JP4065494B2 - Toner production method - Google Patents

Description

（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。）
【００２４】
（Ｃ）式で示されるジオール類；
【００２５】
【化２】

【００２６】
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。
【００２７】
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べ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、べ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。
【００２８】
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。
【００２９】
〔磁性体〕
本発明のトナーを磁性トナーとして用いる場合、磁性トナーに含まれる磁性材料としては、通常使用されている磁性体であれば特に限定されないが、例えばマグネタイト、マグヘマイト、フェライトの如き酸化鉄、及び他の金属酸化物を含む酸化鉄；Ｆｅ、Ｃｏ、Ｎｉのような金属、または、これらの金属とＡｌ、Ｃｏ、Ｃｕ、Ｐｂ、Ｍｇ、Ｎｉ、Ｓｎ、Ｚｎ、Ｓｂ、Ｂｅ、Ｂｉ、Ｃｄ、Ｃａ、Ｍｎ、Ｓｅ、Ｔｉ、Ｗ、Ｖのような金属との合金、及びこれらの混合物等が挙げられる。
【００３０】
具体的には、磁性材料としては、四三酸化鉄（Ｆｅ₃Ｏ₄）、三二酸化鉄（γ−Ｆｅ₂Ｏ₃）、酸化鉄イットリウム（Ｙ₃Ｆｅ₅Ｏ₁₂）、酸化鉄カドミウム（ＣｄＦｅ₂Ｏ₄）、酸化鉄ガドリニウム（Ｇｄ₃Ｆｅ₅Ｏ₁₂）、酸化鉄銅（ＣｕＦｅ₂Ｏ₄）、酸化鉄鉛（ＰｂＦｅ₁₂Ｏ₁₉）、酸化鉄ニッケル（ＮｉＦｅ₂Ｏ₄）、酸化鉄ニオジム（ＮｄＦｅ₂Ｏ₃）、酸化鉄バリウム（ＢａＦｅ₁₂Ｏ₁₉）、酸化鉄マグネシウム（ＭｇＦｅ₂Ｏ₄）、酸化鉄ランタン（ＬａＦｅＯ₃）、鉄粉（Ｆｅ）、コバルト粉（Ｃｏ）、ニッケル粉（Ｎｉ）等が挙げられる。上述した磁性材料を単独でまたは二種以上組み合わせて使用する。特に好適な磁性材料は、四三酸化鉄またはγ−三二酸化鉄の微粉末である。
【００３１】
これらの強磁性体は平均粒径が０．０５〜２μｍで、７９５．８ｋＡ／ｍ印加での磁気特性が抗磁力１．６〜１２．０ｋＡ／ｍ、飽和磁化５０〜２００Ａｍ²／ｋｇ（好ましくは５０〜１００Ａｍ²／ｋｇ）、残留磁化２〜２０Ａｍ²／ｋｇのものが、特に電子写真画像形成方法に用いる上で好ましい。
【００３２】
更に、これらの磁性体は、結着樹脂１００質量部に対して、６０〜２００質量部、更に好ましくは８０〜１５０質量部含有させることが好ましい。
【００３３】
〔ワックス〕
本発明に用いられるワックスには、従来より離型剤として知られている種々のワックス成分を用いることができ、次のようなものがある。例えば炭化水素系ワックスとしては、低分子量ポリエチレン、低分子量ポリプロピレン、ポリオレフィン共重合物、ポリオレフィンワックス、マイクロクリスタリンワックス、パラフィンワックス、フィッシャートロプシュワックスの如き脂肪族炭化水素系ワックス等がある。
【００３４】
官能基を有するワックスとしては、酸化ポリエチレンワックスの如き脂肪族炭化水素系ワックスの酸化物；または、それらのブロック共重合物；キャンデリラワックス、カルナバワックス、木ろう、ホホバろうの如き植物系ワックス；みつろう、ラノリン、鯨ろうの如き動物系ワックス；オゾケライト、セレシン、ペトロラクタムの如き鉱物系ワックス；モンタン酸エステルワックス、カスターワックスの如き脂肪族エステルを主成分とするワックス類：脱酸カルナバワックスの如き脂肪族エステルを一部または全部を脱酸化したものが挙げられる。
【００３５】
更に、パルミチン酸、ステアリン酸、モンタン酸、または更に長鎖のアルキル基を有する長鎖アルキルカルボン酸類の如き飽和直鎖脂肪酸；ブラシジン酸、エレオステアリン酸、バリナリン酸の如き不飽和脂肪酸；ステアリルアルコール、エイコシルアルコール、ベヘニルアルコール、カウナビルアルコール、セリルアルコール、メリシルアルコール、または更に長鎖のアルキル基を有するアルキルアルコールの如き飽和アルコール；ソルビトールの如き多価アルコール；リノール酸アミド、オレイン酸アミド、ラウリン酸アミドの如き脂肪族アミド；メチレンビスステアリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、ヘキサメチレンビスステアリン酸アミドの如き飽和脂肪族ビスアミド；エチレンビスオレイン酸アミド、ヘキサメチレンビスオレイン酸アミド、Ｎ，Ｎ’−ジオレイルアジピン酸アミド、Ｎ，Ｎ’−ジオレイルセバシン酸アミドの如き不飽和脂肪酸アミド類；ｍ−キシレンビスステアリン酸アミド、Ｎ，Ｎ’−ジステアリルイソフタル酸アミドの如き芳香族系ビスアミド；ステアリン酸カルシウム、ラウリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸マグネシウムの如き脂肪族金属塩（一般に金属石けんといわれているもの）；ベヘニン酸モノグリセリドの如き脂肪酸と多価アルコールの部分エステル化物；植物性油脂を水素添加することによって得られるヒドロキシル基を有するメチルエステル化合物等が挙げられる。
【００３６】
ビニルモノマーでグラフトされたワックスとしては、脂肪族炭化水素系ワックスにスチレンやアクリル酸の如きビニル系モノマーを用いてグラフト化させたワックスがある。
【００３７】
好ましく用いられるワックスとしては、オレフィンを高圧下でラジカル重合したポリオレフィン；高分子量ポリオレフィン重合時に得られる低分子量副生成物を精製したポリオレフィン；低圧下でチーグラー触媒、メタロセン触媒の如き触媒を用いて重合したポリオレフィン；放射線、電磁波または光を利用して重合したポリオレフィン；パラフィンワックス、マイクロクリスタリンワックス、フィッシャートロプシュワックス；ジントール法、ヒドロコール法、アーゲ法等により合成される合成炭化水素ワックス；炭素数一個の化合物をモノマーとする合成ワックス；水酸基、カルボキシル基またはエステル基の如き官能基を有する炭化水素系ワックス；炭化水素系ワックスと官能基を有する炭化水素系ワックスとの混合物；これらのワックスを母体としてスチレン、マレイン酸エステル、アクリレート、メタクリレート、無水マレイン酸の如きビニルモノマーでグラフト変性したワックスが挙げられる。
【００３８】
また、これらのワックスを、プレス発汗法、溶剤法、再結晶法、真空蒸留法、超臨界ガス抽出法または融液晶析法を用いて分子量分布をシャープにしたものや低分子量固形脂肪酸、低分子量固形アルコール、低分子量固形化合物、その他の不純物を除去したものも好ましく用いられる。
【００３９】
〔荷電制御剤〕
本発明のトナーは、その帯電性を更に安定化させるために、必要に応じて荷電制御剤を用いることができる。荷電制御剤は、結着樹脂１００質量部当たり０．１〜１０質量部、好ましくは１〜５質量部使用するのが、トナーの帯電性を制御する上で好ましい。
【００４０】
荷電制御剤としては、従来より知られている種々の荷電制御剤を使用することができるが、例えば以下のものが挙げられる。
【００４１】
トナーを負荷電性にする負荷電性制御剤として、例えば有機金属錯体またはキレート化合物が有効である。モノアゾ金属錯体、芳香族ヒドロキシカルボン酸の金属錯体、芳香族ジカルボン酸系の金属錯体が挙げられる。他には、芳香族ヒドロキシカルボン酸、芳香族モノ及びポリカルボン酸及びその金属塩、その無水物、またはそのエステル類、または、ビスフェノールのフェノール誘導体類等が挙げられる。好ましいものとしては、モノアゾ金属化合物で、置換基としてアルキル基、ハロゲン、ニトロ基、カルバモイル基等を有するフェノール、ナフトールから合成されるモノアゾ染料の、Ｃｒ、Ｃｏ、Ｆｅの金属錯化合物が挙げられる。また芳香族カルボン酸の金属化合物も好ましく用いられ、アルキル基、ハロゲン、ニトロ基等を有する、ベンゼン、ナフタレン、アントラセン、フェナントレンのカルボン酸、ヒドロキシカルボン酸、ジカルボン酸の金属化合物が挙げられる。
【００４２】
トナーを正荷電性にする正荷電性制御剤としては、ニグロシン、ニグロシン誘導体、トリフェニルメタン化合物、有機四級アンモニウム塩等が挙げられる。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などの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等の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、リンタングステン酸、リンモリブデン酸、リン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、フェロシアン化物など）、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などの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などのジオルガノスズボレート類；これらを単独で或いは２種類以上組み合せて用いることができる。
【００４３】
〔外添剤〕
本発明のトナーは、前述したように、トナー粒子の他に、トナーの流動性や帯電性等を調整するための外添剤を含むことが一般的である。このような外添剤として、本発明のトナーに流動性向上剤を添加しても良い。流動性向上剤は、トナー粒子に外添することにより、流動性が添加前後を比較すると増加し得るものである。例えば、フッ化ビニリデン微粉末の如きフッ素系樹脂粉末；湿式製法シリカ、乾式製法シリカの如き微粉末シリカ、微粉末酸化チタン、微粉末アルミナ、それらをシラン化合物、チタンカップリング剤、シリコーンオイルにより表面処理を施した処理微粉末等がある。
【００４４】
疎水化方法としては、微粉体と反応または物理吸着する有機ケイ素化合物等で化学的に処理することによって付与される。
【００４５】
有機ケイ素化合物としては、ヘキサメチルジシラザン、トリメチルシラン、トリメチルクロロシラン、トリメチルエトキシシラン、ジメチルジクロロシラン、メチルトリクロロシラン、アリルジメチルクロロシラン、アリルフェニルジクロロシラン、ベンジルジメチルクロロシラン、ブロモメトリジメチルクロロシラン、α−クロロエチルトリクロロシラン、β−クロロエチルトリクロロシラン、クロロメチルジメチルクロロシラン、トリオルガノシリルメルカプタン、トリメチルシリルメルカプタン、トリオルガノシリルアクリレート、ビニルジメチルアセトキシシラン、ジメチルエトキシシラン、ジメチルジメトキシシラン、ジフェニルジエトキシシラン、へキサメチルジシロキサン、１，３−ジビニルテトラメチルジシロキサン、１，３−ジフェニルテトラメチルジシロキサン及び１分子当たり２〜１２個のシロキサン単位を有し末端に位置する単位にそれぞれ一個宛のＳｉに結合した水酸基を含有するジメチルポリシロキサン等がある。更に、ジメチルシリコーンオイルの如きシリコーンオイルが挙げられる。これらは一種または二種以上の混合物で用いられる。
【００４６】
本発明で用いられる０．１〜５．０μｍの粒子としては無機微粒子、有機微粒子、及びこれらの混合物及び複合物が使用可能である。具体的には、チタン酸ストロンチウム、酸化セリウム、酸化アルミニウム、酸化マグネシウム等の金属酸化物、及び、フッ素樹脂粉末、樹脂微粒子等が挙げられる。特に帯電特性的にもチタン酸ストロンチウム、酸化セリウムが好ましい。
【００４７】
〔荷電制御剤ＩＩ〕
本発明のトナーは荷電制御剤を含有することが好ましい。
【００４８】
トナーを負荷電性に制御するものとして下記化合物が挙げられる。
【００４９】
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、芳香族ダイカルボン酸の金属錯体が挙げられる。他には、芳香族ハイドロキシカルボン酸、芳香族モノ及びポリカルボン酸及びその金属塩、無水物、エステル類、ビスフェノールのフェノール誘導体類が挙げられる。
【００５０】
中でも、下記式（１）で表されるアゾ系金属錯体が好ましい。
【００５１】
【化３】

〔式中、Ｍは配位中心金属を表し、Ｓｃ，Ｔｉ，Ｖ，Ｃｒ，Ｃｏ，Ｎｉ，ＭｎまたはＦｅ等が挙げられる。Ａｒはアリール基であり、フェニル基、ナフチル基の如きアリール基であり、置換基を有してもよい。この場合の置換基としては、ニトロ基、ハロゲン基、カルボキシル基、アニリド基及び炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基がある。Ｘ，Ｘ’，Ｙ及びＹ’は−Ｏ−，−ＣＯ−，−ＮＨ−，−ＮＲ−（Ｒは炭素数１〜４のアルキル基）である。Ｃ⁺はカウンターイオンを示し、水素、ナトリウム、カリウム、アンモニウム、脂肪族アンモニウム或いはそれらの混合イオンを示す。〕
【００５２】
特に中心金属としてはＦｅまたはＣｒが好ましく、置換基としてはハロゲン、アルキル基またはアニリド基が好ましく、カウンターイオンとしては水素、アルカリ金属、アンモニウムまたは脂肪族アンモニウムが好ましい。カウンターイオンの異なる錯塩の混合物も好ましく用いられる。
【００５３】
下記式（２）に示した塩基性有機金属錯体も負帯電性を与える荷電制御剤として好ましい。
【００５４】
【化４】

【００５５】
トナーを正荷電性に制御するものとして下記の化合物がある。
【００５６】
ニグロシン及び脂肪酸金属塩等によるニグロシン変成物；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などの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、りんタングステン酸、リンモリブデン酸、リン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、フェロシアン化物など）；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；グアニジン化合物；イミダゾール化合物が挙げられる。これらを単独で或いは２種類以上組み合わせて用いることができる。
【００５７】
これらの中でも、トリフェニルメタン化合物、カウンターイオンがハロゲンでない四級アンモニウム塩が好ましく用いられる。下記式（３）
【００５８】
【化５】

〔式中Ｒ₁はＨまたはＣＨ₃を示し、Ｒ₂及びＲ₃は置換または未置換のアルキル基（好ましくは、Ｃ₁〜Ｃ₄）を示す。〕
で表されるモノマーの単重合体；前述したスチレン、アクリル酸エステル、メタクリル酸エステルの如き重合性モノマーとの共重合体を正荷電性制御剤として用いることができる。この場合、この単重合体及び共重合体は荷電制御剤としての機能と、結着樹脂（の全部または一部）としての機能を有する。
【００５９】
特に下記式（４）で表される化合物が本発明のトナー正荷電性制御剤として好ましい。
【００６０】
【化６】

〔式中、Ｒ₁，Ｒ₂，Ｒ₃，Ｒ₄，Ｒ₅及びＲ₆は、各々互いに同一でも異なっていてもよく、水素原子、置換もしくは未置換のアルキル基または、置換もしくは未置換のアリール基を表す。Ｒ₇，Ｒ₈及びＲ₉は、各々互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、アルキル基、アルコキシ基を表す。Ａ^-は、硫酸イオン、硝酸イオン、ホウ酸イオン、リン酸イオン、水酸イオン、有機硫酸イオン、有機スルホン酸イオン、有機リン酸イオン、カルボン酸イオン、有機ホウ酸イオン、テトラフルオロボレートの如き陰イオンを示す。〕
【００６１】
電荷制御剤をトナーに含有させる方法としては、トナー粒子内部に添加する方法と外添する方法がある。これらの電荷制御剤の使用量としては、結着樹脂の種類、他の添加剤の有無、分散方法を含めたトナー製造方法によって決定されるもので、一義的に限定されるものではないが、好ましくは結着樹脂１００質量部に対して０．１〜１０質量部、より好ましくは０．１〜５質量部の範囲で用いられる。
【００６２】
次に、上記に挙げたようなトナーの形成材料及び外添剤等を用いて、本発明のトナーの製造方法でトナーを製造する手順について説明する。
【００６３】
まず、原料混合工程では、トナー内添剤として、少なくとも樹脂、着色剤を所定量秤量して配合し、混合する。混合装置の一例としては、ダブルコン・ミキサー、Ｖ型ミキサー、ドラム型ミキサー、スーパーミキサー、ヘンシェルミキサー、ナウターミキサー等がある。
【００６４】
更に、上記で配合し、混合したトナー原料を溶融混練して、樹脂類を溶融し、その中に着色剤等を分散させる。その溶融混練工程では、例えば、加圧ニーダー、バンバリィミキサー等のバッチ式練り機や、連続式の練り機を用いることができる。近年では、連続生産できる等の優位性から、１軸または２軸押出機が主流となっており、例えば、神戸製鋼所社製ＫＴＫ型２軸押出機、東芝機械社製ＴＥＭ型２軸押出機、ケイ・シー・ケイ社製２軸押出機、ブス社製コ・ニーダー等が一般的に使用される。更に、トナー原料を溶融混練することによって得られる着色樹脂組成物は、溶融混練後、２本ロール等で圧延され、水冷等で冷却する冷却工程を経て冷却される。
【００６５】
上記で得られた着色樹脂組成物の冷却物は、次いで、粉砕工程で所望の粒径にまで粉砕される。粉砕工程では、まず、クラッシャー、ハンマーミル、フェザーミル等で粗粉砕され、更に、機械式粉砕機で微粉砕される。粉砕工程では、このように段階的に所定のトナー粒度まで粉砕される。更に、機械式粉砕機で得られた微粉砕品を表面改質工程で表面改質＝球形化処理を行い表面改質粒子を得る。その後、必要に応じて表面改質粒子を慣性分級方式のエルボージェット（日鉄鉱業社製）、遠心力分級方式のターボプレックス（ホソカワミクロン社製）等の分級機或いは、風力式篩のハイボルター（新東京機械社製）等の篩分機を用いて分級し、重量平均粒子径３乃至１１μｍのトナーを得る。
【００６６】
尚、分級工程で分級されて発生したトナー粗粉は、再度粉砕工程に戻して粉砕する。また表面改質工程で発生した微粉は、トナー原料の配合工程に戻して再利用することがトナー生産性上好ましい。
【００６７】
更に、本発明のトナーの製造方法においては、上記のようにして得られたトナーに、少なくとも平均粒径が５０ｎｍ以下の無機微粒子を外添剤として外添する。トナーに外添剤を外添処理する方法としては、分級されたトナーと公知の各種外添剤を所定量配合し、ヘンシェルミキサー、スーパーミキサー等の粉体にせん断力を与える高速撹拌機を外添機として用いて、撹拌・混合することが好ましい。この際、外添機内部で発熱を生じ、凝集物を生成し易くなるので、外添機の容器部周囲を水で冷却する等の手段で温度調整をする方が好ましい。
【００６８】
次に、本発明のトナーの粉砕工程で使用される機械式粉砕機及び該機械式粉砕機を利用したトナーの製造方法について、更に、表面改質工程で使用される表面改質装置及び表面改質装置を利用したトナーの製造方法について、図面を参照しながら具体的に説明する。
【００６９】
図１は、本発明に使用する機械式粉砕機を組込んだトナー粒子の粉砕装置システムの一例を示し、図２は図１において高速回転する回転子の斜視図を示し、図３・４・５は、図１におけるＤ−Ｄ’面での概略的断面図を示す。
【００７０】
図１に示す機械式粉砕機３０１では、ケーシング３１３、ケーシング３１３内にあって冷却水を通水できるジャケット３１６、ケーシング３１３内にあって中心回転軸３１２に取り付けられた回転体からなる高速回転する表面に多数の溝が設けられている回転子３１４、回転子３１４の外周に一定間隔を保持して配置されている表面に多数の溝が設けられている固定子３１０、更に、被処理原料を導入するための原料投入口３１１、処理後の粉体を排出するための原料排出口３０２とから構成されている。回転子３１４と固定子３１０との間隔部分が粉砕ゾーンである。
【００７１】
以上のように構成してなる機械式粉砕機では、図１に示した定量供給機３１５から機械式粉砕機の原料投入口３１１へ所定量の粉体原料が投入されると、粒子は、粉砕処理室内に導入され、該粉砕処理室内で高速回転する表面に多数の溝が設けられている回転子３１４と、表面に多数の溝が設けられている固定子３１０との間の発生する衝撃と、この背後に生じる多数の超高速渦流、並びにこれによって発生する高周波の圧力振動によって瞬間的に粉砕される。その後、原料排出口３０２を通り、排出される。トナー粒子を搬送しているエアー（空気）は粉砕処理室を経由し、原料排出口３０２、パイプ２１９、補集サイクロン２２９、バグフィルター２２２、及び吸引ブロワー２２４を通って装置システムの系外に排出される。本発明においては、この様にして、粉体原料の粉砕が行われるため、微粉及び粗粉を増やすことなく所望の粉砕処理を容易に行うことができる。
【００７２】
このような機械式粉砕としては、例えば、川崎重工業（株）製粉砕機クリプトロン、ターボ工業（株）製ターボミル、ホソカワミクロン（株）製イノマイザ、日清エンジニアリング（株）製スーパーローター等を挙げることができる。
【００７３】
本発明の機械式粉砕機においては、図３・４・５に示す通り、該回転子及び該固定子は、いずれも波形形状の複数の凸部と、該凸部と該凸部との間に形成される凹部とを有し、該回転子及び該固定子の少なくとも一方が有する凹部が底部に平坦面を有する形状とすることが好ましい。
【００７４】
本発明のトナーの製造方法において、機械式粉砕機の該回転子及び固定子は、いずれも波形形状の複数の凸部と、該凸部と該凸部との間に形成される凹部とを有し、該回転子及び該固定子の少なくとも一方が有する凹部が底部に平坦面を有する形状とすることにより、凹部の断面積を広げることができ、この部分での圧損を小さくできるので、従来の機械式粉砕機に比べ、より効率の良い粉砕ができることがわかった。
【００７５】
即ち、従来の機械式粉砕機の回転子／固定子の粉砕面形状（図９・１０・１１）に比べ、本発明の回転子及び／又は固定子の粉砕面形状（図３・４・５）では、凹部の形状がその底部において、平坦面を有する形状とすることにより、全体としては台形形状となるため、この部分での圧損を小さくでき、回転子と固定子との間に発生する衝撃がより強くなり、粉砕効率が向上する。
【００７６】
即ち、従来の機械式粉砕機で得られる粒度分布を、より高い粉砕供給量で得ることができ、トナー生産効率の向上が可能となる。
【００７７】
また、凹部の底部は、平坦面の両端に曲面を有していることにより、この部分に発生する渦流が、従来の機械式粉砕機（図９・１１）に比べ、より高速で、且つ、効率良く発生するため、トナー生産効率の向上が可能となる。
【００７８】
また、回転子は、凸部が湾曲面で形成され、固定子は、凹部の底部が平坦面で形成されていることにより、従来の機械式粉砕機（図１０）に比べ、トナーに対する衝撃力がより強くなるため、効率の良い粉砕が可能となり、トナー生産効率の向上が可能となる。
【００７９】
更に、本発明のトナーの製造方法においては、該回転子及び固定子は、いずれも波形形状の複数の凸部と、該凸部と該凸部との間に形成される凹部とを有し、該回転子及び該固定子の少なくとも一方が有する凹部が底部に平坦面を有し、且つ、
該回転子の凹部底面から立ち上がる凸部の回転子回転方向後方側の斜面を回転子第１斜面とした場合、
該回転子第１斜面は、回転軸中心と該回転子第１斜面の立ち上がりの箇所（Ａ）とを結んだ線を基準線として、マイナス側に１０°以上８０°未満の傾斜角（α１）を有することが好ましく（更に好ましくは４５°）、且つ、
該固定子の凹部底面から立ち上がる凸部の回転子回転方向前方側の斜面を固定子第１斜面とした場合、
該固定子第１斜面は、回転軸中心と該固定子第１斜面の立ち上がりの箇所（Ａ’）とを結んだ線を基準線として、プラス側に１０°以上８０°未満の傾斜角（β１）を有することが好ましく（更に好ましくは４５°）、且つ、
該回転子の凹部底面から立ち上がる凸部の回転子回転方向前方側の斜面を回転子第２斜面とした場合、
該回転子第２斜面は、回転軸中心と該回転子第２斜面の頂点（Ｃ）とを結んだ線を基準線として、プラス側に２０°未満の傾斜角（α２）を有することが好ましく（更に好ましくは１０°）、且つ、
該固定子の凹部底面から立ち上がる凸部の回転子回転方向後方側の斜面を固定子第２斜面とした場合、
該固定子第２斜面は、回転軸中心と該固定子第２斜面の頂点（Ｃ’）とを結んだ線を基準線として、マイナス側に２０°未満の傾斜角（β２）を有することが好ましい（更に好ましくは１０°）。
【００８０】
更に、本発明のトナーの製造方法においては、回転軸方向に垂直な面の回転子又は固定子の断面図（図３・４・５）において、凸部の高さＨが１．００乃至３．００ｍｍであることが好ましく、更に、凹部の底部の平坦面の長さＬ１が０．６０乃至２．００ｍｍであることが好ましい。更に、凸部の高さＨと、凹部の底部の平坦面の長さＬ１とが下記関係
０．２５Ｈ≦Ｌ１≦２．５Ｈ
を満足していることが好ましい。
【００８１】
更に、本発明のトナーの製造方法においては、該回転子及び固定子の凸部上面の長さをＬ２とし、凸部該上面と対向している面の長さをＬ３として場合に、Ｌ２及びＬ３が下記条件
Ｌ２＜Ｌ３
を満足していることが好ましい。
【００８２】
即ち、上記の規定及び関係を満足することにより、従来の機械式粉砕機で得られる粒度分布を、より高い粉砕供給量で得ることができ、トナー生産効率の向上が可能となる。
【００８３】
次に、表面改質工程で使用される表面改質装置及び表面改質装置を利用したトナーの製造方法について、図面を参照しながら具体的に説明する。
【００８４】
図６は、本発明に使用する表面改質装置の一例を示し、図７は図６において高速回転する回転子の上面図の一例を示す。
【００８５】
図６に示す表面改質装置では、ケーシング３０、冷却水或いは不凍液を通水できるジャケット（図示しない）、表面改質手段である、ケーシング３０内にあって中心回転軸に取り付けられた、上面に角型のディスク或いは円筒型のピン４０を複数個有し、高速で回転する円盤上の回転体である分散ローター３６、分散ローター３６の外周に一定間隔を保持して配置されている表面に多数の溝が設けられているライナー３４（尚、ライナー表面上の溝はなくても構わない）、更に、表面改質された原料を所定粒径に分級するための手段である分級ローター３１、更に、冷風を導入するための冷風導入口３５、被処理原料を導入するための原料供給口３３、更に、表面改質時間を自在に調整可能となるように、開閉可能なように設置された排出弁３８、処理後の粉体を排出するための粉体排出口３７、更に、分級手段である分級ローター３１と表面改質手段である分散ローター３６−ライナー３４との間の空間を、分級手段へ導入される前の第一の空間４１と、分級手段により微粉を分級除去された粒子を表面処理手段へ導入するための第二の空間４２に仕切る案内手段である円筒形のガイドリング３９とから構成されている。分散ローター３６とライナー３４との間隙部分が表面改質ゾーンであり、分級ローター４及びローター周辺部分が分級ゾーンである。
【００８６】
尚、分級ローター３１の設置方向は図６に示したように縦型でも構わないし、横型でも構わない。また、分級ローター３１の個数は図６に示したように単体でも構わないし、複数でも構わない。
【００８７】
以上のように構成してなる表面改質装置では、排出弁３８を閉とした状態で原料供給口３３から微粉砕品を投入すると、投入された微粉砕品は、まずブロワー（図示しない）により吸引され、分級ローター３１で分級される。その際、分級された所定粒径以下の微粉は装置外へ連続的に排出除去され、所定粒径以上の粗粉は遠心力によりガイドリング（案内板）３９の内周（第二の空間４２）に沿いながら分散ローター３６により発生する循環流に乗り表面改質ゾーンへ導かれる。表面改質ゾーンに導かれた原料は分散ローター３６とライナー３４間で機械式衝撃力を受け、表面改質処理される。表面改質された表面改質粒子は、機内を通過する冷風に乗って、ガイドリング３９の外周（第一の空間４１）に沿いながら分級ゾーンに導かれ、分級ローター４により、再度微粉は機外へ排出され、粗粉は、循環流に乗り、再度表面改質ゾーンに戻され、繰り返し表面改質作用を受ける。一定時間経過後、排出弁３８を開とし、排出口３７より表面改質粒子を回収する。
【００８８】
本発明のトナーの製造方法の特徴は、図１に示す機械式粉砕機を使用してトナー原料を微粉砕し、且つ、微粉砕されたトナーを図６に示す回分式の表面改質装置を使用することにより、トナーの表面形状を所望のものにコントロールし、更に、微粉カット分級を行うことによりシャープな粒度分布を持つ表面改質粒子を得ることである。
【００８９】
即ち、本発明者が検討した結果、粉砕工程で使用する機械式粉砕機は、図１に示す様な、機械式粉砕機とし、表面改質工程で使用する表面改質装置は、図６に示す様な、回分式の表面改質装置とし、更に、該回分式の表面改質装置は、表面改質粒子を所定粒径に分級する分級ローターを内蔵する表面改質装置とすることが、トナーの表面改質を行う上で好ましいことが分かった。
【００９０】
即ち、本発明者が検討した結果、粉砕工程で使用する粉砕機を図１に示す様な、機械式粉砕機とすることで、トナーの過度な粉砕を防止し、トナーの粒度分布をシャープ化し、微粉量を少なくすることができる。更に、表面改質工程で使用する表面改質装置を図６に示す様な回分式の表面改質装置とし、表面改質粒子を所定粒径に分級する分級ローターを内蔵するタイプとし、更に微粉砕品を表面改質する際、該表面改質装置の表面改質ゾーンのおける設定を適切な状態に制御することにより、過粉砕されやすいトナーを表面改質する場合においても、表面改質時における微粉量の増加を防止し、且つ、トナーの粒度分布をシャープに分級することができる。更に、排出弁を開放する時間を任意に設定することにより、装置内におけるトナーの滞留時間を調整でき、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。
【００９１】
上記の理由として、トナーの粒度分布は、粉砕機内でのトナーの粉砕効率に依存している。つまり、トナーの粒度分布をシャープ化するには、過粉砕による微粉増を防止し、且つ、粗粉を発生させないことが重要である。即ち、機械式粉砕機では、トナーを粉砕する際、過粉砕されにくいため、微粉の発生量を少なくすることができ、トナーの粒度分布をよりシャープにすることができる。更に、トナーの表面形状は、表面改質装置内でのトナーの滞留時間に依存している。つまり、トナーの表面形状をコントロールするためには、表面改質装置内のトナーの滞留時間をコントロールすることが重要である。本発明において、表面改質工程で使用する表面改質装置を、図１に示す様な、回分式の表面改質装置とすることで、排出弁開放までの時間（＝サイクルタイム）、分散ローター上面の歯形状及び回転周速、分散ローターとライナーとの間隔、ガイドリングと分散ローターとの間隔等を適切な状態に制御することにより、表面改質時における微粉増加を防止し、トナーの表面改質装置内での滞留時間をコントロールでき、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。また、表面改質されたトナーを所定粒径に分級する分級ローターを内蔵することで、分級ローターの回転周速を適切な状態に制御することにより、所定粒子以下の微粉は装置外へ連続的に排出され、粗粉は再度表面改質できるため、所定粒径以下の微粉が除かれたシャープな粒度分布を持つ表面改質粒子を得ることができる。
【００９２】
本発明者が検討した結果、表面改質装置における表面改質時間（＝サイクルタイム）としては、５秒以上１８０秒以下、更に好ましくは、１５秒以上１２０秒以下であることが好ましい。表面改質時間が５秒未満の場合、改質時間が短時間過ぎるため、表面改質粒子が得られずトナー品質上好ましくない。また、改質時間が１８０秒超の場合、改質時間が長時間過ぎるため、表面改質時に発生する熱によるトナーの表面変質や、機内融着の発生、及び処理能力の低下を招くので、トナー生産性上好ましくない。
【００９３】
尚、表面改質粒子の表面改質の度合を示すものとして、本発明においては平均円形度をその指標とした。
【００９４】
本発明における平均円形度は、粒子の形状を定量的に表現する簡便な方法として用いたものであり、本発明では東亜医用電子製フロー式粒子像分析装置ＦＰＩＡ−１０００を用いて測定を行い、測定された粒子の円形度を下式により求め、測定された全粒子の円形度の総和を全粒子数で除した値を平均円形度と定義する。
【００９５】
【数１】

【００９６】
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５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。
【００９７】
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の指標であり、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。
【００９８】
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。
【００９９】
本発明のトナーはＴＨＦ可溶分のＧＰＣにより測定される分子量分布において、分子量２，０００〜５０，０００の領域に少なくとも一つピークを有し、分子量１０００〜３００００の成分が５０〜９０％存在することを特徴とし、好ましくは分子量５，０００〜３０，０００の領域に少なくとも一つのピークが存在し、分子量１０００〜３００００の成分が５５〜９０％存在することをしているものが良い。分子量が５０００未満の場合、トナーとして適度な弾性を持てなくなるため、定着性は向上するものの表面処理中に微粉の発生が増加しこの微粉がトナー粒子に付着することにより帯電が不均一になりトナーの環境安定性が悪化する。従って、高温高湿のような環境で画像濃度が低下する。更に帯電が不均一になることによりカブリ、画質が悪化する。更に、保存性も悪化する。また、低分子側の分子量が５０，０００超の場合、トナーとしての弾性が高くなるため、表面処理の処理量が減少し生産性が低下する。また、定着性が悪化するため、耐久初期において定着部材への付着が生じ易くなる。
【０１００】
分子量１０００〜３００００の成分が５５％未満の場合トナーとしての弾性が高くなるため、表面処理の処理量が減少し生産性が低下する。また、定着性が悪化するため、耐久初期において定着部材への付着が生じ易くなる。また、分子量１０００〜３００００の成分が９０％よりも多い場合、トナーとして適度な弾性を持てなくなるため、定着性は向上するものの表面処理中に微粉の発生が増加しこの微粉がトナー粒子に付着することにより帯電が不均一になりトナーの環境安定性が悪化する。従って、高温高湿のような環境で画像濃度が低下する。更に帯電が不均一になることによりカブリ、画質が悪化する。更に、保存性も悪化する。
【０１０１】
このように、トナーのＴＨＦ可溶分のＧＰＣによる分子量分布において、この様なピークを有するトナーは定着性、耐オフセット及び保存性がバランスよく保たれるだけではなく、表面処理による微粉発生が効果的に抑えられ、トナーの帯電性を均一にし現像性、画質の優れたトナーとなる。
【０１０２】
本発明において、トナー及び結着樹脂のＴＨＦ（テトラヒドロフラン）を溶媒としたＧＰＣによる分子量分布は次の条件で測定される。
【０１０３】
４０℃のヒートチャンバー中でカラムを安定化させ、この温度におけるカラムに溶媒としてＴＨＦを毎分１ｍｌの流速で流し、ＴＨＦ試料溶液を約１００μｌ注入して測定する。試料の分子量測定にあたっては試料の有する分子量分布を数種の単分散ポリスチレン標準試料により作成された検量線の対数値とカウント値との関係から算出した。検量線作成用の標準ポリスチレン試料としては例えば、東ソー社製あるいは昭和電工社製の分子量が１０²〜１０⁷程度のものを用い、少なくとも１０点程度の標準ポリスチレン試料を用いるのが適当である。また、検出器はＲＩ（屈折率）検出器を用いる。尚、カラムとしては市販のポリスチレンジェルカラムを複数本組み合せるのが良く、例えば昭和電工社製のｓｈｏｄｅｘＧＰＣ ＫＦ−８０１，８０２，８０３，８０４，８０５，８０６，８０７，８００Ｐの組み合せや、東ソー社製のＴＳＫｇｅｌ Ｇ１０００Ｈ（Ｈ_XL）、Ｇ２０００Ｈ（Ｈ_XL）、Ｇ３０００Ｈ（Ｈ_XL）、Ｇ４０００Ｈ（Ｈ_XL）、Ｇ５０００Ｈ（Ｈ_XL）、Ｇ６０００Ｈ（Ｈ_XL）、Ｇ７０００Ｈ（Ｈ_XL）、ＴＳＫｇｕｒｄｃｏｌｕｍｎの組み合せを挙げることができる。
【０１０４】
また、試料は以下のようにして作製する。
【０１０５】
試料をＴＨＦ中に入れ、数時間放置した後、十分振とうしＴＨＦとよく混ぜ（試料の合一体が無くなるまで）、更に１２時間以上静置する。その時ＴＨＦ中への放置時間が２４時間以上となるようにする。その後、サンプル処理フィルター（ポアサイズ０．２〜０．５μｍ、例えばマイショリディスクＨ−２５−２（東ソー社製）など使用できる。）を通過させたものをＧＰＣの試料とする。また、試料濃度は、樹脂成分が０．５〜５ｍｇ／ｍｌとなるように調整する。
【０１０６】
更に、本発明のトナーの製造方法においては、表面改質装置で得られる表面改質粒子の個数平均径が、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、更に、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
１．０２≦Ｂ／Ａ≦２．００
を満足していることが好ましい。
【０１０７】
即ち、上記の規定及び関係を満足することにより、所定粒径以下の微粉が除かれたシャープな粒度分布を持つ表面改質粒子を得ることができる。
【０１０８】
更に、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、更に好ましくは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。
【０１０９】
また、該表面改質装置内に導入する冷風の発生装置で使用する冷媒としては、地球全体の環境問題という点から代替フロンが好ましい。
【０１１０】
代替フロンとしては、Ｒ１３４ａ、Ｒ４０４Ａ、Ｒ４０７ｃ、Ｒ４１０Ａ、Ｒ５０７Ａ、Ｒ７１７等が挙げられるが、この中で、省エネルギー性や安全性という点から、特にＲ４０４Ａが好ましい。
【０１１１】
尚、該表面改質装置内に導入する冷風は、装置内の結露防止という面から、除湿したものであることが好ましい。除湿装置としては公知のものが使用できる。給気露点温度としては、−１５℃以下が好ましく、更には−２０℃以下が好ましい。
【０１１２】
更に、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、更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。
【０１１３】
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、更に好ましくは−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十分満足できるものではない。
【０１１４】
更に、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（更に好ましくは５０℃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十分満足できるものではない。
【０１１５】
更に、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十分満足できるものではない。
【０１１６】
更に、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、更には、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、更には、８５ｍ／ｓｅｃ乃至１４０ｍ／ｓｅｃとすることが好ましい。更に、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、更には、５．０ｍｍ乃至４５．０ｍｍとすることが好ましい。
【０１１７】
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所望のもの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。
【０１１８】
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十分満足できるものではない。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十分満足できるものではない。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、トナー生産性上十分満足できるものではない。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十分満足できるものではない。
【０１１９】
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十分満足できるものではない。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十分満足できるものではない。
【０１２０】
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。
【０１２１】
【実施例】
次に、本発明の実施例及び比較例を挙げて本発明を更に具体的に説明する。
【０１２２】
［実施例１］
・結着樹脂 １００質量部
（スチレン−アクリル酸ブチル−マレイン酸ブチルハーフエステル共重合体）
（Ｔｇ６２℃、分子量：Ｍｐ１３０００、Ｍｗ６０００００、分子量１０００〜３００００の成分の存在比：６０％）
・磁性酸化鉄 ９０質量部
（平均粒子径０．２２μｍ、７９５．８ｋＡ／ｍ磁場での特性Ｈｃ５．１ｋＡ／ｍ、σｓ８５．１Ａｍ²／ｋｇ、σｒ５．１Ａｍ²／ｋｇ）
・モノアゾ金属錯体（負荷電制御剤） ２質量部
・低分子量エチレン−プロピレン共重合体 ３質量部
上記の処方の材料を、ヘンシェルミキサーでよく混合した後、温度１３０℃に設定した２軸混練機にて混練した。得られた混練物を冷却し、ハンマーミルにて２ｍｍ以下に粗粉砕し、トナー製造用粉体原料である粉体原料（粗粉砕物）を得た。
【０１２３】
得られた粉体原料を、図１に示す機械式粉砕機３０１（ターボ工業社製ターボミルＴ２５０−ＲＳ型を以下の通り改造した改造機）で微粉砕し、得られた微粉砕品を、図６に示す表面改質装置にて表面改質した。
【０１２４】
本実施例では、機械式粉砕機３０１の回転子３１４及び固定子３１０の粉砕面形状を図３に示す形式のものとした。即ち、固定子のβ１の角度を４５°、β２を１０°、固定子の凸部の高さＨを２．０ｍｍ、固定子の凹部低部の平坦面の長さＬ１を１．４ｍｍとした。また、回転子３１４の周速を１１５ｍ／ｓｅｃ、回転子３１４と固定子３１０の間隙を１．３ｍｍとし、粉砕供給量１９．５ｋｇ／ｈｒとして、重量平均粒径が７．０μｍであり、個数平均粒径が４．９μｍであり、４．００μｍ以下％が４８個数％のトナーを得た。
【０１２５】
また得られた微粉砕品の平均円形度を測定した結果、０．９４９であった。
【０１２６】
得られた微粉砕品を、図６に示す表面改質装置で表面改質した。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８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。また分散ローターの回転周速を１１５ｍ／ｓｅｃとし、ブロワー風量を１５ｍ³／ｍｉｎとした。また微粉砕品の投入量を２０ｋｇとし、サイクルタイムを３０ｓｅｃとした。またジャケットに通す冷媒の温度及び冷風温度Ｔ１を０℃とした。
【０１２７】
この状態で１２分間運転した結果、分級ローター後方の温度Ｔ２は３９℃で安定した。従って、ΔＴ（Ｔ２−Ｔ１）は３９℃であった。
【０１２８】
この時、得られる表面改質粒子の目標粒度を、重量平均径７．５±０．５μｍ、４．００μｍ以下％１５個数％以下とした。本実施例においては、分級ローターの周速を７５ｍ／ｓｅｃとすることで、重量平均径が７．６μｍであり、個数平均径が５．８μｍであり、４．００μｍ以下の粒子が１３個数％含有するシャープな粒度分布を有する表面改質粒子を回収率７８％で得ることができた。
【０１２９】
従って、表面改質工程に導入された微粉砕品の個数平均径Ａが４．９μｍであり、該表面改質装置で得られる粒子の個数平均径Ｂが５．８μｍなので、Ｂ／Ａは１．１８であった。
【０１３０】
尚、トナーの平均粒径及び粒度分布は、コールターカウンターＴＡ−ＩＩ型或いはコールターマルチサイザー（コールター社製）等を用い、個数分布，体積分布を出力するインターフェイス（日科機製）及びＰＣ９８０１パーソナルコンピューター（ＮＥＣ製）を接続し、電解液は１級塩化ナトリウムを用いて１％ＮａＣｌ水溶液を調製する。電解液としては、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フォン酸塩）を０．１〜５ｍｌ加え、更に測定試料を２〜２０ｍｇ加える。試料を懸濁した電解液は超音波分散器で約１〜３分間分散処理を行い、前記コールターカウンターＴＡ−ＩＩ型によりアパーチャーとして１００μｍアパーチャーを用いて、２μｍ以上のトナーの体積，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、本発明に係わる体積分布から求めた体積基準の重量平均粒径（Ｄ４：各チャンネルの中央値をチャンネルの代表値とする）と、個数分布から求めた４．００μｍ以下のトナーの累積個数を求めた。ここで、微粉を４．００μｍ以下と定義する。即ち、４．００μｍ以下の値が小さいほど、粒度分布がシャープなことを示し、大きいとブロードな粒度分布であることを示す。
【０１３１】
また、回収率は、微粉砕品の投入量に対する、表面改質粒子の回収量の割合で算出した。
【０１３２】
次に、上記の表面改質装置で得られた表面改質粒子を、図８に示す遠心力分級方式のターボプレックス（ホソカワミクロン社製）に導入して粗粉カット分級し、分級品トナーを得た。得られたトナーの平均円形度を測定した結果、０．９６３であった。従って、表面改質工程に導入された微粉砕品の平均円形度に対して、図６に示す表面化改質装置により平均円形度が０．０１４アップした表面改質粒子を得ることができた。
【０１３３】
更に、分級品トナーの表面形状観察を電界放射形走査電子顕微鏡（ＦＥ−ＳＥＭ：日立製作所 Ｓ−８００）を用い、倍率を１００００倍とし、目視にて観察し、以下の基準で評価した。結果を表１に示す。
Ａ：円形なシルエット
Ｂ：多少楕円形なシルエット
Ｃ：曲面であるが、異形
Ｄ：角形なシルエット
【０１３４】
次に、該分級品トナー１００質量部に、ヘキサメチルジシラザンとシリコーンオイルで疎水化処理された一次粒径１２ｎｍの乾式シリカを１．０質量部添加し、ヘンシェルミキサーにて外添混合して評価用トナーとした。
【０１３５】
このトナーを用いて、キヤノン製のＬＢＰ−９３０改造機（２３５ｍｍ／ｓｅｃに相当する１．５倍のプリントスピードに改造）に搭載して画出し試験を行い、以下の項目でトナーの画像特性を評価した。
【０１３６】
（評価−１）
評価用トナーを現像器中に入れ、常温常湿室（２３℃，６０％）に一晩（１２時間以上）放置する。１０００枚画出し後、画像濃度を測定する。現像器を取出して、高温高湿室（３２．５℃，８５％）に一晩（１２時間）放置する。現像器を常温常湿室へ戻した後、速やかに２０枚画出しを行い前日と同様にして画像濃度を測定する。前日ラスト画像濃度と一枚目画像濃度を比較する。評価レベルは１０００枚目濃度（前日ラスト）と放置後濃度の差で確認する（値が小さい程良い）。本実施例においては、表２に示したように、濃度差０．０５未満であった。
Ａ：０．０５未満
Ｂ：０．０５以上、０．１０未満
Ｃ：０．１０以上、０．３０未満
Ｄ：０．３０以上
【０１３７】
（評価−２）
評価用トナーを現像器中に入れ、高温高湿室（３２．５℃，８５％）に一晩（１２時間）放置する。現像器の質量を測定後、現像器を設置し、現像スリーブを３分間から回転させた。この時、本体内のクリーナー部及び廃トナー回収部は事前に一旦取外し、質量を測定しておく。印字比率６％のテストチャートを用いて、５００枚画出しを行い、転写率を評価した。本実施例においては、表２に示したように、転写効率は９３％となった。
【０１３８】
尚、転写率は以下の計算式で算出した。
転写率＝
｛現像器減少量―（クリーナー部増量＋廃トナー回収部増量）｝／現像器減少量×１００
Ａ：９０％以上
Ｂ：８８％以上、９０％未満
Ｃ：８６％以上、８８％未満
Ｄ：８５％以下
【０１３９】
また、表面改質装置運転終了後、機内融着について目視で確認し、下記の基準で判断した。本実施例においては、運転終了後機内点検したところ、分散ローター及びライナーに融着は発生していなかった。
Ａ：機内融着なし
Ｂ：機内融着が軽微見られるが実用可
Ｃ：機内融着が若干見られるが実用可
Ｄ：機内融着が顕著に見られ、実用不可
【０１４０】
［実施例２］
実施例１で得た微粉砕品を図６に示す表面改質装置で表面改質した。その際、本実施例においては、サイクルタイムを４５ｓｅｃとした以外は実施例１と同様とした。
【０１４１】
この状態で１２分間運転した結果、分級ローター後方の温度Ｔ２は４４℃で安定した。従って、ΔＴ（Ｔ２−Ｔ１）は４４℃であった。
【０１４２】
この時、得られる表面改質粒子の目標粒度を、実施例１と同様とした。本実施例においては、分級ローターの周速を７５ｍ／ｓｅｃとすることで、重量平均径が７．８μｍであり、個数平均径が６．０μｍであり、４．００μｍ以下の粒子が１１個数％含有するシャープな粒度分布を有する表面改質粒子を回収率７６％で得ることができた。
【０１４３】
従って、表面改質工程に導入された微粉砕品の個数平均径Ａが４．９μｍであり、該表面改質装置で得られる粒子の個数平均径Ｂが６．０μｍなので、Ｂ／Ａは１．２２であった。
【０１４４】
次に、上記の機械式粉砕機で粉砕されて得られた微粉砕品を、実施例１と同様に分級し、分級品トナーを得た。得られたトナーの平均円形度を測定した結果、０．９６５であった。従って、表面改質工程に導入された微粉砕品の円形度に対して、図６に示す表面化改質装置により平均円形度が０．０１６アップした表面改質粒子を得ることができた。更に、このトナーの表面形状をＳＥＭ写真により観察した。結果を表１に示す。
【０１４５】
次に、該分級品トナーを実施例１と同様に外添混合処理を行い、評価用トナーとした。その結果、表２に示すように、良好な結果が得られた。また、運転終了後機内点検したところ、分散ローター及びライナーに融着は発生していなかった。
【０１４６】
［実施例３］
実施例１で得た微粉砕品を図６に示す表面改質装置で表面改質した。その際、本実施例においては、サイクルタイムを６０ｓｅｃとした以外は実施例１と同様とした。
【０１４７】
この状態で１２分間運転した結果、分級ローター後方の温度Ｔ２は４８℃で安定した。従って、ΔＴ（Ｔ２−Ｔ１）は４８℃であった。
【０１４８】
この時、得られる表面改質粒子の目標粒度を、実施例１と同様とした。本実施例においては、分級ローターの周速を７５ｍ／ｓｅｃとすることで、重量平均径が７．５μｍであり、個数平均径が５．９μｍであり、４．００μｍ以下の粒子が１０個数％含有するシャープな粒度分布を有する表面改質粒子を回収率７０％で得ることができた。
【０１４９】
従って、表面改質工程に導入された微粉砕品の個数平均径Ａが４．９μｍであり、該表面改質装置で得られる粒子の個数平均径Ｂが５．９μｍなので、Ｂ／Ａは１．２０であった。
【０１５０】
次に、上記の機械式粉砕機で粉砕されて得られた微粉砕品を、実施例１と同様に分級し、分級品トナーを得た。得られたトナーの円形度を測定した結果、０．９６７であった。従って、表面改質工程に導入された微粉砕品の平均円形度に対して、図６に示す表面化改質装置により平均円形度が０．０１８アップした表面改質粒子を得ることができた。更に、このトナーの表面形状をＳＥＭ写真により観察した。結果を表１に示す。
【０１５１】
次に、該分級品トナーを実施例１と同様に外添混合処理を行い、評価用トナーとした。その結果、表２に示すように、良好な結果が得られた。また、運転終了後機内点検したところ、分散ローター及びライナーに融着は発生していなかった。
【０１５２】
【表１】

【０１５３】
［実施例４］
実施例１で得た微粉砕品を図６に示す表面改質装置で表面改質した。その際、本実施例においては、ブロワー風量を２０ｍ^３／ｍｉｎとした以外は実施例１と同様とした。
【０１５４】
この状態で１２分間運転した結果、分級ローター後方の温度Ｔ２は３９℃で安定した。従って、ΔＴ（Ｔ２−Ｔ１）は３９℃であった。
【０１５５】
この時、得られる表面改質粒子の目標粒度を、実施例１と同様とした。本実施例においては、分級ローターの周速を８０ｍ／ｓｅｃとすることで、重量平均径が７．７μｍであり、個数平均径が６．０μｍであり、４．００μｍ以下の粒子が１０個数％含有するシャープな粒度分布を有する表面改質粒子を回収率７０％で得ることができた。
【０１５６】
従って、表面改質工程に導入された微粉砕品の個数平均径Ａが４．９μｍであり、該表面改質装置で得られる粒子の個数平均径Ｂが６．０μｍなので、Ｂ／Ａは１．２２であった。
【０１５７】
次に、上記の機械式粉砕機で粉砕されて得られた微粉砕品を、実施例１と同様に分級し、分級品トナーを得た。得られたトナーの平均円形度を測定した結果、０．９６１であった。従って、表面改質工程に導入された微粉砕品の平均円形度に対して、図６に示す表面化改質装置により平均円形度が０．０１２アップした表面改質粒子を得ることができた。更に、このトナーの表面形状をＳＥＭ写真により観察した。結果を表２に示す。
【０１５８】
次に、該分級品トナーを実施例１と同様に外添混合処理を行い、評価用トナーとした。その結果、表２に示すように、良好な結果が得られた。また、運転終了後機内点検したところ、分散ローター及びライナーに融着は発生していなかった。
【０１５９】
［実施例５］
実施例１で得た微粉砕品を図６に示す表面改質装置で表面改質した。その際、本実施例においては、ブロワー風量を１０ｍ³／ｍｉｎとした以外は実施例１と同様とした。
【０１６０】
この状態で１２分間運転した結果、分級ローター後方の温度Ｔ２は４８℃で安定した。従って、ΔＴ（Ｔ２−Ｔ１）は４８℃であった。
【０１６１】
この時、得られる表面改質粒子の目標粒度を、実施例１と同様とした。本実施例においては、分級ローターの周速を７０ｍ／ｓｅｃとすることで、重量平均径が７．７μｍであり、個数平均径が５．９μｍであり、４．００μｍ以下の粒子が１４個数％含有するシャープな粒度分布を有する表面改質粒子を回収率７８％で得ることができた。
【０１６２】
従って、表面改質工程に導入された微粉砕品の個数平均径Ａが４．９μｍであり、該表面改質装置で得られる粒子の個数平均径Ｂが５．９μｍなので、Ｂ／Ａは１．２０であった。
【０１６３】
次に、上記の機械式粉砕機で粉砕されて得られた微粉砕品を、実施例１と同様に分級し、分級品トナーを得た。得られたトナーの平均円形度を測定した結果、０．９６７であった。従って、表面改質工程に導入された微粉砕品の平均円形度に対して、図６に示す表面化改質装置により平均円形度が０．０１８アップした表面改質粒子を得ることができた。更に、このトナーの表面形状をＳＥＭ写真により観察した。結果を表２に示す。
【０１６４】
次に、該分級品トナーを実施例１と同様に外添混合処理を行い、評価用トナーとした。その結果、表２に示すように、良好な結果が得られた。また、運転終了後機内点検したところ、分散ローター及びライナーに融着は発生していなかった。
【０１６５】
［実施例６］
実施例１で得た微粉砕品を図６に示す表面改質装置で表面改質した。その際、本実施例においては、ジャケットに通す冷媒の温度及び冷風温度Ｔ１を−１０℃とした以外は実施例１と同様とした。
【０１６６】
この状態で１２分間運転した結果、分級ローター後方の温度Ｔ２は３０℃で安定した。従って、ΔＴ（Ｔ２−Ｔ１）は３０℃であった。
【０１６７】
この時、得られる表面改質粒子の目標粒度を、実施例１と同様とした。本実施例においては、分級ローターの周速を７５ｍ／ｓｅｃとすることで、重量平均径が７．６μｍであり、個数平均径が５．７μｍであり、４．００μｍ以下の粒子が１１個数％含有するシャープな粒度分布を有する表面改質粒子を回収率７８％で得ることができた。
【０１６８】
従って、表面改質工程に導入された微粉砕品の個数平均径Ａが４．９μｍであり、該表面改質装置で得られる粒子の個数平均径Ｂが５．７μｍなので、Ｂ／Ａは１．１６であった。
【０１６９】
次に、上記の機械式粉砕機で粉砕されて得られた微粉砕品を、実施例１と同様に分級し、分級品トナーを得た。得られたトナーの平均円形度を測定した結果、０．９６３であった。従って、表面改質工程に導入された微粉砕品の平均円形度に対して、図６に示す表面化改質装置により平均円形度が０．０１４アップした表面改質粒子を得ることができた。更に、このトナーの表面形状をＳＥＭ写真により観察した。結果を表２に示す。
【０１７０】
次に、該分級品トナーを実施例１と同様に外添混合処理を行い、評価用トナーとした。その結果、表２に示すように、良好な結果が得られた。また、運転終了後機内点検したところ、分散ローター及びライナーに融着は発生していなかった。
【０１７１】
【表２】

【０１７２】
［実施例７］
・結着樹脂 １００質量部
（スチレン−アクリル酸ブチル−マレイン酸ブチルハーフエステル共重合体）
（Ｔｇ６２℃、分子量：Ｍｐ１３０００、Ｍｗ２４００００、分子量１０００〜３００００の成分の存在比：７５％）
・磁性酸化鉄 ９０質量部
（平均粒子径０．２２μｍ、７９５．８ｋＡ／ｍ磁場での特性Ｈｃ５．１ｋＡ／ｍ、σｓ８５．１Ａｍ²／ｋｇ、σｒ５．１Ａｍ²／ｋｇ）
・モノアゾ金属錯体（負荷電制御剤） ２質量部
・低分子量エチレン−プロピレン共重合体 ３質量部
上記の処方の材料を、ヘンシェルミキサーでよく混合した後、温度１３０℃に設定した２軸混練機にて混練した。得られた混練物を冷却し、ハンマーミルにて２ｍｍ以下に粗粉砕し、トナー製造用粉体原料である粉体原料（粗粉砕物）を得た。
【０１７３】
得られた粉体原料を、図１に示す機械式粉砕機３０１（ターボ工業社製ターボミルＴ２５０−ＲＳ型を以下の通り改造した改造機）で微粉砕し、得られた微粉砕品を、図６に示す表面改質装置にて表面改質した。その際、本実施例においては、各装置の運転条件を実施例１と同様とした。結果を表３に示す。
【０１７４】
［実施例８］
・結着樹脂 １００質量部
（スチレン−アクリル酸ブチル−マレイン酸ブチルハーフエステル共重合体）
（Ｔｇ６２℃、分子量：Ｍｐ４００００、Ｍｗ５０００００、分子量１０００〜３００００の成分の存在比：５２％）
・磁性酸化鉄 ９０質量部
（平均粒子径０．２２μｍ、７９５．８ｋＡ／ｍ磁場での特性Ｈｃ５．１ｋＡ／ｍ、σｓ８５．１Ａｍ²／ｋｇ、σｒ５．１Ａｍ²／ｋｇ）
・モノアゾ金属錯体（負荷電制御剤） ２質量部
・低分子量エチレン−プロピレン共重合体 ３質量部
上記の処方の材料を、ヘンシェルミキサーでよく混合した後、温度１３０℃に設定した２軸混練機にて混練した。得られた混練物を冷却し、ハンマーミルにて２ｍｍ以下に粗粉砕し、トナー製造用粉体原料である粉体原料（粗粉砕物）を得た。
【０１７５】
得られた粉体原料を、図１に示す機械式粉砕機３０１（ターボ工業社製ターボミルＴ２５０−ＲＳ型を以下の通り改造した改造機）で微粉砕し、得られた微粉砕品を、図６に示す表面改質装置にて表面改質した。その際、本実施例においては、各装置の運転条件を実施例１と同様とした。結果を表３に示す。
【０１７６】
［実施例９］
・結着樹脂 １００質量部
（スチレン−アクリル酸ブチル−マレイン酸ブチルハーフエステル共重合体）
（Ｔｇ６２℃、分子量：Ｍｐ８０００、Ｍｗ３０００００、分子量１０００〜３００００の成分の存在比：８５％）
・磁性酸化鉄 ９０質量部
（平均粒子径０．２２μｍ、７９５．８ｋＡ／ｍ磁場での特性Ｈｃ５．１ｋＡ／ｍ、σｓ８５．１Ａｍ²／ｋｇ、σｒ５．１Ａｍ²／ｋｇ）
・モノアゾ金属錯体（負荷電制御剤） ２質量部
・低分子量エチレン−プロピレン共重合体 ３質量部
上記の処方の材料を、ヘンシェルミキサーでよく混合した後、温度１３０℃に設定した２軸混練機にて混練した。得られた混練物を冷却し、ハンマーミルにて２ｍｍ以下に粗粉砕し、トナー製造用粉体原料である粉体原料（粗粉砕物）を得た。
【０１７７】
得られた粉体原料を、図１に示す機械式粉砕機３０１（ターボ工業社製ターボミルＴ２５０−ＲＳ型を以下の通り改造した改造機）で微粉砕し、得られた微粉砕品を、図６に示す表面改質装置にて表面改質した。その際、本実施例においては、各装置の運転条件を実施例１と同様とした。結果を表３に示す。
【０１７８】
【表３】

【０１７９】
［実施例１０］
・結着樹脂 １００質量部
（スチレン−アクリル酸ブチル−マレイン酸ブチルハーフエステル共重合体）
（Ｔｇ６２℃、分子量：Ｍｐ２５００、Ｍｗ１５００００、分子量１０００〜３００００の成分の存在比：９２％）
・磁性酸化鉄 ９０質量部
（平均粒子径０．２２μｍ、７９５．８ｋＡ／ｍ磁場での特性Ｈｃ５．１ｋＡ／ｍ、σｓ８５．１Ａｍ²／ｋｇ、σｒ５．１Ａｍ²／ｋｇ）
・モノアゾ金属錯体（負荷電制御剤） ２質量部
・低分子量エチレン−プロピレン共重合体 ３質量部
上記の処方の材料を、ヘンシェルミキサーでよく混合した後、温度１３０℃に設定した２軸混練機にて混練した。得られた混練物を冷却し、ハンマーミルにて２ｍｍ以下に粗粉砕し、トナー製造用粉体原料である粉体原料（粗粉砕物）を得た。
【０１８０】
得られた粉体原料を、図１に示す機械式粉砕機３０１（ターボ工業社製ターボミルＴ２５０−ＲＳ型を以下の通り改造した改造機）で微粉砕し、得られた微粉砕品を、図６に示す表面改質装置にて表面改質した。その際、本実施例においては、各装置の運転条件を実施例１と同様とした。結果を表４に示す。
【０１８１】
［実施例１１］
・結着樹脂 １００質量部
（スチレン−アクリル酸ブチル−マレイン酸ブチルハーフエステル共重合体）
（Ｔｇ６２℃、分子量：Ｍｐ５３０００、Ｍｗ６５００００、分子量１０００〜３００００の成分の存在比：４８％）
・磁性酸化鉄 ９０質量部
（平均粒子径０．２２μｍ、７９５．８ｋＡ／ｍ磁場での特性Ｈｃ５．１ｋＡ／ｍ、σｓ８５．１Ａｍ²／ｋｇ、σｒ５．１Ａｍ²／ｋｇ）
・モノアゾ金属錯体（負荷電制御剤） ２質量部
・低分子量エチレン−プロピレン共重合体 ３質量部
上記の処方の材料を、ヘンシェルミキサーでよく混合した後、温度１３０℃に設定した２軸混練機にて混練した。得られた混練物を冷却し、ハンマーミルにて２ｍｍ以下に粗粉砕し、トナー製造用粉体原料である粉体原料（粗粉砕物）を得た。
【０１８２】
得られた粉体原料を、図１に示す機械式粉砕機３０１（ターボ工業社製ターボミルＴ２５０−ＲＳ型を以下の通り改造した改造機）で微粉砕し、得られた微粉砕品を、図６に示す表面改質装置にて表面改質した。その際、本実施例においては、各装置の運転条件を実施例１と同様とした。結果を表４に示す。
【０１８３】
【表４】

【０１８４】
［比較例１］
実施例１で得た微粉砕品を図１３に示す気流式分級機にて分級し、重量平均粒径７．２μｍ、４．００μｍ以下％１５個数％の分級品トナーを得た。その後、該分級品を図１２に示す表面改質装置で表面改質した。
【０１８５】
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。
【０１８６】
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、粒子の角取り又は球形化が行なわれる。この状態は粒子の飛行と衝突に伴って進んで行く。即ち、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。
【０１８７】
固定化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。
【０１８８】
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。
【０１８９】
得られた表面改質粒子の粒度分布を測定したところ、本比較例においては、重量平均径が６．９μｍであり、４．００μｍ以下の粒子が２６個数％含有しており、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。得られたトナーの円形度を測定した結果、０．９６０であった。従って、表面改質工程に導入された微粉砕品の円形度に対して、図１２に示す表面化改質装置により０．０１１円形度がアップした表面改質粒子を得ることができた。更に、このトナーの表面形状をＳＥＭ写真により観察した。結果を表５に示す。
【０１９０】
次に、該分級品トナーを実施例１と同様に外添混合処理を行い、評価用トナーとした。その結果、表５に示すように、実施例と比べ劣る結果となった。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。
【０１９１】
［比較例２］
実施例１で得た微粉砕品を図１３に示す気流式分級機にて分級し、重量平均粒径７．２μｍ、４．００μｍ以下％１５個数％の分級品トナーを得た。その後、該分級品を図１に示す機械式粉砕機３０１で表面改質した。
【０１９２】
本比較例では、機械式粉砕機３０１の回転子３１４及び固定子３１０の粉砕面形状を図９に示す形式のものとした。また、回転子３１４の周速を９０ｍ／ｓｅｃ、回転子３１４と固定子３１０の間隙を１．５ｍｍとし、粉砕供給量１５ｋｇ／ｈｒとして表面改質粒子を得た。
【０１９３】
得られた表面改質粒子の粒度分布を測定したところ、本比較例においては、重量平均径が７．０μｍであり、４．００μｍ以下の粒子が２０個数％含有しており、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。得られたトナーの平均円形度を測定した結果、０．９５９であった。従って、表面改質工程に導入された微粉砕品の平均円形度に対して、図１２に示す表面化改質装置により平均円形度が０．０１０アップした表面改質粒子を得ることができた。更に、このトナーの表面形状をＳＥＭ写真により観察した。結果を表５に示す。
【０１９４】
次に、該分級品トナーを実施例１と同様に外添混合処理を行い、評価用トナーとした。その結果、表５に示すように、実施例と比べ劣る結果となった。また、運転終了後機内点検したところ、粉砕ローター及びライナーに融着が若干発生していた。
【０１９５】
【表５】

【０１９６】
【発明の効果】
以上説明してきたことにより、本発明によれば、粉砕工程における粉砕機を少なくとも粗粉砕物を微粉砕するために粉砕手段内に投入するための粉体投入口と、固定子と、少なくとも中心回転軸に取り付けられた回転子と微粉砕された粉体を粉砕手段から排出するための粉体排出口とを少なくとも有し、該固定子は該回転子を内包しており、該固定子の表面と該回転子の表面とは所定の間隙を有するように回転子は配置されて粉砕ゾーンを形成しており、粉砕ゾーンにおいて、該回転子の回転に伴って粗粉砕物が微粉砕されることを特徴とする機械式粉砕機とすることにより、微粉量が少なく、シャープな粒度分布を持つトナーを得ることができ、更に、表面改質工程における表面改質装置を、回分式の表面改質装置とし、該表面改質装置を、所定粒径以下の微粉を装置外へ連続的に排出除去する分級手段と、機械式衝撃力を用いる表面処理手段、及び分級手段と表面処理手段との間の空間を分級手段へ導入される前の第一の空間と分級手段により微粉を分級除去された粒子を表面処理手段へ導入するための第二の空間に仕切る案内手段を有することを特徴とする表面改質装置とし、該表面改質装置を適切な状態に制御して運転することにより、トナーの表面改質に伴う過度な粉砕を防止し、熱の影響が少なく、微粉の少ないシャープな粒度分布を有する表面改質粒子が得られ、また、表面改質粒子の表面形状を所望のもの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、長寿命のトナーが得られるトナーの製造方法が提供される。
【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機械式粉砕機の概略的断面図である。
【図２】図１に示す回転子の斜視図である。
【図３】図１の機械式粉砕機におけるＤ−Ｄ’面での概略的断面図である。
【図４】本発明の機械式粉砕機の他の実施形態におけるＤ−Ｄ’面での概略的断面図である。
【図５】本発明の機械式粉砕機の更に他の実施形態におけるＤ−Ｄ’面での概略的断断面図である。
【図６】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７】図６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８】本発明の分級工程において使用される一例の分級装置の概略的断面図である。
【図９】従来の機械式粉砕機におけるＤ−Ｄ’面での概略的断面図である。
【図１０】従来の機械式粉砕機におけるＤ−Ｄ’面での概略的断面図である。
【図１１】従来の機械式粉砕機におけるＤ−Ｄ’面での概略的断面図である。
【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。
【図１３】比較例の分級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】
３０：ケーシング
３１：分級ローター
３２：微粉回収
３３：原料供給口
３４：ライナー（固定体）
３５：冷風導入口
３６：分散ローター（回転体）
３７：製品排出口
３８：排出弁
３９：ガイドリング（案内手段）
４０：角型ディスク
４１：第一の空間
４２：第二の空間
１１９：排出シュート
１２１、２０１：本体ケーシング
１２２：分級室
１２３：案内室
１２４：分級ローター
１２５：原料投入口
１２６：エアー投入口
１２８：排出弁制御装置
１２９：微粉排出管
１３０、１３４：微粉回収手段
１３１：吸引ファン
１３２：ホッパー
１３３：ローターリーバルブ
１３５：分散ルーバー
１３６：周波数変換機
１５１：本体ケーシング
１５５：ローターブレード
１５８：ステーター
１５９：排出バルブ
１６３：リサイクルパイプ
１６４：原料投入シュート
１６８：衝撃室
１７７：ステータージャケット
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
２４１，２４２： 側壁
２４３，２４４： 分級エッジブロック
２４５： コアンダブロック
２４６，２４７： 分級エッジ
２４８，２４９： 原料供給管
２５０：分級室上部壁
２５１： 入気エッジ
２５２，２５３： 入気管
２５５： 気体導入調節手段
２５６，２５７： 静圧計
２５８，２５９，２６０： 排出口
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： 第１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
３２１、３２９： 固定子凸部の波形形状
３２２、３３０： 固定子凹部底部の平坦面
３２３、３３１： 固定子凹部の台形形状
３２４： 回転子凹凸部の波形形状
３２５： 固定子凹凸部の波形形状
３２６、３３２： 回転子凹部の台形形状
３２７、３３３： 回転子凹部底部の平坦面
３２８、３３４： 回転子凸部の波形形状
３３５、３３７、３３９： 固定子の凹凸部の波形形状
３３６、３３８、３４０： 回転子の凹凸部の波形形状
３３７： 回転子の第１斜面
３３８： 回転子の第２斜面
３３９： 固定子の第１斜面
３４０： 固定子の第２斜面
３４１： 回転子粉砕刃
３４２： 固定子粉砕刃
３４３： 回転子凸部
３４４： 回転子凹部
３４５： 固定子凸部
３４６： 固定子凹部[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 heat is fixed to a print sheet such as a transfer material.
[0002]
[Prior art]
In general, as a method for producing a toner, there is a method for producing a toner by mixing raw materials and heating, melting, and dispersing with a kneader to obtain a uniform composition, and then cooling, pulverizing and classifying the mixture. From the viewpoint of mass productivity, cost, etc., the current mainstream.
[0003]
However, since the toner particles produced by such a kneading and pulverizing method are uneven in shape, the toner characteristics are likely to vary, and there are demands for toner in technical trends such as miniaturization, simplification, and high image quality of electrophotographic apparatuses. Today's performance has been so sophisticated that we are not fully satisfied with the current situation.
[0004]
Further, in recent years, in order to achieve cleaner-less and waste toner reduction, improvement in toner transferability is required, so it is necessary to modify the surface shape of the toner = to make it spherical. .
[0005]
For example, as a method for producing the above-described toner, Japanese Patent Application Laid-Open No. 63-235953 proposes a toner that is spheroidized by a mechanical impact force. In addition to the method using the mechanical impact force described above, a method for melting the surface with hot air, a method using heat, and the like are known as methods for making the toner shape spherical.
[0006]
However, the toner has a problem that the surface composition changes due to heat. In particular, since the state of the wax component added as a release agent changes, the method of melting the surface by heat is not preferable in terms of toner quality. Further, in the method using a mechanical impact force, excessive pulverization is likely to occur at the time of spheroidization, and particularly in the case of toner, the toner is pulverized by the impact associated with the spheronization and the amount of fine powder increases. Yes, an unfavorable aspect remains in terms of toner productivity.
[0007]
Thus, since the toner requires many different properties, the properties of the toner are often influenced by the method of producing the toner in addition to the raw materials used. Furthermore, in the toner surface modification process, it is required to produce a high-quality toner stably and efficiently at a low cost without generating fine powder during the spheronization process.
[0008]
[Problems to be solved by the invention]
The object of the present invention is to eliminate such problems, suppress the influence of heat and the generation of fine powder during surface modification, control the toner surface shape to a desired one, and control the toner surface shape. Accordingly, it is an object of the present invention to provide a method for producing a toner that can provide a long-life toner having good developability, transferability, cleaning property, and stable chargeability.
[0009]
Another 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.
[0010]
[Means for Solving the Problems]
The present invention includes a fine pulverization step in which 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 the method for producing a toner having a surface modification step of obtaining a surface modification treatment particle by subjecting the finely pulverized product to a surface modification treatment,
The pulverization step is performed using a mechanical pulverizer,
The mechanical pulverizer is finely pulverized with at least a powder inlet for charging into a pulverizing means to finely pulverize coarsely pulverized material, a stator, and a rotor attached to at least a central rotating shaft. At least a powder discharge port for discharging the powder from the pulverizing means, the stator enclosing the rotor, and the surface of the stator and the surface of the rotor have a predetermined gap The rotor is arranged so as to have a grinding zone, and in the grinding zone, the coarsely pulverized product is finely pulverized as the rotor rotates,
The pulverization step is a step of obtaining a pulverized product having a weight average particle diameter of 3 to 11 μm,
The surface modification step is performed using a batch type surface modification device,
The batch type surface reforming apparatus includes a classifying means for continuously discharging and removing fine powder having a predetermined particle size or less to the outside of the apparatus, a surface treatment means using a mechanical impact force, and the classification means and the surface treatment means. Guide means for partitioning the space between the first space and the second space, the finely pulverized product is introduced into the first space, and fine powder having a predetermined particle size or less is removed from the apparatus by the classification means. While continuously discharging and removing, through the second space, introduced into the surface treatment means using mechanical impact force to perform surface modification treatment, and again circulating to the first space, A method for producing a toner, characterized in that it is a step of obtaining surface-modified particles from which a predetermined amount of fine powder having a particle size equal to or less than a predetermined particle size has been removed by repeating surface modification using a predetermined time classification and mechanical impact force About.
[0011]
As a result of intensive studies to solve the above-described problems of the prior art, the present inventor, as a result, a powder input port for supplying the pulverizer in the pulverization step into the pulverizing means for finely pulverizing at least the coarsely pulverized product, A stator, at least a rotor attached to the central rotating shaft, and a powder discharge port for discharging the finely pulverized powder from the pulverizing means; the stator enclosing the rotor The rotor is arranged so as to have a predetermined gap between the surface of the stator and the surface of the rotor to form a grinding zone. In the grinding zone, coarse grinding is performed as the rotor rotates. By using a mechanical pulverizer characterized in that the product is finely pulverized, a toner having a small amount of fine powder and a sharp particle size distribution can be obtained. A batch-type surface modification device, The surface reforming apparatus classifies the classifying means for continuously discharging and removing fine powder having a predetermined particle size or less to the outside of the apparatus, the surface treatment means using mechanical impact force, and the space between the classification means and the surface treatment means. A surface reforming apparatus comprising a first space before being introduced into the means and a guide means for partitioning the particles from which fine powder has been removed by classification means into a second space for introducing the particles into the surface treatment means. By controlling the surface modification device to an appropriate state and operating it, the surface having a sharp particle size distribution that prevents excessive pulverization associated with the surface modification of the toner, is less affected by heat, and has less fine powder. The modified particles can be obtained, and the surface shape of the surface modified particles can be arbitrarily controlled, and a long-life toner having good developability, transferability and cleaning properties, and stable chargeability can be obtained. Knowing this invention Led was.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.
[0013]
First, raw materials for toner particles containing at least a binder resin and a colorant used in the present invention will be described.
[0014]
〔resin〕
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.
[0015]
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.
[0016]
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 becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.
[0017]
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.
[0018]
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.
[0019]
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 acrylate of the above compounds with methacrylate; ether bond Examples of diacrylate compounds linked by an alkyl chain containing, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, 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.
[0020]
Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds in place of methacrylate; triallylcia Examples thereof include nurate and triallyl trimellitate.
[0021]
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.
[0022]
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);
[0023]
[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.)
[0024]
(C) diols represented by the formula;
[0025]
[Chemical 2]

[0026]
Or polyhydric alcohols, such as glycerin, sorbit, sorbitan, etc. are mentioned.
[0027]
As the acid component, carboxylic acid can be preferably exemplified, and as the divalent carboxylic acid, benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof; succinic acid, Alkyl dicarboxylic acids such as adipic acid, sebacic acid and azelaic acid or their anhydrides; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid or their anhydrides, etc. Examples of carboxylic acids include trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and anhydrides thereof.
[0028]
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.
[0029]
[Magnetic material]
When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner is not particularly limited as long as it is a commonly used magnetic material, but for example, iron oxide such as magnetite, maghemite, ferrite, and other Iron oxide containing metal oxides; metals such as Fe, Co, Ni, or these metals and Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Examples thereof include alloys with metals such as Mn, Se, Ti, W, and V, and mixtures thereof.
[0030]
Specifically, as the magnetic material, triiron tetroxide (Fe _Three O _Four ), Iron sesquioxide (γ-Fe ₂ O _Three ), Iron yttrium oxide (Y _Three Fe _Five O ₁₂ ), Cadmium oxide (CdFe ₂ O _Four ), Gadolinium oxide (Gd) _Three Fe _Five O ₁₂ ), Copper iron oxide (CuFe ₂ O _Four ), Lead iron oxide (PbFe ₁₂ O ₁₉ ), Nickel iron oxide (NiFe) ₂ O _Four ), Iron niobium oxide (NdFe) ₂ O _Three ), Iron barium oxide (BaFe) ₁₂ O ₁₉ ), Magnesium iron oxide (MgFe ₂ O _Four ), Iron lanthanum oxide (LaFeO) _Three ), Iron powder (Fe), cobalt powder (Co), nickel powder (Ni) and the like. The above-described magnetic materials are used alone or in combination of two or more. A particularly suitable magnetic material is a fine powder of iron tetroxide or γ-iron sesquioxide.
[0031]
These ferromagnets have an average particle size of 0.05 to 2 μm, a magnetic property of 795.8 kA / m applied, a coercive force of 1.6 to 12.0 kA / m, and a saturation magnetization of 50 to 200 Am. ² / Kg (preferably 50-100 Am ² / Kg), residual magnetization 2-20 Am ² / Kg is particularly preferred for use in an electrophotographic image forming method.
[0032]
Further, these magnetic materials are preferably contained in an amount of 60 to 200 parts by mass, and more preferably 80 to 150 parts by mass with respect to 100 parts by mass of the binder resin.
[0033]
〔wax〕
In the wax used in the present invention, various wax components conventionally known as mold release agents can be used, and there are the following. Examples of hydrocarbon waxes include low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymers, polyolefin wax, microcrystalline wax, paraffin wax, and aliphatic hydrocarbon wax such as Fischer-Tropsch wax.
[0034]
Examples of the wax having a functional group include oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; or block copolymers thereof; plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax; Animal waxes such as beeswax, lanolin and whale wax; mineral waxes such as ozokerite, ceresin and petrolactam; waxes based on aliphatic esters such as montanate wax and castor wax: deacidified carnauba wax What deoxidized aliphatic ester partially or entirely is mentioned.
[0035]
Further, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a long-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, valinalic acid; stearyl alcohol Saturated alcohols such as eicosyl alcohol, behenyl alcohol, cunavir alcohol, seryl alcohol, melyl alcohol, or alkyl alcohol having a long chain alkyl group; polyhydric alcohols such as sorbitol; linoleic acid amide, oleic acid amide, lauric acid Aliphatic amides such as acid amides; saturated aliphatic bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amides, ethylene bislauric acid amides, hexamethylene bisstearic acid amides; Unsaturated fatty acid amides such as inamide, hexamethylenebisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, Aromatic bisamides such as N'-distearylisophthalamide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soap); such as behenic acid monoglyceride Examples include partially esterified products of fatty acids and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and the like.
[0036]
Examples of the wax grafted with a vinyl monomer include a wax obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylic acid.
[0037]
Preferred waxes include polyolefins obtained by radical polymerization of olefins under high pressure; polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins; polymerized using catalysts such as Ziegler catalysts and metallocene catalysts under low pressures Polyolefins; polyolefins polymerized using radiation, electromagnetic waves or light; paraffin wax, microcrystalline wax, Fischer-Tropsch wax; synthetic hydrocarbon waxes synthesized by the Gintor method, Hydrocol method, Age method, etc. Synthetic waxes containing compounds as compounds; hydrocarbon waxes having functional groups such as hydroxyl groups, carboxyl groups or ester groups; mixtures of hydrocarbon waxes and hydrocarbon waxes having functional groups; Styrene scan as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.
[0038]
In addition, these waxes have a sharp molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a melt liquid crystal deposition method, a low molecular weight solid fatty acid, a low molecular weight A solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.
[0039]
[Charge control agent]
In the toner of the present invention, a charge control agent can be used as necessary in order to further stabilize the chargeability. The charge control agent is preferably used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the binder resin, from the viewpoint of controlling the chargeability of the toner.
[0040]
As the charge control agent, various conventionally known charge control agents can be used, and examples thereof include the following.
[0041]
For example, an organometallic complex or a chelate compound is effective as a negative charge control agent that makes the toner negatively charged. Examples include monoazo metal complexes, aromatic hydroxycarboxylic acid metal complexes, and aromatic dicarboxylic acid metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides or esters thereof, or phenol derivatives of bisphenol. Preferable examples include metal complexes of Cr, Co, and Fe, which are monoazo dyes synthesized from phenol or naphthol, which is a monoazo metal compound having an alkyl group, halogen, nitro group, carbamoyl group or the like as a substituent. A metal compound of an aromatic carboxylic acid is also preferably used, and examples thereof include benzene, naphthalene, anthracene, phenanthrene carboxylic acid, hydroxycarboxylic acid, and dicarboxylic acid metal compounds having an alkyl group, a halogen, a nitro group, and the like.
[0042]
Examples of the positive charge control agent that makes the toner positively charged include nigrosine, nigrosine derivatives, triphenylmethane compounds, and organic quaternary ammonium salts. For example, modified products with nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and phosphonium salts that are analogs thereof Onium salts and their lake pigments, triphenylmethane dyes and their lake pigments (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 dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicycline Diorgano tin borate such as hexyl tin borate; can be used in combination singly, or two or more kinds.
[0043]
(External additive)
As described above, the toner of the present invention generally contains an external additive in addition to the toner particles for adjusting the fluidity and chargeability of the toner. As such an external additive, a fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner particles to increase the fluidity before and after the addition. For example, fluorine resin powder such as vinylidene fluoride fine powder; wet-process silica, fine-powder silica such as dry process silica, fine-powder titanium oxide, fine-powder alumina, and silane compound, titanium coupling agent, silicone oil There are treated fine powders.
[0044]
The hydrophobizing method is applied by chemically treating with an organosilicon compound that reacts or physically adsorbs with fine powder.
[0045]
Examples of organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethridimethylchlorosilane, and α-chloro. Ethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyl Disiloxane, 1,3-divinyltetramethyldisiloxane, 1,3 -Diphenyltetramethyldisiloxane and dimethylpolysiloxane containing 2 to 12 siloxane units per molecule and containing a hydroxyl group bonded to one Si at each terminal unit. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These are used in one kind or a mixture of two or more kinds.
[0046]
As the particles of 0.1 to 5.0 μm used in the present invention, inorganic fine particles, organic fine particles, and mixtures and composites thereof can be used. Specifically, metal oxides such as strontium titanate, cerium oxide, aluminum oxide, and magnesium oxide, fluorine resin powder, resin fine particles, and the like can be given. Particularly in terms of charging characteristics, strontium titanate and cerium oxide are preferable.
[0047]
[Charge Control Agent II]
The toner of the present invention preferably contains a charge control agent.
[0048]
Examples of the toner that controls the negative charge include the following compounds.
[0049]
Organic metal complexes and chelate compounds are effective, and examples include monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid metal complexes. Others include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives of bisphenol.
[0050]
Among these, an azo metal complex represented by the following formula (1) is preferable.
[0051]
[Chemical 3]

[In the formula, M represents a coordination center metal, and examples thereof include Sc, Ti, V, Cr, Co, Ni, Mn, and Fe. Ar is an aryl group, which is an aryl group such as a phenyl group or a naphthyl group, and may have a substituent. In this case, examples of the substituent include a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. X, X ′, Y and Y ′ are —O—, —CO—, —NH—, —NR— (R is an alkyl group having 1 to 4 carbon atoms). C ⁺ Represents a counter ion, and represents hydrogen, sodium, potassium, ammonium, aliphatic ammonium, or a mixed ion thereof. ]
[0052]
In particular, Fe or Cr is preferable as the central metal, halogen, alkyl group, or anilide group is preferable as the substituent, and hydrogen, alkali metal, ammonium, or aliphatic ammonium is preferable as the counter ion. A mixture of complex salts having different counter ions is also preferably used.
[0053]
A basic organometallic complex represented by the following formula (2) is also preferable as a charge control agent imparting negative chargeability.
[0054]
[Formula 4]

[0055]
The following compounds are used to control the toner to be positively charged.
[0056]
Nigrosine modified products such as nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and analogs such as phosphonium salts 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, Ferrocyanide, etc.); metal salt of higher fatty acid; diorganotin oxide such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, di Black hexyl scan such diorgano tin borate such tin borate; guanidine compounds; imidazole compounds. These can be used alone or in combination of two or more.
[0057]
Among these, triphenylmethane compounds and quaternary ammonium salts whose counter ions are not halogen are preferably used. Following formula (3)
[0058]
[Chemical formula 5]

[In the formula, R ₁ Is H or CH _Three R ₂ And R _Three Is a substituted or unsubstituted alkyl group (preferably C ₁ ~ C _Four ). ]
A copolymer with a polymerizable monomer such as styrene, acrylic acid ester or methacrylic acid ester described above can be used as a positive charge control agent. In this case, the homopolymer and copolymer have a function as a charge control agent and a function as a binder resin (all or a part thereof).
[0059]
In particular, a compound represented by the following formula (4) is preferable as the toner positive charge control agent of the present invention.
[0060]
[Chemical 6]

[In the formula, R ₁ , R ₂ , R _Three , R _Four , R _Five And R ₆ Each may be the same as or different from each other and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ₇ , R ₈ And R ₉ Each may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. A ^- Is an anion such as sulfate ion, nitrate ion, borate ion, phosphate ion, hydroxide ion, organic sulfate ion, organic sulfonate ion, organic phosphate ion, carboxylate ion, organic borate ion, tetrafluoroborate Indicates. ]
[0061]
As a method of incorporating the charge control agent into the toner, there are a method of adding it inside the toner particles and a method of adding it externally. The amount of use of these charge control agents is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin.
[0062]
Next, a procedure for producing a toner by the toner production method of the present invention using the toner forming material and the external additive as described above will be described.
[0063]
First, in the raw material mixing step, as a toner internal additive, at least a resin and a colorant are weighed and mixed in a predetermined amount and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer.
[0064]
Further, the toner raw materials blended and mixed as described above are melt-kneaded to melt the resins and disperse the colorant and the like therein. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. In general, a twin-screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, or the like is used. Furthermore, the colored resin composition obtained by melt-kneading the toner raw material is rolled by a two-roll roll after melt-kneading, and then cooled through a cooling step of cooling by water cooling or the like.
[0065]
The cooled product of the colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization step, first, coarse pulverization is performed by a crusher, a hammer mill, a feather mill or the like, and further, fine pulverization is performed by a mechanical pulverizer. In the pulverization step, the toner is pulverized to a predetermined toner particle size step by step. Further, the finely pulverized product obtained by the mechanical pulverizer is subjected to surface modification = spheronization treatment in a surface modification step to obtain surface modified particles. After that, if necessary, the surface modified particles are classified into classifiers such as an inertia class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), a centrifugal classifier turboplex (manufactured by Hosokawa Micron Co., Ltd.), or a high-voltage winder (new) Classification is performed using a sieving machine such as Tokyo Machine Co., Ltd. to obtain a toner having a weight average particle diameter of 3 to 11 μm.
[0066]
The toner coarse powder generated in the classification step is returned to the pulverization step and pulverized. Further, it is preferable in terms of toner productivity that the fine powder generated in the surface modification process is returned to the toner raw material blending process and reused.
[0067]
Furthermore, in the method for producing a toner of the present invention, inorganic fine particles having an average particle size of 50 nm or less are externally added as an external additive to the toner obtained as described above. As a method of externally adding an external additive to the toner, a predetermined amount of classified toner and various known external additives are blended, and a high-speed stirrer that gives shearing force to powder such as a Henschel mixer or a super mixer is removed. It is preferable to use it as an accessory and stir and mix. At this time, since heat is generated inside the external addition machine and agglomerates are easily generated, it is preferable to adjust the temperature by means such as cooling the periphery of the container portion of the external addition machine with water.
[0068]
Next, regarding the mechanical pulverizer used in the toner pulverizing step of the present invention and the toner production method using the mechanical pulverizer, the surface modifying apparatus and surface modification used in the surface modifying step are further described. A toner manufacturing method using a quality device will be described in detail with reference to the drawings.
[0069]
FIG. 1 shows an example of a toner particle pulverizer system incorporating a mechanical pulverizer used in the present invention. FIG. 2 shows a perspective view of a rotor that rotates at a high speed in FIG. 5 shows a schematic cross-sectional view along the line DD ′ in FIG.
[0070]
In the mechanical pulverizer 301 shown in FIG. 1, the casing 313, the jacket 316 in the casing 313 that can pass cooling water, and the rotating body in the casing 313 attached to the central rotating shaft 312 rotate at high speed. A rotor 314 provided with a large number of grooves on the surface, a stator 310 provided with a large number of grooves on the outer surface of the rotor 314 at a constant interval, and a raw material to be treated. A raw material inlet 311 for introduction and a raw material outlet 302 for discharging the processed powder are configured. A space between the rotor 314 and the stator 310 is a grinding zone.
[0071]
In the mechanical pulverizer configured as described above, when a predetermined amount of powder raw material is charged from the quantitative supply device 315 shown in FIG. 1 into the raw material inlet 311 of the mechanical pulverizer, the particles are pulverized. The impact generated between the rotor 314 introduced into the processing chamber and rotating at high speed in the pulverization processing chamber and provided with a number of grooves on the surface and the stator 310 provided with a number of grooves on the surface; These are crushed instantaneously by a large number of ultra high-speed vortices generated behind them and high-frequency pressure vibrations generated thereby. Thereafter, the material passes through the material discharge port 302 and is discharged. The air carrying the toner particles passes through the pulverization chamber and is discharged out of the apparatus system through the raw material discharge port 302, the pipe 219, the collecting cyclone 229, the bag filter 222, and the suction blower 224. Is done. In the present invention, since the powder raw material is pulverized in this manner, a desired pulverization treatment can be easily performed without increasing the fine powder and coarse powder.
[0072]
Examples of such mechanical crushing include crusher kryptron manufactured by Kawasaki Heavy Industries, Ltd., turbo mill manufactured by Turbo Industry, inomizer manufactured by Hosokawa Micron Co., Ltd., super rotor manufactured by Nissin Engineering Co., Ltd., and the like. it can.
[0073]
In the mechanical pulverizer of the present invention, as shown in FIGS. 3, 4, and 5, each of the rotor and the stator includes a plurality of corrugated convex portions, and a portion between the convex portions and the convex portions. It is preferable that at least one of the rotor and the stator has a flat surface at the bottom.
[0074]
In the toner manufacturing method of the present invention, each of the rotor and the stator of the mechanical pulverizer includes a plurality of corrugated convex portions and a concave portion formed between the convex portions. Since the concave portion of at least one of the rotor and the stator has a flat surface at the bottom, the cross-sectional area of the concave portion can be widened, and the pressure loss at this portion can be reduced. It was found that more efficient pulverization can be achieved as compared with the mechanical pulverizer.
[0075]
That is, compared with the pulverized surface shape of the rotor / stator of the conventional mechanical pulverizer (FIGS. 9, 10, and 11), the pulverized surface shape of the rotor and / or stator of the present invention (FIGS. 3, 4, and 5). ), The concave portion is shaped like a trapezoid as a whole at the bottom, so that the pressure loss at this portion can be reduced and occurs between the rotor and the stator. The impact becomes stronger and the grinding efficiency is improved.
[0076]
That is, the particle size distribution obtained by a conventional mechanical pulverizer can be obtained with a higher pulverization supply amount, and the toner production efficiency can be improved.
[0077]
Further, the bottom of the recess has curved surfaces at both ends of the flat surface, so that the vortex generated in this part is faster than the conventional mechanical pulverizer (FIGS. 9 and 11), and Since the toner is efficiently generated, the toner production efficiency can be improved.
[0078]
Further, the rotor has a convex portion formed with a curved surface, and the stator has a concave portion formed with a flat surface, so that the impact force on the toner is higher than that of a conventional mechanical pulverizer (FIG. 10). Therefore, efficient pulverization is possible, and toner production efficiency can be improved.
[0079]
Furthermore, in the toner manufacturing method of the present invention, each of the rotor and the stator has a plurality of corrugated convex portions and concave portions formed between the convex portions. The recess of at least one of the rotor and the stator has a flat surface at the bottom, and
When the slope on the rear side in the rotor rotation direction of the convex portion rising from the bottom surface of the concave portion of the rotor is the rotor first slope,
The first inclined surface of the rotor has an inclination angle (α1) of 10 ° or more and less than 80 ° on the negative side with a line connecting the center of the rotation axis and the rising portion (A) of the first inclined surface of the rotor as a reference line. Preferably (more preferably 45 °), and
When the slope on the front side in the rotor rotation direction of the convex portion rising from the bottom surface of the concave portion of the stator is the stator first slope,
The first slope of the stator has an inclination angle (β1) of 10 ° or more and less than 80 ° on the plus side with a line connecting the center of the rotation axis and the rising portion (A ′) of the first slope of the stator as a reference line. ) (Preferably 45 °), and
When the slope on the front side in the rotor rotation direction of the convex portion rising from the bottom surface of the concave portion of the rotor is the rotor second slope,
The rotor second slope preferably has an inclination angle (α2) of less than 20 ° on the plus side with a line connecting the center of the rotation axis and the apex (C) of the rotor second slope as a reference line. (More preferably 10 °), and
When the slope on the rear side in the rotor rotation direction of the convex portion rising from the bottom surface of the concave portion of the stator is the stator second slope,
The stator second inclined surface may have an inclination angle (β2) of less than 20 ° on the minus side with a line connecting the rotation axis center and the apex (C ′) of the stator second inclined surface as a reference line. Preferred (more preferably 10 °).
[0080]
Further, in the toner manufacturing method of the present invention, the height H of the convex portion is 1.00 to 3 in the cross-sectional views (FIGS. 3, 4 and 5) of the rotor or stator on the plane perpendicular to the rotation axis direction. The length L1 of the flat surface at the bottom of the recess is preferably 0.60 to 2.00 mm. Furthermore, the height H of the convex portion and the length L1 of the flat surface at the bottom of the concave portion have the following relationship:
0.25H ≦ L1 ≦ 2.5H
Is preferably satisfied.
[0081]
Further, in the toner manufacturing method of the present invention, when the length of the upper surface of the convex portion of the rotor and the stator is L2, and the length of the surface facing the upper surface of the convex portion is L3, L2 and L3 is the following conditions
L2 <L3
Is preferably satisfied.
[0082]
That is, by satisfying the above rules and relationships, the particle size distribution obtained by a conventional mechanical pulverizer can be obtained with a higher pulverization supply amount, and the toner production efficiency can be improved.
[0083]
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.
[0084]
FIG. 6 shows an example of a surface modification apparatus used in the present invention, and FIG. 7 shows an example of a top view of a rotor that rotates at a high speed in FIG.
[0085]
In the surface reforming apparatus shown in FIG. 6, a casing 30, a jacket (not shown) through which cooling water or antifreeze liquid can be passed, a surface reforming means, which is in the casing 30 and attached to the central rotating shaft, There are a plurality of rectangular disks or cylindrical pins 40, and a dispersion rotor 36, which is a rotating body on a disk that rotates at a high speed, and a large number of surfaces arranged on the outer periphery of the dispersion rotor 36 at regular intervals. Liner 34 provided with a groove of (there is no need to have a groove on the liner surface), a classification rotor 31 which is a means for classifying the surface-modified raw material into a predetermined particle size, and , A cold air inlet 35 for introducing cold air, a raw material supply port 33 for introducing the raw material to be treated, and a discharge installed so as to be openable and closable so that the surface modification time can be freely adjusted. valve 8. The space between the powder discharge port 37 for discharging the processed powder and the classification rotor 31 as the classification means and the dispersion rotor 36-the liner 34 as the surface modification means to the classification means. From the first space 41 before being introduced, and a cylindrical guide ring 39 which is a guide means for partitioning the particles from which fine powder has been classified and removed by the classifying means into a second space 42 for introducing the particles into the surface treatment means. It is configured. A gap portion between the dispersion rotor 36 and the liner 34 is a surface modification zone, and a classification rotor 4 and a rotor peripheral portion are classification zones.
[0086]
The classifying rotor 31 may be installed in a vertical or horizontal direction as shown in FIG. Further, the number of classification rotors 31 may be single as shown in FIG. 6 or plural.
[0087]
In the surface reforming apparatus configured as described above, when a finely pulverized product is introduced from the raw material supply port 33 with the discharge valve 38 closed, the introduced finely pulverized product is firstly fed by a blower (not shown). Suctioned and classified by the classification rotor 31. At that time, the classified fine powder having a predetermined particle diameter or less is continuously discharged out of the apparatus, and the coarse powder having a predetermined particle diameter or more is removed by centrifugal force from the inner periphery (second space 42) of the guide ring (guide plate) 39. ) Along the circulation flow generated by the dispersion rotor 36 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 36 and the liner 34. 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 41) of the guide ring 39. After being discharged to the outside, the coarse powder rides on the circulating flow, returns to the surface modification zone again, and repeatedly undergoes surface modification. After a certain period of time, the discharge valve 38 is opened and the surface modified particles are recovered from the discharge port 37.
[0088]
The toner production method of the present invention is characterized by finely pulverizing the toner raw material using the mechanical pulverizer shown in FIG. 1, and using the batch-type surface modifying apparatus shown in FIG. By using the toner, the surface shape of the toner is controlled to a desired one, and further, fine powder cut classification is performed to obtain surface modified particles having a sharp particle size distribution.
[0089]
That is, as a result of examination by the present inventor, the mechanical pulverizer used in the pulverization process is a mechanical pulverizer as shown in FIG. 1, and the surface modification apparatus used in the surface modification process is shown in FIG. As shown, a batch type surface modification device, and further, the batch type surface modification device is a surface modification device incorporating a classification rotor for classifying the surface modification particles into a predetermined particle size, It has been found that it is preferable for the surface modification of the toner.
[0090]
That is, as a result of the study by the present inventor, the pulverizer used in the pulverization process is a mechanical pulverizer as shown in FIG. 1, thereby preventing excessive pulverization of the toner and sharpening the toner particle size distribution. The amount of fine powder can be reduced. Furthermore, the surface modification device used in the surface modification step is a batch type surface modification device as shown in FIG. 6 and has a built-in classification rotor for classifying the surface modification particles into a predetermined particle size. When modifying the surface of a pulverized product, by controlling the setting in the surface modification zone of the surface modification device to an appropriate state, even when modifying the surface of toner that is prone to overgrinding, In addition, the increase in the amount of fine powder can be prevented, and the particle size distribution of the toner can be classified sharply. Furthermore, by arbitrarily setting the time for opening the discharge valve, the residence time of the toner in the device can be adjusted, the surface shape of the toner can be arbitrarily controlled, and good developability, transferability, cleaning property, and stability Thus, a long-life toner having excellent charging properties can be obtained.
[0091]
For the above reason, the toner particle size distribution depends on the pulverization efficiency of the toner in the pulverizer. That is, in order to sharpen the particle size distribution of the toner, it is important to prevent an increase in fine powder due to overgrinding and not to generate coarse powder. That is, in the mechanical pulverizer, when the toner is pulverized, it is difficult to be excessively pulverized, so that the amount of fine powder generated can be reduced, and the particle size distribution of the toner can be made sharper. Furthermore, 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. 1, so that the time until the discharge valve is opened (= cycle time), the distributed rotor By controlling the tooth shape and rotational peripheral speed of the upper surface, 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 surface of the toner The residence time in the reformer 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 outside the apparatus. 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.
[0092]
As a result of the study by the present inventors, the surface modification time (= cycle time) in the surface modification apparatus is preferably 5 seconds or more and 180 seconds or less, more preferably 15 seconds or more and 120 seconds or less. 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.
[0093]
In the present invention, the average circularity is used as an index for indicating the degree of surface modification of the surface modified particles.
[0094]
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.
[0095]
[Expression 1]

[0096]
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 5 minutes. The degree of circularity of the toner is measured with the above apparatus at a dispersion concentration of 5000 to 20000 / μl.
[0097]
The “average circularity” in the present invention is an index of the degree of unevenness of the surface-modified particles, and indicates 1.000 when the toner is a perfect sphere, and the average circularity becomes smaller as the toner shape becomes more complicated. Become.
[0098]
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 mm 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 apparatus as described above.
[0099]
The toner of the present invention has at least one peak in the molecular weight range of 2,000 to 50,000 in the molecular weight distribution measured by GPC of THF-soluble matter, and 50 to 90% of components having a molecular weight of 1,000 to 30,000 are present. Preferably, at least one peak is present in a region having a molecular weight of 5,000 to 30,000, and 55 to 90% of a component having a molecular weight of 1,000 to 30,000 is present. When the molecular weight is less than 5,000, the toner cannot have proper elasticity, so that the fixability is improved, but the generation of fine powder increases during the surface treatment, and the fine powder adheres to the toner particles, resulting in uneven charging. The environmental stability of will deteriorate. Therefore, the image density decreases in an environment such as high temperature and high humidity. Furthermore, fog and image quality deteriorate due to non-uniform charging. Furthermore, the storage stability is also deteriorated. Further, when the molecular weight on the low molecular weight side is more than 50,000, the elasticity as a toner is increased, so that the amount of surface treatment is reduced and the productivity is lowered. In addition, since the fixability is deteriorated, adhesion to the fixing member is likely to occur in the initial durability.
[0100]
When the component having a molecular weight of 1000 to 30000 is less than 55%, the elasticity of the toner is increased, so that the amount of surface treatment is reduced and the productivity is lowered. In addition, since the fixability is deteriorated, adhesion to the fixing member is likely to occur in the initial durability. Further, when the component having a molecular weight of 1000 to 30000 is more than 90%, the toner cannot have an appropriate elasticity. Therefore, although the fixing property is improved, the generation of fine powder increases during the surface treatment, and the fine powder adheres to the toner particles. As a result, the charge becomes non-uniform and the environmental stability of the toner deteriorates. Therefore, the image density decreases in an environment such as high temperature and high humidity. Furthermore, fog and image quality deteriorate due to non-uniform charging. Furthermore, the storage stability is also deteriorated.
[0101]
As described above, in the molecular weight distribution by GPC of the THF soluble part of the toner, the toner having such a peak not only keeps the fixing property, the offset resistance and the storage stability in a well-balanced manner, but also produces fine powder by the surface treatment. Therefore, the toner has uniform chargeability and is excellent in developability and image quality.
[0102]
In the present invention, the molecular weight distribution by GPC using the toner and binder resin THF (tetrahydrofuran) as a solvent is measured under the following conditions.
[0103]
The column is stabilized in a heat chamber at 40 ° C., THF is flowed through the column at this temperature as a solvent at a flow rate of 1 ml / min, and about 100 μl of the THF sample solution is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count value of a calibration curve prepared from several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, a molecular weight of 10 manufactured by Tosoh Corporation or Showa Denko KK is 10 ² -10 ⁷ It is appropriate to use a standard polystyrene sample of about 10 points. The detector uses an RI (refractive index) detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, shodexGPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko KK, or manufactured by Tosoh Corporation TSKgel G1000H (H _XL ), G2000H (H _XL ), G3000H (H _XL ), G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ), A combination of TSKgullcolumn.
[0104]
Moreover, a sample is produced as follows.
[0105]
Place the sample in THF and let stand for several hours, then shake well and mix well with THF (until the sample is no longer united) and let stand for more than 12 hours. At that time, the standing time in THF should be 24 hours or more. After that, a sample processed filter (pore size 0.2 to 0.5 μm, for example, Mysori Disc H-25-2 (manufactured by Tosoh Corporation) can be used) is used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.
[0106]
Further, in the toner production method of the present invention, the number average diameter of the surface modified particles obtained by the surface modifying apparatus is larger than the number average diameter of the finely pulverized product introduced into the surface modifying step, When the number average diameter of the finely pulverized product introduced into the surface modification step is A and the number average diameter of the particles obtained by the surface modification apparatus is B, A and B satisfy the following conditions:
1.02 ≦ B / A ≦ 2.00
Is preferably satisfied.
[0107]
That is, by satisfying the above rules and relationships, 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.
[0108]
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 set to 10 ° C. or less (more preferably 5 ° C. or less, more preferably 0 ° C. or less, particularly preferably −5 ° C. or less). 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.
[0109]
Further, as the refrigerant used in the cold air generating apparatus introduced into the surface reforming apparatus, substitute chlorofluorocarbon is preferable from the viewpoint of the environmental problems of the entire earth.
[0110]
Alternative CFCs include R134a, R404A, R407c, R410A, R507A, R717, etc. Among them, R404A is particularly preferable from the viewpoint of energy saving and safety.
[0111]
In addition, it is preferable that the cold air introduce | transduced in this surface modification apparatus is dehumidified from the surface of the dew condensation prevention in an apparatus. A well-known thing can be used as a dehumidifier. The supply air dew point temperature is preferably −15 ° C. or lower, and more preferably −20 ° C. or lower.
[0112]
Furthermore, 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.
[0113]
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 modification device to 5 ° C. or less (more preferably 0 ° C. or less, more preferably −5 ° C. or less), the surface of the toner due to the 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, the toner surface is easily deteriorated by the heat generated during the surface modification, and the in-machine fusion is liable to occur, which is not satisfactory from the viewpoint of toner productivity. .
[0114]
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 (more preferably 50 ° C. or less), toner surface deterioration due to heat generated during surface modification and in-machine fusion are prevented. be able to. 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 satisfactory from the viewpoint of toner productivity.
[0115]
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 modifying 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, the surface of the toner is easily deteriorated by the heat generated during the surface modification and the in-machine fusion is liable to occur, which is not satisfactory from the viewpoint of toner productivity.
[0116]
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.
[0117]
As a result of investigation by the present inventor, the surface condition of the toner can be controlled to a desired one by controlling the operating condition of the surface reforming device within the above-mentioned range. Thus, a long-life toner having excellent charging properties can be obtained.
[0118]
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 satisfactory from the viewpoint of toner productivity. Further, if the minimum distance between the dispersion rotor and the liner is 15.1 mm or more, the processing capacity must be reduced to obtain surface-modified particles, which is also satisfactory in terms of toner productivity. Absent. Also, if the rotational peripheral speed of the dispersion rotor in the surface reforming apparatus is less than 75 m / sec, the processing capacity must be reduced to obtain a predetermined circularity, and the toner productivity is not satisfactory. Absent. 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 unsatisfactory in terms of toner productivity because it tends to wear.
[0119]
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. Since it easily occurs, it is not satisfactory from the viewpoint of toner productivity. 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 sufficiently satisfactory in terms of toner productivity.
[0120]
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.
[0121]
【Example】
Next, the present invention will be described more specifically with reference to examples and comparative examples of the present invention.
[0122]
[Example 1]
・ Binder resin 100 parts by mass
(Styrene-butyl acrylate-butyl maleate half ester copolymer)
(Tg 62 ° C., molecular weight: Mp13000, Mw 600000, abundance ratio of components having a molecular weight of 1000 to 30000: 60%)
・ 90 parts by mass of magnetic iron oxide
(Characteristic Hc 5.1 kA / m, σs 85.1 Am in an average particle size of 0.22 μm, 795.8 kA / m magnetic field ² / Kg, σr 5.1 Am ² / Kg)
・ Monoazo metal complex (negative charge control agent) 2 parts by mass
・ 3 parts by mass of low molecular weight ethylene-propylene copolymer
The materials having the above formulation were thoroughly mixed with a Henschel mixer and then kneaded with a twin-screw kneader set at a temperature of 130 ° C. The obtained kneaded product was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a powder raw material (coarse pulverized product) which is a powder raw material for toner production.
[0123]
The obtained powder raw material is finely pulverized by the mechanical pulverizer 301 shown in FIG. 1 (modified machine obtained by remodeling Turbomill T250-RS manufactured by Turbo Kogyo Co., Ltd. as follows). Surface modification was performed using the surface modification apparatus shown in FIG.
[0124]
In this embodiment, the pulverized surface shapes of the rotor 314 and the stator 310 of the mechanical pulverizer 301 are of the type shown in FIG. That is, the angle of β1 of the stator is 45 °, β2 is 10 °, the height H of the convex portion of the stator is 2.0 mm, and the length L1 of the flat surface of the lower portion of the concave portion of the stator is 1.4 mm. . Further, the peripheral speed of the rotor 314 is 115 m / sec, the gap between the rotor 314 and the stator 310 is 1.3 mm, the pulverization supply amount is 19.5 kg / hr, the weight average particle diameter is 7.0 μm, A toner having an average particle diameter of 4.9 μm and 48% by number below 4.00 μm was obtained.
[0125]
The average roundness of the finely pulverized product obtained was measured and found to be 0.949.
[0126]
The obtained finely pulverized product was subjected to surface modification using a surface modification apparatus shown in FIG. In this case, in this example, eight 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. The rotating peripheral speed of the dispersion rotor is 115 m / sec, and the blower air volume is 15 m. ^Three / Min. Moreover, the input amount of the finely pulverized product was 20 kg, and the cycle time was 30 sec. The temperature of the refrigerant passed through the jacket and the cold air temperature T1 were set to 0 ° C.
[0127]
As a result of operating for 12 minutes in this state, the temperature T2 behind the classification rotor was stabilized at 39 ° C. Therefore, ΔT (T2−T1) was 39 ° C.
[0128]
At this time, the target particle size of the surface-modified particles obtained was set to a weight average diameter of 7.5 ± 0.5 μm, 4.00 μm or less, and 15 number% or less. In this example, by setting the peripheral speed of the classification rotor to 75 m / sec, the weight average diameter is 7.6 μm, the number average diameter is 5.8 μm, and 13% by number of particles having a diameter of 4.00 μm or less. The surface modified particles having a sharp particle size distribution contained therein could be obtained with a recovery rate of 78%.
[0129]
Therefore, the number average diameter A of the finely pulverized product introduced into the surface modification step is 4.9 μm, and the number average diameter B of the particles obtained by the surface modification apparatus is 5.8 μm. .18.
[0130]
For the average particle size and particle size distribution of the toner, a Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Co., Ltd.) is used. NEC) and 1% NaCl aqueous solution is prepared using 1st grade sodium chloride as the electrolyte. As the electrolytic solution, for example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous 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 treatment for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toners of 2 μm or more are measured using the Coulter counter TA-II with a 100 μm aperture as an aperture. The volume distribution and the number distribution were calculated. Then, the volume-based weight average particle diameter obtained from the volume distribution according to the present invention (D4: the median value of each channel is the representative value of the channel) and the cumulative number of toners less than 4.00 μm obtained from the number distribution. Asked. Here, fine powder is defined as 4.00 μm or less. That is, the smaller the value of 4.00 μm or less, the sharper the particle size distribution, and the larger the value, the broader the particle size distribution.
[0131]
The recovery rate was calculated by the ratio of the recovered amount of the surface modified particles to the input amount of the finely pulverized product.
[0132]
Next, the surface modified particles obtained by the above surface modification device are introduced into a centrifugal classification turboplex (manufactured by Hosokawa Micron Corporation) shown in FIG. 8 to perform coarse powder cut classification to obtain a classified toner. It was. As a result of measuring the average circularity of the obtained toner, it was 0.963. Therefore, it was possible to obtain surface modified particles having an average circularity of 0.014 increased by the surface reforming apparatus shown in FIG. 6 with respect to the average circularity of the finely pulverized product introduced into the surface modifying step.
[0133]
Furthermore, the surface shape of the classified toner was observed with a field emission scanning electron microscope (FE-SEM: Hitachi S-800) at a magnification of 10,000 times, visually observed, and evaluated according to the following criteria. The results are shown in Table 1.
A: Circular silhouette
B: Slightly oval silhouette
C: Curved but irregular
D: Square silhouette
[0134]
Next, 1.0 part by mass of dry silica having a primary particle size of 12 nm hydrophobized with hexamethyldisilazane and silicone oil is added to 100 parts by mass of the classified toner, and externally added and mixed with a Henschel mixer. A toner for evaluation was obtained.
[0135]
Using this toner, it was mounted on a Canon LBP-930 remodeling machine (modified to a printing speed of 1.5 times equivalent to 235 mm / sec), and an image output test was conducted. Evaluated.
[0136]
(Evaluation-1)
The evaluation toner is put in a developing device and left in a room temperature and humidity room (23 ° C., 60%) overnight (12 hours or more). After 1000 images are printed, the image density is measured. The developing unit is taken out and left overnight (12 hours) in a high temperature and high humidity chamber (32.5 ° C., 85%). After returning the developing unit to the room temperature and humidity chamber, 20 sheets are immediately printed out and the image density is measured in the same manner as the previous day. The last image density on the previous day is compared with the first image density. The evaluation level is confirmed by the difference between the density at the 1000th sheet (last on the previous day) and the density after standing (the smaller the value, the better). In this example, as shown in Table 2, the density difference was less than 0.05.
A: Less than 0.05
B: 0.05 or more and less than 0.10
C: 0.10 or more and less than 0.30
D: 0.30 or more
[0137]
(Evaluation-2)
The evaluation toner is put in a developing device and left in a high temperature and high humidity chamber (32.5 ° C., 85%) overnight (12 hours). After measuring the mass of the developing device, the developing device was installed, and the developing sleeve was rotated from 3 minutes. At this time, the cleaner unit and the waste toner collecting unit in the main body are once removed in advance and the mass is measured. Using a test chart with a printing ratio of 6%, 500 images were printed and the transfer rate was evaluated. In this example, as shown in Table 2, the transfer efficiency was 93%.
[0138]
The transfer rate was calculated by the following formula.
Transfer rate =
{Developer reduction amount-(Cleaner part increase + Waste toner recovery part increase)} / Developer reduction amount x 100
A: 90% or more
B: 88% or more and less than 90%
C: 86% or more and less than 88%
D: 85% or less
[0139]
Moreover, after completion | finish of surface modification apparatus operation | movement, it confirmed visually about the in-machine fusion | bonding and judged with the following reference | standard. In this example, when the inside of the machine was inspected after the operation was completed, no fusion occurred on the dispersion rotor and the liner.
A: No in-machine fusion
B: In-machine fusion is slight, but practical
C: Practical use is possible although some in-machine fusion is observed
D: In-machine fusion is noticeable, impractical
[0140]
[Example 2]
The finely pulverized product obtained in Example 1 was surface modified with the surface modifying apparatus shown in FIG. At that time, in the present example, the process was the same as Example 1 except that the cycle time was 45 sec.
[0141]
As a result of operating for 12 minutes in this state, the temperature T2 behind the classification rotor was stabilized at 44 ° C. Therefore, ΔT (T2−T1) was 44 ° C.
[0142]
At this time, the target particle size of the obtained surface-modified particles was the same as that in Example 1. In this example, by setting the peripheral speed of the classification rotor to 75 m / sec, the weight average diameter is 7.8 μm, the number average diameter is 6.0 μm, and 11% by number of particles having a diameter of 4.00 μm or less. The surface modified particles having a sharp particle size distribution contained therein could be obtained with a recovery rate of 76%.
[0143]
Accordingly, the number average diameter A of the finely pulverized product introduced into the surface modification step is 4.9 μm, and the number average diameter B of the particles obtained by the surface modification apparatus is 6.0 μm, so B / A is 1 .22.
[0144]
Next, the finely pulverized product obtained by pulverization by the mechanical pulverizer was classified in the same manner as in Example 1 to obtain a classified toner. As a result of measuring the average circularity of the obtained toner, it was 0.965. Therefore, it was possible to obtain surface modified particles having an average circularity increased by 0.016 with the surface modification apparatus shown in FIG. 6 with respect to the circularity of the finely pulverized product introduced into the surface modification step. Further, the surface shape of the toner was observed with an SEM photograph. The results are shown in Table 1.
[0145]
Next, the classified toner was subjected to an external addition mixing process in the same manner as in Example 1 to obtain an evaluation toner. As a result, good results were obtained as shown in Table 2. In addition, when the in-flight inspection was performed after the operation was completed, no fusion occurred on the dispersion rotor and the liner.
[0146]
[Example 3]
The finely pulverized product obtained in Example 1 was surface modified with the surface modifying apparatus shown in FIG. At that time, in the present example, the process was the same as Example 1 except that the cycle time was set to 60 sec.
[0147]
As a result of operating for 12 minutes in this state, the temperature T2 behind the classification rotor was stabilized at 48 ° C. Therefore, ΔT (T2−T1) was 48 ° C.
[0148]
At this time, the target particle size of the obtained surface-modified particles was the same as that in Example 1. In this example, by setting the peripheral speed of the classification rotor to 75 m / sec, the weight average diameter is 7.5 μm, the number average diameter is 5.9 μm, and 10% by number of particles of 4.00 μm or less. The surface-modified particles having a sharp particle size distribution contained can be obtained at a recovery rate of 70%.
[0149]
Therefore, the number average diameter A of the finely pulverized product introduced into the surface modification step is 4.9 μm, and the number average diameter B of the particles obtained by the surface modification apparatus is 5.9 μm, so B / A is 1 .20.
[0150]
Next, the finely pulverized product obtained by pulverization by the mechanical pulverizer was classified in the same manner as in Example 1 to obtain a classified toner. As a result of measuring the circularity of the obtained toner, it was 0.967. Therefore, it was possible to obtain surface-modified particles having an average circularity increased by 0.018 by the surface modification apparatus shown in FIG. 6 with respect to the average circularity of the finely pulverized product introduced into the surface modification step. Further, the surface shape of the toner was observed with an SEM photograph. The results are shown in Table 1.
[0151]
Next, the classified toner was subjected to an external addition mixing process in the same manner as in Example 1 to obtain an evaluation toner. As a result, good results were obtained as shown in Table 2. In addition, when the in-flight inspection was performed after the operation was completed, no fusion occurred on the dispersion rotor and the liner.
[0152]
[Table 1]

[0153]
[Example 4]
The finely pulverized product obtained in Example 1 was surface modified with the surface modifying apparatus shown in FIG. At that time, in this embodiment, the blower air volume is 20 m. ³ The procedure was the same as in Example 1 except that / min was used.
[0154]
As a result of operating for 12 minutes in this state, the temperature T2 behind the classification rotor was stabilized at 39 ° C. Therefore, ΔT (T2−T1) was 39 ° C.
[0155]
At this time, the target particle size of the obtained surface-modified particles was the same as that in Example 1. In this example, by setting the peripheral speed of the classification rotor to 80 m / sec, the weight average diameter is 7.7 μm, the number average diameter is 6.0 μm, and 10% by number of particles of 4.00 μm or less. The surface-modified particles having a sharp particle size distribution contained can be obtained at a recovery rate of 70%.
[0156]
Accordingly, the number average diameter A of the finely pulverized product introduced into the surface modification step is 4.9 μm, and the number average diameter B of the particles obtained by the surface modification apparatus is 6.0 μm, so B / A is 1 .22.
[0157]
Next, the finely pulverized product obtained by pulverization by the mechanical pulverizer was classified in the same manner as in Example 1 to obtain a classified toner. As a result of measuring the average circularity of the obtained toner, it was 0.961. Therefore, it was possible to obtain surface modified particles having an average circularity increased by 0.012 with the surface modification apparatus shown in FIG. 6 with respect to the average circularity of the finely pulverized product introduced into the surface modification step. Further, the surface shape of the toner was observed with an SEM photograph. The results are shown in Table 2.
[0158]
Next, the classified toner was subjected to an external addition mixing process in the same manner as in Example 1 to obtain an evaluation toner. As a result, good results were obtained as shown in Table 2. In addition, when the in-flight inspection was performed after the operation was completed, no fusion occurred on the dispersion rotor and the liner.
[0159]
[Example 5]
The finely pulverized product obtained in Example 1 was surface modified with the surface modifying apparatus shown in FIG. At that time, in this embodiment, the blower air volume is 10 m. ^Three The procedure was the same as in Example 1 except that / min was used.
[0160]
As a result of operating for 12 minutes in this state, the temperature T2 behind the classification rotor was stabilized at 48 ° C. Therefore, ΔT (T2−T1) was 48 ° C.
[0161]
At this time, the target particle size of the obtained surface-modified particles was the same as that in Example 1. In this example, by setting the peripheral speed of the classification rotor to 70 m / sec, the weight average diameter is 7.7 μm, the number average diameter is 5.9 μm, and 14% by number of particles of 4.00 μm or less. The surface modified particles having a sharp particle size distribution contained therein could be obtained with a recovery rate of 78%.
[0162]
Therefore, the number average diameter A of the finely pulverized product introduced into the surface modification step is 4.9 μm, and the number average diameter B of the particles obtained by the surface modification apparatus is 5.9 μm, so B / A is 1 .20.
[0163]
Next, the finely pulverized product obtained by pulverization by the mechanical pulverizer was classified in the same manner as in Example 1 to obtain a classified toner. As a result of measuring the average circularity of the obtained toner, it was 0.967. Therefore, it was possible to obtain surface-modified particles having an average circularity increased by 0.018 by the surface modification apparatus shown in FIG. 6 with respect to the average circularity of the finely pulverized product introduced into the surface modification step. Further, the surface shape of the toner was observed with an SEM photograph. The results are shown in Table 2.
[0164]
Next, the classified toner was subjected to an external addition mixing process in the same manner as in Example 1 to obtain an evaluation toner. As a result, good results were obtained as shown in Table 2. In addition, when the in-flight inspection was performed after the operation was completed, no fusion occurred on the dispersion rotor and the liner.
[0165]
[Example 6]
The finely pulverized product obtained in Example 1 was surface modified with the surface modifying apparatus shown in FIG. At that time, in the present example, the same procedure as in Example 1 was performed except that the temperature of the refrigerant passed through the jacket and the cold air temperature T1 were set to -10 ° C.
[0166]
As a result of operating for 12 minutes in this state, the temperature T2 behind the classification rotor was stabilized at 30 ° C. Therefore, ΔT (T2−T1) was 30 ° C.
[0167]
At this time, the target particle size of the obtained surface-modified particles was the same as that in Example 1. In this example, by setting the peripheral speed of the classification rotor to 75 m / sec, the weight average diameter is 7.6 μm, the number average diameter is 5.7 μm, and 11% by number of particles of 4.00 μm or less. The surface modified particles having a sharp particle size distribution contained therein could be obtained with a recovery rate of 78%.
[0168]
Therefore, since the number average diameter A of the finely pulverized product introduced into the surface modification step is 4.9 μm and the number average diameter B of the particles obtained by the surface modification apparatus is 5.7 μm, B / A is 1 .16.
[0169]
Next, the finely pulverized product obtained by pulverization by the mechanical pulverizer was classified in the same manner as in Example 1 to obtain a classified toner. As a result of measuring the average circularity of the obtained toner, it was 0.963. Therefore, it was possible to obtain surface modified particles having an average circularity of 0.014 increased by the surface reforming apparatus shown in FIG. 6 with respect to the average circularity of the finely pulverized product introduced into the surface modifying step. Further, the surface shape of the toner was observed with an SEM photograph. The results are shown in Table 2.
[0170]
Next, the classified toner was subjected to an external addition mixing process in the same manner as in Example 1 to obtain an evaluation toner. As a result, good results were obtained as shown in Table 2. In addition, when the in-flight inspection was performed after the operation was completed, no fusion occurred on the dispersion rotor and the liner.
[0171]
[Table 2]

[0172]
[Example 7]
・ Binder resin 100 parts by mass
(Styrene-butyl acrylate-butyl maleate half ester copolymer)
(Tg 62 ° C., molecular weight: Mp 13000, Mw 240000, abundance ratio of components having a molecular weight of 1000 to 30000: 75%)
・ 90 parts by mass of magnetic iron oxide
(Characteristic Hc 5.1 kA / m, σs 85.1 Am in an average particle size of 0.22 μm, 795.8 kA / m magnetic field ² / Kg, σr 5.1 Am ² / Kg)
・ Monoazo metal complex (negative charge control agent) 2 parts by mass
・ 3 parts by mass of low molecular weight ethylene-propylene copolymer
The materials having the above formulation were thoroughly mixed with a Henschel mixer and then kneaded with a twin-screw kneader set at a temperature of 130 ° C. The obtained kneaded product was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a powder raw material (coarse pulverized product) which is a powder raw material for toner production.
[0173]
The obtained powder raw material is finely pulverized by the mechanical pulverizer 301 shown in FIG. 1 (modified machine obtained by remodeling Turbomill T250-RS manufactured by Turbo Kogyo Co., Ltd. as follows). Surface modification was performed using the surface modification apparatus shown in FIG. At this time, in this example, the operating conditions of each device were the same as those in Example 1. The results are shown in Table 3.
[0174]
[Example 8]
・ Binder resin 100 parts by mass
(Styrene-butyl acrylate-butyl maleate half ester copolymer)
(Tg 62 ° C., molecular weight: Mp 40000, Mw 500000, abundance ratio of components having a molecular weight of 1000 to 30000: 52%)
・ 90 parts by mass of magnetic iron oxide
(Characteristic Hc 5.1 kA / m, σs 85.1 Am in an average particle size of 0.22 μm, 795.8 kA / m magnetic field ² / Kg, σr 5.1 Am ² / Kg)
・ Monoazo metal complex (negative charge control agent) 2 parts by mass
・ 3 parts by mass of low molecular weight ethylene-propylene copolymer
The materials having the above formulation were thoroughly mixed with a Henschel mixer and then kneaded with a twin-screw kneader set at a temperature of 130 ° C. The obtained kneaded product was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a powder raw material (coarse pulverized product) which is a powder raw material for toner production.
[0175]
The obtained powder raw material is finely pulverized by the mechanical pulverizer 301 shown in FIG. 1 (modified machine obtained by remodeling Turbomill T250-RS manufactured by Turbo Kogyo Co., Ltd. as follows). Surface modification was performed using the surface modification apparatus shown in FIG. At this time, in this example, the operating conditions of each device were the same as those in Example 1. The results are shown in Table 3.
[0176]
[Example 9]
・ Binder resin 100 parts by mass
(Styrene-butyl acrylate-butyl maleate half ester copolymer)
(Tg 62 ° C., molecular weight: Mp 8000, Mw 300000, abundance ratio of components with molecular weight 1000 to 30000: 85%)
・ 90 parts by mass of magnetic iron oxide
(Characteristic Hc 5.1 kA / m, σs 85.1 Am in an average particle size of 0.22 μm, 795.8 kA / m magnetic field ² / Kg, σr 5.1 Am ² / Kg)
・ Monoazo metal complex (negative charge control agent) 2 parts by mass
・ 3 parts by mass of low molecular weight ethylene-propylene copolymer
The materials having the above formulation were thoroughly mixed with a Henschel mixer and then kneaded with a twin-screw kneader set at a temperature of 130 ° C. The obtained kneaded product was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a powder raw material (coarse pulverized product) which is a powder raw material for toner production.
[0177]
The obtained powder raw material is finely pulverized by the mechanical pulverizer 301 shown in FIG. 1 (modified machine obtained by remodeling Turbomill T250-RS manufactured by Turbo Kogyo Co., Ltd. as follows). Surface modification was performed using the surface modification apparatus shown in FIG. At this time, in this example, the operating conditions of each device were the same as those in Example 1. The results are shown in Table 3.
[0178]
[Table 3]

[0179]
[Example 10]
・ Binder resin 100 parts by mass
(Styrene-butyl acrylate-butyl maleate half ester copolymer)
(Tg 62 ° C., molecular weight: Mp2500, Mw150,000, abundance ratio of components having a molecular weight of 1000 to 30000: 92%)
・ 90 parts by mass of magnetic iron oxide
(Characteristic Hc 5.1 kA / m, σs 85.1 Am in an average particle size of 0.22 μm, 795.8 kA / m magnetic field ² / Kg, σr 5.1 Am ² / Kg)
・ Monoazo metal complex (negative charge control agent) 2 parts by mass
・ 3 parts by mass of low molecular weight ethylene-propylene copolymer
The materials having the above formulation were thoroughly mixed with a Henschel mixer and then kneaded with a twin-screw kneader set at a temperature of 130 ° C. The obtained kneaded product was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a powder raw material (coarse pulverized product) which is a powder raw material for toner production.
[0180]
The obtained powder raw material is finely pulverized by the mechanical pulverizer 301 shown in FIG. 1 (modified machine obtained by remodeling Turbomill T250-RS manufactured by Turbo Kogyo Co., Ltd. as follows). Surface modification was performed using the surface modification apparatus shown in FIG. At this time, in this example, the operating conditions of each device were the same as those in Example 1. The results are shown in Table 4.
[0181]
[Example 11]
・ Binder resin 100 parts by mass
(Styrene-butyl acrylate-butyl maleate half ester copolymer)
(Tg 62 ° C., molecular weight: Mp53000, Mw650000, abundance ratio of components having a molecular weight of 1000 to 30000: 48%)
・ 90 parts by mass of magnetic iron oxide
(Characteristic Hc 5.1 kA / m, σs 85.1 Am in an average particle size of 0.22 μm, 795.8 kA / m magnetic field ² / Kg, σr 5.1 Am ² / Kg)
・ Monoazo metal complex (negative charge control agent) 2 parts by mass
・ 3 parts by mass of low molecular weight ethylene-propylene copolymer
The materials having the above formulation were thoroughly mixed with a Henschel mixer and then kneaded with a twin-screw kneader set at a temperature of 130 ° C. The obtained kneaded product was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a powder raw material (coarse pulverized product) which is a powder raw material for toner production.
[0182]
The obtained powder raw material is finely pulverized by the mechanical pulverizer 301 shown in FIG. 1 (modified machine obtained by remodeling Turbomill T250-RS manufactured by Turbo Kogyo Co., Ltd. as follows). Surface modification was performed using the surface modification apparatus shown in FIG. At this time, in this example, the operating conditions of each device were the same as those in Example 1. The results are shown in Table 4.
[0183]
[Table 4]

[0184]
[Comparative Example 1]
The finely pulverized product obtained in Example 1 was classified by an airflow classifier shown in FIG. 13 to obtain a classified toner having a weight average particle diameter of 7.2 μm, 4.00 μm or less, and 15% by number. Thereafter, the classified product was subjected to surface modification using a surface modification apparatus shown in FIG.
[0185]
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.
[0186]
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 along with the flow of the air flow generated by the rotation of the rotor blade 155. 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.
[0187]
The particles that have been fixed are collected by the bag filter 222 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.
[0188]
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.
[0189]
When the particle size distribution of the obtained surface modified particles was measured, in this comparative example, the weight average diameter was 6.9 μm, and 26% by number of particles of 4.00 μm or less were contained. It was broad compared to the previous classified product particle size. This is presumably because the toner was excessively pulverized and the fine powder increased during the surface modification. As a result of measuring the circularity of the obtained toner, it was 0.960. Therefore, it was possible to obtain surface modified particles having an increased circularity of 0.011 by the surface modification apparatus shown in FIG. 12 with respect to the circularity of the finely pulverized product introduced into the surface modification step. Further, the surface shape of the toner was observed with an SEM photograph. The results are shown in Table 5.
[0190]
Next, the classified toner was subjected to an external addition mixing process in the same manner as in Example 1 to obtain an evaluation toner. As a result, as shown in Table 5, the results were inferior to those of the examples. Further, when the in-flight inspection was performed after the operation was completed, the rotor blade was slightly fused.
[0191]
[Comparative Example 2]
The finely pulverized product obtained in Example 1 was classified by an airflow classifier shown in FIG. 13 to obtain a classified toner having a weight average particle diameter of 7.2 μm, 4.00 μm or less, and 15% by number. Thereafter, the classified product was surface-modified with a mechanical pulverizer 301 shown in FIG.
[0192]
In this comparative example, the pulverized surface shapes of the rotor 314 and the stator 310 of the mechanical pulverizer 301 are of the type shown in FIG. Further, surface modified particles were obtained with a peripheral speed of the rotor 314 of 90 m / sec, a gap between the rotor 314 and the stator 310 of 1.5 mm, and a pulverization supply rate of 15 kg / hr.
[0193]
When the particle size distribution of the obtained surface modified particles was measured, in this comparative example, the weight average diameter was 7.0 μm, and 20% by number of particles of 4.00 μm or less were contained. It was broad compared to the previous classified product particle size. This is presumably because the toner was excessively pulverized and the fine powder increased during the surface modification. As a result of measuring the average circularity of the obtained toner, it was 0.959. Therefore, it was possible to obtain surface-modified particles having an average circularity increased by 0.010 by the surface reforming apparatus shown in FIG. 12 with respect to the average circularity of the finely pulverized product introduced into the surface modification step. Further, the surface shape of the toner was observed with an SEM photograph. The results are shown in Table 5.
[0194]
Next, the classified toner was subjected to an external addition mixing process in the same manner as in Example 1 to obtain an evaluation toner. As a result, as shown in Table 5, the results were inferior to those of the examples. Further, when the inside of the machine was inspected after the operation was completed, there was a slight fusion between the grinding rotor and the liner.
[0195]
[Table 5]

[0196]
【The invention's effect】
As described above, according to the present invention, the pulverizer in the pulverization step is charged with at least the center rotation, the powder input port for introducing the pulverized material into the pulverizing means to pulverize the coarsely pulverized material At least a rotor attached to the shaft and a powder discharge port for discharging finely pulverized powder from the pulverizing means, the stator enclosing the rotor, and a surface of the stator The rotor is arranged so as to have a predetermined gap between the rotor and the surface of the rotor to form a pulverization zone, and in the pulverization zone, the coarsely pulverized product is finely pulverized as the rotor rotates. By using a mechanical pulverizer characterized by the above, it is possible to obtain a toner with a small amount of fine powder and a sharp particle size distribution. And the surface modification device Before introducing the classification means for continuously discharging and removing fine powder having a predetermined particle diameter or less to the outside of the apparatus, the surface treatment means using mechanical impact force, and the space between the classification means and the surface treatment means to the classification means A surface modifying apparatus having a first space and a guiding means for partitioning the particles from which fine powder has been removed by classification means into a second space for introducing the particles into the surface treatment means, and the surface modification By controlling the device to an appropriate state and operating it, it is possible to prevent excessive crushing associated with the surface modification of the toner, and to obtain surface-modified particles with a sharp particle size distribution that is less affected by heat and less dusty. In addition, there is provided a method for producing a toner capable of controlling the surface shape of the surface-modified particles to a desired one and obtaining a long-life toner having good developability, transferability, cleaning property, and stable chargeability. Be done
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of an example of a mechanical pulverizer used in a toner pulverization process of the present invention.
FIG. 2 is a perspective view of the rotor shown in FIG.
FIG. 3 is a schematic cross-sectional view taken along the line DD ′ in the mechanical pulverizer of FIG. 1;
FIG. 4 is a schematic sectional view taken along the line DD ′ in another embodiment of the mechanical pulverizer of the present invention.
FIG. 5 is a schematic sectional view taken along the line DD ′ in yet another embodiment of the mechanical pulverizer of the present invention.
FIG. 6 is a schematic cross-sectional view of an example surface modification apparatus used in the surface modification step of the present invention.
7 is a schematic view showing an example of a top view of the dispersion rotor shown in FIG. 6. FIG.
FIG. 8 is a schematic cross-sectional view of an example classification apparatus used in the classification process of the present invention.
FIG. 9 is a schematic cross-sectional view taken along the line DD ′ in a conventional mechanical pulverizer.
FIG. 10 is a schematic sectional view taken along the line DD ′ in a conventional mechanical pulverizer.
FIG. 11 is a schematic cross-sectional view taken along the line DD ′ in a conventional mechanical pulverizer.
FIG. 12 is a schematic cross-sectional view of an example mechanical pulverizer used in a surface modification step of a comparative example.
FIG. 13 is a schematic cross-sectional view of an example mechanical pulverizer used in a classification process of a comparative example.
[Explanation of symbols]
30: Casing
31: Classification rotor
32: Fine powder recovery
33: Raw material supply port
34: Liner (fixed body)
35: Cold air inlet
36: Distributed rotor (rotating body)
37: Product outlet
38: Discharge valve
39: Guide ring (guide means)
40: Square disk
41: First space
42: Second space
119: Discharge chute
121, 201: Main body casing
122: Classification room
123: Information room
124: Classification rotor
125: Raw material inlet
126: Air inlet
128: Discharge valve control device
129: Fine powder discharge pipe
130, 134: Fine powder recovery means
131: Suction fan
132: Hopper
133: Rotary valve
135: Distributed louver
136: Frequency converter
151: Body casing
155: Rotor blade
158: Stator
159: Discharge valve
163: Recycle pipe
164: Raw material charging chute
168: Shock chamber
177: Stator jacket
212: Swirl chamber
219: Pipe
220: Distributor
222: Bug filter
224: Suction blower
229: Collection cyclone
241,242: Side wall
243, 244: Classification edge block
245: Coanda block
246, 247: Classification edge
248, 249: Raw material supply pipe
250: Upper wall of the classification room
251: Inlet edge
252 and 253: Intake tube
255: Gas introduction adjusting means
256, 257: Static pressure gauge
258, 259, 260: outlet
301: Mechanical crusher
302: Powder outlet
310: Stator
311: Powder inlet
312: Rotating shaft
313: casing
314: Rotor
315: First metering feeder
316: Jacket
317: Cooling water supply port
318: Cooling water outlet
320: Rear room
321, 329: Waveform shape of stator protrusion
322, 330: Flat surface at the bottom of the stator recess
323, 331: Trapezoidal shape of stator recess
324: Wave shape of rotor irregularities
325: Corrugated shape of stator irregularities
326, 332: trapezoidal shape of rotor recess
327, 333: flat surface of rotor concave bottom
328, 334: Waveform shape of rotor protrusion
335, 337, 339: Corrugated shape of the uneven portion of the stator
336, 338, 340: Corrugated shape of the uneven portion of the rotor
337: First slope of rotor
338: Second slope of rotor
339: Stator first slope
340: Second slope of stator
341: Rotor grinding blade
342: Stator grinding blade
343: Rotor convex part
344: Rotor recess
345: Stator convex part
346: Stator recess

Claims (26)

A composition comprising at least a binder resin and a colorant is melt-kneaded, the obtained kneaded product is cooled and solidified, and the cooled and solidified product is finely pulverized to obtain a finely pulverized product, and the obtained finely pulverized product In a method for producing a toner having a surface modification step of surface-treating a product to obtain surface-modified particles,
The pulverization step is performed using a mechanical pulverizer,
The mechanical pulverizer is finely pulverized with at least a powder inlet for charging into a pulverizing means to finely pulverize coarsely pulverized material, a stator, and a rotor attached to at least a central rotating shaft. At least a powder discharge port for discharging the powder from the pulverizing means, the stator enclosing the rotor, and the surface of the stator and the surface of the rotor have a predetermined gap The rotor is arranged so as to have a grinding zone, and in the grinding zone, the coarsely pulverized product is finely pulverized as the rotor rotates,
The pulverization step is a step of obtaining a pulverized product having a weight average particle diameter of 3 to 11 μm,
The surface modification step is performed using a batch type surface modification device,
The batch type surface reforming apparatus includes a classifying means for continuously discharging and removing fine powder having a predetermined particle size or less to the outside of the apparatus, a surface treatment means using a mechanical impact force, and the classification means and the surface treatment means. Guide means for partitioning the space between the first space and the second space, the finely pulverized product is introduced into the first space, and fine powder having a predetermined particle size or less is removed from the apparatus by the classification means. While continuously discharging and removing, through the second space, introduced into the surface treatment means using mechanical impact force to perform surface modification treatment, and again circulating to the first space, A method for producing a toner, characterized in that it is a step of obtaining surface-modified particles from which a predetermined amount of fine powder having a particle size equal to or less than a predetermined particle size has been removed by repeating surface modification using a predetermined time classification and mechanical impact force . The toner introduced into the surface modification apparatus has at least one peak in the molecular weight range of 2,000 to 50,000 in the molecular weight distribution measured by GPC of THF soluble matter, and has a molecular weight of 1,000 to 30,000. The toner production method according to claim 1, wherein the toner comprises 50 to 90% of a component. The surface treatment using the mechanical impact force in the surface modification step has a plurality of rectangular disks or cylindrical pins on the upper surface, and a rotating body on a disk that rotates at high speed and the rotating body. The toner manufacturing method according to claim 1, wherein the toner manufacturing method is performed by a surface treatment apparatus including a fixed body fixedly arranged at intervals. The classification means in the surface modification step is classification means by rotation of an impeller type classification rotor, and the guide means is a cylindrical guide ring. Toner manufacturing method. 5. The toner production method according to claim 1, wherein the batch-type surface reforming apparatus has a discharge valve that can be opened and closed so that the surface treatment time can be arbitrarily adjusted. . 6. The method for producing a toner according to claim 1, wherein the surface treatment time in the batch type surface modification apparatus is 5 seconds or more and 180 seconds or less. The average circularity of particles obtained in the surface modification step is 0.01 to 0.05 larger 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 6. The number average particle size of the surface modified 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. 8. The method for producing a toner according to any one of 7 above. The number average diameter A of the finely pulverized product introduced in 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 method for producing a toner according to any one of claims 1 to 9, 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 of claims 1 to 10, characterized in that surface modification treatment the previous SL finely pulverized product while passing a coolant in the jacket A method for producing the toner according to any one of the above. The method for producing a toner according to any one of claims 1 to 11, wherein the temperature of the refrigerant passed through the jacket of the batch-type surface reforming apparatus is 5 ° C or less. The method for producing toner according to any one of claims 1 to 12, wherein a temperature T2 behind the classification rotor of the classification means of the batch type surface modification device is 60 ° C or less. 14. The method for producing a toner according to claim 1, wherein a temperature difference (T2-T1) between the temperature T1 and the temperature T2 is 80 ° C. or less. The minimum distance between the rotating body and the stationary body of the surface treatment means of the batch type surface modification apparatus is 0.5 mm to 15.0 mm, and the rotating peripheral speed of the rotating body is 75 to 150 m / sec. The minimum distance between the upper part of the rectangular disk or cylindrical pin installed on the rotating body and the lower part of the cylindrical guide ring is 2.0 mm to 50.0 mm. The method for producing a toner according to claim 1. The rotor and the stator of the mechanical pulverizer in the fine pulverization step each have a plurality of corrugated convex portions and a concave portion formed between the convex portions and the convex portion, and the rotation The concave portion of at least one of the child and the stator has a flat surface at the bottom;
A slope on the rear side in the rotor rotation direction of the convex portion rising from the bottom surface of the concave portion of the rotor is a rotor first slope, and the rotor first slope is a center of the rotation axis and a position where the rotor first slope rises ( With the line connecting A) as a reference line, it has an inclination angle (α1) of 10 ° or more and less than 80 ° on the minus side, and
The slope of the convex portion rising from the bottom surface of the concave portion of the stator is the stator first slope, and the stator first slope is the center of the rotation axis and the rising portion of the stator first slope ( 16. The method for producing a toner according to claim 1, wherein a line connecting A ′) is used as a reference line, and an inclination angle (β1) of 10 ° or more and less than 80 ° is provided on the plus side. . In the mechanical pulverizer in the fine pulverization step, the slope on the front side in the rotor rotation direction of the convex part rising from the bottom of the concave part of the rotor is the rotor second slope,
The rotor second slope has an inclination angle (α2) of less than 20 ° on the plus side with a line connecting the center of the rotation axis and the apex (C) of the rotor second slope as a reference line. The method for producing a toner according to claim 1. The slope on the rear side in the rotor rotation direction of the convex portion rising from the bottom surface of the concave portion of the stator is the stator second slope,
The stator second slope has an inclination angle (β2) of less than 20 ° on the minus side, with a line connecting the rotation axis center and the apex (C ′) of the stator second slope as a reference line. The method for producing a toner according to claim 1, wherein the toner is a toner. The slope on the front side in the rotor rotation direction of the convex portion rising from the bottom surface of the concave portion of the rotor is the rotor second slope,
The rotor second slope has an inclination angle (α2) of less than 20 ° on the plus side with a line connecting the rotation axis center and the apex (C) of the rotor second slope as a reference line, and ,
The slope on the rear side in the rotor rotation direction of the convex portion rising from the bottom surface of the concave portion of the stator is the stator second slope,
The stator second slope has an inclination angle (β2) of less than 20 ° on the minus side, with a line connecting the rotation axis center and the apex (C ′) of the stator second slope as a reference line. The method for producing a toner according to claim 1, wherein the toner is a toner. The toner manufacturing method according to claim 1, wherein the lower portion of the concave portion has curved surfaces at both ends of the flat surface. 21. The toner manufacturing method according to claim 1, wherein a part of a convex portion of the rotor is formed with a curved surface, and a bottom of the concave portion of the stator is formed with a flat surface. The toner manufacturing method according to claim 1, wherein the rotor has a convex portion formed with a curved surface, and the stator has a bottom portion of the concave portion formed with a flat surface. In the cross-sectional view of the stator on the plane perpendicular to the rotation axis direction, the height H (mm) of the convex portion is 1.00 to 3.00 mm, and the length L1 (mm) of the flat surface at the bottom of the concave portion is 0. The method for producing a toner according to any one of claims 1 to 22, wherein the toner is 60 to 2.00 mm. The height H of the convex portion and the length L1 of the flat surface at the bottom of the concave portion have the following relationship 0.25H ≦ L1 ≦ 2.5H
The toner production method according to claim 1, wherein: When the length of the upper surface of the convex portion of the rotor and / or stator is L2, and the length of the surface facing the upper surface of the convex portion is L3, L2 and L3 satisfy the following condition L2 <L3
The toner production method according to claim 1, wherein: 26. The method for producing a toner according to claim 1, wherein the toner is a magnetic toner containing 60 to 200 parts by mass of a magnetic material with respect to 100 parts by mass of the binder resin.

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