JP3890240B2 - Toner production method - Google Patents

Description

【００３７】
測定方法としては、ノニオン型界面活性剤約０．１ｍｇを溶解している水１０ｍｌにトナー約５ｍｇを分散させ分散液を調製し、超音波（２０ｋＨｚ、５０Ｗ）を分散液に３分間照射し、分散液濃度を５０００〜２００００個／μｌとして、前記装置によりトナーの円形度を測定する。
【００３８】
本発明における「平均円形度」とは、表面改質粒子の凹凸の度合を示す指標であり、トナーが完全な球形の場合１．０００を示し、トナー形状が複雑になるほど平均円形度は小さな値となる。
【００３９】
本発明のトナー製造方法によれば、該表面改質工程で得られた粒子の平均円形度は、該表面改質工程に導入された微粉砕品の平均円形度よりも０．０１乃至０．０５大きくすることができる。これは、上述した通り、該表面改質装置の表面改質時間を任意にコントロールすることにより、トナーの表面形状を任意にコントロールすることができるためである。
【００４０】
本発明のトナーの製造方法によれば、表面改質工程において、微粉を除去しながら表面改質を行うため、表面改質装置で得られる表面改質粒子の個数平均径は、該表面改質工程に導入された微粉砕品の個数平均径よりも大きく、さらに、該表面改質工程に導入された微粉砕品の個数平均径をＡとし、該表面改質装置で得られる粒子の個数平均径をＢとした場合に、ＡとＢが下記条件
０２≦Ｂ／Ａ≦２．００
を満足していることが好ましい。
【００４１】
さらに、本発明のトナーの製造方法においては、該表面改質装置内に導入する冷風温度Ｔ１を１０℃以下とすることが好ましい。該表面改質装置内に導入する冷風温度Ｔ１を１０℃以下（より好ましくは５℃以下、さらに好ましくは０℃以下、特に好ましくは−５℃以下）とすることにより、表面改質時に発生する熱によるトナーの表面変質や、機内融着を防止することができる。該表面改質装置内に導入する冷風温度Ｔ１を６℃以上とすると、表面改質時に発生する熱によるトナーの表面変質や、機内融着を起こしやすいので、トナー生産性という点から好ましくない。
【００４２】
さらに、本発明のトナーの製造方法においては、該表面改質装置内は、機内冷却用のジャケットを具備しており、該ジャケットに冷媒（好ましくは冷却水、さらに好ましくはエチレングリコール等の不凍液）を通しながら微粉砕物を表面改質処理することが好ましい。該ジャケットによる機内冷却により、トナー表面改質時における熱によるトナー表面変質や機内融着を防止することができる。
【００４３】
尚、表面改質装置の該ジャケット内に通す冷媒の温度は５℃以下とすることが好ましい。表面改質装置内の該ジャケット内に通す冷媒の温度を５℃以下（より好ましくは０℃以下、さらに好ましくは−５℃以下）とすることにより、表面改質時に発生する熱によるトナーの表面変質や、機内融着を防止することができる。該ジャケット内に導入する冷媒の温度を６℃以上とすると、表面改質時に発生する熱によるトナーの表面変質や、機内融着を起こしやすいので、トナー生産性という点から好ましくない。
【００４４】
さらに、本発明のトナーの製造方法においては、該表面改質装置内の分級ローター後方の温度Ｔ２を６０℃以下とすることが好ましい。該表面改質装置内の分級ローター後方の温度Ｔ２を６０℃以下（好ましくは４０℃以下、さらに好ましくは３０℃以下）とすることにより、表面改質時に発生する熱によるトナーの表面変質や、機内融着を防止することができる。該表面改質装置内の分級ローター後方の温度Ｔ２を６１℃以上とすると、表面改質ゾーンにおいては、それ以上の温度が影響するため、表面改質時に発生する熱によるトナーの表面変質や、機内融着を起こしやすいので、トナー生産性という点から好ましくない。
【００４５】
さらに、本発明のトナーの製造方法においては、該表面改質装置内の分級ローター後方の温度Ｔ２と、該表面改質装置に導入する冷風温度Ｔ１との温度差ΔＴ（Ｔ２−Ｔ１）を８０℃以下とすることが好ましい。該表面改質装置内の分級ローター後方の温度Ｔ２と、該表面改質装置に導入する冷風温度Ｔ１との温度差ΔＴ（Ｔ２−Ｔ１）を８０℃以下（更に好ましくは７０℃以下）とすることにより、表面改質時に発生する熱によるトナーの表面変質や、機内融着を防止することができる。該表面改質装置内の分級ローター後方の温度Ｔ２と、該表面改質装置に導入する冷風温度Ｔ１との温度差ΔＴ（Ｔ２−Ｔ１）を８１℃以上とすると、表面改質ゾーンにおいては、それ以上の温度が影響するため、表面改質時に発生する熱によるトナーの表面変質や、機内融着を起こしやすいので、トナー生産性という点から好ましくない。
【００４６】
さらに、本発明のトナーの製造方法においては、表面改質装置内の該分散ローターとライナーとの間の最小間隔が０．５ｍｍ乃至１５．０ｍｍとすることが好ましく、さらには、２．０ｍｍ乃至１０．０ｍｍとすることが好ましい。また、該分散ローターの回転周速は７５ｍ／ｓｅｃ乃至１５０ｍ／ｓｅｃとすることが好ましく、さらには、８５ｍ／ｓｅｃ乃至１４０ｍ／ｓｅｃとすることが好ましい。さらに、表面改質装置内の該分散ローター上面に設置されている角型のディスク或いは円筒形のピンの上部と、該円筒型のガイドリングの下部との間の最小間隔が２．０ｍｍ乃至５０．０ｍｍとすることが好ましく、さらには、５．０ｍｍ乃至４５．０ｍｍとすることが好ましい。
【００４７】
本発明者が検討した結果、表面改質装置の運転条件を上述の範囲に制御することにより、トナーの表面形状を任意にコントロールでき、良好な現像性、転写性並びにクリーニング性、及び安定した帯電性を有する、長寿命のトナーを得ることができる。
【００４８】
表面改質装置内の該分散ローターと該ライナーとの間の最小間隔を０．５ｍｍ未満とすると、装置自体の負荷が大きくなるのと同時に、表面改質時に過粉砕され熱によるトナーの表面変質や機内融着を起こしやすいのでトナー生産性という点から好ましくない。また、該分散ローターと該ライナーとの間の最小間隔を１５．１ｍｍ以上とすると、表面改質粒子を得るために処理能力を落とさなければならず、こちらもトナー生産性上好ましくない。また、表面改質装置内の該分散ローターの回転周速を７５ｍ／ｓｅｃ未満とすると、所定の円形度を得るためには処理能力を落とさなければならず、トナー生産性上好ましくない。また、該粉砕ローターの回転周速を１４１ｍ／ｓｅｃ以上とすると、装置自体の負荷が大きくなるのと同時に、表面改質時にトナーが過粉砕されると同時に、熱によるトナーの表面変質や機内融着を起こしやすいので、こちらもトナー生産性という点から好ましくない。
【００４９】
また、表面改質装置内の該分散ローター上面に設置されている角型のディスク或いは円筒形のピンの上部と、該円筒型のガイドリングの下部との間の最小間隔が２．０ｍｍ未満とすると、装置自体の負荷が大きくなるのと同時に、ガイドリング３９の内側の第一の空間４１での滞留時間が長くなり、表面改質時に過粉砕され熱によるトナーの表面変質や機内融着を起こしやすいのでトナー生産性という点から好ましくない。また、該分散ローター上面に設置されている角型のディスク或いは円筒形のピンの上部と、該円筒型のガイドリングの下部との間の最小間隔を５０．１ｍｍ以上とすると、表面改質粒子が十分に表面改質されない状態でガイドリング３９の外側の第二の空間４２へ流出するというショートパスを起こす可能性があり、こちらもトナー生産性上好ましくない。
【００５０】
本発明において、該表面改質装置内の分散ローター及びライナーの粉砕面は耐摩耗処理されていることがトナー生産性上好ましい。尚、耐摩耗処理方法は何ら限定されるものではない。また、該表面改質装置内の分散ローター及びライナーの刃形状に関しても、何ら限定されるものではない。
【００５１】
真比重が１．２ｇ／ｃｍ³以下のトナー粒子、所謂フルカラー用のトナー粒子を製造する場合において、真比重が１．２ｇ／ｃｍ³を超える磁性トナーに比較して分級しづらいため収率が劣る傾向にあるが、本発明においては、真比重が１．２ｇ／ｃｍ³以下であるようなトナー粒子フルカラー用のトナー粒子の製造おいても、分散ローターの近傍に分級ローターを内蔵しているため、高い収率を維持することが可能であるため微粉除去分級の点からも好適に適用される。重量平均粒径が７μｍ以下、さらに好ましくは、６μｍ以下の粒径の小さいシャープな粒度分布を有するトナー粒子を製造する際の収率の向上効果が顕著である。
【００５２】
本発明に係る結着樹脂、着色剤及びワックスを含有するトナー粒子の構成素材について説明する。
【００５３】
本発明に用いられる結着樹脂としては、従来より結着樹脂として知られている種々の樹脂化合物を使用することができ、例えば、ビニル系樹脂、フェノール樹脂、天然樹脂変性フェノール樹脂、天然樹脂変性マレイン酸樹脂、アクリル樹脂、メタクリル樹脂、ポリ酢酸ビニル、シリコーン樹脂、ポリエステル樹脂、ポリウレタン、ポリアミド樹脂、フラン樹脂、エポキシ樹脂、キシレン樹脂、ポリビニルブチラール、テルペン樹脂、クマロインデン樹脂、石油系樹脂等が挙げられる。中でもビニル系樹脂とポリエステル系樹脂が帯電性や定着性の点で好ましい。
【００５４】
ビニル系樹脂としては、例えばスチレン；ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチレンスチレン、ｐ−メトキシスチレン、ｐ−フェニルスチレン、ｐ−クロルスチレン、３，４−ジクロルスチレン、ｐ−エチルスチレン、２，４−ジメチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−デシルスチレン、ｐ−ｎ−ドデシルスチレンの如きスチレン誘導体；エチレン、プロピレン、ブチレン、イソブチレンの如きエチレン不飽和モノオレフィン類；ブタジエンの如き不飽和ポリエン類；塩化ビニル、塩化ビニリデン、臭化ビニル、弗化ビニルの如きハロゲン化ビニル類；酢酸ビニル、プロピオン酸ビニル、ベンゾエ酸ビニルの如きビニルエステル類；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸ｎ−オクチル、メタクリル酸ドデシル、メタクリル酸２−エチルヘキシル、メタクリル酸ステアリル、メタクリル酸フェニル、メタクリル酸ジメチルアミノエチル、メタクリル酸ジエチルアミノエチルの如きα−メチレン脂肪族モノカルボン酸エステル類；アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸プロピル、アクリル酸ｎ−オクチル、アクリル酸ドデシル、アクリル酸２−エチルヘキシル、アクリル酸ステアリル、アクリル酸２−クロルエチル、アクリル酸フェニルの如きアクリル酸エステル類；ビニルメチルエーテル、ビニルエチルエーテル、ビニルイソブチルエーテルの如きビニルエーテル類；ビニルメチルケトン、ビニルヘキシルケトン、メチルイソプロペニルケトンの如きビニルケトン類；Ｎ−ビニルピロール、Ｎ−ビニルカルバゾール、Ｎ−ビニルインドール、Ｎ−ビニルピロリドンの如きＮ−ビニル化合物；ビニルナフタリン類：アクリロニトリル、メタクリロニトリル、アクリルアミドの如きアクリル酸またはメタクリル酸誘導体；α，β−不飽和酸のエステル、二塩基酸のジエステル類；アクリル酸、メタクリル酸、α−エチルアクリル酸、クロトン酸、ケイヒ酸、ビニル酢酸、イソクロトン酸、アンゲリカ酸等のアクリル酸及びそのα−またはβ−アルキル誘導体；フマル酸、マレイン酸、シトラコン酸、アルケニルコハク酸、イタコン酸、メサコン酸、ジメチルマレイン酸、ジメチルフマル酸等の不飽和ジカルボン酸及びそのモノエステル誘導体または無水物等のビニル系モノマーを用いた重合体が挙げられる。
【００５５】
上記ビニル系樹脂では、前述したようなビニル系モノマーが単独または二つ以上で用いられる。これらの中でもスチレン系共重合体、スチレン−アクリル系共重合体となるようなモノマーの組合せが好ましい。
【００５６】
また、本発明に用いられる結着樹脂は、必要に応じて以下に例示するような架橋性モノマーで架橋された重合体または共重合体であってもよい。
【００５７】
前記架橋性モノマーとしては、架橋可能な二以上の不飽和結合を有するモノマーを用いることができる。このような架橋性モノマーとしては、以下に示すような種々のモノマーが従来より知られており、本発明のトナーに好適に用いることができる。
【００５８】
前記架橋性モノマーには、芳香族ジビニル化合物として例えば、ジビニルベンゼン、ジビニルナフタレンが挙げられ；アルキル鎖で結ばれたジアクリレート化合物として例えば、エチレングリコールジアクリレート、１，３−ブチレングリコールジアクリレート、１，４−ブタンジオールジアクリレート、１，５−ペンタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられ；エーテル結合を含むアルキル鎖で結ばれたジアクリレート化合物類としては、例えば、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコール＃４００ジアクリレート、ポリエチレングリコール＃６００ジアクリレート、ジプロピレングリコールジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられ；芳香族基及びエーテル結合を含む鎖で結ばれたジアクリレート化合物類として例えば、ポリオキシエチレン（２）−２，２−ビス（４−ヒドロキシフェニル）プロパンジアクリレート、ポリオキシエチレン（４）−２，２−ビス（４−ヒドロキシフェニル）プロバンジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられ；ポリエステル型ジアクリレート類として例えば、商品名ＭＡＮＤＡ（日本化薬）等が挙げられる。
【００５９】
多官能の架橋剤としては、ペンタエリスリトールトリアクリレート、トリメチロールエタントリアクリレート、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラアクリレート、オリゴエステルアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたもの；トリアリルシアヌレート、トリアリルトリメリテート等が挙げられる。
【００６０】
本発明に用いられる結着樹脂としては、以下に示すポリエステル樹脂も好ましい。ポリエステル樹脂は、全成分中４５〜５５ｍｏｌ％がアルコール成分であり、５５〜４５ｍｏｌ％が酸成分であることが好ましい。
【００６１】
アルコール成分としては、エチレングリコール、プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、２，３−ブタンジオール、ジエチレングリコール、トリエチレングリコール、１，５−ペンタンジオール、１，６−へキサンジオール、ネオペンチルグリコール、２−エチル−１，３−ヘキサンジオール、水素化ビスフェノールＡ、下記（Ｂ）式で表されるビスフェノール誘導体；
【００６２】
【化１】

（式中、Ｒはエチレンまたはプロピレン基を示し、ｘ及びｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。）
【００６３】
（Ｃ）式で示されるジオール類；
【００６４】
【化２】

【００６５】
またはグリセリン、ソルビット、ソルビタン等の多価アルコール類等が挙げられる。
【００６６】
また、酸成分としてはカルボン酸が好ましくは例示することができ、二価のカルボン酸としてはフタル酸、テレフタル酸、イソフタル酸、無水フタル酸の如きベンゼンジカルボン酸類またはその無水物；コハク酸、アジピン酸、セバシン酸、アゼライン酸の如きアルキルジカルボン酸類またはその無水物；フマル酸、マレイン酸、シトラコン酸、イタコン酸の如き不飽和ジカルボン酸またはその無水物等が挙げられ、また、３価以上のカルボン酸としてはトリメリット酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸やその無水物等が挙げられる。
【００６７】
特に好ましいポリエステル樹脂のアルコール成分としては、前記（Ｂ）式で示されるビスフェノール誘導体であり、酸成分としては、フタル酸、テレフタル酸、イソフタル酸またはその無水物、コハク酸、ｎ−ドデセニルコハク酸またはその無水物、フマル酸、マレイン酸、無水マレイン酸の如きジカルボン酸類；トリメリット酸またはその無水物のトリカルボン酸類が挙げられる。これらの酸成分及びアルコール成分から得られたポリエステル樹脂を結着樹脂として使用した熱ローラ定着用トナーとして定着性が良好で、耐オフセット性に優れているからである。
【００６８】
本発明に係るトナーに用いられる着色剤は、黒色着色剤としては、カーボンブラック，磁性体，以下に示すイエロー着色剤、マゼンタ着色剤及びシアン着色剤の如き有彩色着色剤によって黒色に調色されるように組み合わせたものが利用される。
【００６９】
イエロー着色剤としては、縮合アゾ化合物，イソインドリノン化合物，アンスラキノン化合物，アゾ金属錯体，メチン化合物，アリルアミド化合物に代表される化合物が用いられる。具体的には、Ｃ．Ｉ．ピグメントイエロー１２、１３、１４、１５、１７、６２、７４、８３、９３、９４、９５、９７、１０９、１１０、１１１、１２０、１２７、１２８、１２９、１４７、１６８、１７４、１７６、１８０、１８１、１９１が好適に用いられる。
【００７０】
マゼンタ着色剤としては、縮合アゾ化合物，ジケトピロロピロール化合物，アンスラキノン，キナクリドン化合物，塩基染料レーキ化合物，ナフトール化合物，ベンズイミダゾロン化合物，チオインジゴ化合物，ペリレン化合物が用いられる。具体的には、Ｃ．Ｉ．ピグメントレッド２、３、５、６、７、２３、４８：２、４８：３、４８：４、５７：１、８１：１、１４４、１４６、１６６、１６９、１７７、１８４、１８５、２０２、２０６、２２０、２２１、２５４が特に好ましい。
【００７１】
シアン着色剤としては、銅フタロシアニン化合物及びその誘導体，アンスラキノン化合物，塩基染料レーキ化合物が利用できる。具体的には、Ｃ．Ｉ．ピグメントブルー１、７、１５、１５：１、１５：２、１５：３、１５：４、６０、６２、６６等が特に好適に利用できる。
【００７２】
これらの着色剤は、単独又は混合しさらには固溶体の状態で用いることができる。本発明において、着色剤は、色相角，彩度，明度，耐候性，ＯＨＰ透明性，トナー中への分散性を考慮して選択される。これらの有彩色着色剤は、結着樹脂１００質量部に対し１〜２０質量部トナー中に含有される。磁性トナーとして、磁性体を用いる場合は、結着樹脂１００質量部に対し６０〜２００質量部トナー中に含有される。
【００７３】
本発明に係るトナーにおいては、定着時の定着部材からの離型性の向上、定着性の向上の点から次のようなワックス類をトナー中に含有させる。パラフィンワックス及びその誘導体、マイクロクリスタリンワックス及びその誘導体、フィッシャートロプシュワックス及びその誘導体、ポリオレフィンワックス及びその誘導体、カルナバワックス及びその誘導体などで、誘導体には酸化物や、ビニル系モノマーとのブロック共重合物、グラフト変性物を含む。その他、アルコール、脂肪酸、酸アミド、エステル、ケトン、硬化ヒマシ油及びその誘導体、植物系ワックス、動物性ワックス、鉱物系ワックス、ペトロラクタム等も利用できる。
【００７４】
本発明に係るトナーには荷電制御剤をトナー粒子に配合（内添）、またはトナー粒子と混合（外添）して用いることが好ましい。荷電制御剤によって、現像システムに応じた最適の荷電量コントロールが可能となり、特に本発明のトナーにおいては、粒度分布と荷電量とのバランスをさらに安定したものとすることが可能である。トナーを負荷電性に制御するための負荷電制御剤としては、下記物質がある。
【００７５】
例えば有機金属錯体、キレート化合物が有効であり、モノアゾ金属錯体、アセチルアセトン金属錯体、芳香族ハイドロキシカルボン酸金属錯体、芳香族ジカルボン酸金属錯体がある。他には、芳香族ハイドロキシカルボン酸、芳香族モノカルボン酸及び芳香族ポリカルボン酸及びその金属塩、無水物、エステル類、ビスフェノールの如きフェノール誘導体類がある。
【００７６】
トナーを正荷電性に制御するための正荷電制御剤として下記物質がある。
【００７７】
例えば、ニグロシン及び脂肪酸金属塩等による変性物；トリブチルベンジルアンモニウム−１−ヒドロキシ−４−ナフトスルフォン酸塩、テトラブチルアンモニウムテトラフルオロボレートの如き四級アンモニウム塩、及びこれらの類似体であるホスホニウム塩の如きオニウム塩及びこれらのレーキ顔料；トリフェニルメタン染料及びこれらのレーキ顔料（レーキ化剤としては、燐タングステン酸、燐モリブデン酸、燐タングステンモリブデン酸、タンニン酸、ラウリン酸、没食子酸、フェリシアン化物、フェロシアン化物等）；高級脂肪酸の金属塩；ジブチルスズオキサイド、ジオクチルスズオキサイド、ジシクロヘキシルスズオキサイドの如きジオルガノスズオキサイド；ジブチルスズボレート、ジオクチルスズボレート、ジシクロヘキシルスズボレートの如きジオルガノスズボレート類；がある。
【００７８】
これらの荷電制御剤は、単独あるいは２種類以上組み合わせて用いることができる。
【００７９】
上述した荷電制御剤は微粒子状として用いることが好ましく、この場合これらの荷電制御剤の個数平均粒径は４μｍ以下さらには３μｍ以下が特に好ましい。これらの荷電制御剤をトナーに内添する場合は、結着樹脂１００質量部に対して０．１〜２０質量部、特に０．２〜１０質量部トナーに含有されることが好ましい。
【００８０】
本発明に係るトナー粒子を製造するには、例えば、結着樹脂、ワックス、金属塩ないし金属錯体、着色剤としての顔料または染料、磁性体、必要に応じて荷電制御剤、その他の添加剤等をヘンシェルミキサー、ボールミル等の混合器により十分混合してから加熱ロール、ニーダー、エクストルーダーの如き熱混練機を用いて溶融混練して樹脂類をお互いに相溶せしめた中に金属化合物、顔料、染料、磁性体を分散又は溶解せしめ、冷却固化し、固化物を粗粉砕した後、本発明の微粉砕・表面処理方法により、所望の粒径のトナー粒子を得ることができる。この際、所定の粒径以上の粒子が存在する場合には、微粉砕工程の後、または表面処理工程の後に、所定の粒径以上の粒子を取り除くために、分級または、篩分けを行ってもよい。さらに、流動性、転写性等の向上のために該トナー粒子に無機微粉末等の外添剤を外添混合し、トナーとして用いられる。
【００８１】
トナーの粒度分布は、種々の方法によって測定できるが、本発明においては、次の測定装置を用いて行った。
【００８２】
すなわち、測定装置としては、コールターカウンターＴＡ−ＩＩ型あるいはコールターマルチサイザーＩＩ（コールター社製）を用いた。電解液は１級塩化ナトリウムを用いて約１％ＮａＣｌ水溶液を調製する。例えば、ＩＳＯＴＯＮ Ｒ−ＩＩ（コールターサイエンティフィックジャパン社製）が使用できる。測定法としては前記電解液水溶液１００〜１５０ｍｌ中に分散剤として界面活性剤、好ましくはアルキルベンゼンスルホン酸塩を、０．１〜５ｍｌ加え、さらに測定試料を２〜２０ｍｇ加える。試料を懸濁した電解液は超音波分散機で約１〜３分間分散処理を行ない、前記測定装置により、アパチャーとして１００μｍアパチャーを用い、トナーの体積，個数を測定して体積分布と個数分布とを算出した。それから、本発明に係る体積分布から求める重量基準の重量平均粒径を求めた。
【００８３】
【実施例】
以下、トナーの具体的な製造方法、実施例及び比較例をもって本発明を具体的に説明する。
【００８４】
＜実施例１＞
・不飽和ポリエステル樹脂 １００質量部
（ポリオキシプロピレン（２，２）−２，２ビス（４−ヒドロキシフェニル）プロパン／ポリオキシエチレン（２，２）−２，２ビス（４−ヒドロキシフェニル）プロパン／テレフタル酸／無水トリメリット酸／フマル酸からなる不飽和ポリエステル樹脂）
・銅フタロシアニン顔料 ６質量部
（Ｃ．Ｉ．ピグメンブルー１５：３）
・パラフィンワックス ５質量部
（最大吸熱ピーク７３℃）
・荷電制御剤（サリチル酸金属錯体） ２質量部
上記の処方の材料をヘンシェルミキサー（ＦＭ−７５型、三井三池化工機（株）製）でよく混合した後、温度１１０℃に設定した二軸混練機（ＰＣＭ−３０型、池貝鉄工（株）製）にて混練した。得られた混練物を冷却し、ハンマーミルにて１ｍｍ以下に粗粉砕し、トナー製造用の粗砕物を得た。尚、トナー組成物の真比重は、１．１ｇ／ｃｍ³であった。
【００８５】
得られたトナー原料粗砕物を、図１で示した高圧気体を用いた衝突式気流粉砕機（高圧気体圧力：０．６ＭＰａ、流量：２７Ｎｍ³／ｍｉｎ）と、図７で示した気流分級機ターボプレックス（３５０−ＡＴＰ型：ホソカワミクロン（株）製）を図３のように閉回路を組んだ微粉砕装置を用いて粉砕した。得られた微粉砕物は、重量平均径４．８μｍ、個数平均径３．６μｍ（粒径３．１７μｍ以下の粒子を４３個数％含有し、粒径８．００μｍ以上の粒子を０．０体積％含有）であり、平均円形度は０．９３６であった。
【００８６】
次に、得られた微粉砕物を図８及び図９に示したような表面改質装置を用い、微粉砕物を毎回１．３ｋｇ投入し、分級ローター回転数７３００ｒｐｍで微粒子を除去しながら、分散ローター回転数５８００ｒｐｍ（回転周速を１３０ｍ／ｓｅｃ）で６０秒間表面処理を行った（原料供給口３より微粉砕物を投入終了後、６０秒間処理後、排出弁８を開けて処理品として取り出した）。その際、本実施例においては、分散ローター上部に角型のディスクを１０個設置し、ガイドリングと分散ローター上角型ディスクの間隔を３０ｍｍ、分散ローターとライナーとの間隔を５ｍｍとした。またブロワー風量を１４ｍ³／ｍｉｎ、ジャケットに通す冷媒の温度及び冷風温度Ｔ１を−２０℃とした。
【００８７】
この状態で繰り返し、２０分間運転した結果、分級ローター後方の温度Ｔ２は２７℃で安定した。従って、ΔＴ（Ｔ２−Ｔ１）は４７℃であった。
【００８８】
処理後、重量平均径５．２μｍ、個数平均径４．９μｍ（粒径３．１７μｍ以下の粒子を１２個数％含有し、粒径８．００μｍ以上の粒子を０．０体積％含有）、平均円形度は０．９５３のトナー粒子を分級収率８５％で得た（表面処理工程に導入された微粉砕品の個数平均径をＡとし、表面処理装置で得られる粒子の個数平均径をＢとした場合のＢ／Ａは、１．３６）。また、分級ローター及び分散ローターを確認したところ、トナー原材料の融着物は見られなかった。
【００８９】
さらに、網面固定式風力篩ハイボルター（ＮＲ−３００型、新東京機械（株）製：金網の裏にエアーブラシを装着）を用い、これに直径３０ｃｍ、目開き２９μｍ、ワイヤーの平均径が３０μｍの金網を設置し、該トナー粉体を風量５Ｎｍ³／ｍｉｎの気流に乗せて供給し、粗粒を分離し、トナー粒子を得た。粒径１２．７μｍ以上の粒子は、０．１体積％未満であった。また、分離した粗粒は、篩を通過させたトナー粒子の約０．２％であった。
【００９０】
得られたトナー粒子１００質量部に対して、ＢＥＴ法による比表面積が２００ｍ²／ｇである疎水性シリカを１．８質量部外添混合し、トナーを得た。このトナー５質量部に対し、アクリルコートされたフェライトキャリア９５質量部を混合し、現像剤とした。
【００９１】
この現像剤を用いて、キヤノン製フルカラー複写機ＣＬＣ１０００改造機（定着ユニットのオイル塗布機構を取り外した）を用いて常温常湿（２３℃，６０％ＲＨ）下で画出し評価を行ったところ、１０，０００枚耐久においても、初期と耐久後の画像濃度に変化がなく、カブリのない高画質の画像が得られた。さらに両面画像を形成させたが、転写材の表裏面共にオフセットの発生は認められなかった。また、ＯＨＰシートへの画像形成を行ったところ、透明性の良好な画像が得られた。ここで、感光体から転写材（坪量１９９ｇ／ｍ²紙）への転写効率は９３％とかなり高い転写効率を示した。
【００９２】
さらに、高温高湿（３２．５℃，８５％ＲＨ）下においても、同様の画出し評価（５，０００枚耐久）を行ったが、良好な画像が得られた。
【００９３】
＜実施例２＞
実施例１と同様のトナー原料粗砕物を用いて、実施例１と同様の微粉砕装置を用い、微粉砕条件を変更し、微粉砕を行った。得られた微粉砕物の粒径は、重量平均径５．２μｍ、個数平均径４．１μｍ（粒径３．１７μｍ以下の粒子を３７個数％含有し、粒径８．００μｍ以上の粒子を０．４体積％含有する）、平均円形度は０．９３５であった。次に、得られた微粉砕物を実施例１と同様の表面改質装置を用い、同様に微粒子を除去しながら、６０秒間表面処理を行った。
【００９４】
表面改質処理を繰り返し２０分間運転した結果、分級ローター後方の温度Ｔ２は２８℃で安定した。従って、ΔＴ（Ｔ２−Ｔ１）は４８℃であった。
【００９５】
処理後、重量平均径５．２μｍ、個数平均径５．０μｍ（粒径３．１７μｍ以下の粒子を９個数％含有し、粒径８．００μｍ以上の粒子を０．５体積％含有、Ｂ／Ａは、１．２２）、平均円形度は０．９５２のトナー粒子を分級収率８１％で得た。分級ローター及び分散ローターを確認したところ、トナー原材料の融着物は見られなかった。
【００９６】
さらに、同様の網面固定式風力篩ハイボルターを用い、粗粒を分離し、粒径１２．７μｍ以上の粒子が０．１体積％未満のトナー粒子を得た。また、分離した粗粒は、篩を通過させたトナー粒子の約０．２％であった。
【００９７】
得られたトナー粒子に実施例１と同様に疎水性シリカを外添混合しトナーとし、さらにアクリルコートされたフェライトキャリアを混合し、現像剤とした。
【００９８】
この現像剤を用いて、実施例１と同様にキヤノン製フルカラー複写機ＣＬＣ１０００改造機で画出し評価を行ったところ、実施例１と同様に良好な画像が得られた。また、感光体から転写材（坪量１９９ｇ／ｍ²紙）への転写効率は９１％であった。
【００９９】
＜実施例３＞
実施例１と同様のトナー原料粗砕物を用いて、表面改質装置において、表面改質処理時間を４５秒間とした以外は、実施例２と同様に、微粉砕及び、表面改質処理を行った。
【０１００】
表面改質処理を繰り返し２０分間運転した結果、分級ローター後方の温度Ｔ２は２５℃で安定した。従って、ΔＴ（Ｔ２−Ｔ１）は４５℃であった。
【０１０１】
処理後、重量平均径５．２μｍ、個数平均径４．９μｍ（粒径３．１７μｍ以下の粒子を１１個数％含有し、粒径８．００μｍ以上の粒子を０．５体積％含有、Ｂ／Ａは、１．２０）、平均円形度は０．９４８のトナー粒子を分級収率８３％で得た。分級ローター及び分散ローターを確認したところ、トナー原材料の融着物は見られなかった。
【０１０２】
さらに、同様の網面固定式風力篩ハイボルターを用い、粗粒を分離し、粒径１２．７μｍ以上の粒子が０．１体積％未満のトナー粒子を得た。また、分離した粗粒は、篩を通過させたトナー粒子の約０．２％であった。
【０１０３】
得られたトナー粒子に実施例１と同様に疎水性シリカを外添混合しトナーとし、さらにアクリルコートされたフェライトキャリアを混合し、現像剤とした。
この現像剤を用いて、実施例１と同様にキヤノン製フルカラー複写機ＣＬＣ１０００改造機で画出し評価を行ったところ、実施例１と同様に良好な画像が得られた。また、感光体から転写材（坪量１９９ｇ／ｍ²紙）への転写効率は８９％であった。
【０１０４】
＜実施例４＞
実施例１と同様のトナー原料粗砕物を用いて、表面改質装置において、表面改質処理時間を３０秒間とした以外は、実施例２と同様に、微粉砕及び、表面改質処理を行った。
【０１０５】
表面改質処理を繰り返し２０分間運転した結果、分級ローター後方の温度Ｔ２は１９℃で安定した。従って、ΔＴ（Ｔ２−Ｔ１）は３９℃であった。
【０１０６】
処理後、重量平均径５．２μｍ、個数平均径４．８μｍ（粒径３．１７μｍ以下の粒子を１３個数％含有し、粒径８．００μｍ以上の粒子を０．５体積％含有、Ｂ／Ａは、１．１７）、平均円形度は０．９４４のトナー粒子を分級収率８５％で得た。分級ローター及び分散ローターを確認したところ、トナー原材料の融着物は見られなかった。
【０１０７】
さらに、同様の網面固定式風力篩ハイボルターを用い、粗粒を分離し、粒径１２．７μｍ以上の粒子が０．１体積％未満のトナー粒子を得た。また、分離した粗粒は、篩を通過させたトナー粒子の約０．２％であった。
【０１０８】
得られたトナー粒子に実施例１と同様に疎水性シリカを外添混合しトナーとし、さらにアクリルコートされたフェライトキャリアを混合し、現像剤とした。
【０１０９】
この現像剤を用いて、実施例１と同様にキヤノン製フルカラー複写機ＣＬＣ１０００改造機で画出し評価を行ったところ、実施例１と同様に良好な画像が得られた。また、感光体から転写材（坪量１９９ｇ／ｍ²紙）への転写効率は８６％であった。
【０１１０】
＜実施例５＞
実施例１と同様のトナー原料粗砕物を用いて、実施例１と同様の微粉砕装置を用い、微粉砕条件を変更し、微粉砕を行った。得られた微粉砕物の粒径は、重量平均径６．６μｍ、個数平均径５．５μｍ（粒径４．００μｍ以下の粒子を５３個数％含有し、粒径１０．０８μｍ以上の粒子を２．２体積％含有する）、平均円形度は０．９２３であった。次に、得られた微粉砕物を実施例１と同様の表面改質装置を用い、同様に微粒子を除去（ブロワー風量は１５ｍ³／ｍｉｎ）しながら、８０秒間表面処理を行った。
【０１１１】
表面改質処理を繰り返し２０分間運転した結果、分級ローター後方の温度Ｔ２は３１℃で安定した。従って、ΔＴ（Ｔ２−Ｔ１）は５１℃であった。
【０１１２】
処理後、重量平均径６．９μｍ、個数平均径６．６μｍ（粒径４．００μｍ以下の粒子を１２個数％含有し、粒径１０．０８μｍ以上の粒子を２．３体積％含有、Ｂ／Ａは、１．２０）、平均円形度は０．９５３のトナー粒子を分級収率８１％で得た。分級ローター及び分散ローターを確認したところ、トナー原材料の融着物は見られなかった。
【０１１３】
さらに、同様の網面固定式風力篩ハイボルターを用い、粗粒を分離し、粒径１６．０μｍ以上の粒子が０．１体積％未満のトナー粒子を得た。また、分離した粗粒は、篩を通過させたトナー粒子の約０．４％であった。
【０１１４】
得られたトナー粒子に実施例１と同様に疎水性シリカを１．４質量部外添混合しトナーとし、さらにアクリルコートされたフェライトキャリアを混合し、現像剤とした。
【０１１５】
この現像剤を用いて、実施例１と同様にキヤノン製フルカラー複写機ＣＬＣ１０００改造機で画出し評価を行ったところ、実施例１と同様に良好な画像が得られた。また、感光体から転写材（坪量１９９ｇ／ｍ²紙）への転写効率は９１％であった。
【０１１６】
＜比較例１＞
実施例１と同様のトナー原料粗砕物を用いて、図１で示した機械式微粉砕機３０１（ターボ工業（株）製ターボミルＴ２５０−ＲＳ型）を用い、粉砕ローターとライナーとの間隙１．０ｍｍ、粉砕ローター回転数１２３００ｒｐｍ（＝回転子の先端周速１６０ｍ／ｓｅｃ）、風量６Ｎｍ³／ｍｉｎ（入口温度−１５℃）で粉砕した。
【０１１７】
原料粗砕物の供給量を調整しても、重量平均径７．５μｍ、個数平均径が４．４μｍの微粉砕物しか得られなかった。
【０１１８】
＜比較例２＞
実施例１と同様のトナー原料粗砕物を用いて、機械式微粉砕機スーパーローター（日清エンジニアリング（株） ＳＲ−２５型）を用い、粉砕ローターとライナーとの間隙１．０ｍｍ、粉砕ローター回転数１２０００ｒｐｍ（＝回転子の先端周速１６０ｍ／ｓｅｃ）、風量６Ｎｍ³／ｍｉｎ（入口温度−４０℃）で粉砕した。
【０１１９】
原料粗砕物の供給量を調整しても、重量平均径７．２μｍ個数平均径が４．１μｍの微粉砕物しか得られなかった。
【０１２０】
＜比較例３＞
実施例１と同様のトナー原料粗砕物を用いて、機械式微粉砕機スーパーローターＳＲ−２５型と、気流分級機ターボクラシファイア（日清エンジニアリング（株）ＴＣ−２５ＩＩＩＳ型）で閉回路を組み、微粉砕を行ったところ、原料粗砕物の供給量を比較例２の約１／３に調整し、重量平均径４．８μｍ、個数平均径が３．８μｍ（粒径３．１７μｍ以下の粒子を３８個数％含有し、粒径８．００μｍ以上の粒子を０．１体積％含有）、平均円形度は０．９３２の微粉砕物を得た。これは、実施例１の微粉砕物に比べると、球形化が悪いものであった。
【０１２１】
この微粉砕物をエルボジェット分級機（ＥＪ−１５−３型）を用い、重量平均径５．２μｍ、個数平均径４．９μｍ（粒径３．１７μｍ以下の粒子を１２個数％含有し、粒径８．００μｍ以上の粒子を０．０体積％含有）、平均円形度は０．９４１に分級した。
【０１２２】
次に、実施例１と同様に、得られたトナー粒子に疎水性シリカを外添混合しトナーを得、さらにアクリルコートされたフェライトキャリアと混合し、現像剤とした。この現像剤を用いて、実施例１と同様にキヤノン製フルカラー複写機ＣＬＣ１０００改造機で画出し評価を行ったところ、常温常湿下では、良好な画像が得られたが、高温高湿下では、画像濃度が徐々に低下し、カブリが増加した。トナーを顕微鏡で観察したところ、遊離したワックスとみられる未着色の粒子が見られた。これが、帯電性に影響を与えたものと思われる。また、感光体から転写材（坪量１９９ｇ／ｍ²紙）への転写効率は８４％であった。
【０１２３】
＜比較例４＞
実施例５で得たトナー微粉砕物をエルボジェット分級機（ＥＪ−１５−３型）を用い、重量平均径６．９μｍ、個数平均径６．６μｍ（粒径４．００μｍ以下の粒子を１２個数％含有し、粒径１０．０８μｍ以上の粒子を２．３体積％含有する）、平均円形度０．９２６のトナー粒子を得た。
【０１２４】
次に、その後、上記分級品を図１２に示す表面改質装置で表面改質した。
【０１２５】
図１２において１５１は本体ケーシング、１５８はステーター、１７７はステータージャケット、１６３はリサイクルパイプ、１５９は排出バルブ、１１９は排出シュート、１６４は原料投入シュートである。
【０１２６】
該装置において、原料投入シュート１６４から供給された粉体粒子及び他の微小固体粒子は、衝撃室１６８内で主として高速で回転している回転ローター１６２に配置された複数のローターブレード１５５によって瞬間的な打撃作用を受け、さらに周辺のステーター１５８に衝突して粉体粒子同士または、他の微小固体粒子同士の凝集をほぐしながら系内に分散させると同時に、粉体粒子表面に他の微小固体粒子を静電気力、ファンデルワールス力等により付着させるか、粉体粒子のみの場合は、粒子の角取りまたは球形化が行われる。この状態は粒子の飛行と衝突に伴って進んで行く。すなわち、ローターブレード１５５の回転により発生する気流の流れに伴って、該粒子は、１６３のリサイクルパイプを複数回通過することにより処理される。さらにローターブレード１５５及びステーター１５８から該粒子が繰り返し打撃作用を受けることにより、他の微小固体粒子は、粉体粒子表面またはその近傍に均一に分散し固定化されるか、粉体粒子のみの場合は、粒子の形状が球形化されていく。
【０１２７】
処理が完了した該粒子は、排出弁制御装置１２８により排出バルブ１５９を開くことにより、１１９の排出シュートを通過し吸引ブロア２２４と連通しているバグフィルター２２２等により捕集される。
【０１２８】
本比較例においては、ローターブレード１５５を有する回転ローター１６２の最長径が２４２ｍｍであるものを使用し、回転ローター１６２の回転周速は９０ｍ／ｓｅｃとした。また微粉砕品の投入量を３００ｇとし、サイクルタイムを１８０秒として表面改質粒子を得た。
【０１２９】
処理後の表面改質粒子は、重量平均径６．７μｍ、個数平均径６．４μｍ（粒径４．００μｍ以下の粒子を１８個数％含有し、粒径１０．０８μｍ以上の粒子を２．４体積％含有、Ｂ／Ａは、０．９７）、平均円形度は０．９４１であった。
【０１３０】
表面改質する以前の分級品粒度と比較してブロードとなっていた。これは表面改質の際、トナーが過粉砕され、微粉が増加したためと推察される。また、運転終了後機内点検したところ、ローターブレードに若干融着が発生していた。
【０１３１】
次に、実施例５と同様に、得られたトナー粒子に疎水性シリカを外添混合しトナーを得、さらにアクリルコートされたフェライトキャリアと混合し、現像剤とした。この現像剤を用いて、実施例１と同様にキヤノン製フルカラー複写機ＣＬＣ１０００改造機で画出し評価を行ったところ、画像濃度が徐々に低下し、カブリが増加した。トナーを顕微鏡で観察したところ、遊離したワックスとみられる未着色の粒子が見られた。これが、帯電性に影響を与えたものと思われる。また、感光体から転写材（坪量１９９ｇ／ｍ²紙）への転写効率は８６％であった。
【０１３２】
＜実施例６＞
・不飽和ポリエステル樹脂 １００質量部
・マゼンタ顔料 ４質量部
（Ｃ．Ｉ．ピグメントレッド１８４）
・ポリエチレンワックス ４質量部
（最大吸熱ピーク１０２℃）
・荷電制御剤（サリチル酸金属錯体） ２質量部
上記の処方の材料をヘンシェルミキサー（ＦＭ−７５型）でよく混合した後、温度１２０℃に設定した二軸混練機（ＰＣＭ−３０型）にて混練した。得られた混練物を冷却し、ハンマーミルにて１ｍｍ以下に粗粉砕し、トナー製造用の粗砕物を得た。
【０１３３】
得られた粗砕物を図２で示した高圧気体を用いた衝突式気流粉砕機（Ｉ−５型、日本ニューマッチック工業（株）製：高圧気体圧力：０．６ＭＰａ、流量：５Ｎｍ³／ｍｉｎ）と、図６で示した気流分級機を図３のように閉回路を組んだ微粉砕装置を用いて粉砕した。得られた微粉砕物は、重量平均径７．２μｍ、個数平均径４．２μｍ（粒径４．００μｍ以下の粒子を６３個数％含有し、粒径１２．７μｍ以上の粒子を２．１体積％含有）であり、平均円形度は０．９２２であった。
【０１３４】
次に、得られた微粉砕物を実施例１と同様の表面改質装置を用い、同様に分級ローター回転数６８００ｒｐｍで微粒子を除去しながら、分散ローター回転数５２００ｒｐｍ（回転周速を１１５ｍ／ｓｅｃ）で４５秒間表面処理を行った。
【０１３５】
この状態で表面改質処理を繰り返し２０分間運転した結果、分級ローター後方の温度Ｔ２は２７℃で安定した。従って、ΔＴ（Ｔ２−Ｔ１）は４７℃であった。
【０１３６】
処理後、重量平均径７．２μｍ、個数平均径６．８μｍ（粒径４．００μｍ以下の粒子を１２個数％含有し、粒径１２．７μｍ以上の粒子を２．３体積％含有、Ｂ／Ａは、１．６２）、平均円形度は０．９３３のトナー粒子を分級収率７５％で得た。分級ローター及び分散ローターを確認したところ、トナー原材料の融着物は見られなかった。
【０１３７】
さらに、エルボジェット分級機（ＥＪ−１５−３型）を用い１２．７μｍ以上の粗粒を分級除去し、粒径１２．７μｍ以上の粒子が０．１体積％未満のトナー粒子を得た。また、分離した粗粒は、エルボジェット分級機を通過させたトナー粒子の約９％であった。
【０１３８】
得られたトナー粒子に実施例１と同様に疎水性シリカを外添混合しトナーとし、さらにアクリルコートされたフェライトキャリアを混合し、現像剤とした。
【０１３９】
この現像剤を用いて、実施例１と同様にキヤノン製フルカラー複写機ＣＬＣ１０００改造機で画出し評価を行ったところ、実施例１と同様に良好な画像が得られた。また、感光体から転写材（坪量１９９ｇ／ｍ² 紙）への転写効率は８７％であった。
【０１４０】
＜実施例７＞
・スチレン−ｎブチルアクリレート−マレイン酸モノブチルアクリレート
共重合体 １００質量部
・磁性酸化鉄（平均粒径０．２２μｍ） １００質量部
・低分子量エチレン−プロピレン共重合体 ３質量部
・モノアゾ染料の鉄錯体 ２質量部
上記の処方の材料をヘンシェルミキサー（ＦＭ−７５型）でよく混合した後、温度１３０℃に設定した二軸混練機（ＰＣＭ−３０型）にて混練した。得られた混練物を冷却し、ハンマーミルにて１ｍｍ以下に粗粉砕し、トナー製造用の粗砕物を得た。
【０１４１】
得られた粗砕物を図２で示した高圧気体を用いた衝突式気流粉砕機Ｉ−５型（高圧気体圧力：０．６ＭＰａ、流量：５Ｎｍ³／ｍｉｎ）と、図５で示した気流分級機（ＤＳ−５型、日本ニューマッチック工業（株）製）を図３のように閉回路を組んだ微粉砕装置を用いて粉砕した。得られた微粉砕物は、重量平均径７．８μｍ、個数平均径４．７μｍ（粒径４．００μｍ以下の粒子を４９個数％含有し、粒径１２．７μｍ以上の粒子を２．３体積％含有）であり、平均円形度は０．９２３であった。
【０１４２】
次に、得られた微粉砕物を実施例１と同様の表面改質装置（分散ローター回転数５２００ｒｐｍ（回転周速を１１５ｍ／ｓｅｃ）、ジャケットに通す冷媒の温度及び冷風温度Ｔ１を０℃に変更）を用い、微粉砕品を毎回２．０ｋｇ投入し、分級ローター回転数６６００ｒｐｍで微粒子を除去しながら、同様に４５秒間表面処理を行った。
【０１４３】
この状態で表面改質処理を繰り返し２０分間運転した結果、分級ローター後方の温度Ｔ２は４７℃で安定した。従って、ΔＴ（Ｔ２−Ｔ１）は４７℃であった。
【０１４４】
処理後、重量平均径８．０μｍ、個数平均径７．７μｍ（粒径４．００μｍ以下の粒子を１１個数％含有し、粒径１２．７μｍ以上の粒子を２．８体積％含有、Ｂ／Ａは、１．６４）、平均円形度は０．９３３のトナー粒子を分級収率７８％で得た。分級ローター及び分散ローターを確認したところ、トナー原材料の融着物は見られなかった。
【０１４５】
さらに、エルボジェット分級機（ＥＪ−１５−３型）を用い１２．７μｍ以上の粗粒を分級除去し、粒径１２．７μｍ以上の粒子が０．１体積％未満のトナー粒子を得た。このトナー粒子１００質量部に対して、ＢＥＴ法による比表面積が１１０ｍ²／ｇである疎水性シリカを１．２質量部添加し、ヘンシェルミキサーにて外添混合しトナーとした。
【０１４６】
このトナーを用いて、キヤノン製のレーザージェットプリンターＬＢＰ−９５０改造機（Ａ４横送りで３２枚／分から５０枚／分に改造）に搭載して画出し試験を行い、トナーの画像特性を評価した。
【０１４７】
常温常湿下、及び高温高湿下で、５，０００枚の画出し評価を行ったところ、初期と耐久後の画像濃度に変化がなく、カブリのない高画質の画像が得られた。さらに両面画像を形成させたが、転写材の表裏面共にオフセットの発生は認められなかった。
【０１４８】
【発明の効果】
本発明のトナーの製造方法によれば、少なくとも、結着樹脂及び着色剤を含有する組成物を溶融混練し、混練物を冷却固化し、固化物を微粉砕して微粉砕物を得る工程、及び得られた微粉砕物を表面改質処理し表面改質処理粒子を得る表面改質工程を有するトナーの製造方法において、表面改質時における熱の影響や微粉の発生を抑制し、トナーの表面形状を任意にコントロールでき、且つ、トナーの表面形状をコントロールすることにより、良好な現像性、転写性並びにクリーニング性、及び安定した帯電性を有する、長寿命のトナーが得られるトナーの製造方法を提供することができる。したがって、本発明のトナーの製造方法によれば、ワックス成分を含有し、低融点、低軟化点または低ガラス転移点の樹脂が使用されたトナー粒子を効率よく製造し得る。特に重量平均粒径が７μｍ以下（さらには、６μｍ以下）の、表面形状をコントロールしたトナー粒子を効率よく製造し得る。
【図面の簡単な説明】
【図１】本発明のトナーの粉砕工程において使用される一例の衝突式気流粉砕機の概略断面図である。
【図２】本発明のトナーの粉砕工程において使用される他の一例の衝突式気流粉砕機の概略断面図である。
【図３】本発明の微粉砕工程において使用される一例の粉砕装置−分級装置のフロー図である。
【図４】本発明の微粉砕工程において使用される他の一例の粉砕装置−分級装置のフロー図である。
【図５】本発明の微粉砕工程において使用される一例の分級機の概略的断面図である。
【図６】本発明の微粉砕工程において使用される他の一例の分級機の概略的断面図である。
【図７】本発明の微粉砕工程において使用される他の一例の分級機の概略的断面図である。
【図８】本発明の表面改質工程において使用される一例の表面改質装置の概略的断面図である。
【図９】図８に示す分散ローターの上面図の一例を示す概略図である。
【図１０】従来粉砕工程に用いられる機械式粉砕機の概略断面図である。
【図１１】図１０に示す機械式粉砕機の回転子の斜視図である。
【図１２】比較例の表面改質工程において使用される一例の機械式粉砕機の概略的断面図である。
【符号の説明】
１：分級ローター
２：微粉回収
３：原料供給口
４：ライナー（固定体）
５：冷風導入口
６：分散ローター（回転体）
７：製品排出口
８：排出弁
９：ガイドリング（案内板）
１０：角型ディスク
１１：第一の空間
１２：第二の空間
１５：ケーシング
２１：加速管
２２：加速管スロート部
２３：高圧気体供給ノズル
２４：被粉砕物供給口
２５：被粉砕物供給筒
２６：高圧気体供給口
２７：高圧気体チャンバー
２８：高圧気体導入管
２９：加速管出口
３０：衝突部材
３２：粉砕室内壁
３３：粉砕物排出口
３４：粉砕室
３５：粉砕室
３６：衝突部材
３７：衝突面
３８：粉砕室内壁
３９：粉砕物排出口
４１：被粉砕物供給口
４２：加速管
４３：高圧気体供給ノズル
４４：加速管出口
４７：分級ルーバー
４８：分散ルーバー
４９：分級ルーバー
５１：本体ケーシング
５２：分級室
５３：案内室
５４：分級ローター
５５：原料投入口
５６：エアー投入口
５７：分散ルーバー
５８：微粉排出管
５９：ホッパー
２１２：渦巻室
２１９：パイプ
２２０：デイストリビュータ
２２２：バグフィルター
２２４：吸引ブロワー
２２９：捕集サイクロン
３０１：機械式粉砕機
３０２：粉体排出口
３１０：固定子
３１１：粉体投入口
３１２：回転軸
３１３：ケーシング
３１４：回転子
３１５：定量供給機
３１６：ジャケット
３１７：冷却水供給口
３１８：冷却水排出口
３２０：後室[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a toner for developing an electrostatic charge image in an image forming method such as electronic printing or a toner manufacturing method for forming a toner fixed image in a toner jet type image forming method. The present invention relates to a method for producing toner used in a fixing method in which an image is heated and fixed on a print sheet such as a transfer material.
[0002]
[Prior art]
In image forming methods such as electrophotography, electrostatic photography, and electrostatic printing, toner for developing an electrostatic charge image is used. In general, a toner is produced by using, as a raw material, a binder resin for fixing on a transfer material and various colorants for producing a color as a toner, and further, if necessary, a charge for imparting charges to particles. Add other additives such as a control agent, a wax as a mold release agent, and a fluidity-imparting agent and dry-mix them. After that, heat, melt and disperse with a kneader to make a uniform composition. A method for producing a toner by cooling, pulverizing, and classifying the toner has become the current mainstream from the viewpoint of mass productivity and cost. However, the toner particles produced by the kneading and pulverization method have irregular shapes, resulting in variations in toner characteristics, and demands for toner in the recent trend of miniaturization, simplification, higher image quality, and full color of electrophotographic apparatuses. The performance is very advanced and not fully satisfied with the current situation.
[0003]
Further, in recent years, in order to achieve full color, cleaner-less, and reduction of waste toner amount, improvement in toner transferability has been demanded, so it has become essential to make the toner shape spherical.
[0004]
For example, Japanese Patent Laid-Open No. 63-235953 proposes a toner spheroidized by a mechanical impact force. However, the transfer efficiency is still insufficient and further improvement is necessary.
[0005]
In the conventional method using mechanical impact force, a lot of impact and friction are required for spheroidization, and therefore the spheronization process is centered on a batch (circulation) process. At the time of spheronization processing by mechanical impact force, extremely fine powder is generated by the pulverization action by impact force accompanying spheroidization. Therefore, it is necessary to remove the very fine powder after the spheronization processing. In some cases, the fine powder adheres to the toner surface during the batch (circulation) treatment and causes uneven distribution of the toner surface composition.
[0006]
In addition to the mechanical impact force described above, the toner shape can be spheroidized by a method of melting the surface with hot air, a method of using heat, etc., but the toner changes its surface composition due to heat. There is a problem, and in particular, the method of melting the surface with heat is not preferable because the presence state of the wax component added as a release agent changes.
[0007]
In recent years, as a measure to save energy in copying machines, the fixing speed can be fixed even when using a soft resin such as wax as the binder resin to fix the recording material such as transfer material by pressure. In order to reduce the power consumption required for fixing and to fix the toner at a low temperature, a binder resin having a low glass transition point or a low softening point has been used. The method of melting the surface by this is not preferred.
[0008]
On the other hand, various pulverizing devices are used as the fine pulverizing means. Among them, the pulverized toner pulverized product mainly composed of a binder resin is a jet stream type using a high pressure gas such as a jet stream as shown in FIG. A pulverizer, particularly a collision type airflow pulverizer is used.
[0009]
A collision-type airflow crusher using a high-pressure gas such as a jet stream transports the powder raw material by a jet stream and injects it from the exit of the acceleration tube, and the powder material is provided facing the opening surface of the exit of the acceleration tube. The powder raw material is pulverized by the impact force of the collision member.
[0010]
In recent years, energy saving of a manufacturing apparatus has been demanded in order to cope with environmental problems, and a mechanical pulverizer with low power consumption has been attracting attention instead of a collision type airflow pulverizer that requires a large amount of air.
[0011]
For example, in the mechanical pulverizer shown in FIG. 10, a rotor (see FIG. 11) that is a rotating body attached to at least a central rotating shaft, and the rotor surface is arranged around the rotor while maintaining a certain distance. And an annular space formed by maintaining the gap is configured to be in an airtight state.
[0012]
Such a mechanical pulverizer does not need to use a large amount of air unlike a collision type airflow pulverizer, so that it consumes less power and can cope with energy saving of devices that have been demanded in recent years. Further, the toner pulverized by the mechanical pulverizer has the advantage that the shape is rounded due to the mechanical impact force, and further, the generation of fine powder is small due to the pulverization limit.
[0013]
However, in recent years, with higher image quality and higher definition of copying machines, printers, etc., the performance required for toner has become more severe, the required toner particle size has become smaller, and binder resins with poor grindability, For example, in the case of a toner material using a polyester resin, a mechanical pulverizer has a pulverization limit, and it is difficult to pulverize the weight average particle diameter to 7 μm or less (further to 6 μm or less).
[0014]
In addition, if a mechanical pulverizer is combined with a high-performance classifier in combination with a closed circuit to perform pulverization, it is possible to obtain a finely pulverized product having a weight average particle size of 7 μm or less (more than 6 μm). Not only is the throughput reduced, but only low circularity is obtained. In addition, in order to pulverize to such a small particle size, the circulation amount in the closed circuit increases, and a lot of mechanical impact force is received. Therefore, the surface composition of the toner is caused by heat generated by the mechanical impact force. This is not preferable because there is a problem that the wax component added as a mold release agent changes.
[0015]
[Problems to be solved by the invention]
An object of the present invention is to provide a production method capable of solving such problems and obtaining toner particles with higher definition and higher image quality.
[0016]
An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a production method for efficiently producing an electrostatic charge image developing toner.
[0017]
An object of the present invention is to melt and knead a composition containing at least a binder resin and a colorant, cool and solidify the kneaded product, and finely pulverize the solidified product to obtain a finely pulverized product. In a method for producing a toner having a surface modification step of surface-treating a pulverized product to obtain surface-modified particles,
By controlling the surface shape of the toner by controlling the surface shape of the toner by suppressing the influence of heat and the generation of fine powder during surface modification, and by controlling the surface shape of the toner, It is an object of the present invention to provide a toner production method capable of obtaining a long-life toner having stable charging properties.
[0018]
[Means for Solving the Problems]
  In the toner production method of the present invention, a composition containing at least a binder resin and a colorant is melt-kneaded, the obtained kneaded product is cooled and solidified, and the cooled solidified product is finely pulverized to obtain a finely pulverized product. In a toner production method comprising a pulverization step and a surface modification step of obtaining a surface-modified particle by subjecting the obtained finely pulverized product to surface modification treatment,
  The pulverization step is a step of obtaining a pulverized product having a weight average particle diameter of 3 to 11 μm using a collision type air pulverizer using a high-pressure gas such as a jet air flow,
  The surface modification step is performed using a batch type surface modification apparatus, and the batch type surface modification apparatus includes classification means for continuously discharging and removing fine particles having a predetermined particle size or less to the outside of the apparatus. , Surface treatment means using mechanical impact force, and guide means for partitioning the space between the classification means and the surface treatment means into a first space and a second space,
  The finely pulverized product is introduced into the first space, and mechanical impact force is used via the second space while continuously removing and removing fine particles having a predetermined particle diameter or less from the apparatus by the classification means. By introducing into the surface treatment means, performing surface modification treatment, and circulating again to the first space, by repeating predetermined time classification and surface modification treatment using mechanical impact force, the particle size is less than the predetermined particle size. Is a step of obtaining surface-modified particles from which a predetermined amount of fine particles have been removed.The
  The surface treatment using the mechanical impact force in the surface modification step has a plurality of square disks or cylindrical pins on the upper surface, and a rotating body on a disk that rotates at high speed and the rotating body. Is performed by a surface treatment apparatus comprising a fixed body fixedly arranged at intervals.It is characterized by that.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
First, the pulverizing apparatus according to the present invention will be described in detail with reference to the drawings.
[0020]
1 and 2 show an example of a collision type airflow crusher using a high-pressure gas such as a jet airflow used in the present invention.
[0021]
As shown in FIG. 3 or FIG. 4, the collision-type airflow crusher is a finely pulverized product from the fine powder side of the classifier by combining an airflow classifier and a closed circuit and returning particles having a desired particle size or more to the crusher. Take out.
[0022]
As the airflow classifier used here, there are a fixed wall type classifier having no moving part as shown in FIG. 5 or 6 and a rotor rotating type airflow classifier equipped with a rotating rotor as shown in FIG. However, when trying to obtain a smaller finely pulverized product having a weight average particle size of 7 μm or less (or 6 μm or less), the airflow classifier is capable of forcibly increasing the speed of the classified airflow. A rotor rotating air classifier equipped with a rotor is preferred.
[0023]
The true specific gravity is 1.2 g / cm^ThreeIn the case of pulverizing the following toner material having a small specific gravity, a rotor rotating type air classifier equipped with a rotating rotor capable of forcibly increasing the speed of the classifying air flow is also preferable.
[0024]
Next, a surface modifying apparatus used in the surface modifying step and a toner manufacturing method using the surface modifying apparatus will be specifically described with reference to the drawings.
[0025]
FIG. 8 shows an example of a surface modification apparatus used in the present invention, and FIG. 9 shows an example of a top view of a rotor that rotates at a high speed in FIG.
[0026]
In the surface reforming apparatus shown in FIG. 8, the casing 15, a jacket (not shown) through which cooling water or antifreeze liquid can be passed, and surface reforming means, which is in the casing 15 and attached to the central rotating shaft, Dispersion rotor 6 that is a rotating body on a disk that has a plurality of square disk-shaped or cylindrical pins 10 and rotates at a high speed, and a surface that is arranged on the outer periphery of dispersion rotor 6 at a constant interval. Liner 4 provided with a number of grooves (there is no need to have grooves on the liner surface), and further, a classification rotor 1, which is a means for classifying the surface-modified raw material into a predetermined particle size, Furthermore, the cold air introduction port 5 for introducing cold air, the raw material supply port 3 for introducing the raw material to be treated, and the surface modification time were installed so as to be openable and closable. Discharge valve 8, The space between the powder discharge port 7 for discharging the processed powder and the classification rotor 1 as the classification means and the dispersion rotor 6-liner 4 as the surface modification means is introduced into the classification means. And a cylindrical guide ring 9 which is a guide means for partitioning into a second space 12 for introducing particles classified and removed by the classifying means into the surface treatment means. ing. A gap portion between the dispersion rotor 6 and the liner 4 is a surface modification zone, and a classification rotor 4 and a rotor peripheral portion are classification zones.
[0027]
The classifying rotor 1 may be installed vertically as shown in FIG. 8 or horizontally. Further, the number of classification rotors 1 may be single as shown in FIG. 8, or plural.
[0028]
In the surface reforming apparatus configured as described above, when a certain amount of finely pulverized product is introduced from the raw material supply port 3 with the discharge valve 8 closed, the charged finely pulverized product is first blower (not shown). ) And classified by the classification rotor 1. At that time, the classified fine powder having a predetermined particle size or less is continuously discharged out of the apparatus, and the coarse powder having a predetermined particle size or more is removed by centrifugal force from the inner periphery (second space 12) of the guide ring (guide plate) 9. ) Along the circulation flow generated by the dispersion rotor 6 and led to the surface modification zone. The raw material guided to the surface modification zone is subjected to a surface modification treatment by receiving a mechanical impact force between the dispersion rotor 6 and the liner 4. The surface-modified particles having undergone surface modification ride on the cold air passing through the inside of the machine, and are guided to the classification zone along the outer periphery (first space 11) of the guide ring 9. After being discharged to the outside, the coarse powder rides on the circulating flow, returns to the second space 12 again, and repeatedly undergoes a surface modification action in the surface modification zone. After a certain period of time, the discharge valve 8 is opened and the surface modified particles are recovered from the discharge port 7.
[0029]
The toner production method of the present invention is characterized in that a toner raw material is finely pulverized using a collision type airflow pulverizer using a high-pressure gas such as a jet airflow, and the finely pulverized toner is collected as shown in FIG. By using a surface modification device of the formula, surface modified particles having a sharp particle size distribution can be obtained by arbitrarily controlling the surface shape of the toner while continuously performing fine powder removal classification.
[0030]
That is, as a result of intensive studies by the present inventors, the surface reforming apparatus used in the surface reforming process using a collision-type airflow grinder using a high-pressure gas such as a jet stream is shown in FIG. In addition, a batch type surface modification device, and further, the batch type surface modification device may be a surface modification device with a built-in classification rotor for continuously removing fine particles. It turned out to be favorable for quality.
[0031]
That is, as a result of investigation by the present inventors, the pulverizer used in the pulverization step is a collision type airflow pulverizer using a high-pressure gas such as a jet airflow as shown in FIG. 1 or FIG. In addition, even a material that is difficult to pulverize such as containing a polyester resin as a binder resin can be pulverized to a fine particle size of 7 μm or less (and 6 μm or less). Furthermore, the surface modification device used in the surface modification step is a batch type surface modification device as shown in FIG. 8, and is a type with a built-in classification rotor for continuously removing fine powder, and a finely pulverized product. Even when the surface of toner that is easily pulverized is modified by controlling the setting of the surface modification zone of the surface modification device to an appropriate state, the amount of fine powder during surface modification And the toner particle size distribution can be classified sharply. Furthermore, by arbitrarily setting the time for opening the discharge valve, it is possible to adjust the residence time of the toner in the apparatus, and to arbitrarily control the surface shape of the toner, with good developability, transferability, cleaning properties, and stability. Thus, a long-life toner having excellent charging properties can be obtained.
[0032]
The surface shape of the toner depends on the residence time of the toner in the surface modifying apparatus. That is, in order to control the surface shape of the toner, it is important to control the residence time of the toner in the surface modifying device. In the present invention, the surface modification device used in the surface modification step is a batch-type surface modification device as shown in FIG. 8, so that the time until the discharge valve is opened, the tooth shape on the top surface of the dispersion rotor, and By controlling the rotational peripheral speed, the distance between the dispersion rotor and the liner, the distance between the guide ring and the dispersion rotor, etc. to an appropriate state, an increase in fine powder during surface modification is prevented, and the toner surface modification device The residence time of the toner can be controlled, and the surface shape of the toner can be arbitrarily controlled. In addition, by incorporating a classification rotor that classifies the surface-modified toner into a predetermined particle size, by controlling the rotational peripheral speed of the classification rotor to an appropriate state, fine powder below the predetermined particle is continuously discharged out of the device. Since the coarse powder can be surface-modified again, surface-modified particles having a sharp particle size distribution from which fine powder having a predetermined particle size or less is removed can be obtained.
[0033]
As a result of investigation by the present inventors, the surface modification time (= cycle time) in the surface modification apparatus is preferably 5 seconds to 180 seconds, more preferably 15 seconds to 120 seconds. When the surface modification time is less than 5 seconds, since the modification time is too short, surface modified particles cannot be obtained, which is not preferable in terms of toner quality. In addition, when the modification time exceeds 180 seconds, the modification time is too long, so the surface of the toner is altered by the heat generated during surface modification, the occurrence of in-machine fusion, and the processing capacity is reduced. This is not preferable in terms of toner productivity.
[0034]
In the present invention, the average circularity is used as an index for indicating the degree of surface modification of the surface modified particles.
[0035]
The average circularity in the present invention is used as a simple method for quantitatively expressing the shape of particles, and in the present invention, measurement is performed using a flow type particle image analyzer FPIA-1000 manufactured by Toa Medical Electronics, The circularity of the measured particles is obtained by the following formula, and the value obtained by dividing the total circularity of all the measured particles by the total number of particles is defined as the average circularity.
[0036]
[Expression 1]

[0037]
As a measurement method, about 5 mg of toner is dispersed in 10 ml of water in which about 0.1 mg of a nonionic surfactant is dissolved to prepare a dispersion, and ultrasonic waves (20 kHz, 50 W) are irradiated to the dispersion for 3 minutes. The degree of circularity of the toner is measured with the above apparatus at a dispersion concentration of 5000 to 20000 / μl.
[0038]
The “average circularity” in the present invention is an index indicating the degree of unevenness of the surface-modified particles, and is 1.000 when the toner is a perfect sphere, and the average circularity becomes smaller as the toner shape becomes more complicated. It becomes.
[0039]
According to the toner production method of the present invention, the average circularity of the particles obtained in the surface modification step is 0.01 to 0.00 higher than the average circularity of the finely pulverized product introduced into the surface modification step. 05 can be increased. This is because the surface shape of the toner can be arbitrarily controlled by arbitrarily controlling the surface modification time of the surface modifying device as described above.
[0040]
According to the method for producing a toner of the present invention, in the surface modification step, the surface modification is performed while removing fine powder. Therefore, the number average diameter of the surface modified particles obtained by the surface modification apparatus is determined by the surface modification. The number average diameter of the finely pulverized product introduced into the process is larger than the number average diameter of the finely pulverized product introduced into the surface modification step. When the diameter is B, A and B are the following conditions
02 ≦ B / A ≦ 2.00
Is preferably satisfied.
[0041]
Furthermore, in the toner production method of the present invention, it is preferable that the cold air temperature T1 introduced into the surface modifying apparatus is 10 ° C. or less. The cold air temperature T1 introduced into the surface reforming apparatus is 10 ° C. or lower (more preferably 5 ° C. or lower, more preferably 0 ° C. or lower, particularly preferably −5 ° C. or lower). It is possible to prevent toner surface deterioration due to heat and in-machine fusion. If the cold air temperature T1 introduced into the surface reforming apparatus is 6 ° C. or higher, it is not preferable from the viewpoint of toner productivity because the surface of the toner is easily deteriorated due to heat generated during the surface modification and fusion occurs in the machine.
[0042]
Further, in the toner production method of the present invention, the inside of the surface modifying apparatus is provided with a jacket for cooling inside the apparatus, and a refrigerant (preferably cooling water, more preferably an antifreeze such as ethylene glycol) is provided in the jacket. The finely pulverized product is preferably subjected to a surface modification treatment while passing through. In-machine cooling by the jacket can prevent toner surface deterioration and in-machine fusion due to heat during toner surface modification.
[0043]
In addition, it is preferable that the temperature of the refrigerant | coolant passed through this jacket of a surface modification apparatus shall be 5 degrees C or less. By setting the temperature of the refrigerant passed through the jacket in the surface reforming apparatus to 5 ° C. or less (more preferably 0 ° C. or less, more preferably −5 ° C. or less), the surface of the toner due to heat generated during the surface modification Alteration and in-machine fusion can be prevented. If the temperature of the refrigerant introduced into the jacket is 6 ° C. or higher, it is not preferable from the viewpoint of toner productivity because the surface of the toner is easily deteriorated due to heat generated during surface modification and fusion occurs in the machine.
[0044]
Furthermore, in the toner manufacturing method of the present invention, it is preferable that the temperature T2 behind the classification rotor in the surface modifying apparatus is 60 ° C. or less. By setting the temperature T2 behind the classification rotor in the surface reforming apparatus to 60 ° C. or less (preferably 40 ° C. or less, more preferably 30 ° C. or less), the surface modification of the toner due to heat generated during surface modification, In-machine fusion can be prevented. If the temperature T2 behind the classifying rotor in the surface modification device is 61 ° C. or higher, the surface modification zone is affected by the temperature higher than that, so the surface modification of the toner due to heat generated during the surface modification, Since in-machine fusion is likely to occur, it is not preferable from the viewpoint of toner productivity.
[0045]
Furthermore, in the toner manufacturing method of the present invention, the temperature difference ΔT (T2−T1) between the temperature T2 behind the classification rotor in the surface reforming apparatus and the cold air temperature T1 introduced into the surface reforming apparatus is set to 80. It is preferable to set it as below ℃. The temperature difference ΔT (T2−T1) between the temperature T2 behind the classification rotor in the surface reformer and the cold air temperature T1 introduced into the surface reformer is set to 80 ° C. or less (more preferably 70 ° C. or less). As a result, it is possible to prevent toner surface deterioration and in-machine fusion due to heat generated during surface modification. When the temperature difference ΔT (T2−T1) between the temperature T2 behind the classification rotor in the surface reforming apparatus and the cold air temperature T1 introduced into the surface modifying apparatus is 81 ° C. or more, in the surface reforming zone, Since the temperature higher than that influences, it is not preferable from the viewpoint of toner productivity because the toner surface is easily altered by the heat generated during the surface modification and is easily fused in the machine.
[0046]
Furthermore, in the toner production method of the present invention, the minimum distance between the dispersion rotor and the liner in the surface modifying apparatus is preferably 0.5 mm to 15.0 mm, and more preferably 2.0 mm to It is preferable to set it as 10.0 mm. Further, the rotational peripheral speed of the dispersion rotor is preferably 75 m / sec to 150 m / sec, and more preferably 85 m / sec to 140 m / sec. Further, the minimum distance between the upper part of the rectangular disk or cylindrical pin installed on the upper surface of the dispersion rotor in the surface modifying apparatus and the lower part of the cylindrical guide ring is 2.0 mm to 50 mm. 0.0 mm is preferable, and 5.0 mm to 45.0 mm is more preferable.
[0047]
As a result of the study by the present inventors, it is possible to arbitrarily control the surface shape of the toner by controlling the operating condition of the surface reforming device within the above-mentioned range, and good developability, transferability, cleaning property, and stable charging. Thus, a long-life toner can be obtained.
[0048]
If the minimum distance between the dispersion rotor and the liner in the surface reforming apparatus is less than 0.5 mm, the load on the apparatus itself increases, and at the same time, the toner surface changes due to heat that is excessively pulverized during the surface modification. In addition, it is not preferable from the viewpoint of toner productivity because it tends to cause in-machine fusion. Further, if the minimum distance between the dispersion rotor and the liner is 15.1 mm or more, the processing capability must be reduced to obtain surface-modified particles, which is also not preferable in terms of toner productivity. In addition, if the rotational peripheral speed of the dispersion rotor in the surface reforming apparatus is less than 75 m / sec, the processing capability must be lowered to obtain a predetermined circularity, which is not preferable in terms of toner productivity. Further, when the rotational peripheral speed of the grinding rotor is 141 m / sec or more, the load on the apparatus itself is increased, and at the same time, the toner is excessively ground during the surface modification, and at the same time, the toner surface changes due to heat and melts in the machine. This is also not preferable from the viewpoint of toner productivity because it tends to cause adhesion.
[0049]
In addition, the minimum distance between the upper part of the rectangular disk or cylindrical pin installed on the upper surface of the dispersion rotor in the surface modification device and the lower part of the cylindrical guide ring is less than 2.0 mm. As a result, the load on the apparatus itself increases, and at the same time, the residence time in the first space 41 inside the guide ring 39 becomes longer, and the toner is excessively pulverized during surface reforming, causing toner surface alteration and in-machine fusion due to heat. This is not preferable from the viewpoint of toner productivity because it easily occurs. Further, when the minimum distance between the upper part of the rectangular disk or cylindrical pin installed on the upper surface of the dispersion rotor and the lower part of the cylindrical guide ring is 50.1 mm or more, the surface modified particles May cause a short path that flows into the second space 42 outside the guide ring 39 in a state where the surface is not sufficiently modified, which is also not preferable in terms of toner productivity.
[0050]
In the present invention, it is preferable in terms of toner productivity that the pulverized surfaces of the dispersion rotor and liner in the surface modifying apparatus are subjected to abrasion resistance treatment. In addition, the abrasion-resistant processing method is not limited at all. Further, the blade shapes of the dispersion rotor and liner in the surface modification device are not limited at all.
[0051]
True specific gravity is 1.2g / cm^ThreeIn the case of producing the following toner particles, so-called full-color toner particles, the true specific gravity is 1.2 g / cm.^ThreeThe yield tends to be inferior because it is difficult to classify compared with a magnetic toner exceeding 1, but in the present invention, the true specific gravity is 1.2 g / cm 2.^ThreeEven in the production of toner particles for full toner particles such as the following, since a classification rotor is built in the vicinity of the dispersion rotor, it is possible to maintain a high yield, so from the viewpoint of fine powder removal classification Are also preferably applied. The effect of improving the yield when producing toner particles having a small particle size distribution with a weight average particle size of 7 μm or less, more preferably 6 μm or less, is remarkable.
[0052]
The constituent material of the toner particles containing the binder resin, the colorant and the wax according to the present invention will be described.
[0053]
As the binder resin used in the present invention, various resin compounds conventionally known as binder resins can be used. For example, vinyl resins, phenol resins, natural resin-modified phenol resins, natural resin-modified resins. Maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaroindene resin, petroleum resin, etc. . Of these, vinyl resins and polyester resins are preferable in terms of chargeability and fixability.
[0054]
Examples of vinyl resins include styrene; o-methylstyrene, m-methylstyrene, p-methylenestyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethyl. Styrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene Styrene derivatives such as pn-dodecylstyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene; vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride. Vinyl halides such as: vinyl acetate, vinyl propionate, benzo Vinyl esters such as vinyl acid; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, Α-methylene aliphatic monocarboxylic acid esters such as phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, acrylic Acrylic acid esters such as n-octyl acid, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinylmethyl Vinyl ethers such as ether, vinyl ethyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone Vinyl naphthalenes: acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; esters of α, β-unsaturated acids, diesters of dibasic acids; acrylic acid, methacrylic acid, Acrylic acid such as α-ethylacrylic acid, crotonic acid, cinnamic acid, vinyl acetic acid, isocrotonic acid, angelic acid, and α- or β-alkyl derivatives thereof; fumaric acid, maleic acid, citraconic acid, alkenyl succinic acid, itako Examples thereof include polymers using vinyl monomers such as unsaturated dicarboxylic acids such as acid, mesaconic acid, dimethylmaleic acid and dimethylfumaric acid and monoester derivatives or anhydrides thereof.
[0055]
In the vinyl resin, vinyl monomers as described above are used alone or in combination of two or more. Among these, a combination of monomers that is a styrene copolymer or a styrene-acrylic copolymer is preferable.
[0056]
Further, the binder resin used in the present invention may be a polymer or a copolymer crosslinked with a crosslinkable monomer as exemplified below if necessary.
[0057]
As the crosslinkable monomer, a monomer having at least two crosslinkable unsaturated bonds can be used. As such a crosslinkable monomer, various monomers as shown below are conventionally known and can be suitably used for the toner of the present invention.
[0058]
Examples of the crosslinkable monomer include divinylbenzene and divinylnaphthalene as aromatic divinyl compounds; diacrylate compounds linked with an alkyl chain such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1 , 4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of the above compounds with methacrylates; Examples of diacrylate compounds linked with an alkyl chain include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyethylene glycol. Coal # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and the above compounds in which the acrylate is replaced with methacrylate; diacrylate compounds linked by a chain containing an aromatic group and an ether bond For example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and the above The thing which replaced the acrylate of the compound with the methacrylate is mentioned; As a polyester type diacrylate, a brand name MANDA (Nippon Kayaku) etc. are mentioned, for example.
[0059]
Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallylcia Examples thereof include nurate and triallyl trimellitate.
[0060]
As binder resin used for this invention, the polyester resin shown below is also preferable. It is preferable that 45 to 55 mol% of the polyester resin is an alcohol component and 55 to 45 mol% is an acid component in all components.
[0061]
Examples of alcohol components include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, and 1,6- Xanthdiol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol derivatives represented by the following formula (B);
[0062]
[Chemical 1]

(In the formula, R represents an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)
[0063]
(C) diols represented by the formula;
[0064]
[Chemical formula 2]

[0065]
Or polyhydric alcohols, such as glycerin, sorbit, sorbitan, etc. are mentioned.
[0066]
As the acid component, carboxylic acid can be preferably exemplified, and as the divalent carboxylic acid, benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride or anhydrides thereof; succinic acid, adipine Alkyl dicarboxylic acids such as acid, sebacic acid and azelaic acid or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid or anhydrides thereof; Examples of the acid include trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and its anhydride.
[0067]
A particularly preferable alcohol component of the polyester resin is a bisphenol derivative represented by the formula (B), and examples of the acid component include phthalic acid, terephthalic acid, isophthalic acid or anhydride thereof, succinic acid, n-dodecenyl succinic acid, or the like. Examples thereof include dicarboxylic acids such as anhydride, fumaric acid, maleic acid and maleic anhydride; trimellitic acid or tricarboxylic acids of anhydride thereof. This is because the heat roller fixing toner using a polyester resin obtained from these acid components and alcohol components as a binder resin has good fixability and excellent offset resistance.
[0068]
The colorant used in the toner according to the present invention is adjusted to black by a chromatic colorant such as carbon black, a magnetic material, a yellow colorant, a magenta colorant, and a cyan colorant described below as a black colorant. A combination is used.
[0069]
As the yellow colorant, compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 168, 174, 176, 180, 181 and 191 are preferably used.
[0070]
As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 are particularly preferred.
[0071]
As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like can be used particularly preferably.
[0072]
These colorants can be used alone or mixed and further used in the form of a solid solution. In the present invention, the colorant is selected in consideration of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. These chromatic colorants are contained in 1 to 20 parts by mass of toner with respect to 100 parts by mass of the binder resin. When a magnetic material is used as the magnetic toner, it is contained in 60 to 200 parts by mass of toner with respect to 100 parts by mass of the binder resin.
[0073]
In the toner according to the present invention, the following waxes are contained in the toner from the viewpoint of improving releasability from the fixing member during fixing and improving fixability. Paraffin wax and derivatives thereof, microcrystalline wax and derivatives thereof, Fischer-Tropsch wax and derivatives thereof, polyolefin wax and derivatives thereof, carnauba wax and derivatives thereof, and the derivatives include oxides and block copolymers with vinyl monomers. And graft modified products. In addition, alcohols, fatty acids, acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes, mineral waxes, petrolactams and the like can also be used.
[0074]
In the toner according to the present invention, it is preferable to use a charge control agent mixed (internally added) to toner particles or mixed (externally added) with toner particles. The charge control agent makes it possible to control the optimum charge amount according to the development system. In particular, in the toner of the present invention, the balance between the particle size distribution and the charge amount can be further stabilized. The negative charge control agent for controlling the toner to negative charge includes the following substances.
[0075]
For example, organometallic complexes and chelate compounds are effective, and there are monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acid metal complexes, and aromatic dicarboxylic acid metal complexes. Others include aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids and aromatic polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenols.
[0076]
The following substances are used as positive charge control agents for controlling the toner to positive charge.
[0077]
For example, modified products such as nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and analogs of phosphonium salts thereof. Onium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide) Metal salts of higher fatty acids; diorganotin oxides such as dibutyl tin oxide, dioctyl tin oxide, dicyclohexyl tin oxide; dibutyl tin borate, dioctyl tin borate, dicyclohexane Such as diorgano tin borate such Rusuzuboreto; there is.
[0078]
These charge control agents can be used alone or in combination of two or more.
[0079]
The above-described charge control agent is preferably used in the form of fine particles. In this case, the number average particle diameter of these charge control agents is particularly preferably 4 μm or less, and more preferably 3 μm or less. When these charge control agents are internally added to the toner, they are preferably contained in the toner in an amount of 0.1 to 20 parts by weight, particularly 0.2 to 10 parts by weight, based on 100 parts by weight of the binder resin.
[0080]
In order to produce the toner particles according to the present invention, for example, a binder resin, a wax, a metal salt or a metal complex, a pigment or dye as a colorant, a magnetic material, a charge control agent as required, other additives, etc. Are mixed thoroughly by a mixer such as a Henschel mixer and a ball mill, and then melted and kneaded using a heat kneader such as a heating roll, kneader, and extruder to mix the resins with each other. After dispersing or dissolving the dye and the magnetic substance, cooling and solidifying, and coarsely pulverizing the solidified product, toner particles having a desired particle diameter can be obtained by the fine pulverization / surface treatment method of the present invention. At this time, when particles having a predetermined particle size or more are present, classification or sieving is performed after the fine pulverization step or the surface treatment step in order to remove particles having a predetermined particle size or more. Also good. Further, in order to improve fluidity, transferability and the like, the toner particles are externally mixed with an external additive such as an inorganic fine powder and used as a toner.
[0081]
The particle size distribution of the toner can be measured by various methods. In the present invention, the following measurement apparatus was used.
[0082]
That is, a Coulter Counter TA-II type or Coulter Multisizer II (manufactured by Coulter, Inc.) was used as a measuring device. As the electrolytic solution, a 1% NaCl aqueous solution is prepared using first grade sodium chloride. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the aqueous electrolyte solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion process for about 1 to 3 minutes with an ultrasonic disperser. Using the measuring apparatus, a 100 μm aperture is used as an aperture, and the volume and number of toners are measured. Was calculated. Then, the weight-average weight average particle diameter obtained from the volume distribution according to the present invention was obtained.
[0083]
【Example】
Hereinafter, the present invention will be described in detail with specific toner production methods, examples, and comparative examples.
[0084]
<Example 1>
・ Unsaturated polyester resin 100 parts by mass
(Polyoxypropylene (2,2) -2,2bis (4-hydroxyphenyl) propane / polyoxyethylene (2,2) -2,2bis (4-hydroxyphenyl) propane / terephthalic acid / trimellitic anhydride / Unsaturated polyester resin consisting of fumaric acid)
・ 6 parts by mass of copper phthalocyanine pigment
(C.I. Pigment Blue 15: 3)
・ 5 parts by weight of paraffin wax
(Maximum endothermic peak 73 ° C)
Charge control agent (salicylic acid metal complex) 2 parts by mass
After mixing the ingredients of the above formulation with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Kako Co., Ltd.), a twin-screw kneader (PCM-30 type, Ikekai Tekko Co., Ltd.) set at a temperature of 110 ° C. Kneaded). The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized product for toner production. The true specific gravity of the toner composition is 1.1 g / cm.^ThreeMet.
[0085]
The obtained toner raw material crushed material was subjected to a collision type airflow crusher (high pressure gas pressure: 0.6 MPa, flow rate: 27 Nm) using the high pressure gas shown in FIG.^Three/ Min) and the airflow classifier turboplex (350-ATP type: manufactured by Hosokawa Micron Co., Ltd.) shown in FIG. 7 was pulverized using a fine pulverizer equipped with a closed circuit as shown in FIG. The obtained finely pulverized product contains a weight average diameter of 4.8 μm, a number average diameter of 3.6 μm (43% by number of particles having a particle size of 3.17 μm or less, and 0.0 volume of particles having a particle size of 8.00 μm or more). The average circularity was 0.936.
[0086]
Next, using the surface modifying apparatus as shown in FIGS. 8 and 9 for the obtained finely pulverized product, 1.3 kg of the finely pulverized product was charged each time, and while removing fine particles at a classification rotor rotation speed of 7300 rpm, Surface treatment was performed for 60 seconds at a dispersion rotor rotational speed of 5800 rpm (rotational peripheral speed 130 m / sec) (after finishing the introduction of finely pulverized material from the raw material supply port 3, processing for 60 seconds, and then opening the discharge valve 8 as a processed product. Took out). At this time, in this example, ten square disks were installed on the upper part of the dispersion rotor, the distance between the guide ring and the upper square disk of the dispersion rotor was 30 mm, and the distance between the dispersion rotor and the liner was 5 mm. Also, blower air volume is 14m^Three/ Min, the temperature of the refrigerant passed through the jacket and the cold air temperature T1 were set to -20 ° C.
[0087]
As a result of repeating the operation in this state for 20 minutes, the temperature T2 behind the classification rotor was stabilized at 27 ° C. Therefore, ΔT (T2−T1) was 47 ° C.
[0088]
After the treatment, a weight average diameter of 5.2 μm, a number average diameter of 4.9 μm (containing 12% by number of particles having a particle size of 3.17 μm or less and 0.0% by volume of particles having a particle size of 8.00 μm or more), average A toner particle having a circularity of 0.953 was obtained with a classification yield of 85% (the number average diameter of the finely pulverized product introduced into the surface treatment step is A, and the number average diameter of the particles obtained by the surface treatment apparatus is B. B / A is 1.36). Further, when the classification rotor and the dispersion rotor were confirmed, no fused material of the toner raw material was found.
[0089]
Furthermore, using a mesh surface fixed wind sieve high voltor (NR-300 type, manufactured by Shin Tokyo Machine Co., Ltd .: air brush attached to the back of the wire mesh), this has a diameter of 30 cm, an opening of 29 μm, and an average wire diameter of 30 μm A metal mesh is installed, and the toner powder has an air flow of 5 Nm.^Three/ Min. And supplied to a gas stream to separate coarse particles to obtain toner particles. Particles having a particle size of 12.7 μm or more were less than 0.1% by volume. The separated coarse particles were about 0.2% of the toner particles passed through the sieve.
[0090]
The specific surface area by the BET method is 200 m with respect to 100 parts by mass of the obtained toner particles.²A toner was obtained by externally adding 1.8 parts by mass of hydrophobic silica having a / g content. 95 parts by mass of an acrylic-coated ferrite carrier was mixed with 5 parts by mass of the toner to obtain a developer.
[0091]
Using this developer, an image was evaluated under normal temperature and humidity (23 ° C, 60% RH) using a Canon full-color copier CLC1000 remodeled machine (with the oil application mechanism of the fixing unit removed). Even at the endurance of 10,000 sheets, the image density at the initial stage and after the endurance did not change, and a high-quality image without fogging was obtained. Further, double-sided images were formed, but no occurrence of offset was observed on the front and back surfaces of the transfer material. Further, when an image was formed on an OHP sheet, an image with good transparency was obtained. Here, the transfer material (basis weight 199 g / m from the photosensitive member)²The transfer efficiency to paper was as high as 93%.
[0092]
Furthermore, similar image evaluation (5,000 sheets durability) was performed under high temperature and high humidity (32.5 ° C., 85% RH), but a good image was obtained.
[0093]
<Example 2>
Using the same pulverized toner raw material as in Example 1, the same pulverization apparatus as in Example 1 was used, and the pulverization conditions were changed and pulverization was performed. The resulting finely pulverized product has a weight average diameter of 5.2 μm, a number average diameter of 4.1 μm (containing 37% by number of particles having a particle diameter of 3.17 μm or less, and 0 having a particle diameter of 8.00 μm or more). The average circularity was 0.935. Next, the obtained finely pulverized product was subjected to a surface treatment for 60 seconds using the same surface modifying apparatus as in Example 1 while removing fine particles in the same manner.
[0094]
As a result of repeating the surface modification treatment for 20 minutes, the temperature T2 behind the classification rotor was stabilized at 28 ° C. Therefore, ΔT (T2−T1) was 48 ° C.
[0095]
After the treatment, the weight average diameter is 5.2 μm, the number average diameter is 5.0 μm (9% by number of particles having a particle size of 3.17 μm or less, 0.5% by volume of particles having a particle size of 8.00 μm or more, B / A was 1.22), and toner particles having an average circularity of 0.952 were obtained with a classification yield of 81%. When the classification rotor and the dispersion rotor were confirmed, no fused material of the toner raw material was found.
[0096]
Further, using a similar screen-fixed wind screen high voltor, coarse particles were separated to obtain toner particles having a particle size of 12.7 μm or more of less than 0.1% by volume. The separated coarse particles were about 0.2% of the toner particles passed through the sieve.
[0097]
In the same manner as in Example 1, hydrophobic silica was externally mixed with the obtained toner particles to obtain a toner, and further, an acrylic-coated ferrite carrier was mixed to obtain a developer.
[0098]
When this developer was used to evaluate image output on a Canon full-color copying machine CLC1000 remodeled machine in the same manner as in Example 1, a good image was obtained as in Example 1. Also, the transfer material (basis weight 199 g / m²The transfer efficiency to paper was 91%.
[0099]
<Example 3>
Using the same toner raw material crushed material as in Example 1, in the surface modification apparatus, fine pulverization and surface modification treatment were performed in the same manner as in Example 2 except that the surface modification treatment time was 45 seconds. It was.
[0100]
As a result of repeating the surface modification treatment for 20 minutes, the temperature T2 behind the classification rotor was stabilized at 25 ° C. Therefore, ΔT (T2−T1) was 45 ° C.
[0101]
After the treatment, the weight average diameter is 5.2 μm, the number average diameter is 4.9 μm (11% by number of particles having a particle size of 3.17 μm or less, 0.5% by volume of particles having a particle size of 8.00 μm or more, B / A was 1.20), and toner particles having an average circularity of 0.948 were obtained with a classification yield of 83%. When the classification rotor and the dispersion rotor were confirmed, no fused material of the toner raw material was found.
[0102]
Further, using a similar screen-fixed wind screen high voltor, coarse particles were separated to obtain toner particles having a particle size of 12.7 μm or more of less than 0.1% by volume. The separated coarse particles were about 0.2% of the toner particles passed through the sieve.
[0103]
In the same manner as in Example 1, hydrophobic silica was externally mixed with the obtained toner particles to obtain a toner, and further, an acrylic-coated ferrite carrier was mixed to obtain a developer.
When this developer was used to evaluate image output on a Canon full-color copying machine CLC1000 remodeled machine in the same manner as in Example 1, a good image was obtained as in Example 1. Also, the transfer material (basis weight 199 g / m²The transfer efficiency to paper was 89%.
[0104]
<Example 4>
Using the same toner raw material crushed material as in Example 1, in the surface modification device, fine pulverization and surface modification treatment were performed in the same manner as in Example 2 except that the surface modification treatment time was 30 seconds. It was.
[0105]
As a result of repeating the surface modification treatment for 20 minutes, the temperature T2 behind the classification rotor was stabilized at 19 ° C. Therefore, ΔT (T2−T1) was 39 ° C.
[0106]
After the treatment, a weight average diameter of 5.2 μm, a number average diameter of 4.8 μm (containing 13% by number of particles having a particle size of 3.17 μm or less, 0.5% by volume of particles having a particle size of 8.00 μm or more, B / A was 1.17), and toner particles having an average circularity of 0.944 were obtained with a classification yield of 85%. When the classification rotor and the dispersion rotor were confirmed, no fused material of the toner raw material was found.
[0107]
Further, using a similar screen-fixed wind screen high voltor, coarse particles were separated to obtain toner particles having a particle size of 12.7 μm or more of less than 0.1% by volume. The separated coarse particles were about 0.2% of the toner particles passed through the sieve.
[0108]
In the same manner as in Example 1, hydrophobic silica was externally mixed with the obtained toner particles to obtain a toner, and further, an acrylic-coated ferrite carrier was mixed to obtain a developer.
[0109]
When this developer was used to evaluate image output on a Canon full-color copying machine CLC1000 remodeled machine in the same manner as in Example 1, a good image was obtained as in Example 1. Also, the transfer material (basis weight 199 g / m²The transfer efficiency to paper was 86%.
[0110]
<Example 5>
Using the same pulverized toner raw material as in Example 1, the same pulverization apparatus as in Example 1 was used, and the pulverization conditions were changed and pulverization was performed. The obtained finely pulverized product has a weight average particle size of 6.6 μm, a number average particle size of 5.5 μm (containing 53% by number of particles having a particle size of 4.00 μm or less, and 2 particles having a particle size of 10.08 μm or more. The average circularity was 0.923. Next, the obtained finely pulverized product was similarly removed using the same surface modifying apparatus as in Example 1 (the blower air volume was 15 m).^Three/ Min), surface treatment was performed for 80 seconds.
[0111]
As a result of repeating the surface modification treatment for 20 minutes, the temperature T2 behind the classification rotor was stabilized at 31 ° C. Therefore, ΔT (T2−T1) was 51 ° C.
[0112]
After the treatment, a weight average diameter of 6.9 μm, a number average diameter of 6.6 μm (containing 12% by number of particles having a particle size of 4.00 μm or less, 2.3% by volume of particles having a particle size of 10.08 μm or more, B / A was 1.20), and toner particles having an average circularity of 0.953 were obtained with a classification yield of 81%. When the classification rotor and the dispersion rotor were confirmed, no fused material of the toner raw material was found.
[0113]
Further, using the same fixed screen wind-screen sieving high voltor, coarse particles were separated to obtain toner particles having a particle size of 16.0 μm or more of less than 0.1% by volume. Further, the separated coarse particles were about 0.4% of the toner particles passed through the sieve.
[0114]
In the same manner as in Example 1, 1.4 parts by mass of hydrophobic silica was externally added to the obtained toner particles to prepare a toner, and further, an acrylic-coated ferrite carrier was mixed to prepare a developer.
[0115]
When this developer was used to evaluate image output on a Canon full-color copying machine CLC1000 remodeled machine in the same manner as in Example 1, a good image was obtained as in Example 1. Also, the transfer material (basis weight 199 g / m²The transfer efficiency to paper was 91%.
[0116]
<Comparative Example 1>
Using the same coarse toner raw material as in Example 1, the mechanical pulverizer 301 shown in FIG. 1 (Turbo Mill T250-RS type manufactured by Turbo Industry Co., Ltd.) was used, and the gap between the pulverization rotor and the liner was 1.0 mm. Crushing rotor rotation speed 12300 rpm (= rotor tip peripheral speed 160 m / sec), air flow 6 Nm^Three/ Min (inlet temperature -15 ° C).
[0117]
Even if the supply amount of the raw material crushed material was adjusted, only a finely pulverized material having a weight average diameter of 7.5 μm and a number average diameter of 4.4 μm was obtained.
[0118]
<Comparative example 2>
Using the same coarsely-crushed toner raw material as in Example 1, using a mechanical fine crusher super rotor (Nisshin Engineering Co., Ltd. SR-25 type), the gap between the crushing rotor and the liner is 1.0 mm, and the crushing rotor rotation speed 12000rpm (= rotor tip peripheral speed 160m / sec), air flow 6Nm^Three/ Min (inlet temperature −40 ° C.).
[0119]
Even when the supply amount of the raw material crushed material was adjusted, only a finely pulverized material having a weight average diameter of 7.2 μm and a number average diameter of 4.1 μm was obtained.
[0120]
<Comparative Example 3>
Using the same toner raw material crushed material as in Example 1, a closed circuit was assembled by using a super-rotor SR-25 type mechanical pulverizer and a turbo classifier (Nisshin Engineering Co., Ltd. TC-25IIIS type). When pulverization was performed, the supply amount of the raw crushed material was adjusted to about 1/3 that of Comparative Example 2, and the weight average diameter was 4.8 μm, the number average diameter was 3.8 μm (particles having a particle diameter of 3.17 μm or less were 38 A finely pulverized product having an average circularity of 0.932 was obtained. Compared with the finely pulverized product of Example 1, this was poor in spheroidization.
[0121]
Using an elbow jet classifier (EJ-15-3 type), this finely pulverized product contains 12% by number of particles having a weight average diameter of 5.2 μm and a number average diameter of 4.9 μm (particle diameter of 3.17 μm or less). The particles having a diameter of 8.00 μm or more were contained by 0.0 vol%), and the average circularity was classified to 0.941.
[0122]
Next, in the same manner as in Example 1, hydrophobic silica was externally mixed with the obtained toner particles to obtain a toner, which was further mixed with an acrylic-coated ferrite carrier to obtain a developer. Using this developer, image evaluation was carried out with a Canon full-color copying machine CLC1000 remodeled in the same manner as in Example 1. As a result, a good image was obtained under normal temperature and normal humidity. Then, the image density gradually decreased and the fog increased. When the toner was observed under a microscope, uncolored particles that appeared to be free wax were observed. This seems to have influenced the chargeability. Also, the transfer material (basis weight 199 g / m²The transfer efficiency to paper was 84%.
[0123]
<Comparative example 4>
Using a elbow jet classifier (EJ-15-3 type), the finely pulverized toner obtained in Example 5 was 6.9 μm in weight average diameter, 6.6 μm in number average diameter (12 particles having a particle diameter of 4.00 μm or less). Toner particles having an average circularity of 0.926 and a number% of particles containing 2.3% by volume of particles having a particle size of 10.08 μm or more.
[0124]
Next, after that, the classified product was subjected to surface modification using a surface modification apparatus shown in FIG.
[0125]
In FIG. 12, 151 is a main body casing, 158 is a stator, 177 is a stator jacket, 163 is a recycling pipe, 159 is a discharge valve, 119 is a discharge chute, and 164 is a raw material charging chute.
[0126]
In the apparatus, the powder particles and other fine solid particles supplied from the raw material charging chute 164 are instantaneously generated by a plurality of rotor blades 155 disposed in a rotating rotor 162 that rotates mainly at high speed in the impact chamber 168. In addition, the fine particles collide with the surrounding stator 158 and disperse in the system while loosening the agglomeration of the powder particles or other fine solid particles, and at the same time other fine solid particles on the powder particle surface. Is attached by electrostatic force, van der Waals force or the like, or in the case of powder particles only, the particles are rounded or spheroidized. This state advances as the particles fly and collide. That is, the particles are processed by passing through a recycle pipe 163 a plurality of times as the airflow generated by the rotation of the rotor blade 155 flows. Further, when the particles are repeatedly hit from the rotor blade 155 and the stator 158, the other fine solid particles are uniformly dispersed and fixed on the surface of the powder particles or in the vicinity thereof, or only the powder particles are used. The shape of the particles becomes spherical.
[0127]
The particles that have been processed are collected by the bag filter 222 or the like that passes through the discharge chute 119 and communicates with the suction blower 224 by opening the discharge valve 159 by the discharge valve control device 128.
[0128]
In this comparative example, a rotating rotor 162 having a rotor blade 155 with a longest diameter of 242 mm was used, and the rotating peripheral speed of the rotating rotor 162 was 90 m / sec. The amount of finely pulverized product was 300 g and the cycle time was 180 seconds to obtain surface modified particles.
[0129]
The surface-modified particles after the treatment contain a weight average diameter of 6.7 μm, a number average diameter of 6.4 μm (18% by number of particles having a particle size of 4.00 μm or less, and 2.4 particles having a particle size of 10.08 μm or more). Containing% by volume, B / A was 0.97), and the average circularity was 0.941.
[0130]
Compared to the classification particle size before surface modification, it was broad. This is presumably because the toner was excessively pulverized and the fine powder increased during the surface modification. Further, when the in-flight inspection was performed after the operation was completed, the rotor blade was slightly fused.
[0131]
Next, as in Example 5, the toner particles obtained were externally mixed with hydrophobic silica to obtain a toner, which was further mixed with an acrylic-coated ferrite carrier to obtain a developer. Using this developer, image evaluation was carried out with a Canon full color copier CLC1000 remodeled machine as in Example 1. As a result, the image density gradually decreased and fogging increased. When the toner was observed under a microscope, uncolored particles that appeared to be free wax were observed. This seems to have influenced the chargeability. Also, the transfer material (basis weight 199 g / m²The transfer efficiency to paper was 86%.
[0132]
<Example 6>
・ Unsaturated polyester resin 100 parts by mass
・ Magenta pigment 4 parts by mass
(CI Pigment Red 184)
・ Polyethylene wax 4 parts by mass
(Maximum endothermic peak 102 ° C)
Charge control agent (salicylic acid metal complex) 2 parts by mass
The materials of the above formulation were thoroughly mixed with a Henschel mixer (FM-75 type) and then kneaded with a twin-screw kneader (PCM-30 type) set at a temperature of 120 ° C. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized product for toner production.
[0133]
Collision type airflow crusher using the high-pressure gas shown in FIG. 2 (I-5 type, manufactured by Nippon New Match Industrial Co., Ltd .: high-pressure gas pressure: 0.6 MPa, flow rate: 5 Nm^Three/ Min) and the airflow classifier shown in FIG. 6 was pulverized using a fine pulverizer with a closed circuit as shown in FIG. The obtained finely pulverized product contains a weight average diameter of 7.2 μm, a number average diameter of 4.2 μm (63% by number of particles having a particle size of 4.00 μm or less, and 2.1 volumes of particles having a particle size of 12.7 μm or more). The average circularity was 0.922.
[0134]
Next, the obtained finely pulverized product was removed using a surface reformer similar to that of Example 1 and fine particles were similarly removed at a classification rotor rotational speed of 6800 rpm, while a dispersed rotor rotational speed was 5200 rpm (rotational peripheral speed was 115 m / sec. ) For 45 seconds.
[0135]
As a result of repeating the surface modification treatment in this state for 20 minutes, the temperature T2 behind the classification rotor was stabilized at 27 ° C. Therefore, ΔT (T2−T1) was 47 ° C.
[0136]
After the treatment, a weight average diameter of 7.2 μm, a number average diameter of 6.8 μm (containing 12% by number of particles having a particle size of 4.00 μm or less, 2.3% by volume of particles having a particle size of 12.7 μm or more, B / A was 1.62), and toner particles having an average circularity of 0.933 were obtained with a classification yield of 75%. When the classification rotor and the dispersion rotor were confirmed, no fused material of the toner raw material was found.
[0137]
Further, using an elbow jet classifier (EJ-15-3 type), coarse particles having a size of 12.7 μm or more were classified and removed to obtain toner particles having a particle size of 12.7 μm or more of less than 0.1% by volume. Further, the separated coarse particles were about 9% of the toner particles passed through the elbow jet classifier.
[0138]
In the same manner as in Example 1, hydrophobic silica was externally mixed with the obtained toner particles to obtain a toner, and further, an acrylic-coated ferrite carrier was mixed to obtain a developer.
[0139]
When this developer was used to evaluate image output on a Canon full-color copying machine CLC1000 remodeled machine in the same manner as in Example 1, a good image was obtained as in Example 1. Also, the transfer material (basis weight 199 g / m²  The transfer efficiency to paper was 87%.
[0140]
<Example 7>
・ Styrene-nbutyl acrylate-monobutyl acrylate maleate
100 parts by mass of copolymer
・ 100 parts by mass of magnetic iron oxide (average particle size 0.22 μm)
・ 3 parts by mass of low molecular weight ethylene-propylene copolymer
・ Iron complex of monoazo dye 2 parts by mass
The materials of the above formulation were thoroughly mixed with a Henschel mixer (FM-75 type) and then kneaded with a twin-screw kneader (PCM-30 type) set at a temperature of 130 ° C. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized product for toner production.
[0141]
The resulting coarsely crushed product is a collision type airflow crusher type I-5 using the high pressure gas shown in FIG. 2 (high pressure gas pressure: 0.6 MPa, flow rate: 5 Nm).^Three/ Min) and the airflow classifier (DS-5 type, manufactured by Nippon New Matchoc Kogyo Co., Ltd.) shown in FIG. 5 was pulverized by using a fine pulverizer equipped with a closed circuit as shown in FIG. The finely pulverized product thus obtained contained 49% by number of particles having a weight average diameter of 7.8 μm and a number average diameter of 4.7 μm (particle diameter of 4.00 μm or less, and 2.3 volumes of particles having a particle diameter of 12.7 μm or more. %), And the average circularity was 0.923.
[0142]
Next, the obtained finely pulverized product was subjected to the same surface reforming apparatus as in Example 1 (dispersion rotor rotational speed 5200 rpm (rotational peripheral speed 115 m / sec), the temperature of the refrigerant passed through the jacket and the cold air temperature T1 to 0 ° C. The surface treatment was similarly performed for 45 seconds while fine particles were removed at a classification rotor rotational speed of 6600 rpm.
[0143]
As a result of repeating the surface modification treatment in this state for 20 minutes, the temperature T2 behind the classification rotor was stabilized at 47 ° C. Therefore, ΔT (T2−T1) was 47 ° C.
[0144]
After the treatment, a weight average diameter of 8.0 μm, a number average diameter of 7.7 μm (11% by number of particles having a particle size of 4.00 μm or less, 2.8% by volume of particles having a particle size of 12.7 μm or more, B / A was 1.64), and toner particles having an average circularity of 0.933 were obtained with a classification yield of 78%. When the classification rotor and the dispersion rotor were confirmed, no fused material of the toner raw material was found.
[0145]
Further, using an elbow jet classifier (EJ-15-3 type), coarse particles having a size of 12.7 μm or more were classified and removed to obtain toner particles having a particle size of 12.7 μm or more of less than 0.1% by volume. The specific surface area by the BET method is 110 m with respect to 100 parts by mass of the toner particles.²1.2 parts by mass of hydrophobic silica of / g was added and externally added and mixed with a Henschel mixer to obtain a toner.
[0146]
Using this toner, it is mounted on a Canon laser jet printer LBP-950 remodeling machine (modified from A4 horizontal feed to 32 sheets / min. To 50 sheets / min), and an image output test is performed to evaluate the image characteristics of the toner. did.
[0147]
When 5,000 images were printed and evaluated under normal temperature and normal humidity and high temperature and high humidity, there was no change in the image density between the initial stage and the endurance, and a high-quality image without fogging was obtained. Further, double-sided images were formed, but no occurrence of offset was observed on the front and back surfaces of the transfer material.
[0148]
【The invention's effect】
According to the method for producing a toner of the present invention, a step of melt-kneading a composition containing at least a binder resin and a colorant, cooling and solidifying the kneaded product, and finely pulverizing the solidified product to obtain a finely pulverized product, And a toner manufacturing method having a surface modification step of surface-treating the obtained finely pulverized product to obtain surface-modified particles, suppressing the influence of heat and generation of fine powder during the surface modification, Method for producing a toner capable of arbitrarily controlling the surface shape and obtaining a long-life toner having good developability, transferability, cleaning property, and stable chargeability by controlling the surface shape of the toner Can be provided. Therefore, according to the method for producing a toner of the present invention, toner particles containing a wax component and using a resin having a low melting point, a low softening point, or a low glass transition point can be efficiently produced. In particular, toner particles having a weight average particle size of 7 μm or less (more preferably 6 μm or less) and having a controlled surface shape can be efficiently produced.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of an example of a collision-type airflow pulverizer used in a toner pulverization process of the present invention.
FIG. 2 is a schematic cross-sectional view of another example of an impingement airflow pulverizer used in the toner pulverization step of the present invention.
FIG. 3 is a flow diagram of an example pulverizer-classifier used in the fine pulverization step of the present invention.
FIG. 4 is a flowchart of another example of a pulverizer-classifier used in the fine pulverization process of the present invention.
FIG. 5 is a schematic cross-sectional view of an example classifier used in the pulverization process of the present invention.
FIG. 6 is a schematic cross-sectional view of another example classifier used in the pulverization process of the present invention.
FIG. 7 is a schematic cross-sectional view of another example classifier used in the pulverization process of the present invention.
FIG. 8 is a schematic cross-sectional view of an example surface modification apparatus used in the surface modification step of the present invention.
FIG. 9 is a schematic view showing an example of a top view of the dispersion rotor shown in FIG. 8;
FIG. 10 is a schematic sectional view of a mechanical crusher used in a conventional crushing process.
11 is a perspective view of a rotor of the mechanical crusher shown in FIG.
FIG. 12 is a schematic cross-sectional view of an example mechanical pulverizer used in a surface modification step of a comparative example.
[Explanation of symbols]
1: Classification rotor
2: Fine powder recovery
3: Raw material supply port
4: Liner (fixed body)
5: Cold air inlet
6: Distributed rotor (rotating body)
7: Product outlet
8: Discharge valve
9: Guide ring (guide plate)
10: Square disk
11: First space
12: Second space
15: Casing
21: Accelerating tube
22: Acceleration tube throat
23: High pressure gas supply nozzle
24: Object to be crushed
25: Crushable object supply cylinder
26: High-pressure gas supply port
27: High-pressure gas chamber
28: High-pressure gas introduction pipe
29: Acceleration tube exit
30: Colliding member
32: Grinding interior wall
33: Crushing material outlet
34: Crushing chamber
35: Grinding chamber
36: Colliding member
37: Collision surface
38: Interior wall for grinding
39: Crushing material outlet
41: Object to be crushed supply port
42: Accelerating tube
43: High-pressure gas supply nozzle
44: Acceleration tube exit
47: Classification louver
48: Distributed louver
49: Classification louver
51: Main body casing
52: Classification room
53: Information room
54: Classification rotor
55: Raw material inlet
56: Air inlet
57: Distributed louver
58: Fine powder discharge pipe
59: Hopper
212: Swirl chamber
219: Pipe
220: Distributor
222: Bug filter
224: Suction blower
229: Collection cyclone
301: Mechanical crusher
302: Powder outlet
310: Stator
311: Powder inlet
312: Rotating shaft
313: Casing
314: Rotor
315: Fixed quantity feeder
316: Jacket
317: Cooling water supply port
318: Cooling water outlet
320: Rear room

Claims (17)

A composition comprising at least a binder resin and a colorant is melt-kneaded, the resulting kneaded product is cooled and solidified, and the cooled and solidified product is finely pulverized to obtain a finely pulverized product, and the obtained fine pulverization In a toner production method having a surface modification step of surface-treating a product to obtain surface-modified particles,
The pulverization step is a step of obtaining a pulverized product having a weight average particle diameter of 3 to 11 μm using a collision type air pulverizer using a high-pressure gas such as a jet air flow,
The surface modification step is performed using a batch type surface modification apparatus, and the batch type surface modification apparatus includes classification means for continuously discharging and removing fine particles having a predetermined particle size or less to the outside of the apparatus. , Surface treatment means using mechanical impact force, and guide means for partitioning the space between the classification means and the surface treatment means into a first space and a second space,
The finely pulverized product is introduced into the first space, and mechanical impact force is used via the second space while continuously removing and removing fine particles having a predetermined particle diameter or less from the apparatus by the classification means. By introducing into the surface treatment means, performing surface modification treatment, and circulating again to the first space, by repeating predetermined time classification and surface modification treatment using mechanical impact force, the particle size is less than the predetermined particle size. step der the microparticles to obtain a surface modification treatment particles removed predetermined amount is,
The surface treatment using the mechanical impact force in the surface modification step has a plurality of square disks or cylindrical pins on the upper surface, and a rotating body on a disk that rotates at high speed and the rotating body. A method for producing toner, comprising: a surface treatment device comprising a fixed body fixedly arranged at intervals .   2. The toner according to claim 1, wherein the number average particle size of the particles obtained in the surface modification step is larger than the number average particle size of the finely pulverized product introduced into the surface modification step. Manufacturing method. The number average diameter A of the finely pulverized product introduced into the surface modification step and the number average diameter B of the surface modified particles obtained in the surface modification step are as follows: 1.02 ≦ B / A ≦ 2.00
The toner production method according to claim 1, wherein:   The average circularity of particles obtained in the surface modification step is 0.01 to 0.05 greater than the average circularity of the finely pulverized product introduced into the surface modification step. The method for producing a toner according to any one of 1 to 3.   5. The method for producing a toner according to claim 1, wherein the composition containing at least a binder resin and a colorant contains a wax.   6. The method for producing a toner according to claim 1, wherein the binder resin contains at least a polyester resin. The toner production method according to claim 1, wherein the toner particles have a true specific gravity of 1.2 g / cm ³ or less.   8. The method for producing a toner according to claim 1, wherein the toner particles constitute a full-color toner. Is classification means of the surface modification step, a classification means according to the rotation of the impeller type classifying rotor, guide means, a cylindrical, characterized in that a guide ring of claims 1 to 8 according to any one Toner manufacturing method. 該回content type surface modification apparatus, so that the surface treatment time is arbitrarily adjustable method for producing a toner according to any one of claims 1 to 9, characterized in that it has an openable discharge valve . The method for producing a toner according to any one of claims 1 to 10, wherein a surface treatment time in the batch-type surface modification apparatus is 5 seconds or more and 180 seconds or less. The method for producing a toner according to any one of claims 1 to 11 , wherein a cold air temperature T1 introduced into the batch-type surface reforming apparatus is 10 ° C or lower. 該回content type surface modification apparatus has provided a jacket for internal cooling, more of claims 1 to 12, characterized in that the surface modification treatment the year finely pulverized product while passing a coolant in the jacket A method for producing the toner according to claim 1. Method for producing a toner according to any one of claims 1 to 13, wherein the temperature of the refrigerant passing in the jacket of該回content type of the surface modifying apparatus is 5 ° C. or less. In the surface modification apparatus該回subexpression method for producing a toner according to any one of claims 1 to 14, wherein the classifying rotor behind the temperature T2 of該分grade means is 60 ° C. or less. 16. The toner manufacturing method according to claim 1, wherein a temperature difference (T2−T1) between the temperature T1 and the temperature T2 is 80 ° C. or less. In the batch type surface modification apparatus, the minimum distance between the rotating body and the stationary body of the surface treatment means is 0.5 mm to 15.0 mm, and the rotating peripheral speed of the rotating body is 75 to 150 mm / sec. The minimum distance between the upper part of the rectangular disk or cylindrical pin installed on the upper part of the rotating body and the lower part of the cylindrical guide ring is 2.0 mm to 50.0 mm. method for producing a toner according to any one of claims 1 to 16, wherein.

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