight distribution of resin particles and toner)
The molecular weight of the toner according to the present invention is preferably present at a peak or shoulder of 100,000 to 1,000,000 and 1,000 to 50,000, and further has a peak or shoulder of 100,000 to 1,000. More preferably, it is present at 5,000, 25,000 to 150,000 and 1,000 to 50,000.
[0116]
The molecular weight of the resin particles is both a high molecular weight component having a peak or shoulder in the region of 100,000 to 1,000,000 and a low molecular weight component having a peak or shoulder in the region of 1,000 to less than 50,000. A resin containing at least is preferable. More preferably, an intermediate molecular weight resin having a peak or shoulder at a peak molecular weight of 15,000 to 100,000 is preferably used.
[0117]
The molecular weight measurement method of the toner or resin is preferably measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent. That is, 1.0 ml of THF is added to 0.5 to 5 mg of a measurement sample, more specifically 1 mg, and the mixture is sufficiently dissolved by stirring at room temperature using a magnetic stirrer or the like. Subsequently, after processing with a membrane filter having a pore size of 0.45 to 0.50 μm, the solution is injected into GPC. The measurement conditions of GPC are measured by stabilizing the column at 40 ° C., flowing THF at a flow rate of 1.0 ml / min, and injecting about 100 μl of a sample having a concentration of 1 mg / ml. The column is preferably used in combination with a commercially available polystyrene gel column. For example, Shodex GPC KF-801, 802, 803, 804, 805, 806, 807 made by Showa Denko KK, TSKgel G1000H, G2000H, G3000H, G4000H, G5000H, G6000H, G7000H, TSK guard The combination of column etc. can be mentioned. As a detector, a refractive index detector (IR detector) or a UV detector may be used. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve created using monodisperse polystyrene standard particles. About 10 points may be used as polystyrene for preparing a calibration curve.
[0118]
(Flocculant)
The flocculant used in the present invention is preferably selected from metal salts.
[0119]
Examples of the metal salt include monovalent metals such as alkali metal salts such as sodium, potassium and lithium, divalent metals such as alkaline earth metal salts such as calcium and magnesium, and divalent metals such as manganese and copper. Examples thereof include trivalent metal salts such as salts, iron and aluminum.
[0120]
Specific examples of these metal salts are shown below. Specific examples of the monovalent metal salt include sodium chloride, potassium chloride, lithium chloride, and divalent metal salts such as calcium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. Examples of the trivalent metal salt include aluminum chloride and iron chloride. These are appropriately selected according to the purpose. In general, the divalent metal salt has a smaller critical aggregation concentration (coagulation value or coagulation point) than the monovalent metal salt, and the trivalent metal salt has a smaller critical aggregation concentration.
[0121]
The critical flocculation concentration referred to in the present invention is an index related to the stability of the dispersion in the aqueous dispersion, and indicates the concentration at which flocculation occurs when a flocculant is added. This critical coagulation concentration varies greatly depending on the latex itself and the dispersant. For example, it is described in Seizo Okamura et al., Polymer Chemistry 17,601 (1960), etc., and the value can be known by following these descriptions. As another method, a desired salt is added to the target particle dispersion at a different concentration, the ζ potential of the dispersion is measured, and the salt concentration at the point where the ζ potential begins to change is defined as the critical aggregation concentration. It is also possible to do.
[0122]
In the present invention, the polymer fine particle dispersion is treated with a metal salt so as to have a concentration equal to or higher than the critical aggregation concentration. At this time, as a matter of course, whether the metal salt is added directly or as an aqueous solution is arbitrarily selected according to the purpose. When added as an aqueous solution, the added metal salt must be equal to or higher than the critical aggregation concentration of the polymer particles with respect to the volume of the polymer particle dispersion and the total volume of the metal salt aqueous solution.
[0123]
The concentration of the metal salt as a flocculant in the present invention may be not less than the critical aggregation concentration, but is preferably 1.2 times or more, more preferably 1.5 times or more the critical aggregation concentration.
[0124]
(Coloring agent)
The toner according to the present invention is obtained by salting out / fusion-bonding the composite resin particles and the colorant fine particles.
[0125]
Examples of the colorant constituting the toner according to the present invention (colorant fine particles used for salting out / fusion with the composite resin particles) include the yellow colorants described above.
[0126]
These colorants can be used alone or in combination as required. Moreover, the addition amount of a coloring agent is 2-20 mass% with respect to a polymer, Preferably 3-15 mass% is selected.
[0127]
The colorant (colorant fine particles) constituting the toner according to the present invention may be surface-modified. A conventionally well-known thing can be used as a surface modifier, Specifically, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent etc. can be used preferably. Examples of the silane coupling agent include alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, and diphenyldimethoxysilane, siloxanes such as hexamethyldisiloxane, γ-chloropropyltrimethoxysilane, vinyltrimethyl. Chlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureido Examples thereof include propyltriethoxysilane. Examples of titanium coupling agents include TTS, 9S, 38S, 41B, 46B, 55, 138S, and 238S that are commercially available under the trade name “Plenact” manufactured by Ajinomoto Co., Inc., and are commercially available from Nippon Soda Co., Ltd. Product A-1, B-1, TOT, TST, TAA, TAT, TLA, TOG, TBSTA, A-10, TBT, B-2, B-4, B-7, B-10, TBSTA-400, TTS , TOA-30, TSDMA, TTAB, TTOP and the like. Examples of the aluminum coupling agent include “Plenact AL-M” manufactured by Ajinomoto Co., Inc.
[0128]
The addition amount of these surface modifiers is preferably 0.01 to 20% by mass, and more preferably 0.1 to 5% by mass with respect to the colorant.
[0129]
Examples of the method for modifying the surface of the colorant fine particles include a method in which a surface modifier is added to a dispersion of the colorant fine particles and this system is heated and reacted.
[0130]
(Release agent)
The toner used in the present invention is preferably a toner obtained by fusing resin particles encapsulating a release agent in an aqueous medium. In this way, the resin particles in which the release agent is encapsulated in the resin particles are salted out / fused in the colorant fine particles and the aqueous medium, whereby a toner in which the release agent is finely dispersed can be obtained.
[0131]
In the toner according to the present invention, as the release agent, low molecular weight polypropylene (number average molecular weight = 1500 to 9000), low molecular weight polyethylene, or the like is preferable, and an ester compound represented by the following formula is particularly preferable.
[0132]
R¹-(OCO-R²)_n
In the formula, n is an integer of 1 to 4, preferably 2 to 4, more preferably 3 to 4, particularly preferably 4. R¹, R²Each represents a hydrocarbon group which may have a substituent. R¹Has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 2 to 5 carbon atoms. R²Has 1 to 40 carbon atoms, preferably 16 to 30 carbon atoms, and more preferably 18 to 26 carbon atoms.
[0133]
Next, the example of a typical compound is shown below.
[0134]
[Chemical 1]

[0135]
[Chemical 2]

[0136]
The amount of the compound added is 1 to 30% by mass, preferably 2 to 20% by mass, and more preferably 3 to 15% by mass with respect to the whole toner.
[0137]
The toner according to the present invention is preferably prepared by encapsulating the release agent in resin particles by a mini-emulsion polymerization method, and salting out and fusing together with the toner particles.
[0138]
(Charge control agent)
In addition to the colorant and the release agent, a material that can impart various functions as a toner material can be added to the toner. Specific examples include charge control agents. These components can be added simultaneously with the resin particles and the colorant fine particles in the salting-out / fusion step described above, and can be added by various methods such as a method included in the toner and a method of adding to the resin particles themselves.
[0139]
As the charge control agent, various known ones that can be dispersed in water can be used. Specific examples include nigrosine dyes, naphthenic acid or higher fatty acid metal salts, alkoxylated amines, quaternary ammonium salt compounds, azo metal complexes, salicylic acid metal salts or metal complexes thereof.
[0140]
(External additive)
The toner according to the present invention can be used by adding a so-called external additive for the purpose of improving fluidity and improving cleaning properties. These external additives are not particularly limited, and various inorganic fine particles, organic fine particles and lubricants can be used.
[0141]
Examples of inorganic fine particles that can be used as an external additive include conventionally known fine particles. Specifically, silica fine particles, titanium fine particles, alumina fine particles and the like can be preferably used. These inorganic fine particles are preferably hydrophobic.
[0142]
Specific examples of the silica fine particles include commercially available products R-805, R-976, R-974, R-972, R-812, R-809 manufactured by Nippon Aerosil Co., Ltd., HVK-2150, H manufactured by Hoechst Co., Ltd. -200, commercially available products manufactured by Cabot Corporation TS-720, TS-530, TS-610, H-5, MS-5, and the like.
[0143]
Specific examples of the titanium fine particles include, for example, commercial products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., and commercial products MT-100S, MT-100B, MT-500BS, MT-600, and MT manufactured by Teika Co., Ltd. -600SS, JA-1, commercial products TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T manufactured by Fuji Titanium Co., Ltd. Commercial products IT-S, IT-OA manufactured by Idemitsu Kosan Co., Ltd. , IT-OB, IT-OC and the like.
[0144]
Specific examples of the alumina fine particles include commercial products RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd., and commercial products TTO-55 manufactured by Ishihara Sangyo Co., Ltd.
[0145]
Examples of the organic fine particles that can be used as the external additive include spherical fine particles having a number average primary particle diameter of about 10 to 2000 nm. Examples of the constituent material of the organic fine particles include polystyrene, polymethyl methacrylate, and styrene-methyl methacrylate copolymer.
[0146]
Examples of the lubricant that can be used as an external additive include metal salts of higher fatty acids. Specific examples of such higher fatty acid metal salts include zinc stearate, aluminum stearate, copper stearate, magnesium stearate, calcium stearate, and other stearic acid metal salts; zinc oleate, manganese oleate, iron oleate, olein Oleic acid metal salts such as acid copper and magnesium oleate; palmitate metal salts such as zinc palmitate, copper palmitate, magnesium palmitate and calcium palmitate; linoleic acid metal salts such as zinc linoleate and calcium linoleate; ricinol Examples include ricinoleic acid metal salts such as zinc acid and calcium ricinoleate.
[0147]
The addition amount of the external additive is preferably about 0.1 to 5% by mass with respect to the toner.
[0148]
<External additive addition process>
This step is a step of adding an external additive to the dried toner particles.
[0149]
Examples of the apparatus used for adding the external additive include various known mixing apparatuses such as a Turbuler mixer, a Henschel mixer, a Nauter mixer, and a V-type mixer.
[0150]
(Toner particles)
The particle size of the toner according to the present invention is preferably 3 to 10 μm, more preferably 3 to 8 μm, in terms of number average particle size. This particle size can be controlled by the concentration of the flocculant (salting-out agent), the amount of organic solvent added, the fusing time, and the polymer composition in the toner production method.
[0151]
When the number average particle diameter is 3 to 10 μm, toner particles having high adhesion force that fly and adhere to the heating member and generate offset in the fixing process are reduced, and transfer efficiency is increased and halftone The image quality is improved, and the image quality of fine lines and dots is improved.
[0152]
The number average particle diameter of the toner is measured using a laser diffraction particle size measuring device “Coulter Counter TA-II”, “Coulter Multisizer, SLAD1100” (Laser diffraction particle size measuring device manufactured by Shimadzu Corporation), or the like. be able to.
[0153]
In the present invention, a “Coulter Multisizer” is used, and an interface for outputting the particle size distribution (manufactured by Nikkaki Co., Ltd.) and a personal computer are used. The aperture in the Coulter Multisizer was 100 μm, and the volume distribution of toner of 2 μm or more (for example, 2 to 40 μm) was measured to calculate the particle size distribution and average particle size.
[0154]
(Developer)
The toner according to the present invention may be used as a one-component developer or a two-component developer.
[0155]
When used as a one-component developer, a non-magnetic one-component developer or a magnetic one-component developer containing about 0.1 to 0.5 μm of magnetic particles in the toner can be used. be able to.
[0156]
Further, it can be mixed with a carrier and used as a two-component developer. In this case, conventionally known materials such as metals such as iron, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead can be used as the magnetic particles of the carrier. Ferrite particles are particularly preferable. The magnetic particles preferably have a volume average particle size of 15 to 100 μm, more preferably 25 to 80 μm.
[0157]
The volume average particle diameter of the carrier can be typically measured by a laser diffraction particle size distribution measuring apparatus “HELOS” (manufactured by Sympathic Co., Ltd.) equipped with a wet disperser.
[0158]
The carrier is preferably a carrier in which magnetic particles are further coated with a resin, or a so-called resin dispersion type carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited, and for example, olefin resin, styrene resin, styrene-acrylic resin, silicone resin, ester resin, or fluorine-containing polymer resin is used. In addition, the resin for constituting the resin-dispersed carrier is not particularly limited, and a known resin can be used. For example, a styrene-acrylic resin, a polyester resin, a fluorine resin, a phenol resin, or the like is used. be able to.
[0159]
(Image forming method)
Next, an image forming method and an image forming apparatus using the toner of the present invention will be described.
[0160]
FIG. 2 is a cross-sectional configuration diagram of an image forming apparatus showing an example of an image forming method using the toner of the present invention.
[0161]
The image forming apparatus shown in FIG. 2 is a digital image forming apparatus, and includes an image reading unit A, an image processing unit B (not shown), an image forming unit C, and a transfer paper transport unit D as a transfer paper transport unit. It is configured.
[0162]
The upper part of the image reading unit A is provided with automatic document feeding means for automatically conveying the document. The document placed on the document placing table 111 is separated and conveyed by the document conveying roller 112 to the reading position 113a. The image is read. The document after the document reading is completed is discharged onto the document discharge tray 114 by the document transport roller 112.
[0163]
On the other hand, the image of the original when placed on the platen glass 113 is read at a speed v of the first mirror unit 115 including the illumination lamp and the first mirror constituting the scanning optical system, and the V-shaped first image is located. Reading is performed by moving the second mirror unit 116 composed of the two mirrors and the third mirror in the same direction at the speed v / 2.
[0164]
The read image is formed on the light receiving surface of the image sensor CCD, which is a line sensor, through the projection lens 117. The line-shaped optical image formed on the image sensor CCD is sequentially photoelectrically converted into an electric signal (luminance signal) and then A / D converted, and the image processing unit B performs processing such as density conversion and filter processing. Then, the image data is temporarily stored in the memory.
[0165]
In the image forming unit C, as an image forming unit, a drum-shaped photosensitive member (hereinafter also referred to as a photosensitive drum) 121 that is an image carrier, a charger 122 that is a charging unit, and a developing unit that is a developing unit are provided on the outer periphery thereof. A device 123, a transfer device 124 as transfer means, a separator 125 as separation means, a cleaning device (blade cleaning) 126, and a PCL (precharge lamp) 127 are arranged in the order of operation. The photoconductor 121 is formed by coating a photoconductive compound on a drum base. For example, an organic photoconductor (OPC) is preferably used, and is driven to rotate in the clockwise direction shown in the drawing.
[0166]
After the rotating photosensitive member 121 is uniformly charged by the charger 122, the exposure optical system 130 performs image exposure based on the image signal called from the memory of the image processing unit B. The exposure optical system 130 as writing means uses a laser diode (not shown) as a light source, passes through a rotating polygon mirror 131, an fθ lens (no symbol), and a cylindrical lens (no symbol), and the optical path is bent by a reflection mirror 132 to perform main scanning. Thus, image exposure is performed on the photoconductor 121 at the position Ao, and a latent image is formed by rotation (sub-scanning) of the photoconductor 121. In one example of the present embodiment, the character portion is exposed to form a latent image.
[0167]
The latent image on the photoconductor 121 is reversely developed by the developing device 123, and a visible toner image is formed on the surface of the photoconductor 121. In the transfer paper transport section D, paper feed units 141 (A), 141 (B), and 141 (C) are provided below the image forming unit as transfer paper storage means for storing transfer paper P of different sizes. Further, a manual paper feeding unit 142 that performs manual paper feeding is provided on the side, and the transfer paper P selected from any of them is fed along the transport path 140 by the guide roller 143 and fed. The transfer paper P is temporarily stopped by a pair of registration rollers 144 that corrects the inclination and bias of the transfer paper to be transferred, and then re-feeded. The toner image on the photoconductor 121 is transferred to the transfer paper P by the transfer device 124 at the transfer position Bo, and then the charge is removed by the separator 125, so that the transfer paper P is transferred from the surface of the photoconductor 121. Separated, it is conveyed to the fixing device 150 by a conveying device 145.
[0168]
The fixing device 150 has a fixing roller 151 and a pressure roller 152. By passing the transfer paper P between the fixing roller 151 and the pressure roller 152, the toner is fused by heating and pressing. . After the toner image has been fixed, the transfer paper P is discharged onto a paper discharge tray 164.
[0169]
【Example】
The present invention will be specifically described below with reference to examples, but the embodiments of the present invention are not limited to these examples.
[0170]
<< Preparation of pretreatment colorant >>
Three kinds of colorants shown in Table 1 below were heated at 200 ° C. for each treatment time in a nitrogen stream to prepare “pretreatment colorants 2, 3, 5, and 7”. “Pre-treatment colorants 1, 4, 6” were those that were not heat-treated in a nitrogen stream.
[0171]
The amount of aromatic amine in the pretreatment colorant was measured by a headspace gas chromatograph. The aromatic amines were all o-anisidine compounds.
[0172]
Table 1 shows the colorant used, the processing time, and the amount of aromatic amine in the colorant.
[0173]
[Table 1]

[0174]
<< Preparation of wet colorant >>
Ion-exchanged water was added to each of the “pretreatment colorants 1 to 7” so as to have the moisture amount shown in Table 2, and the colorant was dispersed with a biaxial kneader. 7-2 "was prepared.
[0175]
Table 2 shows the water content in the pretreatment colorant and the wet colorant.
[0176]
[Table 2]

[0177]
<< Preparation of Colorant Dispersion >>
[Preparation of Colorant Dispersion 1]
A surfactant aqueous solution (aqueous medium) was prepared by stirring and dissolving 90 g of sodium dodecyl sulfate in 1600 ml of ion-exchanged water. To this aqueous solution, “wet colorant 1” was gradually added with stirring so that the amount of the colorant was 40 g to prepare a colorant-containing solution. Next, the colorant in the solution was dispersed in an aqueous medium using a stirrer “CLEARMIX” (manufactured by M Technique Co., Ltd.) to prepare “Colorant Dispersion Liquid 1”.
[0178]
The mass average particle size (dispersion particle size) and particle size distribution of the colorant in “Colorant Dispersion Liquid 1” were measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.). It is the value.
[0179]
[Preparation of Colorant Dispersion 2-1]
“Colorant dispersion 1” under the same conditions as “Colorant dispersion 1” except that “Wet colorant 1” used in “Colorant dispersion 1” was changed to “Wet colorant 2-1.” 2-1 "was prepared.
[0180]
[Preparation of Colorant Dispersion 2-2]
“Colorant dispersion liquid” under the same conditions as “Colorant dispersion liquid 1” except that “Wet colorant 1” used in “Colorant dispersion liquid 1” was changed to “Wet colorant 2-2”. 2-2 "was prepared.
[0181]
[Preparation of Colorant Dispersion 2-3]
“Colorant dispersion liquid” under the same conditions as “Colorant dispersion liquid 1” except that “Wet colorant 1” used in “Colorant dispersion liquid 1” was changed to “Wet colorant 2-3”. 2-3 "was prepared.
[0182]
[Preparation of Colorant Dispersion 2-4]
“Colorant dispersion 1” under the same conditions as “Colorant dispersion 1” except that “Wet colorant 1” used in “Colorant dispersion 1” was changed to “Wet colorant 2-4”. 2-4 "was prepared.
[0183]
[Preparation of Colorant Dispersion 2-5]
“Colorant dispersion 1” under the same conditions as “Colorant dispersion 1” except that “Wet colorant 1” used in “Colorant dispersion 1” was changed to “Wet colorant 2-5”. 2-5 "was prepared.
[0184]
[Preparation of Colorant Dispersion 3]
“Colorant Dispersion 3” under the same conditions as “Colorant Dispersion 1” except that “Wet Colorant 1” used in “Colorant Dispersion 1” was changed to “Wet Colorant 3”. Was prepared.
[0185]
[Preparation of Colorant Dispersion 4]
“Colorant Dispersion 4” under the same conditions as “Colorant Dispersion 1” except that “Wet Colorant 1” used in “Colorant Dispersion 1” was changed to “Wet Colorant 4”. Was prepared.
[0186]
[Preparation of Colorant Dispersion 5]
“Colorant Dispersion 5” under the same conditions as “Colorant Dispersion 1” except that “Wet Colorant 1” used in “Colorant Dispersion 1” was changed to “Wet Colorant 5”. Was prepared.
[0187]
[Preparation of Colorant Dispersion 6-1]
“Colorant dispersion 1” under the same conditions as “Colorant dispersion 1” except that “Wet colorant 1” used in “Colorant dispersion 1” was changed to “Wet colorant 6-1”. 6-1 "was prepared.
[0188]
[Preparation of Colorant Dispersion 6-2]
“Colorant dispersion 1” under the same conditions as “Colorant dispersion 1” except that “wet colorant 1” used in “colorant dispersion 1” was changed to “wet colorant 6-2”. 6-2 "was prepared.
[0189]
[Preparation of Colorant Dispersion 7-1]
“Colorant dispersion liquid” under the same conditions as “Colorant dispersion liquid 1” except that “Wet colorant 1” used in “Colorant dispersion liquid 1” was changed to “Wet colorant 7-1”. 7-1 "was prepared.
[0190]
[Preparation of Colorant Dispersion 7-2]
“Colorant dispersion 1” under the same conditions as “Colorant dispersion 1” except that “Wet colorant 1” used in “Colorant dispersion 1” was changed to “Wet colorant 7-2”. 7-2 "was prepared.
[0191]
<< Preparation of colored particles >>
[Preparation of colored particles 1]
(Preparation of latex (1HML))
<1: Preparation of core particles (first stage polymerization)>
An anionic surfactant A (C) was added to a 5000 ml separable flask equipped with a stirrer, temperature sensor, condenser, and nitrogen inlet._TenH_{twenty one}(OCH₂CH₂)₂OSO_ThreeA surfactant solution (aqueous medium) in which 4.0 g of Na) was dissolved in 3040 g of ion-exchanged water was charged, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream.
[0192]
To this surfactant solution, an initiator solution in which 10.0 g of a polymerization initiator (potassium persulfate: KPS) was dissolved in 400 g of ion-exchanged water was added, the temperature was adjusted to 75 ° C., 528 g of styrene, and n-butyl acrylate. A monomer mixture consisting of 204 g, methacrylic acid 68.0 g and n-octyl-3-mercaptopropionic acid ester 24.4 g was added dropwise over 1 hour, and the system was heated and stirred at 75 ° C. for 2 hours. Thus, polymerization (first stage polymerization) was performed to prepare latex (a dispersion of resin particles made of high molecular weight resin). This is referred to as “latex (1H)”.
[0193]
<2: Formation of intermediate layer (second stage polymerization)>
In a flask equipped with a stirrer, 95.0 g of styrene, 36.0 g of n-butyl acrylate, 9.0 g of methacrylic acid, 0.59 g of n-octyl-3-mercaptopropionic acid ester, 70 g of the exemplified compound 19) was added as a release agent, and heated and dissolved at 90 ° C. to prepare monomer solution 1.
[0194]
Next, a surfactant solution in which 1.0 g of the anionic surfactant A is dissolved in 1560 ml of ion-exchanged water is heated to 98 ° C., and the latex (dispersed core particles) is added to the surfactant solution. 1H) was added in an amount of 28 g in terms of solid content, and then the monomer solution 1 prepared above was mixed and dispersed for 8 hours using a mechanical disperser “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path. Then, an emulsion containing emulsion particles (oil droplets) having a uniform dispersed particle size (284 nm) was prepared.
[0195]
Next, an initiator solution prepared by dissolving 5.0 g of a polymerization initiator (KPS) in 200 ml of ion-exchanged water and 750 ml of ion-exchanged water are added to this emulsion, and this system is heated and stirred at 98 ° C. for 12 hours. (Second stage polymerization) was performed to obtain latex (a dispersion of composite resin particles having a structure in which the surface of resin particles made of high molecular weight resin was covered with intermediate molecular weight resin). This is referred to as “latex (1HM)”.
[0196]
When the above “latex (1HM)” was dried and observed with a scanning electron microscope, particles (400 to 1000 nm) containing, as a main component, exemplary compound 19) not surrounded by latex were observed.
[0197]
<3: Formation of outer layer (third stage polymerization)>
An initiator solution prepared by dissolving 6.8 g of a polymerization initiator (KPS) in 265 ml of ion-exchanged water is added to the “latex (1HM)” prepared above, and 249 g of styrene and n-butyl acrylate under a temperature condition of 80 ° C. A monomer mixed solution consisting of 88.2 g, methacrylic acid 19.4 g, and n-octyl-3-mercaptopropionic acid ester 7.45 g was added dropwise over 1 hour. After completion of the dropwise addition, polymerization (third-stage polymerization) was performed by heating and stirring for 2 hours, and then cooled to 28 ° C., and latex (a central portion made of a high molecular weight resin, an intermediate layer made of an intermediate molecular weight resin, A dispersion of composite resin particles) having an outer layer made of a low molecular weight resin and containing the exemplary compound 19) as a release agent in the intermediate layer was obtained. This latex is referred to as “latex (1HML)”.
[0198]
<Preparation of latex (2L)>
An initiator solution prepared by dissolving 14.8 g of a polymerization initiator (KPS) in 400 ml of ion-exchanged water was added to a flask equipped with a stirrer, and under a temperature condition of 80 ° C., 600 g of styrene, 190 g of n-butyl acrylate, A monomer mixed solution consisting of 30.0 g of methacrylic acid and 20.8 g of n-octyl-3-mercaptopropionic acid ester was added dropwise over 1 hour. After completion of the dropwise addition, polymerization was carried out by heating and stirring for 2 hours, followed by cooling to 28 ° C. to obtain a latex (a dispersion of resin particles made of a low molecular weight resin). This latex is referred to as “latex (2 L)”.
[0199]
The resin particles constituting the latex (2L) had a molecular weight peak at 11,000, and the mass average particle diameter of the resin particles was 128 nm.
[0200]
(Aggregation / fusion process)
420.7 g (solid content conversion) of the prepared “latex (1HML)”, 900 g of ion-exchanged water, and 200 g of the prepared “colorant dispersion 1” were mixed with a temperature sensor, a cooling tube, a nitrogen introducing device, and a stirring device. It stirred in the reaction container (four necked flask) which attached the apparatus. After adjusting the temperature in the container to 30 ° C., a 5 mol / L sodium hydroxide aqueous solution was added to this solution to adjust the pH to 9.0.
[0201]
Next, an aqueous solution in which 12.1 g of magnesium chloride hexahydrate was dissolved in 1000 ml of ion-exchanged water was added at 30 ° C. over 10 minutes with stirring. After standing for 3 minutes, heating was started, and the aqueous solution was heated to 90 ° C. over 60 minutes to start particle growth. In this state, the particle size of the associated particles was measured with “Coulter Counter TA-II”. When the volume average particle size reached 5.0 μm, 40.2 g of sodium chloride as a stopper was added to 1000 ml of ion-exchanged water. The aqueous solution dissolved in was added to stop particle growth. Further, as the aging treatment, the fusion was continued by heating and stirring at a liquid temperature of 98 ° C. for 2 hours. Then, it cooled to 30 degreeC on the conditions of 8 degreeC / min.
[0202]
(Shelling process)
According to the above, 96 g of the prepared “latex (2 L)” is added to the aggregated / fused particles, and heating and stirring are continued for 3 hours. "Latex (2L)" was shelled. Next, 40.2 g of sodium chloride was added and cooled to 30 ° C. under a temperature drop condition of 8 ° C./min. Then, hydrochloric acid was added to adjust the pH to 2.0, and stirring was stopped.
[0203]
The fused particles thus shelled were filtered, repeatedly washed with ion exchange water at 45 ° C., and then dried with hot air at 40 ° C. to prepare “colored particles 1”.
[0204]
[Preparation of colored particles 2 to 13]
In the preparation of the “colored particles 1”, the “colored particles 1” used in the same manner except that the “colorant dispersion 1” used as the colorant dispersion was changed to “colorant dispersions 2-1 to 7-2”. 2-13 "were prepared.
[0205]
<< Preparation of toner and developer >>
To the prepared “colored particles 1 to 13”, 1.0% by mass of hydrophobic silica (number average primary particle size = 12 nm, degree of hydrophobicity = 68) and hydrophobic titanium oxide (number average primary particle size = 20 nm). , Hydrophobicity = 63) was added in an amount of 1.2 mass% and mixed with a Henschel mixer to prepare “Toners 1 to 13”.
[0206]
Next, a ferrite carrier having a volume average particle diameter of 60 μm coated with a silicone resin was mixed with each of the prepared toners to prepare “Developers 1 to 13” having a toner concentration of 6%.
[0207]
The particle diameter of the toner is a value measured using “Coulter Multisizer” (manufactured by Coulter Co., Ltd.).
[0208]
Table 3 shows the pretreatment colorant number, the wet colorant number, the particle size and particle size distribution of the colorant in the colorant dispersion, the toner particle size, and the amount of aromatic amine in the toner.
[0209]
[Table 3]

[0210]
"Evaluation results"
(Odor)
The digital copier “Konica 7065” (manufactured by Konica Corporation) was modified in a sealed room with a floor of 5 m × 5 m and a height of 2 m, and the fixing roll surface temperature of the fixing device was set to 170 ° C. Using an evaluation machine, 1000 sheets of A4 plate images having a pixel rate of 7% were continuously printed with the “toners 1 to 13” and “developers 1 to 13” prepared above.
[0211]
The evaluation of odor was carried out by 20 evaluators at the end of printing 1000 sheets by the number of persons who felt odor.
[0212]
Evaluation criteria
◎: One evaluator did not feel odor
○: 3 or less evaluators felt odor
X: Four or more evaluators felt odor.
[0213]
(Colored contamination of in-flight components)
A digital copier “Konica 7065” (manufactured by Konica Corporation) was remodeled and an evaluation machine in which the fixing roll surface temperature of the fixing device was set to 170 ° C. was used. 50,000 sheets of A4 plate images having a pixel rate of 7% were continuously printed with “Toners 1 to 13” and “Developers 1 to 13” prepared above at 33 ° C. and 80% RH). .
[0214]
After the printing was completed, the inside of the evaluation machine was observed to evaluate how much the contamination of the colored and contaminated member dropped.
[0215]
Evaluation criteria
○: The level of contamination decreases when a colored contaminated member is touched with a finger.
X: Level at which contamination does not fall even if a colored contaminated member is rubbed with a finger
The evaluation results are shown in Table 4.
[0216]
[Table 4]

[0217]
As is apparent from Table 4, when the toner of the present invention (toner numbers 1, 3, 4, 5, 7, 8, 9, 13) is used, toners of comparative examples (toner numbers 2, 6, 10, 11, 11) are used. Compared to 12), it can be seen that the colored contamination of the in-machine members is easy to remove and the odor generated during heat fixing is small.
[0218]
【The invention's effect】
As demonstrated in the examples, the toner of the present invention, the method for producing the toner, the image forming method using the toner, and the image forming apparatus are excellent in that coloring contamination of in-machine members and generation of odor during heat fixing are reduced. Has an effect.
[Brief description of the drawings]
FIG. 1 shows an example of a dispersion apparatus for preparing a colorant dispersion.
FIG. 2 is a cross-sectional configuration diagram of an image forming apparatus showing an example of an image forming method using the toner of the present invention.
[Explanation of symbols]
101 screen
102 rotor
M stirring chamber
103 Pressurized vacuum attachment
104 Preliminary dispersion inlet
105 Dispersion outlet
107 Cooling jacket
108 Cooling coil
121 photoconductor
122 Charger
123 Developer
124 Transfer device
125 separator
126 Cleaning device
127 PCL (precharge lamp)
130 Exposure optical system
151 Fixing device
P transfer paper

Claims (4)

In the toner for developing an electrostatic charge image containing at least a resin and a colorant, the colorant is a yellow colorant. As the yellow colorant, a wet colorant having a water content of 40 to 80% by mass is dispersed in an aqueous system. A toner for developing an electrostatic image, wherein the toner is used in a polymerization method to be added and the content of an o-anisidine compound is 0.1 to 50 ppm. In the toner for developing an electrostatic charge image containing at least a resin and a colorant, the colorant is a yellow colorant. As the yellow colorant, a wet colorant having a water content of 40 to 80% by mass is dispersed in an aqueous system. A toner for developing an electrostatic image, wherein the toner is used in a polymerization method to be added and the content of an o-anisidine compound is 0.1 to 20 ppm.   3. The method for producing an electrostatic image developing toner according to claim 1 or 2, wherein the toner component is produced through a drying step after the toner component is dispersed in a solvent. Manufacturing method.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the toner is produced through a step of dispersing a wet colorant in an aqueous system.

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