JP4236828B2 - Toner for developing electrostatic image and method for producing the same - Google Patents

Description

【００４２】
（一般式（Ｉ）中、Ｒ¹、Ｒ²は各々独立して水素原子、アルキル基、ハロゲン原子を表し、Ｒ¹又はＲ²の少なくとも１つがハロゲン原子である。また、ＭはＢａ、Ｓｒ、Ｍｎ、Ｃａ、Ｍｇのいずれかを表す。）
【００４３】
【化４】

【００４４】
（一般式（ＩＩ）中、Ａ、Ｂは置換基を有していても良い芳香族環を表す。Ｒ³は水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数１〜５の炭化水素基、炭素数１〜５のアルコキシ基、窒素原子上が置換されていても良いアミノスルホニル基、又は窒素原子上が置換されていても良いアミノカルボニル基を表す。）一般式（ＩＩ）中、Ａ、Ｂはそれぞれ、ベンゼン環又はナフタレン環が好ましい。また、一般式（ＩＩ）で表される化合物の中でも、下記一般式（ＩＩａ）で表される化合物が更に好ましい。
【００４５】
【化５】

【００４６】
（一般式（ＩＩａ）中、Ｒ³〜Ｒ⁶は各々独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数１〜５の炭化水素基、炭素数１〜５のアルコキシ基、窒素原子上が置換されていても良いアミノスルホニル基、又は窒素原子上が置換されていても良いアミノカルボニル基を表す。）
一般式（ＩＩａ）において、窒素原子上が置換されていても良いアミノスルホニル基、又は窒素原子上が置換されていても良いアミノカルボニル基における、窒素原子上の置換基としては、具体的にはアルキル基、アリール基、アルコキシアルキル基、ハロアルキル基、ハロアリール基が挙げられる。
【００４７】
更にまた、Ｒ³が水素原子であり、Ｒ⁴がメトキシ基であり、Ｒ⁵が水素原子であり、Ｒ⁶が塩素である化合物が、分光反射性特性、重合性単量体中への分散性、着色剤分散液への加工性の点で最も好ましい。
次に、本発明に用いられる帯電制御剤について説明する。
本発明では、必要に応じてトナー中に帯電制御剤を含有させることができる。含有させる方法として、重合体一次粒子を得る際に、帯電制御剤をワックスと同時にシードとして用いたり、帯電制御剤をモノマー又はワックスに溶解又は分散させてて用いたり、あるいは重合体一次粒子と同時に帯電制御剤一次粒子を凝集させて粒子凝集体を形成しトナーとしてもよい。しかし、重合体一次粒子を、好ましくは着色剤一次粒子と共に凝集させて粒子凝集体とした後、樹脂微粒子を付着または固着する工程の前、または工程と同時に、または工程の後に帯電制御剤一次粒子を付着又は固着することが好ましい。この場合、帯電制御剤も水中で平均粒径０．０１〜３μｍのエマルション（帯電制御剤一次粒子）として使用することが好ましい。
【００４８】
帯電制御剤としては、公知の任意のものを単独ないしは併用して用いることができ、例えば、正帯電性として４級アンモニウム塩、塩基性・電子供与性の金属物質が挙げられ、負帯電性として金属キレート類、有機酸の金属塩、含金属染料、ニグロシン染料、アミド基含有化合物、フェノール化合物、ナフトール化合物及びそれらの金属塩、ウレタン結合含有化合物、酸性もしくは電子吸引性の有機物質が挙げられる。
【００４９】
また、カラートナー適応性（帯電制御剤自体が無色ないしは淡色でトナーへの色調障害がないこと）を勘案すると、正帯電性としては４級アンモニウム塩化合物が、負帯電性としてはサリチル酸もしくはアルキルサリチル酸のクロム、亜鉛、アルミニウムなどとの金属塩、金属錯体や、ベンジル酸の金属塩、金属錯体、アミド化合物、フェノール化合物、ナフトール化合物、フェノールアミド化合物、４，４’−メチレンビス〔２−〔Ｎ−（４−クロロフェニル）アミド〕−３−ヒドロキシナフタレン〕等のヒドロキシナフタレン化合物が好ましい。その使用量はトナーに所望の帯電量により決定すればよいが、通常はバインダー樹脂１００重量部に対し０．０１〜１０重量部用い、更に好ましくは０．１〜１０重量部用いる。
【００５０】
次に、本発明に用いられる樹脂微粒子について説明する。
本発明のトナーの特徴は、上述の粒子凝集体に更に、樹脂微粒子を被覆（付着又は固着）してトナー粒子を形成するものである。
樹脂微粒子は、乳化剤（前述の界面活性剤）により水または水を主体とする液中に分散してエマルションとして用いる。樹脂微粒子は、乳化重合によって得られたものが好ましい。
【００５１】
また、樹脂微粒子は実質的にワックスを含まないものが好ましい。なお、実質的にワックスを含まないとは、樹脂微粒子中のワックス含有量が、１重量％以下、好ましくは０．５重量％以下、更に好ましくは０．１重量％以下であることを意味する。樹脂微粒子が実質的にワックスを含まない場合は、定着機によってトナーが定着される前にはトナー表面部にワックス浸出しにくく、装置汚れを防ぐことができ、また、耐ブロッキング性も良好となる。
【００５２】
樹脂微粒子としては、好ましくは体積平均粒径が０．０２〜３μｍ、更に好ましくは０．０５〜１．５μｍであって、前述の重合体一次粒子に用いられるモノマーと同様なモノマーを重合して得られたもの等を用いることができる。
また、樹脂微粒子に用いられる樹脂は架橋されているのが好ましい。
架橋剤としては、上述の重合体一次粒子に用いられる多官能性モノマーが使用できる。
【００５３】
樹脂微粒子に架橋樹脂を用いる場合の架橋度は、テトラヒドロフラン不溶分として通常５重量％以上であり、１０重量％以上が好ましく、１５重量％以上が更に好ましく、２０重量％以上が特に好ましい。また、通常７０重量％以下である。上記の好適な範囲のテトラヒドロフラン不溶分とするために、多官能性モノマーの配合率としては、樹脂微粒子に用いられるモノマー混合物中の０．００５重量％以上が好ましく、０．０１重量％以上が更に好ましく、０．０５％以上が特に好ましい。また、５重量％以下が好ましく、３重量％以下が更に好ましく、１重量％以下が特に好ましい。
【００５４】
樹脂微粒子を構成する成分の内、テトラヒドロフラン可溶分の分子量ピーク（Ｍｐ）は、３０，０００以上が好ましく、４０，０００以上が更に好ましい。また、１５０，０００以下が好ましく、１００，０００以下が更に好ましい。
特に、架橋樹脂を用いる場合には、分子量ピークは１００，０００以下が好ましく、６０，０００以下が更に好ましい。
【００５５】
また、樹脂微粒子を構成する成分の内、テトラヒドロフラン可溶分の重量平均分子量（Ｍｗ）は、３０，０００以上が好ましく、５０，０００以上が更に好ましい。また、５００，０００以下が好ましく、３００，０００以下が更に好ましい。
次に、上述の各粒子を凝集する凝集工程について説明する。
【００５６】
本発明の好ましい態様においては、上述の重合体一次粒子、着色剤一次粒子、及び必要に応じて帯電制御剤微粒子、ワックス微粒子、その他の内添剤を、それぞれ乳化して乳化液とし、これらを共凝集して粒子凝集体とする。凝集を行う各成分のうち、帯電制御剤分散液は、凝集工程の途中で添加しても良く、凝集工程後に添加しても良い。
【００５７】
ここで、凝集工程においては、１）加熱して凝集を行う方法、２）電解質を加えて凝集を行う方法とがあり、これらを併用しても良い。
加熱して凝集を行う場合に、凝集温度としては具体的には、５℃〜Ｔｇの温度範囲（但し、Ｔｇは重合体一次粒子のガラス転移温度）であり、（Ｔｇ−１０）℃〜（Ｔｇ−５）℃の範囲が好ましい。上記温度範囲であれば、電解質を用いることなく好ましいトナー粒径に凝集させることができる。
【００５８】
また、加温して凝集を行う場合、凝集工程に引き続いて熟成工程を行う場合には、凝集工程と熟成工程が連続的に行われその境界は曖昧となる場合があるが、（Ｔｇ−２０）℃〜Ｔｇの温度範囲に少なくとも３０分間保持する工程があれば、これを凝集工程とみなす。
凝集温度は所定の温度で通常少なくても３０分保持することにより所望の粒径のトナー粒子とすることが好ましい。所定の温度までは一定速度で昇温しても良いし、ステップワイズに昇温しても良い。保持時間は、（Ｔｇ−２０）℃〜Ｔｇの範囲で３０分以上８時間以下が好ましく、１時間以上４時間未満がさらに好ましい。このようにすることによって、小粒径であり、粒度分布のシャープなトナーを得ることができる。
【００５９】
また、混合分散液に電解質を添加して凝集を行う場合の電解質としては、有機の塩、無機塩のいずれでも良いが、好ましくは１価あるいは２価以上の多価の金属塩が好ましく用いられる。具体的には、ＮａＣｌ、ＫＣｌ、ＬｉＣｌ、Ｎａ₂ＳＯ₄、Ｋ₂ＳＯ₄、Ｌｉ₂ＳＯ₄、ＭｇＣｌ₂、ＣａＣｌ₂、ＭｇＳＯ₄、ＣａＳＯ₄、ＺｎＳＯ₄、Ａｌ₂（ＳＯ₄）₃、Ｆｅ₂（ＳＯ₄）₃、ＣＨ₃ＣＯＯＮａ、Ｃ₆Ｈ₅ＳＯ₃Ｎａ等が挙げられる。
【００６０】
電解質の添加量は、電解質の種類によっても異なるが、通常は混合分散液の固形成分１００重量部に対して、０．０５〜２５重量部が用いられる。好ましくは０．１〜１５重量部、更に好ましくは０．１〜１０重量部である。
電解質添加量が上記範囲より著しく少ない場合には、凝集反応の進行が遅くなり凝集反応後も１μｍ以下の微粉が残ったり、得られた凝集粒子の平均粒径が３μｍ以下となるなどの問題を生じる傾向にある。また、電解質添加量が上記範囲より著しく多い場合には、急速で制御の困難な凝集となりやすく、得られた凝集粒子の中に２５μｍ以上の粗粉が混じったり、凝集体の形状がいびつで不定形の物になるなどの問題を生じる傾向にある。
【００６１】
また、電解質を加えて凝集を行う場合には、凝集温度は５℃〜Ｔｇの温度範囲が好ましい。
凝集工程には、通常の攪拌槽が用いられ、形状としては、略円筒状のものあるいは略球状のものが好ましく用いられる。反応槽のが略円筒状の場合、底面の形状は特に制限はないが、通常の略円弧状のものが好ましく用いられる。
【００６２】
攪拌効率を良好にするためには、混合分散液の体積は、反応槽の体積の２／３以下が好ましく、３／５以下が更に好ましい。また、極端に混合分散液の体積が反応溶液の体積に比べて小さいと、泡立ちが激しく増粘が大きくなり、粗粉粒子が発生しやすく、攪拌翼の形状によっては攪拌されない場合があり、また、生産効率も低下するので、この比率は、１／１０以上が好ましく、１／５以上が更に好ましい。
【００６３】
凝集工程に用いる攪拌翼としては、従来公知であり、市販されている各種の形状の攪拌翼を用いることが出来る。
市販の攪拌翼としては、例えば、アンカー翼、フルゾーン翼（神鋼パンテック社製）、サンメラー翼（三菱重工社製）、マックスブレンド翼（住友重機械工業社製）、Ｈｉ−Ｆミキサー翼（綜研化学社製）、ダブルヘリカルリボン翼（神鋼パンテック社製）等の攪拌翼を挙げることができる。また、攪拌槽にはバッフルを設けても良い。
【００６４】
通常はこれらの攪拌翼の中から、反応液の粘度その他の物性、あるいは反応形態、反応槽の形状及び大きさ等により好適なものを選択し使用されるが、好ましい攪拌翼としては具体的には、ダブルヘリカルリボン翼またはアンカー翼が挙げられ、中でもダブルヘリカルリボン翼が更に好ましい。
次に、本発明のトナーの製造方法においては、凝集工程に引き続き、凝集で得られた凝集粒子（トナー粒子）の安定性を増すためにＴｇ〜（Ｔｇ＋８０）℃、好ましくは（Ｔｇ＋２０）℃〜（Ｔｇ＋８０）℃の温度範囲であり、かつ重合体一次粒子の軟化点以下の温度範囲で、凝集した粒子間の融着を起こす熟成工程を加えることが好ましい。熟成工程を加えることにより、トナー粒子の形状も球状に近いものすることができ、形状制御も可能になる。この熟成工程は、通常１時間から２４時間であり、好ましくは１時間から１０時間である。
【００６５】
この熟成工程は、凝集工程に用いた攪拌槽と同様な攪拌槽を用いて行うことができる。
上記の各工程を経ることにより得たトナー粒子は、公知の方法に従って固液分離し、トナー粒子を回収し、次いで、これを必要に応じて、洗浄した後、乾燥する。
【００６６】
また、本発明のトナーは、必要により流動化剤等の添加剤と共にもちいることができ、そのような流動化剤としては、具体的には、疎水性シリカ、酸化チタン、酸化アルミニウム等の微粉末を挙げることができ、通常、バインダー樹脂１００重量部に対して、０．０１〜５重量部、好ましくは０．１〜３重量部用いられる。
【００６７】
さらに、本発明のトナーは、マグネタイト、フェライト、酸化セリウム、チタン酸ストロンチウム、導電性チタニア等の無機微粉末やスチレン樹脂、アクリル樹脂等の抵抗調節剤や滑剤などが内添剤又は外添剤として用いることができる。これらの添加剤の使用量は所望する性能により適宜選定すれば良く、通常バインダー樹脂１００重量部に対し０．０５〜１０重量部程度が好適である。
【００６８】
本発明の静電荷像現像用トナーは２成分系現像剤又は非磁性１成分系現像剤のいずれの形態で用いてもよい。２成分系現像剤として用いる場合、キャリアとしては、鉄粉、マグネタイト粉、フェライト粉等の磁性物質またはそれらの表面に樹脂コーティングを施したモノや磁性キャリア等公知のものを用いることができる。樹脂コーティングキャリアの被覆樹脂としては一般的に知られているスチレン系樹脂、アクリル系樹脂、スチレンアクリル共重合系樹脂、シリコーン樹脂、変性シリコーン樹脂、フッ素樹脂、またはこれらの混合物等が利用できる。
【００６９】
上述の各成分を用いて製造された本発明のトナーにおいて、重合体一次粒子と樹脂微粒子の少なくとも一方が架橋された樹脂を使用することが好ましい。架橋樹脂を使用した場合には、粘弾性が向上すると共に、ＯＨＰ透明性が確保される。架橋された樹脂を用いた場合テトラヒドロフラン不溶分が高くなり、架橋されていない樹脂を用いた場合には、テトラヒドロフランにほぼ溶解する。また、着色剤は通常テトラヒドロフランには溶解しない。更に、帯電制御剤はテトラヒドロフランに溶解する場合と溶解しない場合があるが、通常、帯電制御剤は他の成分に対してその使用割合が少ないので、これらを考慮して、本発明のトナーのテトラヒドロフラン不溶分が１５〜８０％に制御されることが好ましい。テトラヒドロフラン不溶分は更に好ましくは２０％以上であり、７０％以下である。
【００７０】
また、本発明のトナーは、好ましくは融点３０〜１００℃のワックスを含んでいるが、その含有割合は、トナーのバインダー樹脂（重合体一次粒子を構成する樹脂と、樹脂微粒子を構成する樹脂の合計量）１００重量部に対し、１重量部以上が好ましく、５重量部以上が更に好ましく、１０重量部以上が特に好ましい。また、４０重量部以下が好ましく、３５重量部以下が更に好ましく、３０重量部以下が特に好ましい。
【００７１】
また、本発明のトナーを高解像度のプリンターやコピー機に使用する場合、トナーが比較的小粒径であり、粒度分布がシャープである方が、個々のトナー粒子の帯電量が均一になりやすいことから好ましい。
本発明のトナーの体積平均粒径は通常３〜１２μｍであり、好ましくは４〜１０μｍであり、更に好ましくは５〜９μｍであり、特に好ましくは６〜８μｍである。また、粒度分布を表す指標として、体積平均粒径（Ｄ_V）と個数平均粒径（Ｄ_N）との比（Ｄ_V／Ｄ_N）を用いた場合に、Ｄ_V／Ｄ_Nの値が１．２５以下が好ましく、１．２２以下が更に好ましく、１．２以下が特に好ましい。Ｄ_V／Ｄ_Nの値の最小値は１であり、すべての粒子の径が等しいことを意味し、高解像の画像形成には有利ではあるが、実際的に１となるような粒度分布を得ることは極めて困難であり、従って製造上の観点からＤ_V／Ｄ_Nは１．０３以上であり、好ましくは１．０５以上である。
【００７２】
更に、微粉（過小粒径トナー）が多すぎると、感光体カブリ、装置内への飛散が多くなり、帯電量分布が悪くなる傾向となり、また、粗粉（過大粒径トナー）が多すぎると、帯電量分布が悪くなる傾向となり高解像度の画像を形成するには不適当である。例えば、トナーの平均体積粒径が７〜１０μｍである場合、５μｍ以下の粒径のトナーが、トナー全体の１０重量％以下であることが好ましく、５重量％以下であることが更に好ましい。また１５μｍ以上の粒径のトナーが５重量％以下であることが好ましく、３重量％以下であることが更に好ましい。
【００７３】
このような、比較的小粒径であり、粒度分布がシャープであるトナーを製造する場合には、本発明の乳化重合凝集法による製造法が、懸濁重合法によるものや、混練・粉砕法によるものに比べて有利である。
また、トナーの５０％円形度は、０．９５以上が好ましく、０．９６以上が更に好ましい。５０％円形度の最大値は１であり、これはトナーが実質的に真球状であることを意味するが、この様なトナーを得ることは困難であるので、製造上の観点から、好ましくは０．９９以下である。
【００７４】
次に、本発明のトナーのうち、好ましい実施態様について図と共に説明する。本発明のトナーの好ましい第一の態様は、重合体一次粒子（１）の凝集体に、樹脂微粒子（２）を付着又は固着してなり、該重合体一次粒子（１）がワックス（５）を含んでおり、樹脂微粒子が実質的にワックスを内部に包含しないものである。
【００７５】
この態様では、図１に示す如く、樹脂微粒子（２）を重合体一次粒子（１）の凝集体表面に少なくとも１部に付着または固着させることが好ましい（図１〜３においては、重合体一次粒子（１）と樹脂微粒子（２）のみ示してあり、着色剤微粒子、帯電制御剤微粒子、その他の添加剤等は省略してある）。
樹脂微粒子の使用量は、極端に少ないと被覆の効果が得られない場合があるので、好ましくは重合体一次粒子の３重量％以上であり、更に好ましくは５重量％以上である。また、使用量が極端に多すぎると、ワックスが最外層を除く表面部位に存在しなくなり、定着時のトナーからのワックスの排出が不良となる場合があるので、好ましくは重合体一次粒子の８０重量％以下であり、更に好ましくは４０重量％以下であり、特に好ましくは２０重量％以下である。
【００７６】
また、重量比では、粒子凝集体の重量／樹脂微粒子の重量が、１〜１００が好ましい。
粒子凝集体に樹脂微粒子を被覆するに先だって、重合体一次粒子のガラス転移温度（Ｔｇ）以上の温度、好ましくはＴｇ〜（Ｔｇ＋８０）℃で粒子凝集体を融着してもよい。樹脂微粒子を被覆するに先だって粒子凝集体を融着し、その後樹脂粒子を被覆した場合、図２のように、重合体一次粒子を融着して得た粒子（３）の中に、ワックス（５）を含み、粒子（３）に樹脂微粒子（２）を付着又は固着した形態となる。これが、本発明の好ましい第二の形態である。
【００７７】
図３は、上述した第一又は第二の態様において、重合体一次粒子及び樹脂微粒子を融着した後のトナーの概念図である。
図３の形態のトナーは、図１の形態または、図２の形態のトナーを、重合体一次粒子のガラス転移温度（Ｔｇ）以上の温度、好ましくはＴｇ〜（Ｔｇ＋８０）℃で融着（熟成工程）することにより得られるが、好ましくは、図１の形態のトナーを融着したもの、すなわち、重合体一次粒子を凝集して粒子凝集体とし、これを融着することなく（熟成工程を経ることなく）樹脂微粒子を付着させ、続いて重合体一次粒子と樹脂微粒子の両方を融着させた粒子（４）から形成されたものである。
【００７８】
図３において、点線は、トナー表面から０．１μｍの深さを示す。図３に示すとおり、この構造のトナーは、トナー最外部、具体的にはトナー表面から０．１μｍの深さの範囲内においては、実質的にワックス（５）粒子が存在していない。融着後のトナーでは、元々重合体一次粒子であった部分と樹脂微粒子であった部分の明確な境界は認められないのが普通であり、そして、トナー内部には一定の分布をもってワックス微粒子が存在している。
【００７９】
ここで、実質的にワックス粒子がトナー最外部に存在しないとは、具体的には体積平均粒径が３〜１２μｍであってワックスを含有するトナーの断面を透過型電子顕微鏡（ＴＥＭ）写真により観察した場合、トナー表面から０．１μｍまでの深さにおける平均粒径０．０１μｍ以上のワックス微粒子の濃度（面積比率）が、０．１μｍより深い部分におけるワックス微粒子の濃度（面積比率）の１／１０以下であることを意味する。
【００８０】
また、一定の分布をもってワックス微粒子が存在しているとは、トナー断面において観測されるワックス微粒子の個数平均粒径における半値幅が、０．０６μｍ以下であることを意味する。半値幅は０．０５μｍ以下が好ましい。また、半値幅の理論上の最小値は０であるが、製造上不可能であるので、実際的には半値幅は０．０１μｍ以上である。
【００８１】
図４は、実施例１で製造したトナーの断面のＴＥＭ写真を示した図である。この写真は、泡の形状の支持体上に切断したトナーを置いて観察したものであり、黒い固まりがトナーであり、トナー中の白色部及び淡色部（図では見えない）の固まりがワックスである。トナーの断面を観測した場合に、ワックス微粒子はその中心を通る面で切断されるとは限らず、むしろ中心をはずれた面で切断されることが確率的に多い。従って、トナー断面において観測されるワックス微粒子（面状に観測される）から求めた粒径の値は、実際にトナー中に存在している粒径よりも小さいものとなる。また、トナー粒子を切断する際に力が加わるので、略球形のトナーを切断した場合でも、切断面は円形とはならず崩れた楕円形となるのが通常であり、トナーに含まれるワックス微粒子の断面も崩れた形となる。
【００８２】
トナー断面において観測されるワックス微粒子の個数平均粒径は、通常２０ｎｍ以上であり、３０ｎｍ以上が好ましく、５０ｎｍ以上が更に好ましい。また、通常１５０ｎｍ以下であり、１００ｎｍ以下が好ましい。
本発明において、ワックス微粒子は、重合体一次粒子のシードとして用いられ、従って、ワックスは樹脂に内包化されているので、トナーの製造工程中で粒子凝集体を融着した場合であっても、ワックス微粒子は、重合体一次粒子あるいは樹脂微粒子中に存在した粒径をほぼ維持するものと考えられる。一方、ワックス微粒子を、重合体一次粒子と共凝集した場合には、共凝集の過程でワックス微粒子同士が先に融合する場合があるので、当初のワックス微粒子の粒径のものから、ワックス同士の融合を繰り返すことによってできた、かなり大きな粒径のワックスができることとなる。従って、トナー断面において観測されるワックス微粒子の個数平均粒径の分布は、シード重合で得られた重合体一次粒子を凝集する場合よりも、ワックス微粒子と重合体一次粒子と共凝集した場合の方が広くなる。
【００８３】
本発明のトナーの内部においては、粒径の小さなワックス微粒子が多数分布している。この様な構造は、定着時にトナー表面から一様にワックスの排出が行われると考えられ、離型性に優れる。しかも、定着前にはワックスの排出が抑制されることから、耐ブロッキング性に優れ、装置汚れ等の問題も生じにくい。
本発明の別の好ましい実施態様は、本発明のトナーは、重合体一次粒子と樹脂微粒子の少なくとも一方が架橋された樹脂を使用するものである。更に、重合体一次粒子と樹脂微粒子が共に架橋された樹脂を使用するのが好ましい。
【００８４】
【実施例】
以下に実施例により本発明を更に具体的に説明するが、本発明はこれら実施例に限定されるものではない。
以下の例で「部」とあるのは「重量部」を意味する。また、平均粒径、粒度分布、重量平均分子量、ガラス転移点（Ｔｇ）、５０％円形度、定着温度幅、ＯＨＰ透過性、帯電量、耐ブロッキング性及びテトラヒドロフラン不溶分は、それぞれ下記の方法により測定した。
【００８５】
体積平均粒径、個数平均粒径、５μｍ以下及び１５μｍ以上のトナー粒子の割合：ホリバ社製ＬＡ−５００、日機装社製マイクロトラックＵＰＡ（ｕｌｔｒａｐａｒｔｉｃｌｅ ａｎａｌｙｚｅｒ）、コールター社製コールターカウンターマルチサイザーＩＩ型（以下、コールターカウンターと略す。）により測定した。
【００８６】
重量平均分子量（Ｍｗ）：ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した（装置：東ソー社製ＧＰＣ装置 ＨＬＣ−８０２０、カラム：ポリマーラボラトリー 社製 ＰＬ−ｇｅｌ Ｍｉｘｅｄ−Ｂ １０μ、溶媒：ＴＨＦ、試料濃度：０．１重量％、検量線：標準ポリスチレン）
ガラス転移温度（Ｔｇ）：パーキンエルマー社製ＤＳＣ７により測定した。３０℃から１００℃まで７分で昇温し、１００℃から−２０℃まで急冷し、−２０℃から１００℃まで１２分で昇温し、２回目の昇温時に観察されたＴｇの値を用いた。
【００８７】
５０％円形度：フロー式粒子像分析装置（シスメックス社製「ＦＰＩＡ−２０００」）にてトナーを測定し、下記式より求められた値の５０％における累積粒度値に相当する円形度を用いた。
【００８８】
【数１】
円形度＝粒子投影面積と同じ面積の円の周長／粒子投影像の周長
定着温度幅：未定着のトナー像を担持した記録紙を用意し、加熱ローラの表面温度を１００℃から２２０℃まで変化させ、定着ニップ部に搬送し、排出された時の定着状態を観察した。定着時に加熱ローラにトナーのオフセットが生じず、定着後の記録紙上のトナーが十分に記録紙に接着している温度領域を定着温度領域とした。
【００８９】
定着機の加熱ローラは、芯金としてアルミニウム、弾性体層としてＪＩＳ−Ａ規格によるゴム硬度３゜のジメチル系の低温加硫型シリコーンゴム１．５ｍｍ厚、離型層としてＰＦＡ（テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体）５０μｍ厚が用いられており、直径は３０ｍｍ、日本ゴム協会規格ＳＲＩＳ ０１０１に準拠して測定される定着ローラ表面のゴム硬度は８０である。シリコンオイルの塗布なしで、ニップ幅は４ｍｍで評価した。定着速度は１２０ｍｍ／Ｓ又は３０ｍｍ／Ｓで実施した。
【００９０】
なお、評価範囲が１００℃から２２０℃（但し、比較例１０は１００℃から２００℃）であるため、定着温度の上限が２２０℃と記載のものについては、定着温度の真の上限はさらに高い可能性がある。
ＯＨＰ透過性：上記定着ローラを用い、ＯＨＰシート状の未定着のトナー像を、シリコンオイルの塗布なし、定着速度３０ｍｍ／Ｓ、１８０℃の条件で定着させ、分光光度計（日立製作所社製 Ｕ−３２１０）で、４００ｎｍ〜７００ｎｍの波長範囲で透過率を測定し、最も透過率の高かった波長における透過率（最大透過率（％））と最も透過率の低かった波長における透過率（最小透過率（％））の差（最大透過率−最小透過率）を値として用いた。
【００９１】
帯電量：トナーを非磁性１成分の現像槽（カシオ社製ＣｏｌｏｒＰａｇｅＰｒｅｓｔｏＮ４現像槽、記載のある場合は九州松下社製Ｐｈａｓｅｒ５５０現像槽）に投入し、ローラを一定数回転させた後、ローラ上のトナーを吸引し、帯電量（東芝ケミカル製ブローオフにて測定）と吸引したトナー重量から単位重量あたりの帯電量を求めた。
【００９２】
耐ブロッキング性：現像用トナー１０ｇを円筒形の容器に入れ、２０ｇの荷重をのせ、５０℃の環境下に５時間放置した後トナーを容器から取り出し、上から荷重をかけることで凝集の程度を確認した。
【００９３】
【表１】
○：凝集なし
△：凝集しているが軽い荷重で崩れる
×：凝集していて荷重をかけても崩れない
【００９４】
テトラヒドロフラン（ＴＨＦ）不溶分：トナー、重合体一次粒子、樹脂微粒子のテトラヒドロフラン不溶分の測定は、試料１ｇをテトラヒドロフラン１００ｇに加え２５℃で２４時間静置溶解し、セライト１０ｇを用いて濾過し、濾液の溶媒を留去してテトラヒドロフラン可溶分を定量し、１ｇから差し引いてテトラヒドロフラン不溶分を算出した。
[実施例１]
（ワックス分散液−１）
脱塩水６８．３３部、ベヘン酸ベヘニルを主体とするエステル混合物（ユニスターＭ−２２２２ＳＬ、日本油脂社製）とステアリン酸ステアリルを主体とするエステル混合物（ユニスターＭ９６７６、日本油脂社製）７：３の混合物３０部、ドデシルベンゼンスルホン酸ナトリウム（ネオゲンＳＣ、第一工業製薬社製、有効成分６６％）１．６７部を混合し、９０℃にて高圧剪断をかけ乳化し、エステルワックス微粒子の分散液を得た。ＬＡ−５００で測定したエステルワックス微粒子の平均粒径は３４０ｎｍであった。
（重合体一次粒子分散液−１）
攪拌装置（３枚翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積６０リットル、内径４００ｍｍ）に２８部のワックス分散液−１、１５％ネオゲンＳＣ水溶液１．２部、脱塩水３９３部を仕込み、窒素気流下で９０℃に昇温し、８％過酸化水素水溶液１．６部、８％アスコルビン酸水溶液１．６部を添加した。
【００９５】
その後、下記のモノマー類と乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【００９６】
【表２】
[モノマー類]
スチレン ７９部（５５３０ｇ）
アクリル酸ブチル ２１部
アクリル酸 ３部
オクタンチオール ０．３８部
２−メルカプトエタノール ０．０１部
ヘキサンジオールジアクリレート ０．９部
[乳化剤水溶液]
１５％ネオゲンＳＣ水溶液 １部
脱塩水 ２５部
[開始剤水溶液]
８％過酸化水素水溶液 ９部
８％アスコルビン酸水溶液 ９部
【００９７】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は１１９，０００、ＵＰＡで測定した平均粒子径は１８９ｎｍ、Ｔｇは５７℃、ＴＨＦ不溶分は５２重量％であった。
（樹脂微粒子分散液−１）
攪拌装置（３枚翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積６０リットル、内径４００ｍｍ）に１５％ネオゲンＳＣ水溶液５部、脱塩水３７２部を仕込み、窒素気流下で９０℃に昇温して、８％過酸化水素水溶液１．６部、８％アスコルビン酸水溶液１．６部を添加した。
【００９８】
その後、下記のモノマー類と乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【００９９】
【表３】
[モノマー類]
スチレン ８８部（６１６０ｇ）
アクリル酸ブチル １２部
アクリル酸 ２部
ブロモトリクロロメタン ０．５部
２−メルカプトエタノール ０．０１部
ヘキサンジオールジアクリレート ０．４部
[乳化剤水溶液]
１５％ネオゲンＳＣ水溶液 ２．５部
脱塩水 ２４部
[開始剤水溶液]
８％過酸化水素水溶液 ９部
８％アスコルビン酸水溶液 ９部
【０１００】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は５４，０００、ＵＰＡで測定した平均粒子径は８３ｎｍ、Ｔｇは８５℃、ＴＨＦ不溶分は１５重量％であった。
（着色剤微粒子分散液−１）
ピグメントブルー１５：３の水分散液（ＥＰ−７００ Ｂｌｕｅ ＧＡ、大日精化製、固形分３５％）を用いた。
【０１０１】
ＵＰＡで測定した平均粒径は１５０ｎｍであった。
（帯電制御剤微粒子分散液−１）
４，４'−メチレンビス〔２−〔Ｎ−（４−クロロフェニル）アミド〕−３−ヒドロキシナフタレン〕２０部、アルキルナフタレンスルホン酸塩４部、脱塩水７６部をサンドグラインダーミルにて分散し、帯電制御剤微粒子分散液を得た。ＵＰＡで測定した平均粒径は２００ｎｍであった。
【０１０２】
（現像用トナーの製造−１）
【表４】
重合体一次粒子分散液−１ １０４部（７１ｇ：固形分として）
樹脂微粒子分散液−１ ６部（固形分として）
着色剤微粒子分散液−１ ６．７部（固形分として）
帯電制御剤微粒子分散液−１ ２部（固形分として）
１５％ネオゲンＳＣ水溶液 ０．５部（固形分として）
【０１０３】
上記の各成分を用いて、以下の手順によりトナーを製造した。
反応器（容積１リットル、バッフル付きアンカー翼）に重合体一次粒子分散液と１５％ネオゲンＳＣ水溶液を仕込み、均一に混合してから着色剤微粒子分散液を添加し、均一に混合した。得られた混合分散液を攪拌しながら硫酸アルミニウム水溶液を滴下した（固形分として０．６部）。その後攪拌しながら２０分かけて５１℃に昇温して１時間保持し、さらに６分かけて５８℃に昇温して１時間保持した。帯電制御剤微粒子分散液、樹脂微粒子分散液、硫酸アルミニウム水溶液（固形分として０．０７部）の順に添加し、１０分かけて６０℃に昇温して３０分保持した。１５％ネオゲンＳＣ水溶液（固形分として３部）を添加してから３５分かけて９５℃に昇温して３．５時間保持した。その後冷却し、濾過、水洗し、乾燥することによりトナー（トナー−１）を得た。
【０１０４】
このトナー１００部に対し、疎水性の表面処理をしたシリカを０．６部混合攪拌し、現像用トナー（現像用トナー−１）を得た。
（トナーの評価−１）
現像用トナーのコールターカウンターによる体積平均粒径は７．２μｍ、体積粒径の５μｍ以下の割合は３．５％、１５μｍ以上の割合は０．５％、体積平均粒径と数平均粒径の比は１．１２であった。
【０１０５】
５０％円形度は０．９７であった。
現像用トナー−１の定着性は、定着速度１２０ｍｍ／Ｓでは１７０〜２２０℃で定着し、定着速度３０ｍｍ／Ｓでは１３０〜２２０℃で定着した。ＯＨＰ透過性は７０％だった。
トナー−１の帯電量は−７μＣ／ｇ、現像用トナー−１の帯電量は−１５μＣ／ｇだった。耐ブロッキング性は○だった。
【０１０６】
また、トナーを厚さ８０ｎｍに切り出し、１６０００倍のＴＥＭ写真により解析したところ、ワックス粒子の分散状態は、個数平均粒径９２ｎｍ、個数平均粒径の半値幅は４３ｎｍ、トナー表面から０．１μｍまでの深さの範囲での半径０．０１μｍ以上のワックス微粒子の存在比率は０％、それ以外の部分は４．５％％であった。
【０１０７】
ＴＥＭ写真の様子を図４で示す。また、トナー断面において観察されたワックス微粒子の個数平均粒径の分布を表すグラフを粒径０〜１．５μｍの範囲、粒径０〜０．５μｍの範囲それぞれについて図６、図７に示す。
[実施例２]
（ワックス分散液−２）
ワックス分散液−１と同様に作製したものを用いた。ＬＡ−５００で測定したエステルワックス微粒子の平均粒径は３４０ｎｍであった。
（重合体一次粒子分散液−２）
攪拌装置（３枚翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積６０リットル、内径４００ｍｍ）にワックス分散液−２ ２８部、１５％ネオゲンＳＣ水溶液１．２部、脱塩水３９３部を仕込み、窒素気流下で９０℃に昇温して、８％過酸化水素水溶液１．６部、８％アスコルビン酸水溶液１．６部を添加した。
【０１０８】
その後、下記のモノマー類と乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【０１０９】
【表５】
[モノマー類]
スチレン ７９部
アクリル酸ブチル ２１部
アクリル酸 ３部
ブロモトリクロロメタン ０．４５部
２−メルカプトエタノール ０．０１部
ヘキサンジオールジアクリレート ０．９部
[乳化剤水溶液]
１５％ネオゲンＳＣ水溶液 １部
脱塩水 ２５部
[開始剤水溶液]
８％過酸化水素水溶液 ９部
８％アスコルビン酸水溶液 ９部
【０１１０】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は１４８，０００、ＵＰＡで測定した平均粒子径は２０７ｎｍ、Ｔｇは５５℃、ＴＨＦ不溶分は６０重量％であった。
（着色剤微粒子分散液−２）
２０部のピグメントイエロー７４、ポリオキシエチレンアルキルフェニルエーテル７部、脱塩水７３部をサンドグラインダーミルにて分散し、着色剤微粒子分散液を得た。ＵＰＡで測定した平均粒径は２１１ｎｍであった。
【０１１１】
（現像用トナーの製造−２）
【表６】
重合体一次粒子分散液−２ １０５部（固形分として）
樹脂微粒子分散液−１ ５部（固形分として）
着色剤微粒子分散液−２ ６．７部（固形分として）
帯電制御剤微粒子分散液−１ ２部（固形分として）
【０１１２】
上記の各成分を用いて、以下の手順によりトナーを製造した。
反応器（容積１リットル、バッフル付きアンカー翼）に重合体一次粒子分散液と着色剤微粒子分散液を仕込み、均一に混合した。得られた混合分散液を攪拌しながら硫酸アルミニウム水溶液（固形分として０．６部）を滴下した。その後攪拌しながら２５分かけて５１℃に昇温して１時間保持し、さらに８分かけて５９℃に昇温して４０分保持した。帯電制御剤微粒子分散液、樹脂微粒子分散液、硫酸アルミニウム水溶液（固形分として０．０７部）の順に添加し、１５分かけて６１℃に昇温して３０分保持した。１５％ネオゲンＳＣ水溶液（固形分として３．８部）を添加してから３０分かけて９６℃に昇温して４時間保持した。その後冷却し、濾過、水洗し、乾燥することによりトナー（トナー−２）を得た。
【０１１３】
このトナー１００部に対し、疎水性の表面処理をしたシリカを０．６部混合攪拌し、現像用トナー（現像用トナー−２）を得た。
トナーの評価−２
現像用トナー−２のコールターカウンターによる体積平均粒径は７．５μｍ、体積粒径の５μｍ以下の割合は１．６％、１５μｍ以上の割合は０．７％、体積平均粒径と数平均粒径の比は１．１４であった。５０％円形度は０．９６であった。
【０１１４】
現像用トナー−２の定着性は、定着速度１２０ｍｍ／Ｓでは１５０〜２２０℃で定着し、定着速度３０ｍｍ／Ｓでは１３０〜２２０℃で定着した。
トナー−２の帯電量は−４μＣ／ｇ、現像用トナー−２の帯電量は−３μＣ／ｇだった。
［実施例３］
（着色剤微粒子分散液−３）
ピグメントレッド２３８（下記式（Ａ）の化合物）２０部、アルキルベンゼンスルホン酸塩２.５部、脱塩水７７.５部をサンドグラインダーミルにて分散し、着色剤微粒子分散液を得た。ＵＰＡで測定した平均粒径は１８１ｎｍであった。
【０１１５】
【化６】

【０１１６】
（現像用トナーの製造−３）
【０１１７】
【表７】
重合体一次粒子分散液−１ １０４部（固形分として）
樹脂微粒子分散液−１ ６部（固形分として）
着色剤微粒子分散液−３ ６．７部（固形分として）
帯電制御剤微粒子分散液−１ ２部（固形分として）
１５％ネオゲンＳＣ水溶液 ０．６５部（固形分として）
【０１１８】
上記の各成分を用いて、以下の手順によりトナーを製造した。
反応器（容積１リットル、バッフル付きアンカー翼）に重合体一次粒子分散液と１５％ネオゲンＳＣ水溶液を仕込み、均一に混合してから着色剤微粒子分散液を添加し、均一に混合した。得られた混合分散液を攪拌しながら硫酸アルミニウム水溶液（固形分として０．８部）を滴下した。その後攪拌しながら１５分かけて５１℃に昇温して１時間保持し、さらに６分かけて５９℃に昇温して２０分保持した。帯電制御剤微粒子分散液、樹脂微粒子分散液、硫酸アルミニウム水溶液（固形分として０．０９部）の順に添加し、５９℃で２０分保持した。１５％ネオゲンＳＣ水溶液（固形分として３．７部）を添加してから２５分かけて９５℃に昇温して、さらに１５％ネオゲンＳＣ水溶液（固形分として０．７部）を添加して、３．５時間保持した。その後冷却し、濾過、水洗し、乾燥することによりトナー（トナー−３）を得た。
【０１１９】
このトナー１００部に対し、疎水性の表面処理をしたシリカを０．６部混合攪拌し、現像用トナー（現像用トナー−３）を得た。
（トナーの評価−３）
現像用トナーのコールターカウンターによる体積平均粒径は７．８μｍ、体積粒径の５μｍ以下の割合は２．１％、１５μｍ以上の割合は２．１％、体積平均粒径と数平均粒径の比は１．１５であった。５０％円形度は０．９７であった。
【０１２０】
現像用トナー−３の定着性は、定着速度１２０ｍｍ／Ｓでは１６０〜２２０℃で定着し、定着速度３０ｍｍ／Ｓでは１２０〜２２０℃で定着した。
トナー−３の帯電量は−１７μＣ／ｇ、現像用トナー−３の帯電量は−１７μＣ／ｇだった。
[実施例４]
（ワックス分散液−４）
脱塩水６８．３３部、ペンタエリスリトールのステアリン酸エステルを主体とするエステル混合物（ユニスターＨ４７６、日本油脂製）３０部、ネオゲンＳＣ１．６７部を混合し、９０℃で高圧剪断をかけ乳化し、エステルワックス微粒子の分散液を得た。ＬＡ−５００で測定したエステルワックス微粒子の平均粒径は３５０ｎｍであった。
（重合体一次粒子分散液−４）
攪拌装置（フルゾーン翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積２リットル、内径１２０ｍｍ）にワックス分散液−４ ３５部、脱塩水３９７７部を仕込み、窒素気流下で９０℃に昇温して、８％過酸化水素水溶液１．６部、８％アスコルビン酸水溶液１．６部を添加した。
【０１２１】
その後、下記のモノマー類・乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【０１２２】
【表８】
[モノマー類]
スチレン ７９部（２３７g）
アクリル酸ブチル ２１部
アクリル酸 ３部
オクタンチオール ０ ．３８部
２−メルカプトエタノール ０．０１部
ヘキサンジオールジアクリレート ０．９部
[乳化剤水溶液]
１５％ネオゲンＳＣ水溶液 １部
脱塩水 ２５部
[開始剤水溶液]
８％過酸化水素水溶液 ９部
８％アスコルビン酸水溶液 ９部
【０１２３】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は１３９，０００、ＵＰＡで測定した平均粒子径は２０１ｎｍ、Ｔｇは不明瞭、ＴＨＦ不溶分は５３重量％であった。
（樹脂微粒子分散液−４）
攪拌装置（３枚後退翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積２リットル、内径１２０ｍｍ）に１５％ネオゲンＳＣ水溶液６部、脱塩水３７２部を仕込み、窒素気流下で９０℃に昇温して、８％過酸化水素水溶液１．６部、８％アスコルビン酸水溶液１．６部を添加した。
【０１２４】
その後、下記のモノマー類と乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【０１２５】
【表９】
（モノマー類）
スチレン ８８部（３０８g）
アクリル酸ブチル １２部
アクリル酸 ２部
ブロモトリクロロメタン ０．５部
２−メルカプトエタノール ０．０１部
ヘキサンジオールジアクリレート ０．４部
（乳化剤水溶液）
１５％ネオゲンＳＣ水溶液 ３部
脱塩水 ２３部
（開始剤水溶液）
８％過酸化水素水溶液 ９部
８％アスコルビン酸水溶液 ９部
【０１２６】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は５７，０００、ＵＰＡで測定した平均粒子径は５６ｎｍ、Ｔｇは８４℃、ＴＨＦ不溶分は１０重量％であった。
【０１２７】
（現像用トナーの製造−４）
【表１０】
重合体一次粒子分散液−４ １０５部（７１ｇ：固形分として）
樹脂微粒子分散液−４ ５部（固形分として）
着色剤微粒子分散液−１ ６．７部（固形分として）
帯電制御剤微粒子分散液−１ ２部（固形分として）
１５％ネオゲンＳＣ水溶液 ０．５部（固形分として）
【０１２８】
上記の各成分を用いて、以下の手順によりトナーを製造した。
反応器（容積１リットル、バッフル付きアンカー翼）に重合体一次粒子分散液と１５％ネオゲンＳＣ水溶液を仕込み、均一に混合してから着色剤微粒子分散液を添加し、均一に混合した。得られた混合分散液を攪拌しながら硫酸アルミニウム水溶液（固形分として０．５３部）を滴下した。その後攪拌しながら２５分かけて５０℃に昇温して１時間保持し、さらに３５分かけて６３℃に昇温して２０分保持した。帯電制御剤微粒子分散液、樹脂微粒子分散液、硫酸アルミニウム水溶液（固形分として０．０７部）の順に添加し、１０分かけて６５℃に昇温して３０分保持した。１５％ネオゲンＳＣ水溶液（固形分として３部）を添加してから３０分かけて９６℃に昇温して５時間保持した。その後冷却し、濾過、水洗し、乾燥することによりトナー（トナー−４）を得た。
【０１２９】
このトナー１００部に対し、疎水性の表面処理をしたシリカを０．６部混合攪拌し、現像用トナー（現像用トナー−４）を得た。
（トナーの評価−４）
現像用トナー−４のコールターカウンターによる体積平均粒径は７.９μｍ、体積粒径の５μｍ以下の割合は２％、１５μｍ以上の割合は１．５％、体積平均粒径と数平均粒径の比は１．２０であった。５０％円形度は０．９５であった。
【０１３０】
現像用トナー−４の定着性は、定着速度１２０ｍｍ／Ｓでは１７０〜２２０℃で定着し、定着速度３０ｍｍ／Ｓでは１３０〜２２０℃で定着した。ＯＨＰ透過性は７０％だった。
トナー−４の帯電量は−９μＣ／ｇ、現像用トナー−４の帯電量は−１５μＣ／ｇだった。耐ブロッキング性は○だった。
[実施例５]
（ワックス分散液−５）
脱塩水６８.３３部、ベヘン酸ベヘニルを主体とするエステル混合物（ユニスターＭ−２２２２ＳＬ、日本油脂製）とポリエステルワックス（Ｍｗ約１０００）の７:３の混合物３０部、ネオゲンＳＣ １.６７部を混合し、９０℃で高圧剪断をかけ乳化し、エステルワックス微粒子の分散液を得た。ＬＡ−５００で測定したエステルワックス微粒子の平均粒径は４９０ｎｍであった。
（重合体一次粒子分散液−５）
攪拌装置（フルゾーン翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積２リットル、内径１２０ｍｍ）に２８部のワックス分散液−５、１５％ネオゲンＳＣ水溶液１.２部、脱塩水３９３部を仕込み、窒素気流下で９０℃に昇温して、８％過酸化水素水溶液１.６部、８％アスコルビン酸水溶液１.６部を添加した。
【０１３１】
その後、下記のモノマー類・乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【０１３２】
【表１１】
（モノマー類）
スチレン ７９部
アクリル酸ブチル ２１部
アクリル酸 ３部
ブロモトリクロロメタン ０.５部
２−メルカプトエタノール ０.０１部
ヘキサンジオールジアクリレート ０.９部
（乳化剤水溶液）
１５％ネオゲンＳＣ水溶液 １部
脱塩水 ２５部
（開始剤水溶液）
８％過酸化水素水溶液 ９部
８％アスコルビン酸水溶液 ９部
【０１３３】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は１１７,０００、ＵＰＡで測定した平均粒子径は２０１ｎｍ、Ｔｇは５３℃、ＴＨＦ不溶分は４１重量％であった。
（現像用トナーの製造−５）
【０１３４】
【表１２】
重合体一次粒子分散液−５ １０４部（固形分として）
樹脂微粒子分散液−４ ６部（固形分として）
着色剤微粒子分散液−１ ６.７部（固形分として）
帯電制御剤微粒子分散液−１ ２部（固形分として）
１５％ネオゲンＳＣ水溶液 ０.５部（固形分として）
【０１３５】
上記の各成分を用いて、以下の手順によりトナーを製造した。
反応器（容積１リットル、バッフル付きアンカー翼）に重合体一次粒子分散液と１５％ネオゲンＳＣ水溶液を仕込み、均一に混合してから着色剤微粒子分散液を添加し、均一に混合した。得られた混合分散液を攪拌しながら硫酸アルミニウム水溶液を滴下した（固形分として０.５２部）。その後攪拌しながら２０分かけて５０℃に昇温して１時間保持し、さらに４０分かけて６６℃に昇温して１０分保持した。帯電制御剤微粒子分散液、樹脂微粒子分散液、硫酸アルミニウム水溶液（固形分として０.０８部）の順に添加し、１０分かけて６８℃に昇温して３０分保持した。１５％ネオゲンＳＣ水溶液（固形分として３部）を添加してから２０分かけて９６℃に昇温して４.５時間保持した。その後冷却し、濾過、水洗し、乾燥することによりトナー（トナー−５）を得た。
【０１３６】
このトナー１００部に対し、疎水性の表面処理をしたシリカを０.６部混合攪拌し、現像用トナー（現像用トナー−５）を得た。
（トナーの評価−５）
現像用トナーのコールターカウンターによる体積平均粒径は８.２μｍ、体積粒径の５μｍ以下の割合は０.７％、１５μｍ以上の割合は１.６％、体積平均粒径と数平均粒径の比は１.１４であった。５０％円形度は０.９５であった。
【０１３７】
現像用トナー−５の定着性は、定着速度１２０ｍｍ／Ｓでは１７０〜２２０℃で定着し、定着速度３０ｍｍ／Ｓでは１２０〜２００℃で定着した。
トナー−５の帯電量は−３.５μＣ／ｇ、現像用トナー−５の帯電量は−２１μＣ／ｇだった。
[実施例６]
（ワックス分散液−６）
脱塩水６８.３３部、ベヘン酸ベヘニルを主体とするエステル混合物（ユニスターＭ−２２２２ＳＬ、日本油脂製）３０部、ネオゲンＳＣ １.６７部を混合し、９０℃にて高圧剪断をかけ乳化し、エステルワックス分散液を得た。ＬＡ−５００で測定した平均粒径は３４０ｎｍであった。
（重合体一次粒子分散液−６）
攪拌装置（３枚後退翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積３リットル、内径１５０ｍｍ）にワックス分散液−６３５部、脱塩水３９６部を仕込み、窒素気流下で９０℃に昇温して、８％過酸化水素水溶液１.６部、８％アスコルビン酸水溶液１.６部を添加した。
【０１３８】
その後、下記のモノマー類と乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【０１３９】
【表１３】
（モノマー類）
スチレン ７９部
アクリル酸ブチル ２１部
アクリル酸 ３部
オクタンチオール ０.３８部
２−メルカプトエタノール ０.０１部
ヘキサンジオールジアクリレート ０.７部
[乳化剤水溶液]
１５％ネオゲンＳＣ水溶液 １部
脱塩水 ２５部
[開始剤水溶液]
８％過酸化水素水溶液 ９部
８％アスコルビン酸水溶液 ９部
【０１４０】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は１２７,０００、ＵＰＡで測定した平均粒子径は２０１ｎｍ、Ｔｇは５５℃、ＴＨＦ不溶分は３８重量％であった。
（樹脂微粒子分散液−６）
攪拌装置（３枚後退翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積２l、内径１２０ｍｍ）に１５％ネオゲンＳＣ水溶液４.３部、脱塩水３７６部を仕込み、窒素気流下で９０℃に昇温して、８％過酸化水素水溶液１.６部、８％アスコルビン酸水溶液１.６部を添加した。
【０１４１】
その後、下記のモノマー類と乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【０１４２】
【表１４】
（モノマー類）
スチレン ８８部
アクリル酸ブチル １２部
アクリル酸 ３部
ブロモトリクロロメタン ０.５部
２−メルカプトエタノール ０.０１部
ジビニルベンゼン ０.４部
（乳化剤水溶液）
１５％ネオゲンＳＣ水溶液 ２.２部
脱塩水 ２４部
（開始剤水溶液）
８％過酸化水素水溶液 ９部
８％アスコルビン酸水溶液 ９部
【０１４３】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は１１１,０００、ＵＰＡで測定した平均粒子径は１２１ｎｍ、Ｔｇは８６℃、ＴＨＦ不溶分は２０重量％であった。
（着色剤微粒子分散液−６）
ピグメントレッド４８:２（下記式（Ｂ）の化合物） ２０部、ポリオキシエチレンアルキルフェニルエーテル４部、脱塩水７６部をサンドグラインダーミルにて分散し、着色剤微粒子分散液を得た。ＵＰＡで測定した平均粒径は２０１ｎｍであった。
【０１４４】
【化７】

【０１４５】
（現像用トナーの製造−６）
【表１５】
重合体一次粒子分散液−６ ９９部（固形分として）
樹脂微粒子分散液−６ １１部（固形分として）
着色剤微粒子分散液−６ ６.７部（固形分として）
帯電制御剤微粒子分散液−１ ２部（固形分として）
１５％ネオゲンＳＣ水溶液 ０.２７部（固形分として）
【０１４６】
上記の各成分を用いて、以下の手順によりトナーを製造した。
反応器（容積１リットル、バッフル付きアンカー翼）に重合体一次粒子分散液と１５％ネオゲンＳＣ水溶液を仕込み、均一に混合してから着色剤微粒子分散液を添加し、均一に混合した。得られた混合分散液を攪拌しながら硫酸アルミニウム水溶液を添加した（固形分として０.５２部）。その後攪拌しながら３０分かけて５５℃に昇温して１時間保持し、さらに２０分かけて６１℃に昇温して１５分保持した。帯電制御剤微粒子分散液、樹脂微粒子分散液、硫酸アルミニウム水溶液（固形分として０.０８部）の順に添加し、１０分かけて６３℃に昇温して３０分保持した。１５％ネオゲンＳＣ水溶液（固形分として３部）を添加してから３０分かけて９６℃に昇温して１時間保持した。その後冷却し、濾過、水洗し、乾燥することによりトナー（トナー−６）を得た。
【０１４７】
このトナー１００部に対し、疎水性の表面処理をしたシリカを０.６部混合攪拌し、現像用トナー（現像用トナー−６）を得た。
（トナーの評価−６）
現像用トナー−６のコールターカウンターによる体積平均粒径は７.８μｍ、体積粒径の５μｍ以下の割合は１.３％、１５μｍ以上の割合は２.８％、体積平均粒径と数平均粒径の比は１.１５であった。５０％円形度は０.９８であった。
【０１４８】
現像用トナー−６の定着性は、定着速度１２０ｍｍ／Ｓでは１６０〜２１０℃で定着し、定着速度３０ｍｍ／Ｓでは１２０〜１９０℃で定着した。
トナー−６の帯電量は−１５μＣ／ｇ、現像用トナー−６の帯電量は−２８μＣ／ｇだった。
[比較例７] （樹脂微粒子による被覆を行わない例）
（現像用トナーの製造−７）
【０１４９】
【表１６】
重合体一次粒子分散液−６ １１０部（固形分として）
着色剤微粒子分散液−６ ６.７部（固形分として）
帯電制御剤微粒子分散液−１ ２部（固形分として）
１５％ネオゲンＳＣ水溶液 ０.５部（固形分として）
【０１５０】
上記の各成分を用いて、以下の手順によりトナーを製造した。
反応器（容積１リットル、バッフル付きアンカー翼）に重合体一次粒子分散液と１５％ネオゲンＳＣ水溶液を仕込み、均一に混合してから着色剤微粒子分散液を添加し、均一に混合した。得られた混合分散液を攪拌しながら硫酸アルミニウム水溶液を滴下した（固形分として０.６部）。その後攪拌しながら３０分かけて５５℃に昇温して１時間保持し、さらに２０分かけて６２℃に昇温して１０分保持した。帯電制御剤微粒子分散液を添加し、６２℃で３０分保持した。１５％ネオゲンＳＣ水溶液（固形分として３部）を添加してから３５分かけて９６℃に昇温して１.５時間保持した。その後冷却し、濾過、水洗し、乾燥することによりトナー（トナー−７）を得た。
【０１５１】
このトナー１００部に対し、疎水性の表面処理をしたシリカを０.６部混合攪拌し、現像用トナー（現像用トナー−７）を得た。
（トナーの評価−７）
現像用トナー−７のコールターカウンターによる体積平均粒径は７.３μｍ、体積粒径の５μｍ以下の割合は３.１％、１５μｍ以上の割合は０.５％、体積平均粒径と数平均粒径の比は１.１４であった。５０％円形度は０.９８であった。
【０１５２】
現像用トナー−７の定着性は、定着速度１２０ｍｍ／Ｓでは１５０〜２２０℃で定着し、定着速度３０ｍｍ／Ｓでは１１０〜１８０℃で定着した。
トナー−７の帯電量は−３μＣ／ｇ、現像用トナー−７の帯電量は−１４μＣ／ｇだった。
[実施例８]
（ワックス分散液−８）
ワックス分散液−６と同様に作製したものを用いた。ＬＡ−５００で測定した平均粒径は３４０ｎｍであった。
（重合体一次粒子分散液−８）
重合体一次粒子分散液−６と同じ配合、同様の操作により作成した。
【０１５３】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は９８.０００、ＵＰＡで測定した平均粒子径は１８８ｎｍ、Ｔｇは５７℃、ＴＨＦ不溶分は２５重量％であった。
（現像用トナーの製造−８）
【０１５４】
【表１７】
重合体一次粒子分散液−８ ９９部（固形分として）
樹脂微粒子分散液−６ １１部（固形分として）
着色剤微粒子分散液−１ ６.７部（固形分として）
帯電制御剤微粒子分散液−１ ２部（固形分として）
１５％ネオゲンＳＣ水溶液 ０.５部（固形分として）
【０１５５】
上記の各成分を用いて、以下の手順によりトナーを製造した。
反応器（容積１リットル、バッフル付きアンカー翼）に重合体一次粒子分散液と１５％ネオゲンＳＣ水溶液を仕込み、均一に混合してから着色剤微粒子分散液を添加し、均一に混合した。得られた混合分散液を攪拌しながら硫酸アルミニウム水溶液（固形分として０.６部）を滴下した。その後攪拌しながら２０分かけて５５℃に昇温して１時間保持し、さらに５分かけて５８℃に昇温して１時間保持した。帯電制御剤微粒子分散液、樹脂微粒子分散液、硫酸アルミニウム水溶液（固形分として０.０７部）の順に添加し、２５分かけて６５℃に昇温した。１５％ネオゲンＳＣ水溶液（固形分として４.１部）を添加してから３０分かけて９５℃に昇温して、２時間保持した。その後冷却し、濾過、水洗し、乾燥することによりトナー（トナー−８）を得た。
【０１５６】
このトナー１００部に対し、疎水性の表面処理をしたシリカを０.６部混合攪拌し、現像用トナー（現像用トナー−８）を得た。
（トナーの評価−８）
現像用トナー−８のコールターカウンターによる体積平均粒径は７.３μｍ、体積粒径の５μｍ以下の割合は１.４％、１５μｍ以上の割合は０.３％、体積平均粒径と数平均粒径の比は１.１１であった。５０％円形度は０.９８であった。
【０１５７】
現像用トナー−８の定着性は、定着速度１２０ｍｍ／Ｓでは１８０〜２２０℃で定着し、定着速度３０ｍｍ／Ｓでは１５０〜１８０℃で定着した。
トナー−８の帯電量は−８μＣ／ｇ、現像用トナー−８の帯電量は−１４μＣ／ｇだった。
[実施例９]
（現像用トナーの製造−９）
【０１５８】
【表１８】
重合体一次粒子分散液−８ ９９部（固形分として）
樹脂微粒子分散液−６ １１部（固形分として）
着色剤微粒子分散液−３ ６.７部（固形分として）
帯電制御剤微粒子分散液−１ ２部（固形分として）
１５％ネオゲンＳＣ水溶液 ０.６５部（固形分として）
【０１５９】
上記の各成分を用いて、以下の手順によりトナーを製造した。
反応器（容積１リットル、バッフル付きアンカー翼）に重合体一次粒子分散液と１５％ネオゲンＳＣ水溶液を仕込み、均一に混合してから着色剤微粒子分散液を添加し、均一に混合した。得られた混合分散液を攪拌しながら硫酸アルミニウム水溶液を滴下した（固形分として０.８部）。その後攪拌しながら２５分かけて５５℃に昇温して１時間保持し、帯電制御剤微粒子分散液を添加し、２分かけて５７℃に昇温した。樹脂微粒子分散液を添加し、５７℃で３５分保持した。１５％ネオゲンＳＣ水溶液（固形分として４部）を添加してから４０分かけて９５℃に昇温して、４時間保持した。その後冷却し、濾過、水洗し、乾燥することによりトナー（トナー−９）を得た。
【０１６０】
このトナー１００部に対し、疎水性の表面処理をしたシリカを０.６部混合攪拌し、現像用トナー（現像用トナー−９）を得た。
（トナーの評価−９）
現像用トナー−９のコールターカウンターによる体積平均粒径は７.６μｍ、体積粒径の５μｍ以下の割合は１.６％、１５μｍ以上の割合は２.４％、体積平均粒径と数平均粒径の比は１.１５であった。５０％円形度は０.９７であった。
【０１６１】
現像用トナー−９の定着性は、定着速度１２０ｍｍ／Ｓでは２００〜２２０℃で定着し、定着速度３０ｍｍ／Ｓでは１６０〜１９０℃で定着した。
トナー−９の帯電量は−２０μＣ／ｇ、現像用トナー−９の帯電量は−２５μＣ／ｇだった。
[比較例１０]（樹脂微粒子による被覆無し）
（ワックス分散液−１０）
ワックス分散液−６と同様に作製したものを用いた。ＬＡ−５００で測定した平均粒径は３４０ｎｍであった。
（重合体一次粒子分散液−１０）
攪拌装置（３枚翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積６０リットル、内径４００ｍｍ）にワックス分散液３５部、脱塩水３９５部を仕込み、窒素気流下で９０℃に昇温して、８％過酸化水素水溶液１.６部、８％アスコルビン酸水溶液１.６部を添加した。
【０１６２】
その後、下記のモノマー類と乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【０１６３】
【表１９】
（モノマー類）
スチレン ７９部
アクリル酸ブチル ２１部
アクリル酸 ３部
ブロモトリクロロメタン ０.５部
２−メルカプトエタノール ０.０１部
ジビニルベンゼン ０.４部
（乳化剤水溶液）
１５％ネオゲンＳＣ水溶液 １部
脱塩水 ２５部
（開始剤水溶液）
８％過酸化水素水溶液 ９部
８％アスコルビン酸水溶液 ９部
【０１６４】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は１５４,０００、ＵＰＡで測定した平均粒子径は１９５ｎｍ、Ｔｇは５７℃であった。
【０１６５】
（現像用トナーの製造−１０）
【表２０】
重合体一次粒子分散液−１０ １１０部（固形分として）
着色剤微粒子分散液−３ ６.７部（固形分として）
帯電制御剤微粒子分散液−１ ２部（固形分として）
１５％ネオゲンＳＣ水溶液 ０.６５部（固形分として）
【０１６６】
上記の各成分を用いて、以下の手順によりトナーを製造した。
反応器（容積１リットル、バッフル付きアンカー翼）に重合体一次粒子分散液と１５％ネオゲンＳＣ水溶液を仕込み、均一に混合してから着色剤微粒子分散液を添加し、均一に混合した。得られた混合分散液を攪拌しながら硫酸アルミニウム水溶液を滴下し（固形分として０.９部）、その後帯電制御剤微粒子分散液を添加した。その後攪拌しながら２０分かけて６０℃に昇温して３０分保持し、２分かけて６１℃に昇温して１時間保持した。１５％ネオゲンＳＣ水溶液（固形分として５部）を添加してから２５分かけて９５℃に昇温して、５時間保持した。その後冷却し、濾過、水洗し、乾燥することによりトナー（トナー−１０）を得た。
【０１６７】
このトナー１００部に対し、疎水性の表面処理をしたシリカを０.６部混合攪拌し、現像用トナー（現像用トナー−１０）を得た。
（トナーの評価−１０）
現像用トナー−１０のコールターカウンターによる体積平均粒径は７.５μｍ、体積粒径の５μｍ以下の割合は４.１％、１５μｍ以上の割合は２.３％、体積平均粒径と数平均粒径の比は１.１９であった。５０％円形度は０.９８であった。
【０１６８】
現像用トナー−１０の定着性は、定着速度１２０ｍｍ／Ｓでは１５８〜２００℃で定着し、定着速度３０ｍｍ／Ｓでは１２３〜１８２℃で定着した。
トナー−１０の帯電量は＋１５μＣ／ｇ、現像用トナー−１０の帯電量は＋１１μＣ／ｇだった。
[比較例１１] （重合体一次粒子、樹脂微粒子共にワックスを含有しない例）
（重合体一次粒子分散液−１１）
攪拌装置（３枚翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積６０リットル、内径４００ｍｍ）に１５％ネオゲンＳＣ水溶液２部、脱塩水３７８部を仕込み、窒素気流下で９０℃に昇温して、８％過酸化水素水溶液１.６部、８％アスコルビン酸水溶液１.６部を添加した。
【０１６９】
その後、下記のモノマー類と乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【０１７０】
【表２１】
（モノマー類）
スチレン ７９部
アクリル酸ブチル ２１部
アクリル酸 ３部
ブロモトリクロロメタン ０.４５部
２−メルカプトエタノール ０.０１部
ヘキサンジオールジアクリレート ０.９部
（乳化剤水溶液）
１５％ネオゲンＳＣ水溶液 １部
脱塩水 ２５部
（開始剤水溶液）
８％過酸化水素水溶液 ９部
８％アスコルビン酸水溶液 ９部
【０１７１】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は１２６,０００、ＵＰＡで測定した平均粒子径は１９９ｎｍ、Ｔｇは７０℃、ＴＨＦ不溶分は３０重量％であった。
（現像用トナー−１１の製造）
【０１７２】
【表２２】
重合体一次粒子分散液−１１ ９５部（固形分として）
樹脂微粒子分散液−１ ５部（固形分として）
着色剤微粒子分散液−１ ６.７部（固形分として）
帯電制御剤微粒子分散液−１ ２部（固形分として）
１５％ネオゲンＳＣ水溶液 ０.２部（固形分として）
【０１７３】
上記の各成分を用いて、以下の手順によりトナーを製造した。
反応器（容積１リットル、バッフル付きアンカー翼）に重合体一次粒子分散液と１５％ネオゲンＳＣ水溶液を仕込み、均一に混合してから着色剤微粒子分散液を添加し、均一に混合した。得られた混合分散液を攪拌しながら硫酸アルミニウム水溶液を滴下した（固形分として０.５４部）。その後攪拌しながら２５分かけて５０℃に昇温して１時間保持し、さらに１時間かけて６９℃に昇温して１０分保持した。帯電制御剤微粒子分散液、樹脂微粒子分散液、硫酸アルミニウム水溶液（固形分として０.０６部）の順に添加し、１０分かけて７１℃に昇温して３０分保持した。１５％ネオゲンＳＣ水溶液（固形分として３.３部）を添加してから２５分かけて９６℃に昇温して７時間保持した。その後冷却し、濾過、水洗し、乾燥することによりトナー（トナー−１１）を得た。
【０１７４】
このトナー１００部に対し、疎水性の表面処理をしたシリカを０.６部混合攪拌し、現像用トナー（現像用トナー−１１）を得た。
（トナーの評価−１１）
現像用トナー−１１のコールターカウンターによる体積平均粒径は７．５μｍ、体積粒径の５μｍ以下の割合は２．５％、１５μｍ以上の割合は１．１％、体積平均粒径と数平均粒径の比は１．１４であった。５０％円形度は０.９３であった。
【０１７５】
現像用トナー−１１の定着性は、定着速度１２０ｍｍ／Ｓでは１８０〜１９０℃で定着し、定着速度３０ｍｍ／Ｓでは１４０〜１６０℃で定着した。
トナー−１１の帯電量は−２７μＣ／ｇ、現像用トナー−１１の帯電量は−１１μＣ／ｇだった。
[比較例１２]（最外層にワックスを内包した樹脂微粒子を被覆した例）
（重合体一次粒子分散液−１２）
攪拌装置（３枚翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積６０リットル、内径４００ｍｍ）に１５％ネオゲンＳＣ水溶液２部、脱塩水３７８部を仕込み、窒素気流下で９０℃に昇温して、８％過酸化水素水溶液１.６部、８％アスコルビン酸水溶液１.６部を添加した。
その後、下記のモノマー類と乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【０１７６】
【表２３】
（モノマー類）
スチレン ７９部
アクリル酸ブチル ２１部
アクリル酸 ３部
ブロモトリクロロメタン ０.４５部
２−メルカプトエタノール ０.０１部
ヘキサンジオールジアクリレート ０.９部
（乳化剤水溶液）
１５％ネオゲンＳＣ水溶液 １部
脱塩水 ２５部
（開始剤水溶液）
８％過酸化水素水溶液 ９部
８％アスコルビン酸水溶液 ９部
【０１７７】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は１２６，０００、ＵＰＡで測定した平均粒子径は１９９ｎｍ、Ｔｇは７０℃、ＴＨＦ不溶分は３０重量％であった。
（樹脂微粒子分散液−１２）
攪拌装置（３枚翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積６０リットル、内径４００ｍｍ）にワックス分散液−１を２８部、１５％ネオゲンＳＣ水溶液１.２部、脱塩水３９３部を仕込み、窒素気流下で９０℃に昇温して、８％過酸化水素水溶液１.６部、８％アスコルビン酸水溶液１.６部を添加した。
【０１７８】
その後、下記のモノマー類と乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【０１７９】
【表２４】
（モノマー類）
スチレン ７９部
アクリル酸ブチル ２１部
アクリル酸 ３部
オクタンチオール ０.３８部
２−メルカプトエタノール ０.０１部
ヘキサンジオールジアクリレート ０.９部
（乳化剤水溶液）
１５％ネオゲンＳＣ水溶液 １部
脱塩水 ２５部
（開始剤水溶液）
８％過酸化水素水溶液 ９部
８％アスコルビン酸水溶液 ９部
【０１８０】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は１１９，０００、ＵＰＡで測定した平均粒子径は１８９ｎｍ、Ｔｇは５７℃、ＴＨＦ不溶分は５２重量％であった。
【０１８１】
（現像用トナーの製造−１２）
【表２５】
重合体一次粒子分散液−１２ ７７部（固形分として）
樹脂微粒子分散液−１２ ３３部（固形分として）
着色剤微粒子分散液−１ ６.７部（固形分として）
帯電制御剤微粒子分散液−１ ２部（固形分として）
【０１８２】
上記の各成分を用いて、以下の手順によりトナーを製造した。
反応器（容積１リットル、バッフル付きアンカー翼）に重合体一次粒子分散液と着色剤微粒子分散液を仕込み、均一に混合した。得られた混合分散液を攪拌しながら硫酸アルミニウム水溶液を添滴下した（固形分として０.４９部）。その後攪拌しながら２５分かけて５０℃に昇温して１時間保持し、さらに４０分かけて６７℃に昇温して２０分保持した。帯電制御剤微粒子分散液を添加し、６０℃に冷却し、樹脂微粒子分散液、硫酸アルミニウム水溶液（固形分として０.１１部）の順に添加し、６０℃で３０分保持した。１５％ネオゲンＳＣ水溶液（固形分として３.５部）を添加してから４５分かけて９６℃に昇温して４時間保持した。その後冷却し、濾過、水洗し、乾燥することによりトナー（トナー−１２）を得た。
【０１８３】
このトナー１００部に対し、疎水性の表面処理をしたシリカを０.６部混合攪拌し、現像用トナー（現像用トナー−１２）を得た。
（トナーの評価−１２）
現像用トナーのコールターカウンターによる体積平均粒径は８.１μｍ、体積粒径の５μｍ以下の割合は１.２％、１５μｍ以上の割合は２.８％、体積平均粒径と数平均粒径の比は１.１７であった。５０％円形度は０.９３であった。
【０１８４】
現像用トナー−１２の定着性は、定着速度１２０ｍｍ／Ｓでは１７０−２２０℃で定着し、定着速度３０ｍｍ／Ｓでは１３０−１９０℃で定着した。
トナー−１２の帯電量は−６μＣ／ｇ、現像用トナー−１２の帯電量は+４μＣ／ｇだった。
実施例１〜比較例１２について、トナーの製造に用いた着色剤（顔料）、ワックス（ＷＡＸ）、重合体一次粒子及び樹脂微粒子を第１表に、トナーの評価を第２表にまとめた。
【０１８５】
【表２６】

【０１８６】
【表２７】

【０１８７】
[実施例１３]
（プレミックスモノマー液−１３）
下記のモノマー類とペンタエリスリトールのステアリン酸エステルを主体とするエステル混合物（ユニスターＨ４７６、日本油脂製）８部を予め溶解させた。次にネオゲンＳＣ水溶液（量は下記参照）をジャケット附きのホモジナイザー（Ｔ．Ｋ．オートホモミキサーＭ型、特殊機化工業製）に入れて、６０〜６５℃に加熱した。ホモジナイザーを高速攪拌させてから、槽内へ前述のモノマーのワックス溶解液を注ぎ、プレミックスモノマー（プレミックスモノマー液−１３）を作成した。
【０１８８】
【表２８】
（モノマー類）
スチレン ７９部（３５０g）
アクリル酸ブチル ２１部
アクリル酸 ３部
トリクロロブロモメタン ０．４５部
２−メルカプトエタノール ０．１０部
ヘキサンジオールジアクリレート ０．９０部
（乳化剤水溶液）
１５％ネオゲンＳＣ水溶液 ２部
脱塩水 ５４部
【０１８９】
（重合体一次粒子分散液−１３）
攪拌装置（フルゾーン翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積３リットル、内径１５０ｍｍ）に、１５％ネオゲンＳＣ水溶液３部、脱塩水３８２部を仕込み、窒素気流下で９０℃に昇温し、８％過酸化水素水溶液１．６部、８％アスコルビン酸水溶液１．６部を添加した。その後、プレミックスモノマー液−１３の全量を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
（開始剤水溶液）
８％過酸化水素水溶液 ９部
８％アスコルビン酸水溶液 ９部
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は１９８,０００、ＵＰＡで測定した平均粒子径は１５３ｎｍであった。
（現像用トナーの製造−１３）
【０１９０】
【表２９】
重合体一次粒子分散液−１３ ９５部（２１２ｇ：固形分として）
樹脂微粒子分散液−１ ５部（固形分として）
着色剤微粒子分散液−１ ６．７部（固形分として）
１５％ネオゲンＳＣ水溶液 ０．５部（固形分として）
【０１９１】
上記の各成分を用いて、以下の手順によりトナーを製造した。
反応器（容積２リットル、バッフル付きダブルヘリカル翼）に重合体一次粒子分散液と１５％ネオゲンＳＣ水溶液を仕込み、均一に混合してから着色剤微粒子分散液を添加し、均一に混合した。得られた混合分散液を攪拌しながら硫酸アルミニウム水溶液を滴下した（固形分として０．６部）。その後攪拌しながら２０分かけて５３℃に昇温し、更に９０分かけて６５℃にゆっくり昇温して１時間保持した。樹脂微粒子分散液、硫酸アルミニウム水溶液（固形分として０．０７部）の順に添加し、１０分かけて６７℃に昇温して１０分保持した。１５％ネオゲンＳＣ水溶液（固形分として３部）と総量の０．６倍量の脱塩温水を添加してから３０分かけて９５℃に昇温して２時間保持した。その後冷却し、濾過、水洗し、乾燥することによりトナー（トナー−１３）を得た。
【０１９２】
このトナー１００部に対し、疎水性の表面処理をしたシリカを０．６部混合攪拌し、現像用トナー（現像用トナー−１３）を得た。
トナーの評価−１３
現像用トナーのコールターカウンターによる体積平均粒径は８．２μｍ、体積平均粒径と数平均粒径の比は１．１７であった。
５０％円形度は０．９４であった。
【０１９３】
現像用トナー−１３の定着性は、定着速度１２０ｍｍ／Ｓでは１６０〜２１０℃で定着し、定着速度３０ｍｍ／Ｓでは１４０〜２００℃で定着した。
[実施例１４]
（重合体一次粒子分散液−１４）
攪拌装置（２枚翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積３リットル、内径１５０ｍｍ）に１０％ドデシルベンゼンスルホン酸ナトリウム水溶液５.３部、脱塩水３０９部を仕込み、窒素気流下で９０℃に昇温して、２％過酸化水素水溶液６.４部、２％アスコルビン酸水溶液６.４部を添加した。
【０１９４】
その後、下記のモノマー類・乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【０１９５】
【表３０】
（モノマー類）
スチレン ６０部
アクリル酸ブチル ４０部
アクリル酸 ３部
（乳化剤水溶液）
１０％ドデシルベンゼンスルホン酸ナトリウム水溶液 ２.７部
１％ポリオキシエチレンノニルフェニルエーテル水溶液 １.１部
脱塩水 ２２部
(開始剤水溶液)
２％過酸化水素水溶液 ３６部
２％アスコルビン酸水溶液 ３６部
【０１９６】
重合反応終了後冷却し、乳白色の重合体分散液を得た。
続いて、攪拌装置（２枚翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積３リットル、内径１５０ｍｍ）に上記の重合体分散液１０８部、１０％ドデシルベンゼンスルホン酸ナトリウム水溶液５.３部、脱塩水３１１部を仕込み、窒素気流下で９０℃に昇温して、２％過酸化水素水溶液６.４部、２％アスコルビン酸水溶液６.４部を添加した。
【０１９７】
その後、下記のモノマー類、乳化剤水溶液、開始剤水溶液を添加し、６.５時間乳化重合を行った。
【０１９８】
【表３１】
（モノマー類）
スチレン ６０部
アクリル酸ブチル ４０部
アクリル酸 ３部
ブロモトリクロロメタン １.５部
１％ ２−メルカプトエタノール水溶液 ３部
（乳化剤水溶液）
１０％ドデシルベンゼンスルホン酸ナトリウム水溶液 ２.７部
１％ポリオキシエチレンノニルフェニルエーテル水溶液 １.１部
脱塩水 ２２部
（開始剤水溶液）
２％過酸化水素水溶液 ３６部
２％アスコルビン酸水溶液 ３６部
【０１９９】
重合反応終了後冷却し、乳白色の重合体分散液（重合体一次粒子分散液−１５）を得た。重合体のＴＨＦ可溶分の重量平均分子量は６４，０００、ＵＰＡで測定した平均粒子径は２６８ｎｍ、Ｔｇは３９℃であった。
（樹脂微粒子分散液−１４Ａ）
攪拌装置（３枚後退翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積２リットル、内径１２０ｍｍ）にワックス分散液−１３ ３５部、脱塩水３２８部を仕込み、窒素気流下で９０℃に昇温して、２％過酸化水素水溶液６.４部、２％アスコルビン酸水溶液６.４部を添加した。
その後、下記のモノマー類・乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【０２００】
【表３２】
（モノマー類）
スチレン ７５部
アクリル酸ブチル ２５部
アクリル酸 ３部
ブロモトリクロロメタン ０.５部
１％ ２−メルカプトエタノール １部
（乳化剤水溶液）
１０％ドデシルベンゼンスルホン酸ナトリウム水溶液 ２.７部
１％ポリオキシエチレンノニルフェニルエーテル水溶液 １.１部
脱塩水 ２２部
（開始剤水溶液）
２％過酸化水素水溶液 ３６部
２％アスコルビン酸水溶液 ３６部
【０２０１】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は５８，０００、ＵＰＡで測定した平均粒子径は２４４ｎｍ、Ｔｇは不明瞭であった。
（樹脂微粒子分散液−１４Ｂ）
攪拌装置（３枚後退翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積２リットル、内径１５０ｍｍ）に、脂肪酸ナトリウム（ＮＳソープ、花王製）２部、脱塩水３７４部を仕込み、窒素気流下で７５℃に昇温して、１％過硫酸カリウム水溶液を２０部添加した。
その後、下記のモノマー類を重合開始から３時間２０分かけて添加し、途中で乳化剤水溶液、開始剤水溶液を添加し、さらに１時間４０分保持した。
【０２０２】
【表３３】
（モノマー類）
スチレン ９０部
アクリル酸ブチル １０部
ブロモトリクロロメタン ０.２部
（乳化剤水溶液）
１０％ＮＳソープ水溶液 １０部
（開始剤水溶液）
１％過硫酸カリウム水溶液 １０部
【０２０３】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は１３１，０００、ＵＰＡで測定した平均粒子径は２５ｎｍ、Ｔｇは８４℃であった。
【０２０４】
（現像用トナーの製造−１４）
【表３４】
重合体一次粒子分散液−１４ １００部（固形分として）
樹脂微粒子分散液−１４Ａ ２１.３部（固形分として）
樹脂微粒子分散液−１４Ｂ １０.７部（固形分として）
着色剤微粒子分散液−１ ６.７部（固形分として）
帯電制御剤微粒子分散液−１ ０.６部（固形分として）
【０２０５】
上記の各成分を用いて、以下の手順によりトナーを製造した。
反応器に重合体一次粒子分散液と着色剤微粒子分散液を仕込み、均一に混合した。得られた混合分散液を攪拌しながら１０％塩化ナトリウム水溶液を添加し（固形分として１２部）、３０分保持した。その後攪拌しながら昇温して、粒径が７μｍになったところでｐＨを６.５に調整し、さらに９５℃に昇温して８時間保持し、その後冷却した。濾過により粗粉を除去して反応器（平羽根攪拌翼）に仕込み、室温で攪拌しながらｐＨを２.０に調整し、樹脂微粒子分散液１４Ａを添加し、４０℃に昇温して５時間保持し、その後６２℃に昇温して３時間保持し、その後冷却した。樹脂微粒子分散液１４Ｂを添加し、４０℃に昇温して１時間保持し、帯電制御剤微粒子分散液を添加し、４０℃で２時間保持し、その後６４℃に昇温して４時間保持し、その後冷却した。その後濾過、水洗し、乾燥することによりトナー（トナー−１４）を得た。
【０２０６】
このトナー１００部に対し、疎水性の表面処理をしたシリカを０.６部混合攪拌し、現像用トナー（現像用トナー−１４）を得た。
（トナーの評価−１４）
現像用トナー−１４は、定着速度１２０ｍｍ／Ｓでは１５０〜１７０℃で定着した。トナー−１４の帯電量は−６μＣ／ｇ、現像用トナー−１５の帯電量は−１１μＣ／ｇだった。
［参考製造例］（ワックス微粒子と重合体一次粒子を共重合したもの）
（ワックス分散液−１５）
脱塩水６８.３３部、ベヘン酸ベヘニルを主体とするエステル混合物（ユニスターＭ−２２２２ＳＬ、日本油脂製）とステアリン酸ステアリルを主体とするエステル混合物（ユニスターＭ９６７６、日本油脂製）７:３の混合物３０部、ドデシルベンゼンスルホン酸ナトリウム（ネオゲンＳＣ、第一工業製薬製、有効成分６６％）１.６７部を混合し、９０℃にて高圧剪断をかけ乳化し、エステルワックス微粒子の分散液を得た。ＵＰＡで測定したエステルワックス微粒子の平均粒径は２９０ｎｍであった。
（重合体一次粒子分散液−１５）
攪拌装置（フルゾーン翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器（容積３Ｌ、内径１５０ｍｍ）に１５％ネオゲンＳＣ水溶液２部、脱塩水３７８部を仕込み、窒素気流下で９０℃に昇温し、８％過酸化水素水溶液１.６部、８％アスコルビン酸水溶液１.６部を添加した。
その後、下記のモノマー類・乳化剤水溶液の混合物を重合開始から５時間かけて、開始剤水溶液を重合開始から６時間かけて添加し、さらに３０分保持した。
【０２０７】
【表３５】
（モノマー類）
スチレン ７９部
アクリル酸ブチル ２１部
アクリル酸 ３部
ブロモトリクロロメタン ０.４５部
２−メルカプトエタノール ０.０１部
ヘキサンジオールジアクリレート ０.９部
（乳化剤水溶液）
１５％ネオゲンＳＣ水溶液 １部
脱塩水 ２５部
（開始剤水溶液）
８％過酸化水素水溶液 ９部
８％アスコルビン酸水溶液 ９部
【０２０８】
重合反応終了後冷却し、乳白色の重合体分散液を得た。重合体のＴＨＦ可溶分の重量平均分子量は１５８,０００、ＵＰＡで測定した平均粒子径は２００ｎｍ、Ｔｇは７１℃であった。
（現像用トナーの製造−１５）
【０２０９】
【表３６】
重合体一次粒子分散液−１５ １０５部（固形分として）
樹脂微粒子分散液−１ ５部（固形分として）
着色剤微粒子分散液−１ ６.７部（固形分として）
帯電制御剤微粒子分散液−１ ２部（固形分として）
ワックス分散液−１５ ８.８部（固形分として）
１５％ネオゲンＳＣ水溶液 ０.５部（固形分として）
上記の各成分を用いて、以下の手順によりトナーを製造した。
【０２１０】
反応器（容積１リットル、バッフル付きアンカー翼）に重合体一次粒子分散液と１５％ネオゲンＳＣ水溶液を仕込み、均一に混合してからワックス分散液、着色剤微粒子分散液を添加し、均一に混合した。得られた混合分散液を攪拌しながら硫酸アルミニウム水溶液を滴下した（固形分として０.６部）。その後攪拌しながら１５分かけて５５℃に昇温して１時間保持し、さらに９０分かけて６５℃に昇温して５分保持した。帯電制御剤微粒子分散液、樹脂微粒子分散液、硫酸アルミニウム水溶液（固形分として０.０７部）の順に添加し、１５分かけて６７℃に昇温して１時間保持した。１５％ネオゲンＳＣ水溶液（固形分として３部）を添加してから２０分かけて９５℃に昇温して４時間保持した。その後冷却し、濾過、水洗し、乾燥することによりトナーを得た。
【０２１１】
トナーのコールターカウンターによる体積平均粒径は７.３μｍ、体積粒径の５μｍ以下の割合は３.０％、１５μｍ以上の割合は１.２％、体積平均粒径と数平均粒径の比は１.１４であった。５０％円形度は０.９５であった。
このトナーを、厚さ８０ｎｍに切り出し、ＴＥＭ写真を撮影し、実施例１で得られたトナーと同様に解析したところ、トナー断面において観察されたワックス微粒子の個数平均粒径は２０１ｎｍ、個数平均粒径の半値幅は１００ｎｍであった。
【０２１２】
ＴＥＭ写真の様子を図７に示す。また、ワックス微粒子の個数平均粒径の分布を表すグラフを粒径０〜１．５μｍの範囲、粒径０〜０．５μｍの範囲それぞれについて図６、図７に示す。
【０２１３】
実施例１６〜比較例２１に用いたワックス分散液、重合体一次粒子分散液、樹脂微粒子分散液、着色剤微粒子分散液及び、帯電制御剤微粒子分散液、それぞれの作製法を次に記す。
（ワックス分散液の作製）
ワックス分散液１００部として、ベヘン酸ベヘニル３０部をＮ−ドデシルベンゼンスルホン酸ナトリウム１．６７部の存在下に高圧剪断をかけて乳化し、エステルワックスの分散液を得た。得られた分散液の固形分濃度は３０％であり、ＵＰＡで測定した平均粒径は２２０ｎｍであった（これをワックス分散液Ａとする）。
【０２１４】
ワックス分散液１００部として、ベヘン酸ベヘニル３０部をＮ−ドデシルベンゼンスルホン酸ナトリウム０．２３部の存在下に高圧剪断をかけて乳化し、エステルワックスの分散液を得た。得られた分散液の固形分濃度は３０％であり、ＵＰＡで測定した平均粒径は４００ｎｍであった（これをワックス分散液Ｂとする）。
【０２１５】
（重合体一次粒子分散液の作製）
攪拌装置、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えたガラス製反応器にワックス分散液Ａ ３５部、脱塩水 ４００部を仕込み、窒素気流下で９０℃に昇温した。
その後、下記のモノマー類、乳化剤水溶液、開始剤を添加し、６．５時間乳化重合を行った。
【０２１６】
【表３７】

【０２１７】
重合反応終了後冷却し、乳白色の重合体分散液を得た。得られた重合体分散液の重量平均分子量は９８，０００、ＵＰＡで測定した平均粒子径は１９０ｎｍ、Ｔｇは５７℃であった。（これを重合体一次粒子分散液Ａとする）。
【０２１８】
ワックス分散液Ａの代わりにワックス分散液Ｂを用い、モノマー類を以下の通りに変更する以外は重合体一次粒子分散液Ａと同様にして、乳白色の重合体分散液を得た。得られた重合体分散液の重量平均分子量は７１，０００、ＵＰＡで測定した平均粒子径は１７９ｎｍ、Ｔｇは４８℃であった（これを重合体一次粒子分散液Ｂとする）。
【０２１９】
【表３８】
（モノマー類）
スチレン ６４部
アクリル酸ブチル ３６部
アクリル酸 ３部
ジビニルベンゼン（ＤＶＢ） １部
トリクロロブロモメタン ０．５部
【０２２０】
スチレンを６７部、アクリル酸ブチルを３３部に変更する以外は重合体一次粒子分散液Ｂと同様にして、乳白色の重合体分散液を得た。得られた重合体分散液の重量平均分子量は５２，０００、ＵＰＡで測定した平均粒子径は２０５ｎｍ、Ｔｇは５１℃であった（これを重合体一次粒子分散液Ｃとする）。
【０２２１】
スチレンを７２部、アクリル酸ブチルを２８部に変更する以外は重合体一次粒子分散液Ｂと同様にして、乳白色の重合体分散液を得た。得られた重合体分散液の重量平均分子量は４４，０００、ＵＰＡで測定した平均粒子径は１５８ｎｍ、Ｔｇは５５℃であった（これを重合体一次粒子分散液Ｄとする）。
【０２２２】
（樹脂微粒子分散液の作製）
攪拌装置、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えたガラス製反応器に１０％Ｓ−ＤＢＳ水溶液４．３部、脱塩水 ４００部を仕込み、窒素気流下で９０℃に昇温した。
その後、下記のモノマー類、乳化剤水溶液、開始剤を添加し、６．５時間乳化重合を行った。
【０２２３】
【表３９】
（モノマー類）
スチレン ７９部
アクリル酸ブチル ２１部
アクリル酸 ３部
トリクロロブロモメタン ０．５部
ＤＶＢ ０．４部
（乳化剤水溶液）
１０％Ｓ−ＤＢＳ水溶液 ２．２部
脱塩水 ２５部
（開始剤）
８％過酸化水素水溶液 １０．６部
８％アスコルビン酸水溶液 １０．６部
【０２２４】
重合反応終了後冷却し、乳白色の重合体分散液を得た。得られた重合体分散液の重量平均分子量は１１０，０００、ＵＰＡで測定した平均粒子径は１２０ｎｍ、Ｔｇは８６℃であった（これを樹脂微粒子分散液Ａとする）。
【０２２５】
ＤＶＢを用いないこと以外は樹脂微粒子分散液Ａと同様にして、乳白色の重合体分散液を得た。得られた重合体分散液のＵＰＡで測定した平均粒子径は１５４ｎｍ、Ｔｇは６５℃であった（これを樹脂微粒子分散液Ｂとする）。
【０２２６】
（着色剤微粒子分散液の作製）
着色剤微粒子分散液１００部として、ピグメントブルー１５：３ ３０部をポリオキシエチレンアルキルフェニルエーテル5部の存在下にサンドグラインダーミルにて分散し、着色剤微粒子分散液を得た。得られた分散液の固形分濃度は３５％であり、ＵＰＡで測定した平均粒径は１５０ｎｍであった（これを着色剤微粒子分散液Ａとする）。
【０２２７】
着色剤微粒子分散液１００部として、ピグメントイエロー７４ ２０部を、ポリオキシエチレンアルキルフェニルエーテル７部の存在下にサンドグラインダーミルで６時間分散処理し、着色剤微粒子分散液を得た。得られた分散液の固形分濃度は２０％であり、ＵＰＡで測定した平均粒径は３００ｎｍであった（これを着色剤微粒子分散液Ｂとする）。
【０２２８】
（帯電制御剤微粒子分散液の作製）
帯電制御剤微粒子分散液１００部として、４，４’−メチレンビス〔２−〔Ｎ−（４−クロロフェニル）アミド〕−３−ヒドロキシナフタレン〕２０部をアルキルナフタレンスルフォン酸塩4部の存在下にサンドグラインダーミルにて分散し、帯電制御剤微粒子分散液を得た。得られた分散液の固形分濃度は２４％であり、ＵＰＡで測定した平均粒径は２００ｎｍであった（これを帯電制御剤微粒子分散液Ａとする）。
【０２２９】
【表４０】
[実施例１６]
重合体一次粒子分散液Ａ ９０部（固形分として）
樹脂微粒子分散液Ａ １０部（固形分として）
着色剤微粒子分散液Ｂ ６．７部（固形分として）
帯電制御剤微粒子分散液Ａ ２部（固形分として）
Ｓ−ＤＢＳ水溶液 ０．５部（固形分として）
【０２３０】
上記の各成分を以下のような順序で混合した。
重合体一次粒子分散液ＡにＳ−ＤＢＳ水溶液を添加して、均一に混合してから着色剤微粒子分散液Ａを添加し、均一に混合した。
こうして得られた混合分散液をバッフル付きのアンカー翼で攪拌しながら３０℃で硫酸アルミニウム水溶液を添加した（固形分として０．６部）。硫酸アルミニウム水溶液添加後の混合分散液の平均粒径は２μｍであった。その後、攪拌しながら５５℃に昇温して１時間保持し、更に５８℃に昇温して１時間保持した。その後帯電制御剤微粒子分散液Ａ、樹脂微粒子分散液Ａ、硫酸アルミニウム水溶液（固形分として０．１部）の順に添加した。１時間半保持した後、１０％Ｓ−ＤＢＳ水溶液（固形分として３部）を添加してから９５℃に昇温し、４時間保持した。その後冷却し、桐山ロートで濾過、水洗し、凍結乾燥することによりトナーを得た（これをトナーＡとする）。
【０２３１】
トナー１００部に対して、疎水性の表面処理をしたシリカを０．６部混合攪拌し、現像用トナーを得た（これを現像用トナーＡとする）。
得られたトナーＡのコールターカウンターによる体積平均粒径は７．６μｍであった。また、体積粒径の５μｍ以下の割合は１．５％、１５μｍ以上の割合は０％、体積平均粒径と数平均粒径の比は１．０９であり粒径分布は非常に良好であった。
【０２３２】
現像用トナーＡの定着性を評価したところ、定着速度１２０ｍｍ／ｓでは１６０〜２２０℃で定着し、定着速度３０ｍｍ／ｓでは１４０〜２２０℃で定着した。ＣｏｌｏｒＰａｇｅＰｒｅｓｔｏで測定したトナーＡの帯電量は−３μＣ／ｇ、現像用トナーＡの帯電量は−２１μＣ／ｇであった。
【０２３３】
【表４１】
[実施例１７]
重合体一次粒子分散液Ｂ １００部（固形分として）
樹脂微粒子分散液Ｂ ２１部（固形分として）
着色剤微粒子分散液Ａ ６．７部（固形分として）
帯電制御剤微粒子分散液Ａ ０．１部（固形分として）
【０２３４】
上記の各成分を以下のような順序で混合した。
重合体一次粒子分散液Ｂに着色剤微粒子分散液Ａを添加し、均一に混合した。得られた混合分散液をアンカー翼で攪拌しながら２０℃でＮａＣｌ水溶液を添加した（固形分として１０部）。その後、攪拌しながら４５℃に昇温して１時間保持し、更に９５℃に昇温して５時間保持し、その後冷却してトナー粒子を得た。
【０２３５】
攪拌装置、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えたガラス製反応器に、上記トナー粒子１００部を仕込み、攪拌した。ここに帯電制御剤微粒子分散液Ａ、樹脂微粒子分散液Ｂを添加し、４５℃で２時間保持した。その後冷却し、桐山ロートで濾過、水洗し、凍結乾燥することによりトナーを得た（これをトナーＢとする）。トナー１００部に対して、疎水性の表面処理をしたシリカを０．６部混合攪拌し、現像用トナーを得た（これを現像用トナーＢとする）。
【０２３６】
トナーＢの体積平均粒径は７．１μm、体積平均粒径と数平均粒径の比は１．２０であった。
現像用トナーＢの定着性を評価したところ、定着速度１２０ｍｍ／ｓでは１１０〜２００℃で定着した。Ｐｈａｓｅｒで測定した現像用トナーＢの帯電量は‐２０μＣ／ｇであった。
【０２３７】
[実施例１８]
重合体一次粒子分散液Ｂを重合体一次粒子分散液Ｃに変更する以外は実施例１７と同様にして、トナーＣ、現像用トナーＣを得た。
トナーＣの体積平均粒径は６．８μm、体積平均粒径と数平均粒径の比は１．０５であった。
現像用トナーＣの定着性を評価したところ、定着速度１２０ｍｍ／ｓでは１１５〜２００℃で定着した。Ｐｈａｓｅｒで測定した現像用トナーＣの帯電量は‐１９μＣ／ｇであった。
【０２３８】
[実施例１９]
重合体一次粒子分散液Ｂを重合体一次粒子分散液Ｄに変更し、樹脂微粒子分散液Ｂを１０部に変更する以外は実施例１７と同様にして、トナーＤ、現像用トナーＤを得た。
トナーＤの体積平均粒径は６．３μm、体積平均粒径と数平均粒径の比は１．０４であった。
現像用トナーＤの定着性を評価したところ、定着速度１２０ｍｍ／ｓでは１２０〜２００℃で定着した。Ｐｈａｓｅｒで測定した現像用トナーＤの帯電量は‐２７μＣ／ｇであった。
【０２３９】
[比較例２０]
樹脂微粒子分散液Ａを添加しない以外は実施例１６と同様にして、トナーＥ、現像用トナーＥを得た。トナーＥの体積平均粒径は７．１μmであった。
現像用トナーＥの定着性を評価したところ、定着速度１２０ｍｍ／ｓでは１３８〜２００℃の間で定着し、定着速度３０ｍｍ／ｓでは１１２〜１８２℃で定着した。ＣｏｌｏｒＰａｇｅＰｒｅｓｔｏで帯電量を測定したところ、トナーＥは負帯電しなかった。現像用トナーＥの帯電量は‐１μＣ／ｇであった。
【０２４０】
[比較例２１]
樹脂微粒子分散液Ａを用いない以外は実施例１９と同様にして、トナーＦ、現像用トナーＦを得た。トナーＦの体積平均粒径は６．０μｍ、体積平均粒径／個数平均粒径は１．０２であった。
現像用トナーＦの定着性を評価したところ、定着速度１２０ｍｍ／ｓでは１２０〜２００℃で定着した。Ｐｈａｓｅｒで帯電量を測定したところ、現像用トナーＦは負帯電しなかった。
【０２４１】
【発明の効果】
本発明により、低温定着性及び耐オフセット性に優れたトナーを提供することができる。本発明のトナーは、粒径が小さく、粒度分布がシャープであり、高解像度の画像形成に適している。また、本発明のトナーはＯＨＰ透明性が優れ、耐ブロッキング性に優れている。
【図面の簡単な説明】
【図１】 ワックスを含む重合体一次粒子からなる粒子凝集体に、ワックスを含まない樹脂微粒子が被覆した様子を表す模式図。
【図２】 ワックスを含む重合体一次粒子からなる粒子凝集体を融着した後にワックスを含まない樹脂微粒子が被覆した様子を表す模式図。
【図３】 重合体一次粒子と樹脂微粒子との両方が融着した様子を表す模式図。
【図４】 実施例１で得られたトナー断面のＴＥＭ写真の図
【図５】 参考製造例で得られたトナー断面のＴＥＭ写真の図
【図６】 トナー断面において観察されたワックス微粒子の個数平均粒径の分布を表すグラフ（粒径０〜１．５μｍの範囲）
【図７】 トナー断面において観察されたワックス微粒子の個数平均粒径の分布を表すグラフ（粒径０〜０．５μｍの範囲）
【符号の説明】
１ ワックスを含む重合体一次粒子
２ ワックスを含まない樹脂微粒子
３ 重合体一次粒子を融着して得られた粒子
４ 重合体一次粒子と樹脂微粒子との両方を融着して得られた粒子
５ ワックス[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrostatic charge image developing toner used in electrophotographic copying machines and printers. More specifically, the present invention relates to an electrostatic image developing toner produced by an emulsion polymerization aggregation method, or an electrostatic image developing toner in which wax fine particles are dispersed relatively uniformly in the toner.
[0002]
[Prior art]
Toner for electrostatic image development that has been widely used in electrophotography in the past is a binder resin such as a styrene / acrylate copolymer or polyester, a colorant such as carbon black or a pigment, and a charge as necessary. It has been produced by melting and kneading a mixture containing a control agent and a magnetic substance with an extruder, followed by pulverization and classification. However, the conventional toner obtained by the melt-kneading / pulverization method as described above has a limit in controlling the particle size of the toner, and substantially manufactures a toner having an average particle size of 10 μm or less, particularly 8 μm or less with a high yield. However, it was difficult to achieve the high resolution required for electrophotography in the future.
[0003]
Further, in order to achieve low-temperature fixability, a method of blending a wax having a low softening point into the toner during kneading has been proposed, but in the kneading / pulverization method, blending of about 5% is the limit, A toner having sufficient low-temperature fixing performance could not be obtained. Japanese Patent Laid-Open No. 63-186253 proposes a toner production method by emulsion polymerization / aggregation in order to overcome the problem of particle size control and achieve high resolution. However, even in this method, there is a limit to the amount of wax that can be introduced in the coagulation step, and a sufficient improvement effect has not been obtained with respect to low-temperature fixability. That is, when the present inventors examined by changing the addition amount of the wax based on the patent, when the addition amount of the wax is increased, the particle size distribution of the obtained toner becomes two peaks or 1 μm. There is a problem that the following fine powder remains, and a classification step is required after the aggregation step.
[0004]
In U.S. Pat. No. 5,849,546, JP-A-10-301332, etc., the polymer primary particles obtained by emulsion polymerization are agglomerated, and resin fine particles are fixed on the surface of the obtained agglomerated particles. Although a capsule toner is disclosed and low-temperature fixability and high resolution are achieved, it does not use polymer primary particles or resin fine particles encapsulating wax, and it can always be said that sufficient performance is always obtained. Absent.
[0005]
US Pat. No. 5,965,316 discloses a toner in which particle aggregates are coated with resin fine particles obtained by emulsion polymerization using wax as a seed. However, since the wax is present in the outermost layer of the toner, the wax may be leached out before fixing, causing the apparatus to become dirty.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel toner that overcomes the above-described problems and satisfies high resolution, low-temperature fixability, and offset resistance, and a method for producing the same. It is another object of the present invention to provide a toner having a wide fixing temperature range, excellent OHP transparency, and excellent blocking resistance, and a method for producing the same.
[0007]
[Means for Solving the Problems]
The gist of the present invention is an electrostatic charge developing toner obtained by adhering or fixing resin fine particles to a particle aggregate containing at least polymer primary particles and a colorant, wherein the polymer primary particles contain a wax. And an electrostatic charge image developing toner. Another gist of the present invention is that, in an electrostatic charge image developing toner containing at least a binder resin, a colorant, and a wax, the volume average particle size of the toner is 3 to 12 μm, and the wax when a cross section of the toner is observed. The concentration (area ratio) of wax fine particles having an average particle size of 0.01 μm or more at a depth from the toner surface of 0.1 μm or less at a half-value width of the number average particle size of the fine particles is 0.06 μm or less. The toner for developing an electrostatic charge image is characterized by being 1/10 or less of the concentration (area ratio) of wax fine particles in a portion deeper than 1 μm.
[0008]
Another gist of the present invention is a method for producing a toner for developing an electrostatic charge image, in which at least polymer primary particles and colorant primary particles are aggregated to form particle aggregates, and resin fine particles are adhered or fixed to the particle aggregates. In the method for producing an electrostatic charge image developing toner, the polymer primary particles are obtained by seed emulsion polymerization of a monomer mixture in the presence of wax fine particles.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The toner of the present invention contains wax, polymer primary particles, a colorant, resin fine particles as constituents, and, if necessary, a charge control agent and other additives. The toner of the present invention is produced by an emulsion polymerization aggregation method. In the emulsion polymerization aggregation method, the polymer primary particles obtained by emulsion polymerization and at least the colorant primary particles, and if necessary, the charge control agent primary particles are co-aggregated to form particle aggregates, and further the resin fine particles are adhered. Alternatively, the toner is manufactured by fixing. In the toner of the present invention, the polymer primary particles contain a wax.
[0010]
As the wax used in the present invention, any of known waxes can be used. Specifically, olefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene and copolymer polyethylene; paraffin wax; behenic acid Ester wax having a long chain aliphatic group such as behenyl, montanic acid ester, stearyl stearate; Plant wax such as hydrogenated castor oil carnauba wax; Ketone having a long chain alkyl group such as distearyl ketone; Silicones; higher fatty acids such as stearic acid; long-chain aliphatic alcohols such as eicosanol; carboxylic acid esters or partial esters of polyhydric alcohols obtained from polyhydric alcohols such as glycerin and pentaerythritol and long-chain fatty acids; oleic acid amides; Stearin Higher fatty acid amides, such as amides; low molecular weight polyesters, and the like.
[0011]
In order to improve the fixability among these waxes, the melting point of the wax is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher. Moreover, 100 degrees C or less is preferable, 90 degrees C or less is still more preferable, and 80 degrees C or less is especially preferable. If the melting point is too low, the wax tends to be exposed to the surface after fixing and stickiness tends to occur, and if the melting point is too high, the fixing property at low temperatures is poor.
[0012]
Furthermore, as the wax compound species, ester waxes obtained from aliphatic carboxylic acids and mono- or polyhydric alcohols are preferred, and ester waxes having 20 to 100 carbon atoms are more preferred, Is particularly preferred.
Among the esters of monohydric alcohols and aliphatic carboxylic acids, particularly preferred compounds include behenyl behenate and stearyl stearate. Among the esters of polyhydric alcohols and aliphatic carboxylic acids, particularly preferred compounds include pentaerythritol stearate and partial esters thereof, glycerin montanate and partial esters thereof.
[0013]
The above waxes may be used alone or in combination. Further, the melting point of the wax compound can be appropriately selected depending on the fixing temperature for fixing the toner.
In order to improve the fixability, it is effective to use a mixture of two or more, preferably three or more waxes. Among them, it is preferable that three or more kinds of wax compounds are used in combination, and any wax compound is preferably blended so as not to exceed 60% with respect to the whole wax. More preferably, it is blended so as not to exceed 45%, and it is particularly preferred that it is blended so as not to exceed 40%.
[0014]
Among the wax compounds to be used in combination, at least one of them is preferably the above-described monovalent or polyhydric alcohol carboxylic acid ester. The wax compound having the largest content is more preferably an alkanoic acid ester of a monohydric or polyhydric alcohol, and particularly preferably an alkyl ester of an alkanoic acid. When the wax compound having the largest content is an alkyl ester of alkanoic acid, the wax compound having the second largest blending amount may be a different type of alkanoic acid alkyl ester or an alkanoic acid ester of a polyhydric alcohol. preferable.
[0015]
Moreover, 4 or more types are preferable, and the 5 or more types of wax compound used together is still more preferable. The upper limit of the types of wax compounds used in combination is not particularly limited, but is preferably 50 or less in production.
Further, the total of the two wax compounds having a large blending amount out of at least three kinds of wax compounds is preferably 88% or less, more preferably 85% or less, based on the whole wax. % Or less is particularly preferable.
[0016]
Further, the wax compound having the largest blending amount preferably has a melting point of 40 ° C. or higher, more preferably 50 ° C. or higher. Moreover, the thing of 90 degrees C or less is preferable, and the thing of 80 degrees C or less is still more preferable. Further, it is particularly preferable that the melting points of the two kinds of wax compounds having a large blending amount are 40 ° C. or more and 90 ° C. or less.
As will be described later, the toner of the present invention has a structure in which wax fine particles are relatively uniformly distributed in the toner, and the wax component having a relatively wide temperature range from the start to the end of melting, that is, It is presumed that the lower the purity of the mixture is, the better the wax is discharged from the toner at the time of fixing even if the fixing temperature is changed, and therefore the fixing property is good.
[0017]
The wax fine particles used in the present invention are obtained by emulsifying the wax in the presence of at least one emulsifier selected from known cationic surfactants, anionic surfactants, and nonionic surfactants. Two or more of these surfactants may be used in combination.
In the present invention, it is preferable to emulsify at a temperature equal to or higher than the melting point of the wax. If the melting point of the wax is exceeded, the wax melts into droplets in water, and a dispersion of substantially spherical wax particles can be obtained.
[0018]
Specific examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like.
Specific examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate and the like.
[0019]
Further, specific examples of nonionic surfactants include polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl And sucrose.
[0020]
Of these surfactants, alkali metal salts of linear alkylbenzene sulfonic acids are preferred.
The average particle diameter of the wax fine particles is preferably 0.01 μm to 3 μm, more preferably 0.1 to 2 μm, and particularly preferably 0.3 to 1.5 μm. The average particle diameter can be measured using, for example, LA-500 manufactured by Horiba. If the average particle size of the wax emulsion is larger than 3 μm, the average particle size of the polymer particles obtained by seed polymerization becomes too large, which is not suitable for the production of a small particle toner requiring high resolution. Is appropriate. Further, when the average particle size of the emulsion is smaller than 0.01 μm, it is difficult to prepare a dispersion.
[0021]
Next, the polymer primary particles used in the present invention will be described.
One of the features of the present invention is that the polymer primary particles contain a wax.
As long as the polymer primary particles have a structure containing wax, the production method is not particularly limited. A method of seed emulsion polymerization of a monomer mixture using wax fine particles as a seed, a wax dissolved in a monomer, and emulsion polymerization of the monomer. Obtained by a method or the like.
[0022]
Hereinafter, polymer primary particles obtained by emulsion polymerization using wax fine particles as a seed, which is a preferred embodiment of the present invention, will be described.
In seed emulsion polymerization, a monomer having a Bronsted acidic group (hereinafter sometimes simply referred to as an acidic group) or a Bronsted basic group (hereinafter simply referred to as a basic group) is included. By adding a monomer and a monomer having neither a Bronsted acidic group nor a Bronsted basic group (hereinafter, may be referred to as other monomer), polymerization can be performed in an emulsion containing wax fine particles. Make it progress. At this time, the monomers may be added separately, or a plurality of monomers may be mixed and added in advance. Further, it is possible to change the monomer composition during the monomer addition. Further, the monomer may be added as it is, or may be added as an emulsified liquid previously mixed and adjusted with water or an emulsifier. As the emulsifier, one or two or more combined systems are selected from the above surfactants.
[0023]
In proceeding with the seed emulsion polymerization, an emulsifier (the above-mentioned surfactant) may be added to the emulsion containing a certain amount of wax fine particles. Further, the addition timing of the polymerization initiator may be any before the monomer addition, at the same time as the monomer addition, after the monomer addition, or may be a combination of these addition methods.
Examples of the monomer having a Bronsted acidic group used in the present invention include monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and cinnamic acid, and monomers having a sulfonic acid group such as sulfonated styrene. And monomers having a sulfonamide group such as vinylbenzenesulfonamide.
[0024]
Examples of the monomer having a Bronsted basic group include aromatic vinyl compounds having an amino group such as aminostyrene, nitrogen-containing heterocycle-containing monomers such as vinylpyridine and vinylpyrrolidone, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, And (meth) acrylic acid ester having an amino group such as
[0025]
Moreover, the monomer which has these acidic groups, and the monomer which has a basic group may exist as a salt with a counter ion, respectively.
The blending ratio in the monomer mixture constituting the polymer primary particles of the monomer having a Bronsted acidic group or Bronsted basic group is preferably 0.5% by weight or more, more preferably 1% by weight or more. And preferably 10% by weight or less, more preferably 5% by weight or less.
[0026]
Other comonomers include styrenes such as styrene, methylstyrene, chlorostyrene, dichlorostyrene, p-tert-butylstyrene, pn-butylstyrene, pn-nonylstyrene, methyl acrylate, ethyl acrylate , Propyl acrylate, n-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, ethyl hexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate (Meth) acrylic acid esters such as ethyl hexyl methacrylate, acrylamide, N-propyl acrylamide, N, N-dimethyl acrylamide, N, N-dipropyl acrylamide, N, N-dibutyl acrylate Ruamido, acrylic acid amide. Of these, styrene, butyl acrylate, and the like are particularly preferable.
[0027]
The resin used for the polymer primary particles is preferably a crosslinked resin. Crosslinking is performed by blending a monomer having at least two functional groups (polyfunctional monomer).
When a crosslinked resin is used for the polymer primary particles, a polyfunctional monomer having radical polymerization is used as a crosslinking agent shared with the above-described monomer, such as divinylbenzene, hexanediol diacrylate, ethylene glycol dimethacrylate, Examples include diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol acrylate, and diallyl phthalate. A monomer having a reactive group in a pendant group, such as glycidyl methacrylate, methylol acrylamide, or acrolein, can be used.
[0028]
The blending ratio of such a polyfunctional monomer in the monomer mixture is preferably 0.005% by weight or more, more preferably 0.01% by weight or more, particularly preferably 0.05% by weight or more, Preferably it is 5 weight% or less, More preferably, it is 3 weight% or less, Most preferably, it is 1 weight% or less.
These monomers are used alone or in combination, and in this case, the glass transition temperature of the polymer is preferably 40 to 80 ° C. If the glass transition temperature exceeds 80 ° C., the fixing temperature may become too high, or the deterioration of OHP transparency may be a problem. On the other hand, if the glass transition temperature of the polymer is less than 40 ° C., the storage stability of the toner May get worse.
[0029]
In the present invention, a known water-soluble polymerization initiator can be used as a polymerization initiator for emulsion polymerization. Specifically, for example, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, and the like, and redox initiators that combine these persulfates as a component with a reducing agent such as acidic sodium sulfite, hydrogen peroxide Water-soluble polymerization initiators such as 4,4′-azobiscyanovaleric acid, t-butyl hydroperoxide, cumene hydroperoxide, etc., and reduction of ferrous salts etc. using these water-soluble polymerizable initiators as one component Redox initiator systems in combination with agents, benzoyl peroxide, 2,2′-azobis-isobutyronitrile, and the like are used. These polymerization initiators may be added to the polymerization system before, simultaneously with the addition of the monomer, or after the addition, and these addition methods may be combined as necessary.
[0030]
In the present invention, a known chain transfer agent can be used as necessary. Specific examples of such a chain transfer agent include t-dodecyl mercaptan, 2-mercaptoethanol, diisopropyl xanthogen, tetrachloride. Carbon, trichlorobromomethane, and the like. The chain transfer agent may be used alone or in combination of two or more, and is usually used in the range of 0 to 5 parts by weight with respect to 100 parts by weight of the monomer.
[0031]
The polymer primary particles obtained as described above are polymer particles substantially including a wax, and the morphology thereof takes any form such as a core-shell type, a phase separation type, and an occlusion type. It may be a mixture of these forms. Particularly preferred is the core-shell type.
The volume average particle diameter of the polymer primary particles is usually in the range of 0.02 μm to 3 μm, preferably 0.05 μm to 3 μm, more preferably 0.1 μm to 2 μm, and particularly preferably 0.1 μm to 1 μm. is there. The average particle diameter can be measured using, for example, UPA. When the particle size is smaller than 0.02 μm, it is not preferable because the control of the aggregation rate becomes difficult. On the other hand, if the particle size is larger than 3 μm, the particle size of the toner obtained by agglomeration becomes too large, so that it is unsuitable for applications requiring high resolution as a toner.
[0032]
In the present invention, polymer primary particles are aggregated to form particle aggregates, and resin fine particles (resin fine particles will be described later) are adhered or fixed thereto to obtain a toner. Depending on the toner production conditions, the primary particles in the toner may be obtained. There are cases where particles can be observed, and primary particles cannot be observed due to fusion of primary particles.
In a preferred embodiment of the present invention, the polymer primary particles and the resin fine particles are fused, and the boundary between them is unclear or the boundary is not recognized.
[0033]
In another preferred embodiment, a crosslinked resin is used for either or both of the polymer primary particles and the resin fine particles covering the particle aggregates and has tetrahydrofuran-insoluble matter.
When wax particles having a small particle size are used for the production of the polymer primary particles, and when it is desired to increase the wax content in the toner, when the polymer primary particles are aggregated, another wax fine particle is used. Can also be co-aggregated. However, in consideration of the dispersibility of the wax fine particles in the toner, it is preferable that the wax is substantially entirely contained in the polymer primary particles.
[0034]
In the present invention, when obtaining polymer primary particles, the colorant fine particles may be used as a seed for emulsion polymerization simultaneously with the wax fine particles, or the colorant may be used by dissolving or dispersing in a monomer or wax. It is preferable that the colorant fine particles are aggregated simultaneously with the coalesced primary particles to form a particle aggregate to form a toner core material. At this time, polymer primary particles containing wax are used, but two or more types of polymer primary particles may be used as necessary. Moreover, as a coloring agent used here, any of an inorganic pigment, an organic pigment, an organic dye may be sufficient, or these combination may be sufficient.
[0035]
When a crosslinked resin is used for the polymer primary particles, the tetrahydrofuran insoluble content of the polymer primary particles is preferably 15% by weight or more, more preferably 20% by weight or more, and particularly preferably 25% by weight or more. Moreover, 70% weight or less is preferable. If the tetrahydrofuran-insoluble content is within the above range, offset resistance and OHP transparency tend to be excellent.
[0036]
Of the components constituting the polymer primary particles, the molecular weight peak (Mp) of the tetrahydrofuran-soluble component is preferably 30,000 or more, and more preferably 40,000 or more. Moreover, 150,000 or less is preferable and 100,000 or less is still more preferable. In particular, when a crosslinked resin is used, the molecular weight peak is preferably 100,000 or less, more preferably 60,000 or less.
[0037]
When the molecular weight peak is significantly smaller than the above range, the offset property on the high temperature side is deteriorated, and when it is significantly larger than the above range, the offset property on the low temperature side tends to be deteriorated.
Further, among the components constituting the polymer primary particles, the weight average molecular weight (Mw) of the tetrahydrofuran-soluble component is preferably 30,000 or more, and more preferably 80,000 or more. Moreover, 500,000 or less is preferable and 300,000 or less is still more preferable.
[0038]
Next, the colorant used in the present invention will be described.
Specific examples of the colorant include carbon black, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow, rhodamine dyes, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo, Any known dyes and pigments such as disazo dyes and condensed azo dyes can be used alone or in combination. In the case of a full color toner, it is preferable to use benzidine yellow for yellow, monoazo and condensed azo dyes, magenta for quinacridone and monoazo dyes, and cyan for phthalocyanine blue. The colorant is usually used in an amount of 3 to 20 parts by weight with respect to 100 parts by weight of the binder resin. In the present invention, the “binder resin” means a combination of a resin component constituting the polymer primary particles and a resin component constituting the resin fine particles.
[0039]
In the present invention, as a preferred embodiment for obtaining a particle aggregate (toner core material), the above-described polymer primary particles and colorant primary particles are co-aggregated to obtain a particle aggregate.
As the colorant primary particles, an organic pigment that is substantially insoluble in water is preferably emulsified in water in the presence of an emulsifier and used in the form of an emulsion. In this case, the volume average particle diameter of the colorant primary particles is 0.01 to 3 μm is preferable.
[0040]
In particular, when the magenta colorant contains a colorant compound represented by the following general formula (I) or (II), the combination with the toner having the constitution of the present invention is effective. That is, since the colorant compound represented by the general formula (I) can produce a colorant primary particle dispersion well, the hue of the toner is good. Further, since the compound represented by the general formula (II) is a compound that is easily positively charged, when used for a negatively charged toner, a particle aggregate (toner core material) containing a colorant is covered with resin fine particles. By doing so, the colorant does not appear on the toner surface, and negative chargeability can be imparted. The compound represented by the formula (I) or (II) is particularly advantageous when used as a colorant for the toner of the present invention because it has a good magenta color tone when incorporated in a toner by an emulsion polymerization aggregation method. is there.
[0041]
[Chemical 3]

[0042]
(In the general formula (I), R ¹ , R ² Each independently represents a hydrogen atom, an alkyl group or a halogen atom; ¹ Or R ² At least one of is a halogen atom. M represents any one of Ba, Sr, Mn, Ca, and Mg. )
[0043]
[Formula 4]

[0044]
(In general formula (II), A and B represent an aromatic ring which may have a substituent. R ^Three Is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aminosulfonyl group on which the nitrogen atom may be substituted, or a nitrogen atom Represents an aminocarbonyl group which may be substituted. In general formula (II), A and B are each preferably a benzene ring or a naphthalene ring. Of the compounds represented by the general formula (II), compounds represented by the following general formula (IIa) are more preferable.
[0045]
[Chemical formula 5]

[0046]
(In the general formula (IIa), R ^Three ~ R ⁶ Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aminosulfonyl group on which a nitrogen atom may be substituted. Or an aminocarbonyl group optionally substituted on the nitrogen atom. )
In the general formula (IIa), the substituent on the nitrogen atom in the aminosulfonyl group that may be substituted on the nitrogen atom or the aminocarbonyl group that may be substituted on the nitrogen atom is specifically as follows. Examples thereof include an alkyl group, an aryl group, an alkoxyalkyl group, a haloalkyl group, and a haloaryl group.
[0047]
Furthermore, R ^Three Is a hydrogen atom and R ^Four Is a methoxy group and R ^Five Is a hydrogen atom and R ⁶ A compound in which is chlorine is most preferred from the viewpoints of spectral reflectivity, dispersibility in a polymerizable monomer, and processability to a colorant dispersion.
Next, the charge control agent used in the present invention will be described.
In the present invention, a charge control agent can be contained in the toner as necessary. As a method of inclusion, when obtaining polymer primary particles, the charge control agent is used as a seed simultaneously with the wax, the charge control agent is used by dissolving or dispersing in a monomer or wax, or simultaneously with the polymer primary particles. The charge control agent primary particles may be agglomerated to form a particle aggregate to obtain a toner. However, after the polymer primary particles are preferably aggregated together with the colorant primary particles to form particle aggregates, the charge control agent primary particles before, simultaneously with, or after the step of attaching or fixing the resin fine particles Is preferably attached or fixed. In this case, the charge control agent is also preferably used as an emulsion (charge control agent primary particles) having an average particle size of 0.01 to 3 μm in water.
[0048]
As the charge control agent, any known one can be used alone or in combination, and examples thereof include quaternary ammonium salts and basic / electron-donating metal substances as positive chargeability, and negative chargeability. Examples include metal chelates, metal salts of organic acids, metal-containing dyes, nigrosine dyes, amide group-containing compounds, phenol compounds, naphthol compounds and their metal salts, urethane bond-containing compounds, and acidic or electron-withdrawing organic substances.
[0049]
In consideration of adaptability to color toners (the charge control agent itself is colorless or light in color, and there is no color tone problem on the toner), quaternary ammonium salt compounds are used as positive charge, and salicylic acid or alkylsalicylic acid is used as negative charge. Metal salts with chromium, zinc, aluminum, etc., metal complexes, metal salts of benzylic acid, metal complexes, amide compounds, phenol compounds, naphthol compounds, phenolamide compounds, 4,4′-methylenebis [2- [N- Hydroxynaphthalene compounds such as (4-chlorophenyl) amide] -3-hydroxynaphthalene] are preferred. The amount of use may be determined by the desired charge amount for the toner, but usually 0.01 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, is used with respect to 100 parts by weight of the binder resin.
[0050]
Next, resin fine particles used in the present invention will be described.
The toner of the present invention is characterized in that the above-mentioned particle aggregate is further coated (attached or fixed) with resin fine particles to form toner particles.
The resin fine particles are dispersed in water or a liquid mainly composed of water using an emulsifier (the aforementioned surfactant) and used as an emulsion. The resin fine particles are preferably those obtained by emulsion polymerization.
[0051]
The resin fine particles are preferably substantially free of wax. The phrase “substantially free of wax” means that the wax content in the resin fine particles is 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.1% by weight or less. . When the resin fine particles are substantially free of wax, before the toner is fixed by the fixing machine, it is difficult for the wax to ooze out to the surface of the toner, preventing the apparatus from being soiled, and the blocking resistance is also improved. .
[0052]
The resin fine particles preferably have a volume average particle size of 0.02 to 3 μm, more preferably 0.05 to 1.5 μm, and are obtained by polymerizing a monomer similar to the monomer used for the polymer primary particles described above. What was obtained can be used.
The resin used for the resin fine particles is preferably crosslinked.
As a crosslinking agent, the polyfunctional monomer used for the above-mentioned polymer primary particle can be used.
[0053]
In the case of using a crosslinked resin for the resin fine particles, the degree of crosslinking is usually 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and particularly preferably 20% by weight or more in terms of tetrahydrofuran insolubles. Moreover, it is 70 weight% or less normally. In order to make the above-mentioned preferable range insoluble in tetrahydrofuran, the blending ratio of the polyfunctional monomer is preferably 0.005% by weight or more, more preferably 0.01% by weight or more in the monomer mixture used for the resin fine particles. Preferably, 0.05% or more is particularly preferable. Further, it is preferably 5% by weight or less, more preferably 3% by weight or less, and particularly preferably 1% by weight or less.
[0054]
Among the components constituting the resin fine particles, the molecular weight peak (Mp) of the tetrahydrofuran-soluble component is preferably 30,000 or more, and more preferably 40,000 or more. Moreover, 150,000 or less is preferable and 100,000 or less is still more preferable.
In particular, when a crosslinked resin is used, the molecular weight peak is preferably 100,000 or less, more preferably 60,000 or less.
[0055]
In addition, among the components constituting the resin fine particles, the weight average molecular weight (Mw) of the tetrahydrofuran-soluble component is preferably 30,000 or more, and more preferably 50,000 or more. Moreover, 500,000 or less is preferable and 300,000 or less is still more preferable.
Next, the aggregation process for aggregating the above-mentioned particles will be described.
[0056]
In a preferred embodiment of the present invention, the above-described polymer primary particles, colorant primary particles, and, if necessary, charge control agent fine particles, wax fine particles, and other internal additives are emulsified into emulsions, respectively. Co-aggregate to form particle aggregates. Among the components that perform aggregation, the charge control agent dispersion may be added during the aggregation process or after the aggregation process.
[0057]
Here, in the aggregation step, there are 1) a method of performing aggregation by heating, and 2) a method of performing aggregation by adding an electrolyte, and these may be used in combination.
When aggregation is carried out by heating, the aggregation temperature is specifically a temperature range of 5 ° C. to Tg (where Tg is the glass transition temperature of the polymer primary particles), and (Tg-10) ° C. to ( A range of Tg-5) ° C. is preferred. If it is the said temperature range, it can be made to aggregate to a preferable toner particle size, without using electrolyte.
[0058]
In addition, when agglomeration is performed by heating, when a ripening step is performed subsequent to the agglomeration step, the agglomeration step and the ripening step are continuously performed, and the boundary between them may be ambiguous, but (Tg-20 ) If there is a step for holding at least 30 minutes in the temperature range of ° C to Tg, this is regarded as an agglomeration step.
The aggregation temperature is preferably kept at a predetermined temperature, usually at least 30 minutes, to obtain toner particles having a desired particle diameter. The temperature may be increased at a constant speed up to a predetermined temperature, or may be increased stepwise. The holding time is preferably from 30 minutes to 8 hours in the range of (Tg-20) ° C. to Tg, and more preferably from 1 hour to less than 4 hours. By doing so, a toner having a small particle size and a sharp particle size distribution can be obtained.
[0059]
In addition, as an electrolyte in the case of adding an electrolyte to the mixed dispersion and performing aggregation, either an organic salt or an inorganic salt may be used, but a monovalent or divalent or higher polyvalent metal salt is preferably used. . Specifically, NaCl, KCl, LiCl, Na ₂ SO _Four , K ₂ SO _Four , Li ₂ SO _Four MgCl ₂ , CaCl ₂ , MgSO _Four , CaSO _Four ZnSO _Four , Al ₂ (SO _Four ) _Three , Fe ₂ (SO _Four ) _Three , CH _Three COONa, C ₆ H _Five SO _Three Na etc. are mentioned.
[0060]
The amount of the electrolyte added varies depending on the type of the electrolyte, but usually 0.05 to 25 parts by weight is used with respect to 100 parts by weight of the solid component of the mixed dispersion. Preferably it is 0.1-15 weight part, More preferably, it is 0.1-10 weight part.
When the amount of electrolyte added is significantly smaller than the above range, the progress of the agglutination reaction is slow, and fine particles of 1 μm or less remain after the agglomeration reaction, or the average particle diameter of the obtained agglomerated particles becomes 3 μm or less. Tend to occur. In addition, when the amount of electrolyte added is significantly larger than the above range, agglomeration that is quick and difficult to control tends to occur, and coarse particles of 25 μm or more are mixed in the obtained agglomerated particles, or the shape of the agglomerates is irregular. It tends to cause problems such as becoming a regular product.
[0061]
In addition, when aggregation is performed by adding an electrolyte, the aggregation temperature is preferably in the temperature range of 5 ° C. to Tg.
In the aggregating step, a normal stirring tank is used, and the shape is preferably a substantially cylindrical shape or a substantially spherical shape. When the reaction vessel has a substantially cylindrical shape, the shape of the bottom surface is not particularly limited, but a normal substantially arc shape is preferably used.
[0062]
In order to improve the stirring efficiency, the volume of the mixed dispersion is preferably 2/3 or less, more preferably 3/5 or less of the volume of the reaction vessel. In addition, if the volume of the mixed dispersion is extremely small compared to the volume of the reaction solution, foaming is intense and thickening is increased, coarse particles are likely to be generated, and depending on the shape of the stirring blade, the stirring may not be performed. Since the production efficiency also decreases, this ratio is preferably 1/10 or more, and more preferably 1/5 or more.
[0063]
As the stirring blade used in the agglomeration step, conventionally known stirring blades of various shapes can be used.
Examples of commercially available stirring blades include anchor blades, full zone blades (manufactured by Shinko Pantech Co., Ltd.), sun meller blades (manufactured by Mitsubishi Heavy Industries, Ltd.), max blend blades (manufactured by Sumitomo Heavy Industries, Ltd.), Hi-F mixer blades (soken) And a stirring blade such as a double helical ribbon blade (manufactured by Shinko Pantech Co., Ltd.). Moreover, you may provide a baffle in a stirring tank.
[0064]
Usually, from these stirring blades, suitable ones are selected and used depending on the viscosity and other physical properties of the reaction liquid, the reaction form, the shape and size of the reaction tank, etc. Includes a double helical ribbon wing or an anchor wing, and among them, a double helical ribbon wing is more preferable.
Next, in the toner production method of the present invention, in order to increase the stability of the aggregated particles (toner particles) obtained by aggregation following the aggregation step, Tg to (Tg + 80) ° C., preferably (Tg + 20) ° C. to It is preferable to add an aging step for causing fusion between the aggregated particles in the temperature range of (Tg + 80) ° C. and below the softening point of the polymer primary particles. By adding an aging step, the shape of the toner particles can be made nearly spherical and the shape can be controlled. This aging step is usually 1 hour to 24 hours, preferably 1 hour to 10 hours.
[0065]
This aging process can be performed using the same stirring tank as the stirring tank used in the aggregation process.
The toner particles obtained through each of the above steps are subjected to solid-liquid separation according to a known method, and the toner particles are collected, then washed as necessary and then dried.
[0066]
Further, the toner of the present invention can be used together with additives such as a fluidizing agent, if necessary. Specific examples of such fluidizing agents include fine particles such as hydrophobic silica, titanium oxide, and aluminum oxide. A powder can be mentioned, Usually, 0.01-5 weight part with respect to 100 weight part of binder resin, Preferably 0.1-3 weight part is used.
[0067]
Further, the toner of the present invention includes an inorganic fine powder such as magnetite, ferrite, cerium oxide, strontium titanate, and conductive titania, a resistance adjuster such as styrene resin and acrylic resin, and a lubricant as an internal or external additive. Can be used. The amount of these additives to be used may be appropriately selected depending on the desired performance, and is usually about 0.05 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
[0068]
The toner for developing an electrostatic charge image of the present invention may be used in any form of a two-component developer or a non-magnetic one-component developer. When used as a two-component developer, the carrier may be a magnetic substance such as iron powder, magnetite powder, ferrite powder, or a known material such as a mono or magnetic carrier having a resin coating on the surface thereof. As the coating resin of the resin coating carrier, generally known styrene resin, acrylic resin, styrene acrylic copolymer resin, silicone resin, modified silicone resin, fluororesin, or a mixture thereof can be used.
[0069]
In the toner of the present invention produced using the above-described components, it is preferable to use a resin in which at least one of the polymer primary particles and the resin fine particles is crosslinked. When a cross-linked resin is used, viscoelasticity is improved and OHP transparency is ensured. When a crosslinked resin is used, the insoluble content of tetrahydrofuran is increased, and when an uncrosslinked resin is used, it is almost dissolved in tetrahydrofuran. In addition, the colorant does not usually dissolve in tetrahydrofuran. Further, the charge control agent may or may not dissolve in tetrahydrofuran, but usually the charge control agent is used in a small proportion relative to other components. It is preferable that the insoluble content is controlled to 15 to 80%. The tetrahydrofuran insoluble content is more preferably 20% or more and 70% or less.
[0070]
The toner of the present invention preferably contains a wax having a melting point of 30 to 100 ° C. The content of the toner is determined by the binder resin of the toner (the resin constituting the polymer primary particles and the resin constituting the resin fine particles). The total amount is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and particularly preferably 10 parts by weight or more with respect to 100 parts by weight. Further, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less, and particularly preferably 30 parts by weight or less.
[0071]
Further, when the toner of the present invention is used in a high-resolution printer or copier, the charge amount of individual toner particles tends to be uniform when the toner has a relatively small particle size and a sharp particle size distribution. This is preferable.
The volume average particle size of the toner of the present invention is usually 3 to 12 μm, preferably 4 to 10 μm, more preferably 5 to 9 μm, and particularly preferably 6 to 8 μm. Further, as an index representing the particle size distribution, the volume average particle diameter (D _V ) And number average particle size (D _N ) (D) _V / D _N ), D _V / D _N Is preferably 1.25 or less, more preferably 1.22 or less, and particularly preferably 1.2 or less. D _V / D _N The minimum value of 1 is 1, which means that all particles have the same diameter, which is advantageous for high resolution image formation, but it is extremely difficult to obtain a particle size distribution that is practically 1 Difficult, so from a manufacturing point of view D _V / D _N Is 1.03 or more, preferably 1.05 or more.
[0072]
Furthermore, if there is too much fine powder (toner particle size toner), the amount of scattering to the photoreceptor fog and the device tends to be deteriorated, and the charge amount distribution tends to be deteriorated. If there is too much coarse powder (toner particle size toner). Therefore, the charge amount distribution tends to deteriorate, which is inappropriate for forming a high-resolution image. For example, when the average volume particle size of the toner is 7 to 10 μm, the toner having a particle size of 5 μm or less is preferably 10% by weight or less, and more preferably 5% by weight or less. Further, the toner having a particle diameter of 15 μm or more is preferably 5% by weight or less, and more preferably 3% by weight or less.
[0073]
In the case of producing such a toner having a relatively small particle size and a sharp particle size distribution, the production method by the emulsion polymerization aggregation method of the present invention may be a suspension polymerization method or a kneading / pulverization method. Advantageous compared to
Further, the 50% circularity of the toner is preferably 0.95 or more, and more preferably 0.96 or more. The maximum value of 50% circularity is 1, which means that the toner is substantially spherical, but it is difficult to obtain such a toner. 0.99 or less.
[0074]
Next, preferred embodiments of the toner of the present invention will be described with reference to the drawings. A preferred first embodiment of the toner of the present invention is formed by adhering or fixing the resin fine particles (2) to the aggregates of the polymer primary particles (1), and the polymer primary particles (1) are wax (5). The resin fine particles do not substantially contain wax inside.
[0075]
In this embodiment, as shown in FIG. 1, it is preferable to attach or fix the resin fine particles (2) to at least one part on the surface of the aggregates of the polymer primary particles (1) (in FIGS. Only the particles (1) and the resin fine particles (2) are shown, and the colorant fine particles, the charge control agent fine particles, and other additives are omitted).
Since the coating effect may not be obtained if the amount of the resin fine particles used is extremely small, it is preferably 3% by weight or more, more preferably 5% by weight or more of the polymer primary particles. In addition, if the amount used is excessively large, the wax does not exist on the surface portion excluding the outermost layer, and the wax may not be discharged from the toner at the time of fixing. % By weight or less, more preferably 40% by weight or less, and particularly preferably 20% by weight or less.
[0076]
Further, in terms of the weight ratio, the weight of the particle aggregate / the weight of the resin fine particles is preferably 1 to 100.
Prior to coating the particle aggregates with resin fine particles, the particle aggregates may be fused at a temperature equal to or higher than the glass transition temperature (Tg) of the polymer primary particles, preferably from Tg to (Tg + 80) ° C. When the particle aggregate is fused prior to coating the resin fine particles and then the resin particles are coated, as shown in FIG. 2, wax ( 5), and the resin fine particles (2) are adhered or fixed to the particles (3). This is the preferred second form of the present invention.
[0077]
FIG. 3 is a conceptual diagram of the toner after fusing the polymer primary particles and resin fine particles in the first or second embodiment described above.
The toner in the form of FIG. 3 is fused (ripened) with the toner in the form of FIG. 1 or the form of FIG. 2 at a temperature higher than the glass transition temperature (Tg) of the polymer primary particles, preferably Tg to (Tg + 80) ° C. Preferably, the toner in the form shown in FIG. 1 is fused, that is, the polymer primary particles are aggregated to form particle aggregates, which are not fused (the aging step is performed). It is formed from particles (4) in which resin fine particles are adhered (without passing) and subsequently both the polymer primary particles and resin fine particles are fused.
[0078]
In FIG. 3, the dotted line indicates a depth of 0.1 μm from the toner surface. As shown in FIG. 3, the toner having this structure is substantially free of wax (5) particles in the outermost part of the toner, specifically in the range of a depth of 0.1 μm from the toner surface. In the toner after fusing, it is normal that there is no clear boundary between the portion that was originally the polymer primary particle and the portion that was the resin fine particle, and the wax fine particles have a certain distribution inside the toner. Existing.
[0079]
Here, substantially no wax particles are present at the outermost part of the toner. Specifically, the volume average particle diameter is 3 to 12 μm, and the cross section of the toner containing wax is shown by a transmission electron microscope (TEM) photograph. When observed, the concentration (area ratio) of wax fine particles having an average particle diameter of 0.01 μm or more at a depth from the toner surface to 0.1 μm is 1 of the concentration (area ratio) of the wax fine particles in a portion deeper than 0.1 μm. / 10 or less.
[0080]
In addition, the presence of wax fine particles having a constant distribution means that the half-value width of the number average particle diameter of the wax fine particles observed in the toner cross section is 0.06 μm or less. The half width is preferably 0.05 μm or less. The theoretical minimum value of the half-value width is 0, but cannot be manufactured. Therefore, the half-value width is practically 0.01 μm or more.
[0081]
FIG. 4 is a view showing a TEM photograph of a cross section of the toner manufactured in Example 1. This photograph was observed by placing a cut toner on a foam-shaped support, where the black mass is toner, and the white and light colored portions (not visible in the figure) in the toner are wax. is there. When the cross section of the toner is observed, the wax fine particles are not always cut at a plane passing through the center of the toner, but rather are often cut at a plane off the center. Therefore, the value of the particle size obtained from the wax fine particles (observed in a planar shape) observed in the cross section of the toner is smaller than the particle size actually present in the toner. Further, since a force is applied when cutting the toner particles, even when a substantially spherical toner is cut, the cut surface is usually not a circle but a broken ellipse, and the wax fine particles contained in the toner The cross-section of the is also broken.
[0082]
The number average particle diameter of the wax fine particles observed in the cross section of the toner is usually 20 nm or more, preferably 30 nm or more, and more preferably 50 nm or more. Moreover, it is 150 nm or less normally, and 100 nm or less is preferable.
In the present invention, the wax fine particles are used as seeds of the polymer primary particles, and therefore the wax is encapsulated in the resin. Therefore, even when the particle aggregate is fused in the toner manufacturing process, It is considered that the wax fine particles substantially maintain the particle size present in the polymer primary particles or the resin fine particles. On the other hand, when the wax fine particles are co-aggregated with the polymer primary particles, the wax fine particles may be fused first in the process of co-aggregation. The result is a wax with a fairly large particle size made by repeated fusing. Therefore, the distribution of the number average particle size of the wax fine particles observed in the toner cross section is greater when the wax fine particles and the polymer primary particles are co-aggregated than when the polymer primary particles obtained by seed polymerization are aggregated. Becomes wider.
[0083]
In the toner of the present invention, a large number of wax fine particles having a small particle diameter are distributed. Such a structure is considered that the wax is uniformly discharged from the toner surface at the time of fixing, and is excellent in releasability. Moreover, since the wax discharge is suppressed before fixing, the blocking resistance is excellent, and problems such as device contamination are less likely to occur.
In another preferred embodiment of the present invention, the toner of the present invention uses a resin in which at least one of polymer primary particles and resin fine particles is crosslinked. Furthermore, it is preferable to use a resin in which both polymer primary particles and resin fine particles are crosslinked.
[0084]
【Example】
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
In the following examples, “parts” means “parts by weight”. In addition, the average particle size, particle size distribution, weight average molecular weight, glass transition point (Tg), 50% circularity, fixing temperature width, OHP permeability, charge amount, blocking resistance and tetrahydrofuran insoluble content are as follows. It was measured.
[0085]
Volume average particle diameter, number average particle diameter, ratio of toner particles having a size of 5 μm or less and 15 μm or more: Horiba LA-500, Nikkiso Microtrack UPA (ultraparticulate analyzer), Coulter Coulter Counter Multisizer II , Abbreviated as Coulter Counter).
[0086]
Weight average molecular weight (Mw): measured by gel permeation chromatography (GPC) (apparatus: GPC apparatus HLC-8020 manufactured by Tosoh Corporation, column: PL-gel Mixed-B 10μ manufactured by Polymer Laboratories, solvent: THF, sample concentration : 0.1 wt%, calibration curve: standard polystyrene)
Glass transition temperature (Tg): Measured with DSC7 manufactured by PerkinElmer. The temperature was raised from 30 ° C. to 100 ° C. in 7 minutes, rapidly cooled from 100 ° C. to −20 ° C., heated from −20 ° C. to 100 ° C. in 12 minutes, and the Tg value observed at the second temperature rise was Using.
[0087]
50% circularity: the toner was measured with a flow type particle image analyzer (“FPIA-2000” manufactured by Sysmex Corporation), and the circularity corresponding to the cumulative particle size value at 50% of the value obtained from the following formula was used. .
[0088]
[Expression 1]
Circularity = circumference of a circle with the same area as the projected particle area / circumference of the projected particle image
Fixing temperature range: Recording paper carrying an unfixed toner image was prepared, the surface temperature of the heating roller was changed from 100 ° C. to 220 ° C., conveyed to the fixing nip portion, and the fixing state when discharged was observed. . The temperature range where the toner on the heating roller did not offset during fixing and the toner on the recording paper after fixing was sufficiently adhered to the recording paper was defined as the fixing temperature range.
[0089]
The fixing roller has a heating roller composed of aluminum as a core metal, 1.5 mm thick dimethyl-based low temperature vulcanized silicone rubber having a rubber hardness of 3 ° according to JIS-A standard as an elastic layer, and PFA (tetrafluoroethylene-- as a release layer). A perfluoroalkyl vinyl ether copolymer) having a thickness of 50 μm is used, the diameter is 30 mm, and the rubber hardness of the surface of the fixing roller measured in accordance with Japan Rubber Association Standard SRIS 0101 is 80. Evaluation was made with a nip width of 4 mm without application of silicone oil. The fixing speed was 120 mm / S or 30 mm / S.
[0090]
Since the evaluation range is 100 ° C. to 220 ° C. (however, Comparative Example 10 is 100 ° C. to 200 ° C.), the upper limit of the fixing temperature is 220 ° C., and the true upper limit of the fixing temperature is even higher. there is a possibility.
OHP permeability: An unfixed toner image in the form of an OHP sheet was fixed using the above fixing roller without applying silicone oil, at a fixing speed of 30 mm / S, and at 180 ° C., and a spectrophotometer (U Hitachi, Ltd.) -3210), the transmittance is measured in the wavelength range of 400 nm to 700 nm, the transmittance at the wavelength with the highest transmittance (maximum transmittance (%)) and the transmittance at the wavelength with the lowest transmittance (minimum transmittance). Rate (%)) difference (maximum transmittance−minimum transmittance) was used as a value.
[0091]
Charge amount: The toner is put into a non-magnetic one-component developer tank (ColorPagePrestoN4 developer tank manufactured by Casio Co., Ltd., if available, Phaser 550 developer tank manufactured by Kyushu Matsushita Co., Ltd.), and the toner on the roller is rotated a certain number of times. Then, the charge amount per unit weight was determined from the charge amount (measured by Toshiba Chemical blow-off) and the weight of the sucked toner.
[0092]
Blocking resistance: 10 g of developing toner is put in a cylindrical container, a load of 20 g is put on it, left in a 50 ° C. environment for 5 hours, the toner is taken out of the container, and the degree of aggregation is applied by applying a load from above. confirmed.
[0093]
[Table 1]
○: No aggregation
Δ: Agglomerated but collapsed by light load
×: Aggregated and does not collapse even when a load is applied
[0094]
Tetrahydrofuran (THF) insoluble content: Measurement of the tetrahydrofuran insoluble content of toner, polymer primary particles, and resin fine particles was performed by adding 1 g of a sample to 100 g of tetrahydrofuran and allowing to stand at 25 ° C. for 24 hours, followed by filtration using 10 g of Celite, and filtrate. The tetrahydrofuran-soluble component was quantified by evaporating the solvent, and the tetrahydrofuran-insoluble component was calculated by subtracting from 1 g.
[Example 1]
(Wax dispersion-1)
68.33 parts of demineralized water, an ester mixture mainly composed of behenyl behenate (Unistar M-2222SL, manufactured by Nippon Oil & Fats Co., Ltd.) and an ester mixture mainly composed of stearyl stearate (Unistar M9676, manufactured by Nippon Oil & Fats Co., Ltd.) 7: 3 30 parts of the mixture and 1.67 parts of sodium dodecylbenzenesulfonate (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 66% active ingredient) are mixed, emulsified by applying high-pressure shear at 90 ° C., and dispersion of ester wax fine particles Got. The average particle diameter of the ester wax fine particles measured by LA-500 was 340 nm.
(Polymer primary particle dispersion-1)
28 parts of wax dispersion-1, 15% neogen SC in a reactor (volume 60 liters, inner diameter 400 mm) equipped with a stirrer (3 blades), heating / cooling device, concentrating device, and raw material / auxiliary charging device 1.2 parts of an aqueous solution and 393 parts of demineralized water were charged, the temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% aqueous ascorbic acid solution were added.
[0095]
Thereafter, a mixture of the following monomers and an aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0096]
[Table 2]
[Monomers]
79 parts of styrene (5530 g)
21 parts butyl acrylate
Acrylic acid 3 parts
Octanethiol 0.38 parts
2-mercaptoethanol 0.01 parts
Hexanediol diacrylate 0.9 parts
[Emulsifier aqueous solution]
1 part of 15% Neogen SC aqueous solution
25 parts of demineralized water
[Initiator aqueous solution]
9 parts of 8% hydrogen peroxide solution
9 parts of 8% ascorbic acid aqueous solution
[0097]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component weight-average molecular weight of 119,000, an average particle size measured by UPA of 189 nm, Tg of 57 ° C., and a THF-insoluble component of 52% by weight.
(Resin fine particle dispersion-1)
5 parts of 15% Neogen SC aqueous solution and 372 parts of demineralized water were added to a reactor (capacity 60 liters, inner diameter 400 mm) equipped with a stirrer (three blades), heating / cooling device, concentrating device, and raw material / auxiliary charging device. The temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added.
[0098]
Thereafter, a mixture of the following monomers and an aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0099]
[Table 3]
[Monomers]
88 parts of styrene (6160g)
12 parts butyl acrylate
Acrylic acid 2 parts
Bromotrichloromethane 0.5 parts
2-mercaptoethanol 0.01 parts
Hexanediol diacrylate 0.4 parts
[Emulsifier aqueous solution]
2.5 parts of 15% Neogen SC aqueous solution
24 parts of demineralized water
[Initiator aqueous solution]
9 parts of 8% hydrogen peroxide solution
9 parts of 8% ascorbic acid aqueous solution
[0100]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The weight-average molecular weight of the polymer soluble in THF was 54,000, the average particle size measured by UPA was 83 nm, Tg was 85 ° C., and the THF-insoluble matter was 15% by weight.
(Colorant fine particle dispersion-1)
Pigment Blue 15: 3 aqueous dispersion (EP-700 Blue GA, manufactured by Dainichi Seika Co., Ltd., solid content 35%) was used.
[0101]
The average particle size measured by UPA was 150 nm.
(Charge control agent fine particle dispersion-1)
Disperse 20 parts of 4,4'-methylenebis [2- [N- (4-chlorophenyl) amide] -3-hydroxynaphthalene], 4 parts of alkylnaphthalene sulfonate and 76 parts of demineralized water in a sand grinder mill, A control agent fine particle dispersion was obtained. The average particle size measured by UPA was 200 nm.
[0102]
(Manufacture of developing toner-1)
[Table 4]
Polymer primary particle dispersion-1 104 parts (71 g: as solid content)
Resin fine particle dispersion-1-6 parts (as solid content)
Colorant fine particle dispersion-1 6.7 parts (as solid content)
Charge control agent fine particle dispersion-1 2 parts (as solid content)
0.5 parts of 15% neogen SC aqueous solution (as solids)
[0103]
Using each of the above components, a toner was produced by the following procedure.
The polymer primary particle dispersion and 15% Neogen SC aqueous solution were charged into a reactor (capacity 1 liter, anchor blade with baffle) and mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution was added dropwise (0.6 parts as a solid content). Thereafter, while stirring, the temperature was raised to 51 ° C. over 20 minutes and held for 1 hour, and further heated to 58 ° C. over 6 minutes and held for 1 hour. A charge control agent fine particle dispersion, a resin fine particle dispersion, and an aluminum sulfate aqueous solution (0.07 parts as solid content) were added in this order, and the temperature was raised to 60 ° C. over 10 minutes and held for 30 minutes. After adding 15% Neogen SC aqueous solution (3 parts as solid content), the temperature was raised to 95 ° C. over 35 minutes and held for 3.5 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner-1).
[0104]
To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-1).
(Toner Evaluation-1)
The volume average particle diameter of the developing toner by Coulter counter is 7.2 μm, the ratio of 5 μm or less of the volume particle diameter is 3.5%, the ratio of 15 μm or more is 0.5%, the volume average particle number and the number average particle diameter The ratio was 1.12.
[0105]
The 50% circularity was 0.97.
The fixing property of the developing toner-1 was fixed at 170 to 220 ° C. at a fixing speed of 120 mm / S, and fixed at 130 to 220 ° C. at a fixing speed of 30 mm / S. The OHP permeability was 70%.
The charge amount of Toner-1 was −7 μC / g, and the charge amount of Toner-1 for development was −15 μC / g. The blocking resistance was ○.
[0106]
Further, when the toner was cut to a thickness of 80 nm and analyzed by a TEM photograph of 16000 times, the dispersion state of the wax particles was a number average particle size of 92 nm, the half value width of the number average particle size was 43 nm, and 0.1 μm from the toner surface. The abundance ratio of wax fine particles having a radius of 0.01 μm or more in the depth range of 0% was 0%, and the other part was 4.5%.
[0107]
The state of the TEM photograph is shown in FIG. Further, graphs showing the distribution of the number average particle diameter of the wax fine particles observed in the cross section of the toner are shown in FIGS. 6 and 7 for the particle diameter range of 0 to 1.5 μm and the particle diameter range of 0 to 0.5 μm, respectively.
[Example 2]
(Wax dispersion-2)
What was produced similarly to the wax dispersion-1 was used. The average particle diameter of the ester wax fine particles measured by LA-500 was 340 nm.
(Polymer primary particle dispersion-2)
A reactor (capacity 60 liters, inner diameter 400 mm) equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device 28 parts wax dispersion-2, 15% neogen SC aqueous solution 1.2 parts and 393 parts of demineralized water were added, the temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added.
[0108]
Thereafter, a mixture of the following monomers and an aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0109]
[Table 5]
[Monomers]
79 parts of styrene
21 parts butyl acrylate
Acrylic acid 3 parts
Bromotrichloromethane 0.45 parts
2-mercaptoethanol 0.01 parts
Hexanediol diacrylate 0.9 parts
[Emulsifier aqueous solution]
1 part of 15% Neogen SC aqueous solution
25 parts of demineralized water
[Initiator aqueous solution]
9 parts of 8% hydrogen peroxide solution
9 parts of 8% ascorbic acid aqueous solution
[0110]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The weight-average molecular weight of the polymer soluble in THF was 148,000, the average particle size measured by UPA was 207 nm, Tg was 55 ° C., and the THF-insoluble matter was 60% by weight.
(Colorant fine particle dispersion-2)
20 parts of Pigment Yellow 74, 7 parts of polyoxyethylene alkylphenyl ether and 73 parts of demineralized water were dispersed in a sand grinder mill to obtain a colorant fine particle dispersion. The average particle size measured by UPA was 211 nm.
[0111]
(Manufacture of developing toner-2)
[Table 6]
Polymer primary particle dispersion-2 105 parts (as solids)
Resin fine particle dispersion-1 5 parts (as solid content)
Colorant fine particle dispersion-2 6.7 parts (as solid content)
Charge control agent fine particle dispersion-1 2 parts (as solid content)
[0112]
Using each of the above components, a toner was produced by the following procedure.
The polymer primary particle dispersion and the colorant fine particle dispersion were charged into a reactor (volume: 1 liter, anchor blade with baffle) and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution (0.6 parts as a solid content) was added dropwise. Thereafter, while stirring, the temperature was raised to 51 ° C. over 25 minutes and held for 1 hour, and further heated to 59 ° C. over 8 minutes and held for 40 minutes. A charge control agent fine particle dispersion, a resin fine particle dispersion, and an aqueous aluminum sulfate solution (0.07 parts as a solid content) were added in this order, and the temperature was raised to 61 ° C. over 15 minutes and held for 30 minutes. After adding 15% neogen SC aqueous solution (3.8 parts as a solid content), the temperature was raised to 96 ° C. over 30 minutes and held for 4 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner-2).
[0113]
To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-2).
Toner Evaluation-2
The volume average particle diameter of the developing toner-2 by Coulter counter is 7.5 μm, the ratio of 5 μm or less of the volume particle diameter is 1.6%, the ratio of 15 μm or more is 0.7%, the volume average particle diameter and the number average particle The diameter ratio was 1.14. The 50% circularity was 0.96.
[0114]
The fixing property of the developing toner-2 was fixed at 150 to 220 ° C. at a fixing speed of 120 mm / S, and fixed at 130 to 220 ° C. at a fixing speed of 30 mm / S.
The charge amount of Toner-2 was −4 μC / g, and the charge amount of Toner-2 for development was −3 μC / g.
[Example 3]
(Colorant fine particle dispersion-3)
20 parts of Pigment Red 238 (compound of the following formula (A)), 2.5 parts of alkylbenzene sulfonate, and 77.5 parts of demineralized water were dispersed in a sand grinder mill to obtain a colorant fine particle dispersion. The average particle size measured by UPA was 181 nm.
[0115]
[Chemical 6]

[0116]
(Manufacture of developing toner-3)
[0117]
[Table 7]
Polymer primary particle dispersion-1 104 parts (as solids)
Resin fine particle dispersion-1-6 parts (as solid content)
Colorant fine particle dispersion-3 6.7 parts (as solid content)
Charge control agent fine particle dispersion-1 2 parts (as solid content)
0.65 parts of 15% neogen SC aqueous solution (as solids)
[0118]
Using each of the above components, a toner was produced by the following procedure.
The polymer primary particle dispersion and 15% Neogen SC aqueous solution were charged into a reactor (capacity 1 liter, anchor blade with baffle) and mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution (0.8 part as a solid content) was added dropwise. Thereafter, while stirring, the temperature was raised to 51 ° C. over 15 minutes and held for 1 hour, and further heated to 59 ° C. over 6 minutes and held for 20 minutes. A charge control agent fine particle dispersion, a resin fine particle dispersion, and an aluminum sulfate aqueous solution (0.09 parts as solid content) were added in this order, and the mixture was held at 59 ° C. for 20 minutes. After adding 15% Neogen SC aqueous solution (3.7 parts as solid content), the temperature was raised to 95 ° C. over 25 minutes, and further 15% Neogen SC aqueous solution (0.7 parts as solid content) was added. For 3.5 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner-3).
[0119]
To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-3).
(Evaluation of toner-3)
The volume average particle diameter of the developing toner by Coulter counter is 7.8 μm, the ratio of the volume particle diameter of 5 μm or less is 2.1%, the ratio of 15 μm or more is 2.1%, the volume average particle number and the number average particle diameter The ratio was 1.15. The 50% circularity was 0.97.
[0120]
The fixing property of the developing toner-3 was fixed at 160 to 220 ° C. at a fixing speed of 120 mm / S, and fixed at 120 to 220 ° C. at a fixing speed of 30 mm / S.
The charge amount of Toner-3 was −17 μC / g, and the charge amount of Toner-3 for development was −17 μC / g.
[Example 4]
(Wax dispersion-4)
68.33 parts of demineralized water, 30 parts of an ester mixture mainly composed of pentaerythritol stearate (Unistar H476, manufactured by NOF Corporation) and 1.67 parts of Neogen SC are mixed and emulsified by applying high-pressure shear at 90 ° C. A dispersion of wax fine particles was obtained. The average particle diameter of the ester wax fine particles measured by LA-500 was 350 nm.
(Polymer primary particle dispersion-4)
A reactor equipped with a stirrer (full zone blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device (volume 2 liters, inner diameter 120 mm) was charged with 35 parts of wax dispersion-4 and 3977 parts of demineralized water. The temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added.
[0121]
Thereafter, a mixture of the following monomers / emulsifier aqueous solution was added over 5 hours from the start of polymerization, and an initiator aqueous solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0122]
[Table 8]
[Monomers]
79 parts of styrene (237g)
21 parts butyl acrylate
Acrylic acid 3 parts
Octanethiol 0. 38 parts
2-mercaptoethanol 0.01 parts
Hexanediol diacrylate 0.9 parts
[Emulsifier aqueous solution]
1 part of 15% Neogen SC aqueous solution
25 parts of demineralized water
[Initiator aqueous solution]
9 parts of 8% hydrogen peroxide solution
9 parts of 8% ascorbic acid aqueous solution
[0123]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a weight-average molecular weight of 139,000 in THF-soluble matter, an average particle size measured by UPA of 201 nm, Tg was unclear, and a THF-insoluble matter was 53% by weight.
(Resin fine particle dispersion-4)
6 parts of 15% Neogen SC aqueous solution and 372 parts of demineralized water in a reactor (volume 2 liters, 120 mm inner diameter) equipped with a stirrer (three receding blades), heating / cooling device, concentrating device, and raw material / auxiliary charging device Was heated to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added.
[0124]
Thereafter, a mixture of the following monomers and an aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0125]
[Table 9]
(Monomers)
Styrene 88 parts (308 g)
12 parts butyl acrylate
Acrylic acid 2 parts
Bromotrichloromethane 0.5 parts
2-mercaptoethanol 0.01 parts
Hexanediol diacrylate 0.4 parts
(Emulsifier aqueous solution)
3 parts of 15% Neogen SC aqueous solution
23 parts of demineralized water
(Initiator aqueous solution)
9 parts of 8% hydrogen peroxide solution
9 parts of 8% ascorbic acid aqueous solution
[0126]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component having a weight-average molecular weight of 57,000, an average particle size measured by UPA of 56 nm, Tg of 84 ° C., and a THF-insoluble component of 10% by weight.
[0127]
(Manufacture of developing toner-4)
[Table 10]
Polymer primary particle dispersion-4 105 parts (71 g: as solid content)
Resin fine particle dispersion-5 parts (as solid content)
Colorant fine particle dispersion-1 6.7 parts (as solid content)
Charge control agent fine particle dispersion-1 2 parts (as solid content)
0.5 parts of 15% neogen SC aqueous solution (as solids)
[0128]
Using each of the above components, a toner was produced by the following procedure.
The polymer primary particle dispersion and 15% Neogen SC aqueous solution were charged into a reactor (capacity 1 liter, anchor blade with baffle) and mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution (0.53 parts as a solid content) was added dropwise. Thereafter, while stirring, the temperature was raised to 50 ° C. over 25 minutes and held for 1 hour, and further heated to 63 ° C. over 35 minutes and held for 20 minutes. A charge control agent fine particle dispersion, a resin fine particle dispersion, and an aqueous aluminum sulfate solution (0.07 parts as a solid content) were added in this order, and the temperature was raised to 65 ° C. over 10 minutes and held for 30 minutes. After adding 15% Neogen SC aqueous solution (3 parts as solid content), the temperature was raised to 96 ° C. over 30 minutes and held for 5 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner-4).
[0129]
To 100 parts of this toner, 0.6 parts of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-4).
(Toner Evaluation-4)
The volume average particle diameter of the developing toner-4 by Coulter counter is 7.9 μm, the ratio of the volume particle diameter of 5 μm or less is 2%, the ratio of 15 μm or more is 1.5%, and the volume average particle diameter and number average particle diameter are The ratio was 1.20. The 50% circularity was 0.95.
[0130]
With regard to the fixing property of the developing toner-4, fixing was performed at 170 to 220 ° C. at a fixing speed of 120 mm / S, and fixing was performed at 130 to 220 ° C. at a fixing speed of 30 mm / S. The OHP permeability was 70%.
The charge amount of Toner-4 was −9 μC / g, and the charge amount of Toner-4 for development was −15 μC / g. The blocking resistance was ○.
[Example 5]
(Wax dispersion-5)
68.33 parts of demineralized water, 30 parts of a 7: 3 mixture of an ester mixture mainly composed of behenyl behenate (Unistar M-2222SL, manufactured by Nippon Oil & Fats) and polyester wax (Mw about 1000), 1.67 parts of Neogen SC The mixture was emulsified by applying high-pressure shearing at 90 ° C. to obtain a dispersion of ester wax fine particles. The average particle size of the ester wax fine particles measured by LA-500 was 490 nm.
(Polymer primary particle dispersion-5)
28 parts wax dispersion-5, 15% neogen SC aqueous solution in a reactor (volume 2 liters, inner diameter 120 mm) equipped with a stirrer (full zone blade), heating / cooling device, concentrating device, and raw material / auxiliary charging device 1.2 parts and 393 parts of demineralized water were added, the temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added.
[0131]
Thereafter, a mixture of the following monomers / emulsifier aqueous solution was added over 5 hours from the start of polymerization, and an initiator aqueous solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0132]
[Table 11]
(Monomers)
79 parts of styrene
21 parts butyl acrylate
Acrylic acid 3 parts
Bromotrichloromethane 0.5 parts
2-mercaptoethanol 0.01 parts
0.9 parts of hexanediol diacrylate
(Emulsifier aqueous solution)
1 part of 15% Neogen SC aqueous solution
25 parts of demineralized water
(Initiator aqueous solution)
9 parts of 8% hydrogen peroxide solution
9 parts of 8% ascorbic acid aqueous solution
[0133]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component weight average molecular weight of 117,000, an average particle size measured by UPA of 201 nm, Tg of 53 ° C., and a THF-insoluble component of 41% by weight.
(Manufacture of developing toner-5)
[0134]
[Table 12]
Polymer primary particle dispersion-5 104 parts (as solids)
Resin fine particle dispersion-6 parts (as solid content)
Colorant fine particle dispersion-1 6.7 parts (as solid content)
Charge control agent fine particle dispersion-1 2 parts (as solid content)
0.5 parts of 15% neogen SC aqueous solution (as solids)
[0135]
Using each of the above components, a toner was produced by the following procedure.
The polymer primary particle dispersion and 15% Neogen SC aqueous solution were charged into a reactor (capacity 1 liter, anchor blade with baffle) and mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the resulting mixed dispersion, an aqueous aluminum sulfate solution was added dropwise (0.52 parts as a solid content). Thereafter, while stirring, the temperature was raised to 50 ° C. over 20 minutes and held for 1 hour, and further heated to 66 ° C. over 40 minutes and held for 10 minutes. A charge control agent fine particle dispersion, a resin fine particle dispersion, and an aqueous aluminum sulfate solution (0.08 parts as a solid content) were added in this order, and the temperature was raised to 68 ° C. over 10 minutes and held for 30 minutes. After adding a 15% neogen SC aqueous solution (3 parts as a solid content), the temperature was raised to 96 ° C. over 20 minutes and maintained for 4.5 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner-5).
[0136]
To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-5).
(Evaluation of toner-5)
The volume average particle diameter of the developing toner by Coulter counter is 8.2 μm, the ratio of 5 μm or less of the volume particle diameter is 0.7%, the ratio of 15 μm or more is 1.6%, the volume average particle number and the number average particle diameter The ratio was 1.14. The 50% circularity was 0.95.
[0137]
The fixing property of the developing toner 5 was fixed at 170 to 220 ° C. at a fixing speed of 120 mm / S, and fixed at 120 to 200 ° C. at a fixing speed of 30 mm / S.
The charge amount of Toner-5 was −3.5 μC / g, and the charge amount of Toner-5 for development was −21 μC / g.
[Example 6]
(Wax dispersion-6)
68.33 parts of demineralized water, 30 parts of an ester mixture mainly composed of behenyl behenate (Unistar M-2222SL, manufactured by NOF Corporation) and 1.67 parts of Neogen SC are mixed and emulsified by applying high-pressure shear at 90 ° C. An ester wax dispersion was obtained. The average particle size measured with LA-500 was 340 nm.
(Polymer primary particle dispersion-6)
A reactor equipped with a stirrer (three receding blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device (volume: 3 liters, inner diameter: 150 mm)-635 parts of wax dispersion and 396 parts of demineralized water The temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added.
[0138]
Thereafter, a mixture of the following monomers and an aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0139]
[Table 13]
(Monomers)
79 parts of styrene
21 parts butyl acrylate
Acrylic acid 3 parts
Octanethiol 0.38 parts
2-mercaptoethanol 0.01 parts
Hexanediol diacrylate 0.7 parts
[Emulsifier aqueous solution]
1 part of 15% Neogen SC aqueous solution
25 parts of demineralized water
[Initiator aqueous solution]
9 parts of 8% hydrogen peroxide solution
9 parts of 8% ascorbic acid aqueous solution
[0140]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component having a weight-average molecular weight of 127,000, an average particle size measured by UPA of 201 nm, Tg of 55 ° C., and a THF-insoluble component of 38% by weight.
(Resin fine particle dispersion-6)
4.3 parts of 15% Neogen SC aqueous solution, 376 demineralized water 376 in a reactor (volume 2 l, inner diameter 120 mm) equipped with a stirrer (three receding blades), heating / cooling device, concentrating device, and raw material / auxiliary charging device Then, the temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% aqueous ascorbic acid solution were added.
[0141]
Thereafter, a mixture of the following monomers and an aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0142]
[Table 14]
(Monomers)
88 parts of styrene
12 parts butyl acrylate
Acrylic acid 3 parts
Bromotrichloromethane 0.5 parts
2-mercaptoethanol 0.01 parts
0.4 parts of divinylbenzene
(Emulsifier aqueous solution)
15 parts of 15% neogen SC aqueous solution
24 parts of demineralized water
(Initiator aqueous solution)
9 parts of 8% hydrogen peroxide solution
9 parts of 8% ascorbic acid aqueous solution
[0143]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component weight-average molecular weight of 111,000, an average particle size measured by UPA of 121 nm, a Tg of 86 ° C., and a THF-insoluble component of 20% by weight.
(Colorant fine particle dispersion-6)
Pigment Red 48: 2 (compound of the following formula (B)) 20 parts, 4 parts of polyoxyethylene alkylphenyl ether, and 76 parts of demineralized water were dispersed in a sand grinder mill to obtain a colorant fine particle dispersion. The average particle size measured by UPA was 201 nm.
[0144]
[Chemical 7]

[0145]
(Manufacture of developing toner-6)
[Table 15]
Polymer primary particle dispersion-699 parts (as solids)
Resin fine particle dispersion-6 11 parts (as solid content)
Colorant fine particle dispersion-6 6.7 parts (as solid content)
Charge control agent fine particle dispersion-1 2 parts (as solid content)
15% Neogen SC aqueous solution 0.27 parts (as solids)
[0146]
Using each of the above components, a toner was produced by the following procedure.
The polymer primary particle dispersion and 15% Neogen SC aqueous solution were charged into a reactor (capacity 1 liter, anchor blade with baffle) and mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution was added (0.52 parts as a solid content). Thereafter, while stirring, the temperature was raised to 55 ° C. over 30 minutes and held for 1 hour, and further heated to 61 ° C. over 20 minutes and held for 15 minutes. A charge control agent fine particle dispersion, a resin fine particle dispersion, and an aqueous aluminum sulfate solution (0.08 parts as solid content) were added in this order, and the temperature was raised to 63 ° C. over 10 minutes and held for 30 minutes. After adding 15% Neogen SC aqueous solution (3 parts as solid content), the temperature was raised to 96 ° C. over 30 minutes and held for 1 hour. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner-6).
[0147]
To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-6).
(Evaluation of toner-6)
The volume average particle diameter of the developing toner-6 by Coulter counter is 7.8 μm, the ratio of 5 μm or less of the volume particle diameter is 1.3%, the ratio of 15 μm or more is 2.8%, the volume average particle diameter and the number average particle The diameter ratio was 1.15. The 50% circularity was 0.98.
[0148]
Regarding the fixing property of the developing toner-6, fixing was performed at 160 to 210 ° C. at a fixing speed of 120 mm / S, and fixing was performed at 120 to 190 ° C. at a fixing speed of 30 mm / S.
The charge amount of toner-6 was −15 μC / g, and the charge amount of toner 6 for development was −28 μC / g.
[Comparative Example 7] (Example in which coating with resin fine particles is not performed)
(Manufacture of developing toner-7)
[0149]
[Table 16]
Polymer primary particle dispersion-6 110 parts (as solids)
Colorant fine particle dispersion-6 6.7 parts (as solid content)
Charge control agent fine particle dispersion-1 2 parts (as solid content)
0.5 parts of 15% neogen SC aqueous solution (as solids)
[0150]
Using each of the above components, a toner was produced by the following procedure.
The polymer primary particle dispersion and 15% Neogen SC aqueous solution were charged into a reactor (capacity 1 liter, anchor blade with baffle) and mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution was added dropwise (0.6 parts as a solid content). Thereafter, while stirring, the temperature was raised to 55 ° C. over 30 minutes and held for 1 hour, and further heated to 62 ° C. over 20 minutes and held for 10 minutes. The charge control agent fine particle dispersion was added and held at 62 ° C. for 30 minutes. After adding 15% Neogen SC aqueous solution (3 parts as solid content), the temperature was raised to 96 ° C. over 35 minutes and held for 1.5 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner-7).
[0151]
To 100 parts of this toner, 0.6 parts of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-7).
(Evaluation of toner-7)
The volume average particle diameter of the developing toner 7 by Coulter counter is 7.3 μm, the ratio of the volume particle diameter of 5 μm or less is 3.1%, the ratio of 15 μm or more is 0.5%, the volume average particle diameter and the number average particle The diameter ratio was 1.14. The 50% circularity was 0.98.
[0152]
The fixing property of the developing toner 7 was fixed at 150 to 220 ° C. at a fixing speed of 120 mm / S, and fixed at 110 to 180 ° C. at a fixing speed of 30 mm / S.
The charge amount of Toner-7 was −3 μC / g, and the charge amount of Toner-7 for development was −14 μC / g.
[Example 8]
(Wax dispersion-8)
What was produced like the wax dispersion liquid-6 was used. The average particle size measured with LA-500 was 340 nm.
(Polymer primary particle dispersion-8)
It was prepared by the same composition and the same operation as the polymer primary particle dispersion-6.
[0153]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The weight-average molecular weight of the polymer soluble in THF was 98.000, the average particle size measured by UPA was 188 nm, Tg was 57 ° C., and the THF-insoluble matter was 25% by weight.
(Manufacture of development toner-8)
[0154]
[Table 17]
Polymer primary particle dispersion-899 parts (as solids)
Resin fine particle dispersion-6 11 parts (as solid content)
Colorant fine particle dispersion-1 6.7 parts (as solid content)
Charge control agent fine particle dispersion-1 2 parts (as solid content)
0.5 parts of 15% neogen SC aqueous solution (as solids)
[0155]
Using each of the above components, a toner was produced by the following procedure.
The polymer primary particle dispersion and 15% Neogen SC aqueous solution were charged into a reactor (capacity 1 liter, anchor blade with baffle) and mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the resulting mixed dispersion, an aqueous aluminum sulfate solution (0.6 parts as a solid content) was added dropwise. Thereafter, while stirring, the temperature was raised to 55 ° C. over 20 minutes and held for 1 hour, and further heated to 58 ° C. over 5 minutes and held for 1 hour. A charge control agent fine particle dispersion, a resin fine particle dispersion, and an aqueous aluminum sulfate solution (0.07 parts as a solid content) were added in this order, and the temperature was raised to 65 ° C. over 25 minutes. After adding 15% Neogen SC aqueous solution (4.1 parts as a solid content), the temperature was raised to 95 ° C. over 30 minutes and held for 2 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (Toner-8).
[0156]
To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-8).
(Evaluation of toner-8)
The volume average particle diameter of the developing toner-8 by Coulter counter is 7.3 μm, the ratio of the volume particle diameter of 5 μm or less is 1.4%, the ratio of 15 μm or more is 0.3%, the volume average particle diameter and the number average particle The diameter ratio was 1.11. The 50% circularity was 0.98.
[0157]
With regard to the fixing property of the developing toner-8, fixing was performed at 180 to 220 ° C. at a fixing speed of 120 mm / S, and fixing was performed at 150 to 180 ° C. at a fixing speed of 30 mm / S.
The charge amount of the toner-8 was -8 μC / g, and the charge amount of the developing toner-8 was −14 μC / g.
[Example 9]
(Manufacture of developing toner-9)
[0158]
[Table 18]
Polymer primary particle dispersion-899 parts (as solids)
Resin fine particle dispersion-6 11 parts (as solid content)
Colorant fine particle dispersion-3 6.7 parts (as solid content)
Charge control agent fine particle dispersion-1 2 parts (as solid content)
0.65 parts of 15% neogen SC aqueous solution (as solids)
[0159]
Using each of the above components, a toner was produced by the following procedure.
The polymer primary particle dispersion and 15% Neogen SC aqueous solution were charged into a reactor (capacity 1 liter, anchor blade with baffle) and mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the resulting mixed dispersion, an aqueous aluminum sulfate solution was added dropwise (0.8 parts as a solid content). Thereafter, while stirring, the temperature was raised to 55 ° C. over 25 minutes and held for 1 hour, and the charge control agent fine particle dispersion was added, and the temperature was raised to 57 ° C. over 2 minutes. The resin fine particle dispersion was added and held at 57 ° C. for 35 minutes. After adding 15% neogen SC aqueous solution (4 parts as solid content), the temperature was raised to 95 ° C. over 40 minutes and held for 4 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner-9).
[0160]
To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-9).
(Evaluation of toner-9)
The volume average particle diameter of the developing toner 9 by Coulter counter is 7.6 μm, the ratio of the volume particle diameter of 5 μm or less is 1.6%, the ratio of 15 μm or more is 2.4%, the volume average particle diameter and the number average particle The diameter ratio was 1.15. The 50% circularity was 0.97.
[0161]
The fixing property of the developing toner 9 was fixed at 200 to 220 ° C. at a fixing speed of 120 mm / S, and fixed at 160 to 190 ° C. at a fixing speed of 30 mm / S.
The charge amount of toner-9 was −20 μC / g, and the charge amount of toner 9 for development was −25 μC / g.
[Comparative Example 10] (No coating with resin fine particles)
(Wax dispersion-10)
What was produced like the wax dispersion liquid-6 was used. The average particle size measured with LA-500 was 340 nm.
(Polymer primary particle dispersion-10)
A reactor (capacity 60 liters, inner diameter 400 mm) equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device was charged with 35 parts of wax dispersion and 395 parts of demineralized water, The temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added.
[0162]
Thereafter, a mixture of the following monomers and an aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0163]
[Table 19]
(Monomers)
79 parts of styrene
21 parts butyl acrylate
Acrylic acid 3 parts
Bromotrichloromethane 0.5 parts
2-mercaptoethanol 0.01 parts
0.4 parts of divinylbenzene
(Emulsifier aqueous solution)
1 part of 15% Neogen SC aqueous solution
25 parts of demineralized water
(Initiator aqueous solution)
9 parts of 8% hydrogen peroxide solution
9 parts of 8% ascorbic acid aqueous solution
[0164]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component weight-average molecular weight of 154,000, an average particle size measured by UPA of 195 nm, and Tg of 57 ° C.
[0165]
(Manufacture of toner for development-10)
[Table 20]
Polymer primary particle dispersion-10 110 parts (as solids)
Colorant fine particle dispersion-3 6.7 parts (as solid content)
Charge control agent fine particle dispersion-1 2 parts (as solid content)
0.65 parts of 15% neogen SC aqueous solution (as solids)
[0166]
Using each of the above components, a toner was produced by the following procedure.
The polymer primary particle dispersion and 15% Neogen SC aqueous solution were charged into a reactor (capacity 1 liter, anchor blade with baffle) and mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution was added dropwise (0.9 part as a solid content), and then a charge control agent fine particle dispersion was added. Thereafter, while stirring, the temperature was raised to 60 ° C. over 20 minutes and held for 30 minutes, and the temperature was raised to 61 ° C. over 2 minutes and held for 1 hour. After adding 15% neogen SC aqueous solution (5 parts as solid content), the temperature was raised to 95 ° C. over 25 minutes and held for 5 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner-10).
[0167]
To 100 parts of this toner, 0.6 parts of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-10).
(Toner Evaluation-10)
The volume average particle diameter of the developing toner-10 by Coulter counter is 7.5 μm, the ratio of the volume particle diameter of 5 μm or less is 4.1%, the ratio of 15 μm or more is 2.3%, the volume average particle diameter and the number average particle The diameter ratio was 1.19. The 50% circularity was 0.98.
[0168]
The fixing property of the developing toner 10 was fixed at 158 to 200 ° C. at a fixing speed of 120 mm / S, and fixed at 123 to 182 ° C. at a fixing speed of 30 mm / S.
The charge amount of the toner-10 was +15 μC / g, and the charge amount of the developing toner-10 was +11 μC / g.
[Comparative Example 11] (Example in which neither polymer primary particles nor resin fine particles contain wax)
(Polymer primary particle dispersion-11)
2 parts of 15% Neogen SC aqueous solution and 378 parts of demineralized water were added to a reactor (capacity 60 liters, inner diameter 400 mm) equipped with a stirrer (three blades), heating / cooling device, concentrating device, and each raw material / auxiliary charging device. The temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added.
[0169]
Thereafter, a mixture of the following monomers and an aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0170]
[Table 21]
(Monomers)
79 parts of styrene
21 parts butyl acrylate
Acrylic acid 3 parts
Bromotrichloromethane 0.45 parts
2-mercaptoethanol 0.01 parts
0.9 parts of hexanediol diacrylate
(Emulsifier aqueous solution)
1 part of 15% Neogen SC aqueous solution
25 parts of demineralized water
(Initiator aqueous solution)
9 parts of 8% hydrogen peroxide solution
9 parts of 8% ascorbic acid aqueous solution
[0171]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component having a weight-average molecular weight of 126,000, an average particle size measured by UPA of 199 nm, Tg of 70 ° C., and a THF-insoluble component of 30% by weight.
(Manufacture of developing toner-11)
[0172]
[Table 22]
95 parts of polymer primary particle dispersion-11 (as solid content)
Resin fine particle dispersion-1 5 parts (as solid content)
Colorant fine particle dispersion-1 6.7 parts (as solid content)
Charge control agent fine particle dispersion-1 2 parts (as solid content)
0.2 parts of 15% Neogen SC aqueous solution (as solids)
[0173]
Using each of the above components, a toner was produced by the following procedure.
The polymer primary particle dispersion and 15% Neogen SC aqueous solution were charged into a reactor (capacity 1 liter, anchor blade with baffle) and mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution was added dropwise (0.54 parts as a solid content). Thereafter, while stirring, the temperature was raised to 50 ° C. over 25 minutes and held for 1 hour, and further heated to 69 ° C. over 1 hour and held for 10 minutes. A charge control agent fine particle dispersion, a resin fine particle dispersion, and an aqueous aluminum sulfate solution (0.06 parts as a solid content) were added in this order, and the temperature was raised to 71 ° C. over 10 minutes and held for 30 minutes. After adding 15% Neogen SC aqueous solution (3.3 parts as solid content), the temperature was raised to 96 ° C. over 25 minutes and held for 7 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner-11).
[0174]
To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-11).
(Toner Evaluation-11)
The volume average particle diameter of the developing toner 11 by Coulter counter is 7.5 μm, the ratio of the volume particle diameter of 5 μm or less is 2.5%, the ratio of 15 μm or more is 1.1%, the volume average particle diameter and the number average particle The diameter ratio was 1.14. The 50% circularity was 0.93.
[0175]
The fixing property of the developing toner 11 was fixed at 180 to 190 ° C. at a fixing speed of 120 mm / S, and fixed at 140 to 160 ° C. at a fixing speed of 30 mm / S.
The charge amount of Toner-11 was −27 μC / g, and the charge amount of Toner-11 for development was −11 μC / g.
[Comparative Example 12] (Example in which the outermost layer is coated with resin fine particles containing wax)
(Polymer primary particle dispersion-12)
2 parts of 15% Neogen SC aqueous solution and 378 parts of demineralized water were added to a reactor (capacity 60 liters, inner diameter 400 mm) equipped with a stirrer (three blades), heating / cooling device, concentrating device, and each raw material / auxiliary charging device. The temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added.
Thereafter, a mixture of the following monomers and an aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0176]
[Table 23]
(Monomers)
79 parts of styrene
21 parts butyl acrylate
Acrylic acid 3 parts
Bromotrichloromethane 0.45 parts
2-mercaptoethanol 0.01 parts
0.9 parts of hexanediol diacrylate
(Emulsifier aqueous solution)
1 part of 15% Neogen SC aqueous solution
25 parts of demineralized water
(Initiator aqueous solution)
9 parts of 8% hydrogen peroxide solution
9 parts of 8% ascorbic acid aqueous solution
[0177]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component weight average molecular weight of 126,000, an average particle size measured by UPA of 199 nm, Tg of 70 ° C., and a THF-insoluble component of 30% by weight.
(Resin fine particle dispersion-12)
Reactor (capacity 60 liters, inner diameter 400 mm) equipped with a stirrer (3 blades), heating / cooling device, concentrating device, and raw material / auxiliary charging device 28 parts of wax dispersion-1 and 15% neogen SC 1.2 parts of an aqueous solution and 393 parts of demineralized water were added, the temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added.
[0178]
Thereafter, a mixture of the following monomers and an aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0179]
[Table 24]
(Monomers)
79 parts of styrene
21 parts butyl acrylate
Acrylic acid 3 parts
Octanethiol 0.38 parts
2-mercaptoethanol 0.01 parts
0.9 parts of hexanediol diacrylate
(Emulsifier aqueous solution)
1 part of 15% Neogen SC aqueous solution
25 parts of demineralized water
(Initiator aqueous solution)
9 parts of 8% hydrogen peroxide solution
9 parts of 8% ascorbic acid aqueous solution
[0180]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component weight-average molecular weight of 119,000, an average particle size measured by UPA of 189 nm, Tg of 57 ° C., and a THF-insoluble component of 52% by weight.
[0181]
(Manufacture of developing toner-12)
[Table 25]
Polymer primary particle dispersion-12 77 parts (as solids)
Resin fine particle dispersion-12 33 parts (as solid content)
Colorant fine particle dispersion-1 6.7 parts (as solid content)
Charge control agent fine particle dispersion-1 2 parts (as solid content)
[0182]
Using each of the above components, a toner was produced by the following procedure.
The polymer primary particle dispersion and the colorant fine particle dispersion were charged into a reactor (volume: 1 liter, anchor blade with baffle) and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution was added dropwise (0.49 parts as solid content). Thereafter, while stirring, the temperature was raised to 50 ° C. over 25 minutes and held for 1 hour, and further heated to 67 ° C. over 40 minutes and held for 20 minutes. A charge control agent fine particle dispersion was added, cooled to 60 ° C., a resin fine particle dispersion and an aluminum sulfate aqueous solution (0.11 part as solid content) were added in this order, and the mixture was held at 60 ° C. for 30 minutes. After adding 15% Neogen SC aqueous solution (3.5 parts as solid content), the temperature was raised to 96 ° C. over 45 minutes and held for 4 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner-12).
[0183]
To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-12).
(Toner Evaluation-12)
The volume average particle diameter of the developing toner by Coulter counter is 8.1 μm, the ratio of the volume particle diameter of 5 μm or less is 1.2%, the ratio of 15 μm or more is 2.8%, the volume average particle diameter and the number average particle diameter The ratio was 1.17. The 50% circularity was 0.93.
[0184]
The fixing property of the developing toner-12 was fixed at 170-220 ° C. at a fixing speed of 120 mm / S, and fixed at 130-190 ° C. at a fixing speed of 30 mm / S.
The charge amount of the toner-12 was -6 μC / g, and the charge amount of the developing toner-12 was +4 μC / g.
For Example 1 to Comparative Example 12, the colorant (pigment), wax (WAX), polymer primary particles and resin fine particles used in the production of the toner are summarized in Table 1, and the evaluation of the toner is summarized in Table 2.
[0185]
[Table 26]

[0186]
[Table 27]

[0187]
[Example 13]
(Premixed monomer solution-13)
8 parts of an ester mixture (Unistar H476, manufactured by NOF Corporation) mainly composed of the following monomers and pentaerythritol stearate ester were dissolved in advance. Next, an aqueous solution of neogen SC (see below for the amount) was placed in a jacketed homogenizer (TK auto homomixer M type, manufactured by Tokushu Kika Kogyo Co., Ltd.) and heated to 60 to 65 ° C. The homogenizer was stirred at high speed, and the wax solution of the above monomer was poured into the tank to prepare a premix monomer (premix monomer solution-13).
[0188]
[Table 28]
(Monomers)
79 parts of styrene (350 g)
21 parts butyl acrylate
Acrylic acid 3 parts
0.45 part of trichlorobromomethane
2-mercaptoethanol 0.10 parts
Hexanediol diacrylate 0.90 parts
(Emulsifier aqueous solution)
2 parts of 15% Neogen SC aqueous solution
54 parts of demineralized water
[0189]
(Polymer primary particle dispersion-13)
A reactor equipped with a stirrer (full zone blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device (volume 3 liters, inner diameter 150 mm), 3 parts of 15% Neogen SC aqueous solution and 382 parts of demineralized water. The temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added. Thereafter, the entire amount of Premix Monomer Liquid-13 was added over 5 hours from the start of polymerization, and an initiator aqueous solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
(Initiator aqueous solution)
9 parts of 8% hydrogen peroxide solution
9 parts of 8% ascorbic acid aqueous solution
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component weight average molecular weight of 198,000 and an average particle size measured by UPA of 153 nm.
(Manufacture of developing toner-13)
[0190]
[Table 29]
Polymer primary particle dispersion-13 95 parts (212 g: as solid content)
Resin fine particle dispersion-1 5 parts (as solid content)
Colorant fine particle dispersion-1 6.7 parts (as solid content)
0.5 parts of 15% neogen SC aqueous solution (as solids)
[0191]
Using each of the above components, a toner was produced by the following procedure.
The polymer primary particle dispersion and 15% neogen SC aqueous solution were charged into a reactor (volume: 2 liters, double helical blade with baffle), mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution was added dropwise (0.6 parts as a solid content). Thereafter, the temperature was raised to 53 ° C. over 20 minutes with stirring, and the temperature was slowly raised to 65 ° C. over 90 minutes and held for 1 hour. A resin fine particle dispersion and an aqueous aluminum sulfate solution (0.07 part as solid content) were added in this order, and the temperature was raised to 67 ° C. over 10 minutes and held for 10 minutes. A 15% neogen SC aqueous solution (3 parts as a solid content) and 0.6 times the total amount of demineralized warm water were added and the temperature was raised to 95 ° C. over 30 minutes and held for 2 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (Toner-13).
[0192]
To 100 parts of this toner, 0.6 parts of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-13).
Toner Evaluation-13
The volume average particle diameter of the developing toner measured by a Coulter counter was 8.2 μm, and the ratio of the volume average particle diameter to the number average particle diameter was 1.17.
The 50% circularity was 0.94.
[0193]
The fixing property of the developing toner 13 was fixed at 160 to 210 ° C. at a fixing speed of 120 mm / S, and fixed at 140 to 200 ° C. at a fixing speed of 30 mm / S.
[Example 14]
(Polymer primary particle dispersion-14)
5.3 parts of 10% sodium dodecylbenzenesulfonate aqueous solution in a reactor (volume: 3 liters, inner diameter: 150 mm) equipped with a stirrer (two blades), heating / cooling device, concentrating device, and raw material / auxiliary charging device, 309 parts of demineralized water was charged, the temperature was raised to 90 ° C. under a nitrogen stream, and 6.4 parts of a 2% aqueous hydrogen peroxide solution and 6.4 parts of a 2% ascorbic acid aqueous solution were added.
[0194]
Thereafter, a mixture of the following monomers / emulsifier aqueous solution was added over 5 hours from the start of polymerization, and an initiator aqueous solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0195]
[Table 30]
(Monomers)
60 parts of styrene
40 parts butyl acrylate
Acrylic acid 3 parts
(Emulsifier aqueous solution)
2.7 parts of 10% sodium dodecylbenzenesulfonate aqueous solution
1.1 parts of 1% polyoxyethylene nonylphenyl ether aqueous solution
22 parts of demineralized water
(Initiator aqueous solution)
36 parts of 2% hydrogen peroxide solution
36 parts of 2% ascorbic acid aqueous solution
[0196]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion.
Subsequently, 108 parts of the above polymer dispersion were added to a reactor (volume: 3 liters, inner diameter: 150 mm) equipped with a stirrer (two blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device. A 5.3% aqueous solution of sodium dodecylbenzenesulfonate and 311 parts of demineralized water were added, the temperature was raised to 90 ° C. under a nitrogen stream, and 6.4 parts of a 2% aqueous hydrogen peroxide solution, 6.4 parts of a 2% aqueous ascorbic acid solution. Parts were added.
[0197]
Thereafter, the following monomers, an aqueous emulsifier solution and an aqueous initiator solution were added, and emulsion polymerization was performed for 6.5 hours.
[0198]
[Table 31]
(Monomers)
60 parts of styrene
40 parts butyl acrylate
Acrylic acid 3 parts
1.5 parts of bromotrichloromethane
1% 2-mercaptoethanol aqueous solution 3 parts
(Emulsifier aqueous solution)
2.7 parts of 10% sodium dodecylbenzenesulfonate aqueous solution
1.1 parts of 1% polyoxyethylene nonylphenyl ether aqueous solution
22 parts of demineralized water
(Initiator aqueous solution)
36 parts of 2% hydrogen peroxide solution
36 parts of 2% ascorbic acid aqueous solution
[0199]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion (polymer primary particle dispersion-15). The polymer had a THF-soluble component weight-average molecular weight of 64,000, an average particle size measured by UPA of 268 nm, and Tg of 39 ° C.
(Resin fine particle dispersion-14A)
A reactor equipped with a stirrer (three receding blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device (volume: 2 liters, inner diameter: 120 mm): 35 parts of wax dispersion-13, 328 parts of demineralized water Was heated to 90 ° C. under a nitrogen stream, and 6.4 parts of 2% aqueous hydrogen peroxide solution and 6.4 parts of 2% ascorbic acid aqueous solution were added.
Thereafter, a mixture of the following monomers / emulsifier aqueous solution was added over 5 hours from the start of polymerization, and an initiator aqueous solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0200]
[Table 32]
(Monomers)
75 parts of styrene
25 parts butyl acrylate
Acrylic acid 3 parts
Bromotrichloromethane 0.5 parts
1% 2-mercaptoethanol 1 part
(Emulsifier aqueous solution)
2.7 parts of 10% sodium dodecylbenzenesulfonate aqueous solution
1.1 parts of 1% polyoxyethylene nonylphenyl ether aqueous solution
22 parts of demineralized water
(Initiator aqueous solution)
36 parts of 2% hydrogen peroxide solution
36 parts of 2% ascorbic acid aqueous solution
[0201]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The weight-average molecular weight of the THF soluble part of the polymer was 58,000, the average particle size measured by UPA was 244 nm, and Tg was unclear.
(Resin fine particle dispersion-14B)
2 parts of fatty acid sodium (NS soap, manufactured by Kao) in a reactor (volume: 2 liters, inner diameter: 150 mm) equipped with a stirrer (three receding blades), heating / cooling device, concentrating device, and raw material / auxiliary charging device Then, 374 parts of demineralized water was charged, the temperature was raised to 75 ° C. under a nitrogen stream, and 20 parts of a 1% potassium persulfate aqueous solution was added.
Then, the following monomers were added over 3 hours and 20 minutes from the start of polymerization, an emulsifier aqueous solution and an aqueous initiator solution were added on the way, and the mixture was further maintained for 1 hour and 40 minutes.
[0202]
[Table 33]
(Monomers)
90 parts of styrene
10 parts butyl acrylate
Bromotrichloromethane 0.2 parts
(Emulsifier aqueous solution)
10 parts of 10% NS soap solution
(Initiator aqueous solution)
10 parts of 1% aqueous potassium persulfate solution
[0203]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component weight-average molecular weight of 131,000, an average particle size measured by UPA of 25 nm, and Tg of 84 ° C.
[0204]
(Manufacture of developing toner-14)
[Table 34]
Polymer primary particle dispersion-14 100 parts (as solids)
Resin fine particle dispersion-14A 21.3 parts (as solid content)
Resin fine particle dispersion-14B 10.7 parts (as solid content)
Colorant fine particle dispersion-1 6.7 parts (as solid content)
Charge control agent fine particle dispersion-1 0.6 part (as solid content)
[0205]
Using each of the above components, a toner was produced by the following procedure.
The polymer primary particle dispersion and the colorant fine particle dispersion were charged into the reactor and mixed uniformly. While stirring the obtained mixed dispersion, a 10% aqueous sodium chloride solution was added (12 parts as a solid content) and held for 30 minutes. Thereafter, the temperature was raised while stirring, and when the particle size reached 7 μm, the pH was adjusted to 6.5, the temperature was further raised to 95 ° C. and held for 8 hours, and then cooled. The coarse powder was removed by filtration and charged into a reactor (flat blade stirring blade). The pH was adjusted to 2.0 while stirring at room temperature, the resin fine particle dispersion 14A was added, the temperature was raised to 40 ° C., and 5 The time was maintained, then the temperature was raised to 62 ° C., maintained for 3 hours, and then cooled. Add resin fine particle dispersion 14B, raise to 40 ° C. and hold for 1 hour, add charge control agent fine particle dispersion, hold at 40 ° C. for 2 hours, then raise to 64 ° C. and hold for 4 hours And then cooled. Thereafter, the resultant was filtered, washed with water, and dried to obtain a toner (toner-14).
[0206]
To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-14).
(Evaluation of toner-14)
The developing toner-14 was fixed at 150 to 170 ° C. at a fixing speed of 120 mm / S. The charge amount of Toner-14 was −6 μC / g, and the charge amount of Toner 15 for Development was −11 μC / g.
[Reference Production Example] (copolymerized wax fine particles and polymer primary particles)
(Wax dispersion-15)
Mixture of 6:33 parts of demineralized water, ester mixture mainly composed of behenyl behenate (Unistar M-2222SL, manufactured by Nippon Oil & Fats) and ester mixture mainly composed of stearyl stearate (Unistar M9676, manufactured by Nippon Oil & Fats) 7: 3 30 1.67 parts of sodium dodecylbenzenesulfonate (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 66%) were mixed and emulsified by applying high-pressure shearing at 90 ° C. to obtain a dispersion of ester wax fine particles. . The average particle diameter of the ester wax fine particles measured by UPA was 290 nm.
(Polymer primary particle dispersion-15)
A reactor equipped with a stirrer (full zone blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device (volume 3 L, inner diameter 150 mm) was charged with 2 parts of 15% Neogen SC aqueous solution and 378 parts of demineralized water, The temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added.
Thereafter, a mixture of the following monomers / emulsifier aqueous solution was added over 5 hours from the start of polymerization, and an initiator aqueous solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[0207]
[Table 35]
(Monomers)
79 parts of styrene
21 parts butyl acrylate
Acrylic acid 3 parts
Bromotrichloromethane 0.45 parts
2-mercaptoethanol 0.01 parts
0.9 parts of hexanediol diacrylate
(Emulsifier aqueous solution)
1 part of 15% Neogen SC aqueous solution
25 parts of demineralized water
(Initiator aqueous solution)
9 parts of 8% hydrogen peroxide solution
9 parts of 8% ascorbic acid aqueous solution
[0208]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The polymer had a THF-soluble component weight-average molecular weight of 158,000, an average particle size measured by UPA of 200 nm, and Tg of 71 ° C.
(Manufacture of developing toner-15)
[0209]
[Table 36]
Polymer primary particle dispersion-15 105 parts (as solids)
Resin fine particle dispersion-1 5 parts (as solid content)
Colorant fine particle dispersion-1 6.7 parts (as solid content)
Charge control agent fine particle dispersion-1 2 parts (as solid content)
Wax dispersion-15 8.8 parts (as solids)
0.5 parts of 15% neogen SC aqueous solution (as solids)
Using each of the above components, a toner was produced by the following procedure.
[0210]
Charge the polymer primary particle dispersion and 15% Neogen SC aqueous solution into a reactor (capacity 1 liter, anchor blade with baffle) and mix uniformly, then add wax dispersion and colorant fine particle dispersion and mix uniformly. did. While stirring the obtained mixed dispersion, an aqueous aluminum sulfate solution was added dropwise (0.6 parts as a solid content). Thereafter, while stirring, the temperature was raised to 55 ° C. over 15 minutes and held for 1 hour, and further heated to 65 ° C. over 90 minutes and held for 5 minutes. A charge control agent fine particle dispersion, a resin fine particle dispersion, and an aluminum sulfate aqueous solution (0.07 parts as a solid content) were added in this order, and the temperature was raised to 67 ° C. over 15 minutes and held for 1 hour. After adding 15% Neogen SC aqueous solution (3 parts as solid content), the temperature was raised to 95 ° C. over 20 minutes and held for 4 hours. Thereafter, it was cooled, filtered, washed with water, and dried to obtain a toner.
[0211]
The volume average particle diameter of the toner by Coulter counter is 7.3 μm, the ratio of the volume particle diameter of 5 μm or less is 3.0%, the ratio of 15 μm or more is 1.2%, and the ratio of the volume average particle diameter to the number average particle diameter is 1.14. The 50% circularity was 0.95.
This toner was cut into a thickness of 80 nm, a TEM photograph was taken and analyzed in the same manner as the toner obtained in Example 1. As a result, the number average particle diameter of the wax fine particles observed in the toner cross section was 201 nm. The half width of the diameter was 100 nm.
[0212]
A state of the TEM photograph is shown in FIG. Moreover, the graph showing the distribution of the number average particle diameter of the wax fine particles is shown in FIGS. 6 and 7 for the particle diameter range of 0 to 1.5 μm and the particle diameter range of 0 to 0.5 μm, respectively.
[0213]
Production methods of the wax dispersion, polymer primary particle dispersion, resin fine particle dispersion, colorant fine particle dispersion, and charge control agent fine particle dispersion used in Example 16 to Comparative Example 21 are described below.
(Preparation of wax dispersion)
As 100 parts of the wax dispersion, 30 parts of behenyl behenate was emulsified by applying high-pressure shear in the presence of 1.67 parts of sodium N-dodecylbenzenesulfonate to obtain an ester wax dispersion. The resulting dispersion had a solid content concentration of 30%, and the average particle size measured by UPA was 220 nm (this is referred to as wax dispersion A).
[0214]
As 100 parts of the wax dispersion, 30 parts of behenyl behenate was emulsified by high-pressure shearing in the presence of 0.23 part of sodium N-dodecylbenzenesulfonate to obtain an ester wax dispersion. The resulting dispersion had a solid content concentration of 30%, and the average particle size measured by UPA was 400 nm (this is designated as wax dispersion B).
[0215]
(Preparation of polymer primary particle dispersion)
35 parts of wax dispersion A and 400 parts of demineralized water were charged into a glass reactor equipped with a stirrer, heating / cooling device, concentrating device, and each raw material / auxiliary charging device, and the temperature was raised to 90 ° C. under a nitrogen stream. .
Thereafter, the following monomers, an aqueous emulsifier solution and an initiator were added, and emulsion polymerization was performed for 6.5 hours.
[0216]
[Table 37]

[0217]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The resulting polymer dispersion had a weight average molecular weight of 98,000, an average particle size measured by UPA of 190 nm, and Tg of 57 ° C. (This is referred to as polymer primary particle dispersion A).
[0218]
A milky white polymer dispersion was obtained in the same manner as the polymer primary particle dispersion A except that the wax dispersion B was used in place of the wax dispersion A and the monomers were changed as follows. The obtained polymer dispersion had a weight average molecular weight of 71,000, an average particle size measured by UPA of 179 nm, and Tg of 48 ° C. (this is referred to as polymer primary particle dispersion B).
[0219]
[Table 38]
(Monomers)
64 parts of styrene
36 parts butyl acrylate
Acrylic acid 3 parts
1 part of divinylbenzene (DVB)
0.5 parts of trichlorobromomethane
[0220]
A milky white polymer dispersion was obtained in the same manner as the polymer primary particle dispersion B except that 67 parts of styrene and 33 parts of butyl acrylate were changed. The obtained polymer dispersion had a weight average molecular weight of 52,000, an average particle size measured by UPA of 205 nm, and Tg of 51 ° C. (this is referred to as polymer primary particle dispersion C).
[0221]
A milky white polymer dispersion was obtained in the same manner as the polymer primary particle dispersion B except that 72 parts of styrene and 28 parts of butyl acrylate were changed. The obtained polymer dispersion had a weight average molecular weight of 44,000, an average particle size measured by UPA of 158 nm, and Tg of 55 ° C. (this is referred to as polymer primary particle dispersion D).
[0222]
(Preparation of resin fine particle dispersion)
A glass reactor equipped with a stirrer, a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device was charged with 4.3 parts of a 10% S-DBS aqueous solution and 400 parts of demineralized water, and 90 ° C. under a nitrogen stream The temperature was raised to.
Thereafter, the following monomers, an aqueous emulsifier solution and an initiator were added, and emulsion polymerization was performed for 6.5 hours.
[0223]
[Table 39]
(Monomers)
79 parts of styrene
21 parts butyl acrylate
Acrylic acid 3 parts
0.5 parts of trichlorobromomethane
DVB 0.4 part
(Emulsifier aqueous solution)
10% S-DBS aqueous solution 2.2 parts
25 parts of demineralized water
(Initiator)
8% aqueous hydrogen peroxide solution 10.6 parts
10.6 parts of 8% ascorbic acid aqueous solution
[0224]
After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The obtained polymer dispersion had a weight average molecular weight of 110,000, an average particle size measured by UPA of 120 nm, and Tg of 86 ° C. (this is referred to as resin fine particle dispersion A).
[0225]
A milky white polymer dispersion was obtained in the same manner as the resin fine particle dispersion A except that DVB was not used. The resulting polymer dispersion had an average particle size measured by UPA of 154 nm and Tg of 65 ° C. (this is referred to as resin fine particle dispersion B).
[0226]
(Preparation of colorant fine particle dispersion)
As 100 parts of the colorant fine particle dispersion, 30 parts of Pigment Blue 15: 3 were dispersed in a sand grinder mill in the presence of 5 parts of polyoxyethylene alkylphenyl ether to obtain a colorant fine particle dispersion. The obtained dispersion had a solid content concentration of 35%, and the average particle size measured by UPA was 150 nm (this is called Colorant Fine Particle Dispersion A).
[0227]
As 100 parts of the colorant fine particle dispersion, 20 parts of Pigment Yellow 74 was dispersed in a sand grinder mill for 6 hours in the presence of 7 parts of polyoxyethylene alkylphenyl ether to obtain a colorant fine particle dispersion. The obtained dispersion had a solid content concentration of 20%, and the average particle size measured by UPA was 300 nm (this is called Colorant Fine Particle Dispersion B).
[0228]
(Preparation of charge control agent fine particle dispersion)
As 100 parts of the charge control agent fine particle dispersion, 20 parts of 4,4′-methylenebis [2- [N- (4-chlorophenyl) amido] -3-hydroxynaphthalene] was added in the presence of 4 parts of alkyl naphthalene sulfonate. Dispersion was performed with a grinder mill to obtain a charge control agent fine particle dispersion. The resulting dispersion had a solid content concentration of 24%, and the average particle size measured by UPA was 200 nm (this is referred to as charge control agent fine particle dispersion A).
[0229]
[Table 40]
[Example 16]
Polymer primary particle dispersion A 90 parts (as solids)
Resin fine particle dispersion A 10 parts (as solid content)
Colorant fine particle dispersion B 6.7 parts (as solid content)
Charge control agent fine particle dispersion A 2 parts (as solid content)
0.5 part of S-DBS aqueous solution (as solid content)
[0230]
The above components were mixed in the following order.
The S-DBS aqueous solution was added to the polymer primary particle dispersion A and mixed uniformly, and then the colorant fine particle dispersion A was added and mixed uniformly.
While stirring the mixed dispersion thus obtained with an anchor blade with a baffle, an aqueous aluminum sulfate solution was added at 30 ° C. (0.6 parts as a solid content). The average particle diameter of the mixed dispersion after addition of the aqueous aluminum sulfate solution was 2 μm. Thereafter, the temperature was raised to 55 ° C. with stirring and held for 1 hour, and further heated to 58 ° C. and held for 1 hour. Thereafter, the charge control agent fine particle dispersion A, the resin fine particle dispersion A, and an aluminum sulfate aqueous solution (0.1 part as solid content) were added in this order. After holding for 1 hour and a half, 10% S-DBS aqueous solution (3 parts as a solid content) was added, and then the temperature was raised to 95 ° C. and kept for 4 hours. Thereafter, the mixture was cooled, filtered with a Kiriyama funnel, washed with water, and freeze-dried to obtain a toner (this toner is referred to as “toner A”).
[0231]
To 100 parts of toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (this is called developing toner A).
The obtained toner A had a volume average particle diameter of 7.6 μm as measured by a Coulter counter. In addition, the ratio of the volume particle diameter of 5 μm or less is 1.5%, the ratio of 15 μm or more is 0%, the ratio of the volume average particle diameter to the number average particle diameter is 1.09, and the particle size distribution is very good. It was.
[0232]
When the fixing property of the developing toner A was evaluated, the toner was fixed at 160 to 220 ° C. at a fixing speed of 120 mm / s and fixed at 140 to 220 ° C. at a fixing speed of 30 mm / s. The charge amount of the toner A measured by ColorPagePresto was −3 μC / g, and the charge amount of the developing toner A was −21 μC / g.
[0233]
[Table 41]
[Example 17]
Polymer primary particle dispersion B 100 parts (as solids)
Resin fine particle dispersion B 21 parts (as solid content)
Colorant fine particle dispersion A 6.7 parts (as solid content)
Charge control agent fine particle dispersion A 0.1 part (as solid content)
[0234]
The above components were mixed in the following order.
The colorant fine particle dispersion A was added to the polymer primary particle dispersion B and mixed uniformly. While stirring the obtained mixed dispersion with an anchor blade, an aqueous NaCl solution was added at 20 ° C. (10 parts as a solid content). Thereafter, the temperature was raised to 45 ° C. with stirring and held for 1 hour, further raised to 95 ° C. and held for 5 hours, and then cooled to obtain toner particles.
[0235]
100 parts of the toner particles were charged and stirred in a glass reactor equipped with a stirrer, a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device. The charge control agent fine particle dispersion A and the resin fine particle dispersion B were added thereto and held at 45 ° C. for 2 hours. Thereafter, the mixture was cooled, filtered with a Kiriyama funnel, washed with water, and freeze-dried to obtain a toner (this toner is referred to as toner B). To 100 parts of toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (this is called developing toner B).
[0236]
Toner B had a volume average particle diameter of 7.1 μm and a ratio of the volume average particle diameter to the number average particle diameter of 1.20.
When the fixing property of the developing toner B was evaluated, it was fixed at 110 to 200 ° C. at a fixing speed of 120 mm / s. The charge amount of the developing toner B measured by Phaser was −20 μC / g.
[0237]
[Example 18]
A toner C and a developing toner C were obtained in the same manner as in Example 17 except that the polymer primary particle dispersion B was changed to the polymer primary particle dispersion C.
Toner C had a volume average particle size of 6.8 μm and a ratio of the volume average particle size to the number average particle size of 1.05.
When the fixing property of the developing toner C was evaluated, it was fixed at 115 to 200 ° C. at a fixing speed of 120 mm / s. The charge amount of the developing toner C measured by Phaser was −19 μC / g.
[0238]
[Example 19]
A toner D and a developing toner D were obtained in the same manner as in Example 17 except that the polymer primary particle dispersion B was changed to the polymer primary particle dispersion D and the resin fine particle dispersion B was changed to 10 parts. .
Toner D had a volume average particle size of 6.3 μm and a ratio of the volume average particle size to the number average particle size of 1.04.
When the fixing property of the developing toner D was evaluated, it was fixed at 120 to 200 ° C. at a fixing speed of 120 mm / s. The charge amount of the developing toner D measured by Phaser was −27 μC / g.
[0239]
[Comparative Example 20]
A toner E and a developing toner E were obtained in the same manner as in Example 16 except that the resin fine particle dispersion A was not added. Toner E had a volume average particle diameter of 7.1 μm.
When the fixing property of the developing toner E was evaluated, it was fixed at 138 to 200 ° C. at a fixing speed of 120 mm / s, and fixed at 112 to 182 ° C. at a fixing speed of 30 mm / s. When the charge amount was measured with ColorPagePresto, Toner E was not negatively charged. The charge amount of the developing toner E was −1 μC / g.
[0240]
[Comparative Example 21]
A toner F and a developing toner F were obtained in the same manner as in Example 19 except that the resin fine particle dispersion A was not used. Toner F had a volume average particle diameter of 6.0 μm and a volume average particle diameter / number average particle diameter of 1.02.
When the fixing property of the developing toner F was evaluated, it was fixed at 120 to 200 ° C. at a fixing speed of 120 mm / s. When the charge amount was measured by Phaser, the developing toner F was not negatively charged.
[0241]
【The invention's effect】
According to the present invention, it is possible to provide a toner excellent in low-temperature fixability and offset resistance. The toner of the present invention has a small particle size and a sharp particle size distribution, and is suitable for high-resolution image formation. In addition, the toner of the present invention has excellent OHP transparency and excellent blocking resistance.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing a state where particle aggregates composed of polymer primary particles containing wax are coated with resin fine particles not containing wax.
FIG. 2 is a schematic view showing a state where resin particles not containing wax are coated after fusing particle aggregates made of polymer primary particles containing wax.
FIG. 3 is a schematic view showing a state where both polymer primary particles and resin fine particles are fused.
4 is a TEM photograph of a cross section of the toner obtained in Example 1. FIG.
FIG. 5 is a TEM photograph of a cross section of a toner obtained in a reference production example.
FIG. 6 is a graph showing the distribution of the number average particle size of wax particles observed in the toner cross section (range of particle size of 0 to 1.5 μm).
FIG. 7 is a graph showing the distribution of the number average particle size of the wax fine particles observed in the toner cross section (particle size range of 0 to 0.5 μm).
[Explanation of symbols]
1 Polymer primary particles containing wax
2 Resin fine particles not containing wax
3 Particles obtained by fusing polymer primary particles
4 Particles obtained by fusing both polymer primary particles and resin fine particles
5 Wax

Claims (30)

  Electrostatic charge image development, wherein the primary polymer particles contain a wax in a toner for electrostatic charge development in which resin fine particles are adhered or fixed to a particle aggregate containing at least polymer primary particles and a colorant. Toner.   The electrostatic charge image developing toner according to claim 1, wherein the resin fine particles contain substantially no wax.   The electrostatic charge image developing toner according to claim 1, wherein the polymer primary particles are obtained by emulsion polymerization using wax fine particles as seeds.   The electrostatic charge image developing toner according to claim 3, wherein the volume average particle size of the wax fine particles which are seeds of the polymer primary particles is 0.01 μm to 3 μm.   The toner for developing an electrostatic charge image according to any one of claims 1 to 4, wherein the primary particle of the polymer has a volume average particle diameter of 0.02 to 3 µm.   6. The electrostatic charge image developing toner according to claim 1, wherein the resin fine particles have a volume average particle size of 0.02 to 3 [mu] m.   7. The electrostatic image developing toner according to claim 1, wherein the polymer primary particles contain a compound having a Bronsted acidic group or a Bronsted basic group as a polymerization unit.   The electrostatic image developing toner according to claim 1, wherein the resin fine particles contain a compound having a Bronsted acidic group or a Bronsted basic group as a polymerization unit.   The wax is contained in an amount of 1 to 40 parts by weight with respect to a total of 100 parts by weight of the resin constituting the polymer primary particles and the resin constituting the resin fine particles. Toner for developing electrostatic images.   The toner for developing an electrostatic charge image according to any one of claims 1 to 9, wherein the primary particle of the polymer has an insoluble content in tetrahydrofuran of 15 to 70% by weight.   The toner for developing an electrostatic charge image according to any one of claims 1 to 10, wherein a ratio of the polyfunctional monomer is 0.005 to 5% by weight in the monomer unit constituting the polymer primary particle.   The toner for developing an electrostatic charge image according to any one of claims 1 to 11, wherein the tetrahydrofuran insoluble content of the resin fine particles is 5 to 70% by weight.   The toner for developing an electrostatic charge image according to any one of claims 1 to 12, wherein a proportion of the polyfunctional monomer is 0.005 to 5% by weight in the monomer unit constituting the resin fine particles.   The electrostatic charge image developing toner according to claim 1, wherein the toner has a volume average particle diameter of 3 to 12 μm.   15. The ratio of the weight of the particle aggregate constituting the toner to the weight of the resin fine particles covering the toner (the weight of the particle aggregate / the weight of the resin fine particles) is 1 to 100. Toner for developing electrostatic images. The toner according to any one of claims 1 to 15 volume average particle diameter of the toner is 4 to 10 [mu] m. The toner according to any one of claims 1 to 16 the melting point of the wax is 30 to 100 ° C.. The toner for developing an electrostatic charge image according to any one of claims 1 to 17 , wherein a content of the wax is 1 to 35 parts by weight with respect to 100 parts by weight of the binder resin. The toner according to any one of claims 1 to 18 colorant contains a compound represented by the following general formula (I).

(In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or a halogen atom, and at least one of R ¹ or R ² is a halogen atom. M is Ba, Sr. , Mn, Ca, or Mg.) The toner according to any one of claims 1 to 18 colorant contains a compound represented by the following general formula (II).

(In general formula (II), A and B represent an aromatic ring which may have a substituent. R ³ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a hydrocarbon having 1 to 5 carbon atoms. Group, an alkoxy group having 1 to 5 carbon atoms, an aminosulfonyl group which may be substituted on the nitrogen atom, or an aminocarbonyl group which may be substituted on the nitrogen atom.) The toner according to claim 19 or 20 the toner is negatively chargeable. The toner for developing an electrostatic charge image according to any one of claims 1 to 21 , wherein the toner has a volume average particle diameter to number average particle diameter ratio (volume average particle diameter / number average particle diameter) of 1 to 1.25. Toner according to any one of claims 1 to 22 50% circularity of the toner is 0.95 (where a circle having the same area as Circularity = particle projected area perimeter / particles Projected image perimeter). The toner for developing an electrostatic charge image according to any one of claims 1 to 23 , wherein the toner has a volume average particle diameter of 7 to 10 µm and a ratio of toner particles having a particle diameter of 5 µm or less is 10 vol% or less. The toner for developing an electrostatic charge image according to any one of claims 1 to 24 , wherein a ratio of toner particles having a particle diameter of 15 µm or more is 5% by volume or less.  A method for producing a toner for developing an electrostatic image in which at least polymer primary particles and colorant primary particles are aggregated to form particle aggregates, and resin fine particles are adhered or fixed to the particle aggregates, wherein the polymer primary particles are waxes. A method for producing a toner for developing an electrostatic charge image, which is obtained by seed emulsion polymerization of a monomer mixture in the presence of fine particles. At least polymer primary particles and colorant primary particles are aggregated to form particle aggregates, and resin fine particles are adhered to the particle aggregates, and then Tg to (Tg + 80) with respect to the glass transition temperature (Tg) of the polymer primary particles. 27. The method for producing a toner for developing an electrostatic charge image according to claim 26 , wherein the particle aggregate and the resin fine particles are fused in a temperature range of ° C. The method of producing an electrostatic charge image developing toner according to claim 26 or 27 resin fine particles are those which do not substantially contain a wax. Are aggregated with at least primary polymer particles colorant primary particles in the particle aggregates, toner according to any one of claims 26 to 28 attached or fixed charge control agent particles to the particle aggregate Manufacturing method. 30. The method for producing a toner for developing an electrostatic charge image according to any one of claims 26 to 29 , wherein the monomer mixture constituting the polymer primary particles contains a compound having a Bronsted acidic group or a Bronsted basic group.

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