JP4174353B2 - Non-magnetic toner - Google Patents

Description

【００３４】
【数２】

【００３５】
ここで、「粒子投影面積」とは二値化されたトナー粒子像の面積であり、「粒子投影像の周囲長」とは該トナー粒子像のエッジ点を結んで得られる輪郭線の長さと定義する。
【００３６】
本発明における円形度はトナー粒子の凹凸の度合いを示す指標であり、トナー粒子が完全な球形の場合に１．０００を示し、表面形状が複雑になる程、円形度は小さな値となる。
【００３７】
本発明において、トナーの個数基準の粒径頻度分布の平均値を意味する円相当個数平均径Ｄ１（μｍ）と粒径標準偏差ＳＤｄは、粒度分布の分割点ｉでの粒径（中心値）をｄｉ、頻度をｆiとすると次式から算出される。
【００３８】
【数３】

【００３９】
【数４】

【００４０】
また、円形度頻度分布の平均値を意味する平均円形度Ｃと円形度標準偏差ＳＤｃは、粒度分布の分割点ｉでの円形度（中心値）をｃｉ、頻度をｆｃｉとすると、次式から算出される。
【００４１】
【数５】

【００４２】
【数６】

【００４３】
具体的な測定方法としては、容器中に予め不純固形物などを除去したイオン交換水１０ｍｌを用意し、その中に分散剤として界面活性剤、好ましくはアルキルベンゼンスルホン酸塩を加えた後、更に測定試料を０．０２ｇ加え、均一に分散させる。分散させる手段としては、超音波分散機「Ｔｅｔｏｒａ１５０型」（日科機バイオス社製）を用い、２分間分散処理を行い、測定用の分散液とする。その際、該分散液の温度が４０℃以上とならない様に適宜冷却する。
【００４４】
トナー粒子の形状測定には、前記フロー式粒子像測定装置を用い、測定時のトナー粒子濃度が３０００〜１万個／μｌとなる様に該分散液濃度を再調整し、トナー粒子を１０００個以上計測する。計測後、このデータを用いて、３μｍ以下のデータをカットして、トナー粒子の平均円形度Ｃや円形度頻度分布から０.９６０以上の粒子の個数基準累積値Ｙ（％）を求める。
【００４５】
また本発明は、上記のようにトナーの性能、具体的にはトナーの表面における離型剤の量を規定する。トナー表面近傍の離型剤の量は、簡易且つ精度の高い方法として、メタノール４５体積％水溶液における透過率を測定することで、トナー粒子全体を把握することができる。この測定方法はトナーを一度混合溶媒中で強制分散させて、トナー粒子一粒一粒の離型剤の存在量の特徴を出やすくした上で、一定時間後の透過率を測定することで、トナー全体の離型剤の存在量を正確に把握できるものである。つまり表面に疎水性である離型剤がトナー表面に多く存在すると、溶媒に分散しにくく凝集し沈殿するため、透過率が７０％のような高い値になる。逆に離型剤がトナー表面に存在しないと、親水性である結着樹脂のポリエステルユニットが凡そ表面を占めるため、均一分散し透過率が１０％未満のような小さな値になる。
【００４６】
本発明のトナーは、トナーを４５体積％メタノール水溶液に攪拌混合した混合液の紫外可視分光分析による波長６００ｎｍの光の透過率が１０乃至７０％である。前記透過率が前記範囲内にあれば、トナー粒子の表面における離型剤の量が適当であることを示している。前記透過率は、トナー粒子の球形化処理の条件や処理方法によって調整することが可能である。
【００４７】
前記透過率は、以下に示す操作によって測定することができる。測定に用いられる浸とう器及び分光光度計は以下に例示する機器に限定されない。
【００４８】
（1）トナー分散液の調整
メタノール：水の体積混合比が４５：５５の水溶液を作製する。この水溶液１０ｍｌを３０ｍｌのサンプルビン（日電理化硝子：ＳＶ-３０）に入れ、トナー２０ｍｇを液面上に侵し、ビンのフタをする。その後、ヤヨイ式振とう器（モデル：ＹＳ-ＬＤ）により１５０ｒｐｍで５秒間振とうさせる。この時、振とうする角度は、振とう器の真上（垂直）を０度とすると、前方に１５度、後方に２０度、振とうする支柱が動くようにする。サンプルビンは支柱の先に取り付けた固定用ホルダー（サンプルビンの蓋が支柱中心の延長上に固定されたもの）に固定する。サンプルビンを取り出した後、３０秒静置後の分散液を測定用分散液とする。
【００４９】
（2）透過率測定
（1）で得た分散液を１ｃｍ角の石英セルに入れて分光光度計ＭＰＳ２０００（島津製作所社製）を用いて、１０分後の分散液の波長６００ｎｍにおける透過率（％）（次式参照）を測定する。
【００５０】
【数７】
透過率（％）＝Ｉ／Ｉ₀×１００
（ただしＩは入射光束であり、Ｉ₀は透過光束である。）
【００５１】
前記透過率が７０％以上であると、トナー粒子の表面に存在する離型剤量が多いことを示しており、トナーの流動性の悪化や、現像スリーブや帯電部材の汚染が生じ、カブリやトナー飛散が発生しやすい。また、透過率が１０％より小さいと、トナー粒子の中の離型剤の染み出しがトナー粒子の表面の樹脂物性に左右されるため、融点の高い樹脂を用いるとホットオフセット能が低下しやすい。
【００５２】
次に、本発明で使用する離型剤について説明する。
本発明で使用される離型剤は、少なくともビニル系ユニットを有する炭化水素系ワックスが使用できる。ビニル系ユニットを有する炭化水素系ワックスは、ビニル系ユニットが炭化水素系ワックスの水素の１つあるいは複数が置換され、結合している化合物であり、ワックスにビニル系モノマー、あるいはビニル系コポリマーがグラフトされているものを示す。本発明において、ビニル系ユニットを有する炭化水素系ワックスはトナー中への分散性が向上しているため、トナー表面に出難くなるが、さらに鋭意検討の結果、表面改質装置によってトナー粒子を球形化するための表面処理時間を短縮できることが分かった。
【００５３】
この原因の詳細は定かではないが、おそらく次のようであると考えた。ビニル系ユニットを有する炭化水素系ワックスはトナー中で高度に微分散されているため、トナー粒子の可塑性が向上し、より効果的に表面改質される。このことにより、トナー粒子の平均円形度がコントロールし易くなるとともに、少ない処理時間で表面処理出来るため、トナー表面の離型剤の量もコントロールし易くなった。
【００５４】
本発明では、ビニル系ユニットを有する炭化水素系ワックスの一種又は二種以上を用いることができ、またビニル系ユニットを有する炭化水素系ワックスと他の種類のワックスとを併用しても良い。
【００５５】
ビニル系ユニットを有する炭化水素系ワックスは、ビニル系モノマーを用い、通常の方法及び、条件に従って炭化水素ワックスを処理することにより作製することができる。具体的には例えば、放射線を利用する方法、ラジカル触媒を用いる方法等を利用することができるが、ラジカル触媒を用いる方法が好ましい。
【００５６】
前記炭化水素系ワックスとしては、最大吸熱ピークの極大温度が６０〜１１０℃のパラフィンワックス、ポリオレフィンワックス等の炭化水素系ワックスが好ましく使用できるが、特に好ましいのはパラフィン炭化水素系ワックスである。なお、ワックスの最大吸熱ピークの極大温度は、示差走査熱量計（ＤＳＣ測定装置）で測定される。パラフィン炭化水素系ワックスとしては、天然パラフィンワックス、合成パラフィンワックス、マイクロクリスタリンワックス、また、フィッシャー・トロプシュワックス等の、公知のものが使用できる。
【００５７】
前記ビニル系モノマーには、スチレン系モノマーや不飽和カルボン酸系モノマー等の種々のビニル系モノマーを用いることができる。まず、スチレン系モノマーとしてはスチレン、α−メチルスチレン、ビニルトルエン、イソプロペニルトルエン、ｐ−メチルスチレン、p−メトキシスチレン、ｍ−メチルスチレン等が挙げられる。
【００５８】
不飽和カルボン酸系モノマーとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸−ｓｅｃ−ブチル、アクリル酸イソブチル、アクリル酸プロピル、アクリル酸イソプロピル、アクリル酸−２−オクチル、アクリル酸ドデシル、アクリル酸ステアリル、アクリル酸ヘキシル、アクリル酸イソヘキシル、アクリル酸フェニル、アクリル酸−２−クロロフェニル、アクリル酸ジエチルアミノエチル、アクリル酸−３−メトキシブチル、アクリル酸ジエチレングリコールエトキシレート、アクリル酸−２，２，２−トリフルオロエチル等のアクリル酸エステル類、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸−ｎ−ブチル、メタクリル酸−ｓｅｃ−ブチル、メタクリル酸イソブチル、メタクリル酸プロピル、メタクリル酸イソプロピル、メタクリル酸−２−オクチル、メタクリル酸ドデシル、メタクリル酸ステアリル、メタクリル酸ヘキシル、メタクリル酸デシル、メタクリル酸フェニル、メタクリル酸−２−クロロヘキシル、メタクリル酸ジエチルアミノエチル、メタクリル酸−２−ヘキシルエチル、メタクリル酸−２，２，２−トリフルオロエチル等のメタクリル酸エステル類、その他に、マレイン酸エチル、マレイン酸プロピル、マレイン酸ブチル、マレイン酸ジエチル、マレイン酸ジプロピル、マレイン酸ジブチル等のマレイン酸エステル類、フマル酸エチル、フマル酸ブチル、フマル酸ジブチル等のフマル酸エステル類、イタコン酸エチル、イタコン酸ジエチル、イタコン酸ブチル等のイタコン酸エステル類等が挙げられる。
【００５９】
ラジカル触媒としては、有機ペルオキシド、有機ペルエステル、例えばベンゾイルペルオキシド、ジクロルベンゾイルペルオキシド、ジクミルペルオキシド、ジ−ｔｅｒｔ−ブチルペルオキシド、２，５−ジメチル−２，５−ジ（ペルオキシドベンゾエート）ヘキシン−３、１，４−ビス（ｔｅｒｔ−ブチルペルオキシイソプロピル）ベンゼン、ラウロイルペルオキシド、ｔｅｒｔ−ブチルペルアセテート、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキシン−３、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキサン、ｔｅｒｔ−ブチルペルベンゾエート、ｔｅｒｔ−ブチルペルフェニルアセテート、ｔｅｒｔ−ブチルペルイソブチレート、ｔｅｒｔ−ブチルペル−ｓｅｃ−オクトエート、ｔｅｒｔ−ブチルペルピバレート、クミルペルピバレートおよびｔｅｒｔ−ブチルペルジエチルアセテート；その他アゾ化合物、例えばアゾビスイソブチルニトリル、ジメチルアゾイソブチレートなどがある。これらの中ではジクミルペルオキシド、ジ−ｔｅｒｔ−ブチルペルオキシド、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキシン−３、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキサン、１，４−ビス（ｔｅｒｔ−ブチルペルオキシイソプロピル）ベンゼンなどのジアルキルペルオキシドが好ましい。
【００６０】
前記ビニル系モノマーは、一種類のモノマーであっても良いし、又は二種以上のモノマーであっても良く、モノマーの種類や数に限定されるものはない。また、複数種のビニル系モノマーを用いる場合では、モノマーを処理する順番についても限定はない。さらに本発明では、処理によりビニル系モノマーの重合体も生成されるが、本発明においては、前記重合体の生成の有無や種類は何ら限定されるものはない。本発明により処理されたビニル系ユニットを有する炭化水素系ワックスの最大吸熱ピークの極大温度は、処理される前の炭化水素系ワックスとは一般に大きくは変わらない。
【００６１】
本発明で使用される離型剤は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）による分子量測定で二つのピークを有し、これらのピークのうちの高分子側のピークの面積をαとし、低分子側のピークの面積をβとしたときに、下記式（１）を満足することが好ましい。より好ましくは０．３≦β／（α＋β）≦０．８である。
【００６２】
【数８】
０．２≦β／（α＋β）≦０．９ （１）
【００６３】
前記高分子側のピークは、ビニル系ユニットを有するワックス及びビニル系モノマーの重合体のピークであり、前記低分子側のピークは、わずかに反応したワックス及び未反応のワックスのピークである。これは未処理の炭化水素系ワックスをＧＰＣで分析した結果、ピークトップの位置が、前記低分子側のピークとほぼ一致したことから判断した。
【００６４】
また、前記高分子側のピークの成分を抽出したものと、処理により使用したビニル系モノマーとを容積比１：１の割合で加熱混合し、抽出成分とビニル系モノマーとが相分離するまでしばらく放置し、容積比を確認すると、ほぼ１：１のままであった。このことから、ビニル系モノマーの重合体は極わずかであると判断した。
【００６５】
本発明では、定着性の点からも、未反応ワックスは存在していることが好ましい。なおピークが三つ以上存在する場合では、全ピークの内、最も低分子成分側のものの１つを前記低分子側のピークとし、残りのピーク部分の総和を高分子側のピークとすればよい。
【００６６】
β／（α＋β） が０．２よりも小さいと、離型剤としての効果が不十分となり、定着性が十分に向上しないことがある。また、β／（α＋β）が０．８よりも大きいと、トナー粒子の表面における離型剤の分散性が若干悪くなる傾向にある。
【００６７】
前記高分子側のピークの面積αは、図１に示すように、ＧＰＣ分子量分布曲線の谷から垂直に横軸に降ろした線、ＧＰＣ分子量分布曲線、及び前記横軸によって区切られる区域のうち、前記高分子側のピークを含む区域の面積である。前記低分子側のピークの面積βは、図１に示すように、ＧＰＣ分子量分布曲線の谷から垂直に横軸に降ろした線、ＧＰＣ分子量分布曲線、及び前記横軸によって区切られる区域のうち、前記低分子側のピークを含む区域の面積である。
【００６８】
また、各ピークにショルダーが含まれる場合は、ショルダーを含めて一つのピークとして前記面積を求める。
【００６９】
また、本発明で使用される離型剤は、トナー粒子中の樹脂成分１００質量部に対して総量で１〜１０質量部含有されていることが好ましく、３〜８質量部含有されていることが、優れた定着性と現像性を両立させる上でより好ましい。他のワックスと併用して使用する時は各ワックスの総量が離型剤の総量となる。前記離型剤の含有量が１質量部よりも少ないと、トナーの低温定着性及び耐オフセット性が低下することがあり、前記離型剤の含有量が１０質量部よりも多いと、飛び散りやカブリが発生しやすくなり、また耐久に伴い転写効率が低下しやすくなる。
【００７０】
次に本発明で使用する結着樹脂について説明する。
本発明で使用できる結着樹脂は、市販のものが使用できるが、好ましいのは（ａ）ポリエステル樹脂、（ｂ）ポリエステルユニットとビニル系共重合体ユニットを有しているハイブリッド樹脂、（ｃ）ハイブリッド樹脂とビニル系共重合体との混合物、（ｄ）ポリエステル樹脂とビニル系共重合体との混合物、（ｅ）ハイブリッド樹脂とポリエステル樹脂との混合物、及び（f）ポリエステル樹脂とハイブリッド樹脂とビニル系共重合体との混合物から選択される樹脂である。
【００７１】
結着樹脂としてポリエステル樹脂を用いる場合は、多価アルコールと多価カルボン酸、もしくは多価カルボン酸無水物、多価カルボン酸エステル等が原料モノマーとして使用できる。
【００７２】
具体的には、例えば二価アルコール成分としては、ポリオキシプロピレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシプロピレン（３．３）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシエチレン（２．０）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシプロピレン（２．０）−ポリオキシエチレン（２．０）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシプロピレン（６）−２，２−ビス（４−ヒドロキシフェニル）プロパン等のビスフェノールＡのアルキレンオキシド付加物、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，４−ブタンジオール、ネオペンチルグリコール、１，４−ブテンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，４−シクロヘキサンジメタノール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ビスフェノールＡ、水素添加ビスフェノールＡ等が挙げられる。
【００７３】
三価以上のアルコール成分としては、例えばソルビトール、１，２，３，６−ヘキサンテトロール、１，４−ソルビタン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、１，２，４−ブタントリオール、１，２，５−ペンタントリオール、グリセロール、２−メチルプロパントリオール、２−メチル−１，２，４−ブタントリオール、トリメチロールエタン、トリメチロールプロパン、１，３，５−トリヒドロキシメチルベンゼン等が挙げられる。
【００７４】
多価カルボン酸成分としては、フタル酸、イソフタル酸及びテレフタル酸の如き芳香族ジカルボン酸類又はその無水物；こはく酸、アジピン酸、セバシン酸及びアゼライン酸の如きアルキルジカルボン酸類又はその無水物；炭素数６〜１２のアルキル基で置換されたこはく酸もしくはその無水物；フマル酸、マレイン酸及びシトラコン酸の如き不飽和ジカルボン酸類又はその無水物；が挙げられる。
【００７５】
それらの中でも、特に、下記一般式（1）で代表されるビスフェノール誘導体をジオール成分とし、二価以上のカルボン酸又はその酸無水物、又はその低級アルキルエステルとからなるカルボン酸成分（例えば、フマル酸、マレイン酸、無水マレイン酸、フタル酸、テレフタル酸、トリメリット酸、ピロメリット酸等）を酸成分として、これらを縮重合したポリエステル樹脂が、カラートナーとして、良好な帯電特性を有するので好ましい。
【００７６】
【化１】

【００７７】
本発明のトナーに含有される結着樹脂において、「ハイブリッド樹脂」とは、ビニル系重合体ユニットとポリエステルユニットが化学的に結合された樹脂を意味する。具体的には、ポリエステルユニットと（メタ）アクリル酸エステルの如きカルボン酸エステル基を有するモノマーを重合したビニル系重合体ユニットとがエステル交換反応によって形成する樹脂であり、好ましくはビニル系重合体を幹重合体、ポリエステルユニットを枝重合体としたグラフト共重合体（あるいはブロック共重合体）である。
【００７８】
なお、本発明において「ポリエステルユニット」とはポリエステルに由来する部分を示し、「ビニル系重合体ユニット」とはビニル系重合体に由来する部分を示す。ポリエステルユニットを構成するポリエステル系モノマーとしては、多価カルボン酸成分と多価アルコール成分であり、ビニル系重合体ユニットとは、ビニル基を有するモノマー成分であり、モノマー中に多価カルボン酸成分とビニル基を有するモノマー、または多価アルコール成分とビニル基を有するモノマーにについては「ポリエステルユニット」成分として定義する。
【００７９】
ビニル系重合体ユニットを生成するためのビニル系モノマーとしては、スチレン；ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、α−メチルスチレン、ｐ−フェニルスチレン、ｐ−エチルスチレン、２，４−ジメチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−デシルスチレン、ｐ−ｎ−ドデシルスチレン、ｐ−メトキシスチレン、ｐ−クロルスチレン、３，４−ジクロルスチレン、ｍ−ニトロスチレン、ｏ−ニトロスチレン、ｐ−ニトロスチレンの如きスチレン及びその誘導体；エチレン、プロピレン、ブチレン、イソブチレンの如きスチレン不飽和モノオレフィン類；ブタジエン、イソプレンの如き不飽和ポリエン類；塩化ビニル、塩化ビニルデン、臭化ビニル、フッ化ビニルの如きハロゲン化ビニル類；酢酸ビニル、プロピオン酸ビニル、ベンゾエ酸ビニルの如きビニルエステル類；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸−ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸−ｎ−オクチル、メタクリル酸ドデシル、メタクリル酸−２−エチルヘキシル、メタクリル酸ステアリル、メタクリル酸フェニル、メタクリル酸ジメチルアミノエチル、メタクリル酸ジエチルアミノエチルの如きα−メチレン脂肪族モノカルボン酸エステル類；アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸−ｎ−ブチル、アクリル酸イソブチル、アクリル酸−ｎ−オクチル、アクリル酸ドデシル、アクリル酸−２−エチルヘキシル、アクリル酸ステアリル、アクリル酸−２−クロルエチル、アクリル酸フェニルの如きアクリル酸エステル類；ビニルメチルエーテル、ビニルエチルエーテル、ビニルイソブチルエーテルの如きビニルエーテル類；ビニルメチルケトン、ビニルヘキシルケトン、メチルイソプロペニルケトンの如きビニルケトン類；Ｎ−ビニルピロール、Ｎ−ビニルカルバゾール、Ｎ−ビニルインドール、Ｎ−ビニルピロリドンの如きＮ−ビニル化合物；ビニルナフタリン類；アクリロニトリル、メタクリロニトリル、アクリルアミドの如きアクリル酸もしくはメタクリル酸誘導体等が挙げられる。
【００８０】
さらに、マレイン酸、シトラコン酸、イタコン酸、アルケニルコハク酸、フマル酸、メサコン酸の如き不飽和二塩基酸；マレイン酸無水物、シトラコン酸無水物、イタコン酸無水物、アルケニルコハク酸無水物の如き不飽和二塩基酸無水物；マレイン酸メチルハーフエステル、マレイン酸エチルハーフエステル、マレイン酸ブチルハーフエステル、シトラコン酸メチルハーフエステル、シトラコン酸エチルハーフエステル、シトラコン酸ブチルハーフエステル、イタコン酸メチルハーフエステル、アルケニルコハク酸メチルハーフエステル、フマル酸メチルハーフエステル、メサコン酸メチルハーフエステルの如き不飽和二塩基酸のハーフエステル；ジメチルマレイン酸、ジメチルフマル酸の如き不飽和二塩基酸エステル；アクリル酸、メタクリル酸、クロトン酸、ケイヒ酸の如きα，β−不飽和酸；クロトン酸無水物、ケイヒ酸無水物の如きα，β−不飽和酸無水物、前記α，β−不飽和酸と低級脂肪酸との無水物；アルケニルマロン酸、アルケニルグルタル酸、アルケニルアジピン酸、これらの酸無水物及びこれらのモノエステルの如きカルボキシル基を有するモノマーが挙げられる。
【００８１】
さらに、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレートなどのアクリル酸またはメタクリル酸エステル類；４−（１−ヒドロキシ−１−メチルブチル）スチレン、４−（１−ヒドロキシ−１−メチルヘキシル）スチレンの如きヒドロキシ基を有するモノマーが挙げられる。
【００８２】
本発明のトナーにおいて、結着樹脂のビニル系重合体ユニットは、ビニル基を二個以上有する架橋剤で架橋された架橋構造を有していてもよい。この場合に用いられる架橋剤には、芳香族ジビニル化合物として例えば、ジビニルベンゼン、ジビニルナフタレンが挙げられ；アルキル鎖で結ばれたジアクリレート化合物類として例えば、エチレングリコールジアクリレート、１，３−ブチレングリコールジアクリレート、１，４−ブタンジオールジアクリレート、１，５−ペンタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられ；エーテル結合を含むアルキル鎖で結ばれたジアクリレート化合物類としては、例えば、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコール＃４００ジアクリレート、ポリエチレングリコール＃６００ジアクリレート、ジプロピレングリコールジアクリレート及び以上の化合物のアクリレートをメタアクリレートに代えたものが挙げられ；芳香族基及びエーテル結合を含む鎖で結ばれたジアクリレート化合物類として例えば、ポリオキシエチレン（２）−２，２−ビス（４−ヒドロキシフェニル）プロパンジアクリレート、ポリオキシエチレン（４）−２，２−ビス（４−ヒドロキシフェニル）プロパンジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられる。
【００８３】
多官能の架橋剤としては、ペンタエリスリトールトリアクリレート、トリメチロールエタントリアクリレート、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラアクリレート、オリゴエステルアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたもの；トリアリルシアヌレート、トリアリルトリメリテートが挙げられる。
【００８４】
本発明ではビニル系重合体ユニット及びポリエステルユニットのいずれか一方又は両方の中に、両樹脂ユニットの成分と反応し得るモノマー成分を含むことが好ましい。ポリエステル樹脂ユニットを構成するモノマーのうちビニル系重合体ユニットの成分と反応し得るものとしては、例えば、フタル酸、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又はその無水物などが挙げられる。ビニル系重合体ユニットを構成するモノマーのうちポリエステルユニットの成分と反応し得るものとしては、カルボキシル基又はヒドロキシ基を有するものや、アクリル酸もしくはメタクリル酸エステル類が挙げられる。
【００８５】
ビニル系重合体ユニットとポリエステルユニットの反応生成物を得る方法としては、先に挙げたビニル系重合体ユニット及びポリエステルユニットのそれぞれと反応しうるモノマー成分を含むポリマーが存在しているところで、どちらか一方もしくは両方の樹脂の重合反応を行うことにより得る方法が好ましい。
【００８６】
本発明に用いられるビニル系重合体ユニットを製造する場合に用いられる重合開始剤としては、例えば、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、ジメチル−２，２’−アゾビスイソブチレート、１，１’−アゾビス（１−シクロヘキサンカルボニトリル）、２−（カーバモイルアゾ）−イソブチロニトリル、２，２’−アゾビス（２，４，４−トリメチルペンタン）、２−フェニルアゾ−２，４−ジメチル−４−メトキシバレロニトリル、２，２’−アゾビス（２−メチル−プロパン）、メチルエチルケトンパーオキサイド、アセチルアセトンパーオキサイド、シクロヘキサノンパーオキサイドの如きケトンパーオキサイド類、２，２−ビス（ｔ−ブチルパーオキシ）ブタン、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、１，１，３，３−テトラメチルブチルハイドロパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルクミルパーオキサイド、ジ−クミルパーオキサイド、α，α’−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン、イソブチルパーオキサイド、オクタノイルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、３，５，５−トリメチルヘキサノイルパーオキサイド、ベンゾイルパーオキサイド、ｍ−トリオイルパーオキサイド、ジ−イソプロピルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ジ−ｎ−プロピルパーオキシジカーボネート、ジ−２−エトキシエチルパーオキシカーボネート、ジ−メトキシイソプロピルパーオキシジカーボネート、ジ（３−メチル−３−メトキシブチル）パーオキシカーボネート、アセチルシクロヘキシルスルホニルパーオキサイド、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシネオデカノエイト、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシベンゾエイト、ｔ−ブチルパーオキシイソプロピルカーボネート、ジ−ｔ−ブチルパーオキシイソフタレート、ｔ−ブチルパーオキシアリルカーボネート、ｔ−アミルパーオキシ−２−エチルヘキサノエート、ジ−ｔ−ブチルパーオキシヘキサハイドロテレフタレート、ジ−ｔ−ブチルパーオキシアゼレートが挙げられる。
【００８７】
本発明のトナーに用いられるハイブリッド樹脂を調製できる製造方法としては、例えば、以下の（１）〜（６）に示す製造方法を挙げることができる。
【００８８】
（１）ビニル系重合体、ポリエステル樹脂及びハイブリッド樹脂をそれぞれ製造後にブレンドする方法であり、ブレンド品は、有機溶剤（例えば、キシレン）に前記樹脂成分を溶解・膨潤した後に有機溶剤を留去することによって製造される。尚、ハイブリッド樹脂には、ビニル系重合体とポリエステル樹脂を別々に製造後、少量の有機溶剤に溶解・膨潤させ、エステル化触媒及びアルコールを添加し、加熱することによりエステル交換反応を行って合成されるエステル化合物を用いることができる。
【００８９】
（２）ビニル系重合体ユニット製造後に、これの存在下にポリエステルユニット及びハイブリッド樹脂成分を製造する方法である。ハイブリッド樹脂成分はビニル系重合体ユニット（必要に応じてビニル系モノマーも添加できる）とポリエステルモノマー（多価アルコール、多価カルボン酸）との反応、及び前記ユニット及びモノマーと必要に応じて添加されるポリエステルとの反応により製造される。この場合も適宜、有機溶剤を使用することができる。
【００９０】
（３）ポリエステルユニット製造後に、これの存在下にビニル系重合体ユニット及びハイブリッド樹脂成分を製造する方法である。ハイブリッド樹脂成分はポリエステルユニット（必要に応じてポリエステルモノマーも添加できる）とビニル系モノマーとの反応、及び前記ユニット及びモノマーと必要に応じて添加されるビニル系重合体ユニットとの反応により製造される。この場合も適宜、有機溶剤を使用することができる。
【００９１】
（４）ビニル系重合体ユニット及びポリエステルユニット製造後に、これらの重合体ユニット存在下にビニル系モノマー及びポリエステルモノマー（多価アルコール、多価カルボン酸）のいずれか一方又は両方を添加し、添加したモノマーに応じた条件の重合反応を行うことにより、ハイブリッド樹脂成分を製造することができる。この場合も適宜、有機溶剤を使用することができる。
【００９２】
（５）ハイブリッド樹脂を製造後、ビニル系モノマー及びポリエステルモノマー（多価アルコール、多価カルボン酸）のいずれか一方又は両方を添加して、付加重合及び縮重合反応のいずれか一方又は両方を行うことにより、ビニル系重合体ユニット及びポリエステルユニットを製造する。この場合、ハイブリッド樹脂成分には、上記（２）乃至（４）の製造方法により製造されるものを使用することもでき、必要に応じて公知の製造方法により製造されたものを使用することもできる。さらに、適宜、有機溶剤を使用することができる。
【００９３】
（６）ビニル系モノマー及びポリエステルモノマー（多価アルコール、多価カルボン酸等）を混合して付加重合及び縮重合反応を連続して行うことによりビニル系重合体ユニット、ポリエステルユニット及びハイブリッド樹脂成分が製造される。さらに、適宜、有機溶剤を使用することができる。
【００９４】
上記（１）乃至（５）の製造方法において、ビニル系重合体ユニット及びポリエステルユニットには、分子量や架橋度の異なる複数種の重合体ユニットを使用することができる。なお、本発明におけるビニル系重合体又はビニル系重合体ユニットとは、ビニル系単重合体若しくはビニル系共重合体又はビニル系単重合体ユニット若しくはビニル系共重合体ユニットを意味するものである。
【００９５】
本発明で使用される着色剤として、黒色着色剤としては、カーボンブラック、磁性体、イエロー、マゼンタ、及びシアン着色剤を用い黒色に調色したものが利用される。黒色着色剤として磁性体を用いる場合には、他の着色剤と異なり、樹脂１００質量部に対し３０〜２００質量部添加して用いられる。
【００９６】
磁性体としては、鉄、コバルト、ニッケル、銅、マグネシウム、マンガン、アルミニウム、ケイ素等の元素を含む金属酸化物等がある。中でも四三酸化鉄，γ−酸化鉄等、酸化鉄を主成分とするものが好ましい。また、トナーの帯電性のコントロールの観点から、ケイ素元素及びアルミニウム元素等、他の金属元素を含有していてもよい。前記磁性体は、窒素吸着法によるＢＥＴ比表面積が２〜３０ｍ²／ｇ、特に３〜２８ｍ²／ｇが好ましく、更にモース硬度が５〜７であることが好ましい。
【００９７】
磁性体量は結着樹脂１００質量部に対し３０〜２００質量部、好ましくは４０〜２００質量部、さらには５０〜１５０質量部が好ましい。３０質量部未満では着色力が不足したり、トナー搬送に磁気力を用いる現像器においては、搬送性が不十分で現像剤担持体上の現像剤層にムラが生じ、画像ムラが発生する傾向があり、さらに現像剤トリボの上昇に起因する画像濃度の低下が生じ易い傾向がある。一方、２００質量部を超えると定着性に問題が生ずる傾向がある。
【００９８】
本発明のトナーをカラートナーとして用いる場合の着色剤としては、公知の染料及び顔料使用することができる。
【００９９】
マゼンタトナー用着色顔料としてはＣ．Ｉ．ピグメントレッド１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２１、２２、２３、３０、３１、３２、３７、３８、３９、４０、４１、４８、４９、５０、５１、５２、５３、５４、５５、５７、５８、６０、６３、６４、６８、８１、８３、８７、８８、８９、９０、１１２、１１４、１２２、１２３、１６３、２０２、２０６、２０７．２０９、２３８、Ｃ．Ｉ．ピグメントバイオレット１９；Ｃ．Ｉ．バットレッド１、２、１０、１３、１５、２３、２９、３５などが挙げられる。
【０１００】
着色剤には、顔料を単独で使用してもかまわないが、染料と顔料とを併用してその鮮明度を向上させた方がフルカラー画像の画質の点からより好ましい。
【０１０１】
マゼンタトナー用染料としては、Ｃ．Ｉソルベントレッド１、３、８、２３、２４、２５、２７、３０、４９、８１、８２、８３、８４、１００、１０９、１２１；Ｃ．Ｉ．ディスパースレッド９；Ｃ．Ｉ．ソルベントバイオレット８、１３、１４、２１、２７；Ｃ．Ｉ．ディスパーバイオレット１の如き油溶染料、Ｃ．Ｉ．ベーシックレッド１、２、９、１２、１３、１４、１５、１７、１８、２２、２３、２４、２７、２９、３２、３４、３５、３６、３７、３８、３９、４０；Ｃ．Ｉ．ベーシックバイオレット１、３、７、１０、１４、１５、２１、２５、２６、２７、２８などの塩基性染料が挙げられる。
【０１０２】
シアントナー用着色顔料としては、Ｃ．Ｉ．ピグメントブルー２、３、１５：３、１５：４、１６、１７；Ｃ．Ｉ．バットブルー６；Ｃ．Ｉ．アシッドブルー４５、及び下記式で示される構造を有するフタロシアニン骨格にフタルイミドメチル基を１〜５個置換した銅フタロシアニン顔料などが挙げられる。
【０１０３】
【化２】

【０１０４】
イエロー用着色顔料としては、Ｃ．Ｉ．ピグメントイエロー１、２、３、４、５、６、７、１０、１１、１２、１３、１４、１５、１６、１７、２３、６２、６５、７３、７４、８３、９３、９４、９５、９７、１０９、１１０、１１１、１２０、１２７、１２８、１２９、１４７、１５１、１５４、１５５、１６８、１７４、１７５、１７６、１８０、１８１、１８５；Ｃ．Ｉ．バットイエロー１、３、２０などが挙げられる。
【０１０５】
イエロー用着色染料としては、Ｃ．Ｉ．ソルベントイエロー１６２等があり、顔料と染料を併用することも好ましい。
【０１０６】
着色剤の使用量は、結着樹脂１００重量部に対して好ましくは０．１〜１５重量部であり、より好ましくは０．５〜１２重量部であり、最も好ましくは３〜１０重量部である。
【０１０７】
本発明においてトナーに含有される荷電制御剤としては、公知のものが利用できるが、特に、無色でトナーの帯電スピードが速く且つ一定の帯電量を安定して維持できる芳香族カルボン酸の金属化合物が好ましい。
【０１０８】
ネガ系荷電制御剤としては、サリチル酸金属化合物、ナフトエ酸金属化合物、ダイカルボン酸金属化合物、スルホン酸又はカルボン酸を側鎖に持つ高分子型化合物、ホウ素化合物、尿素化合物、ケイ素化合物、カリックスアレーン等が利用できる。ポジ系荷電制御剤としては、四級アンモニウム塩、前記四級アンモニウム塩を側鎖に有する高分子型化合物、グアニジン化合物、イミダゾール化合物等が利用できる。荷電制御剤はトナー粒子に対して内添しても良いし外添しても良い。荷電制御剤の添加量は結着樹脂１００質量部に対し総量で０．２〜１０質量部が好ましい。
【０１０９】
本発明のトナーには、流動性向上のため、外添剤が添加されている。外添剤としては、ケイ酸微粉体、酸化チタン、酸化アルミニウム等の無機微粉体が好ましい。前記無機微粉体は、シランカップリング剤、シリコーンオイル又はそれらの混合物の如き疎水化剤で疎水化されていることが好ましい。
【０１１０】
外添剤は、通常、トナー粒子１００質量部に対して０．１〜５質量部使用される。本発明は非磁性一成分現像、非磁性二成分現像においても非常に有効である。トナー粒子がフルカラー画像形成用の非磁性のカラートナー粒子である場合は、外添剤として、酸化チタン微粒子を使用することが好ましい。トナー粒子と外添剤との混合は、ヘンシェルミキサーの如き公知の混合機を用いることができる。
【０１１１】
本発明のトナーを二成分系現像剤に用いる場合は、トナーは磁性キャリアと混合して使用される。磁性キャリアとしては、例えば表面酸化又は未酸化の鉄、ニッケル、銅、亜鉛、コバルト、マンガン、クロム、希土類の如き金属粒子、それらの合金粒子、酸化物粒子及びフェライト等が使用できる。
【０１１２】
上記磁性キャリア粒子の表面を樹脂で被覆した被覆キャリアは、現像スリーブに交流バイアスを印加する現像法において特に好ましい。被覆方法としては、樹脂の如き被覆材を溶剤中に溶解もしくは懸濁せしめて調製した塗布液を磁性キャリア粒子表面に付着せしめる方法、磁性キャリア粒子と被覆材とを粉体の状態で混合する方法等、従来公知の方法が適用できる。
【０１１３】
磁性キャリア粒子の表面への被覆材料としては、シリコーン樹脂、ポリエステル樹脂、スチレン系樹脂、アクリル系樹脂、ポリアミド、ポリビニルブチラール、アミノアクリレート樹脂が挙げられる。これらは、単独或いは複数で用いられる。
【０１１４】
上記被覆材料の処理量は、磁性キャリア粒子に対し０．１〜３０重量％（好ましくは０．５〜２０重量％）が好ましい。磁性キャリアの平均粒径は１０〜１００μｍであることが好ましく、２０〜７０μｍであることがより好ましい。
【０１１５】
本発明のトナーと磁性キャリアとを混合して二成分系現像剤を調製する場合、その混合比率は現像剤中のトナー濃度として２重量％〜１５重量％にすると通常良好な結果が得られ、より好ましくは４重量％〜１３重量％である。
【０１１６】
本発明のトナーの物性の測定法として、好適な測定法を以下に示す。
【０１１７】
＜ＧＰＣ測定＞
ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるクロマトグラムの分子量は次の条件で測定される。
【０１１８】
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テトラヒドロフラン（ＴＨＦ）を毎分１ｍｌの流速で流し、試料濃度として０．０５〜０．６質量％に調整した樹脂のＴＨＦ試料溶液を約５０〜２００μｌ注入して測定する。検出器にはＲＩ（屈折率）検出器を用いる。カラムとしては、１０³〜２×１０⁶の分子量領域を的確に測定するために、市販のポリスチレンジェルカラムを複数本組み合わせるのが良く、例えば昭和電工社製のｓｈｏｄｅｘ ＧＰＣ ＫＦ−８０１、８０２、８０３、８０４、８０５、８０６、８０７の組み合わせや、Ｗａｔｅｒｓ社製のμ−ｓｔｙｒａｇｅｌ ５００、１０３、１０４、１０５の組み合わせを挙げることができる。
【０１１９】
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数（リテンションタイム）との関係から算出する。検量線作成用の標準ポリスチレン試料としては、例えば東ソー社製或いはＰｒｅｓｓｕｒｅ Ｃｈｅｍｉｃａｌ Ｃｏ．製の分子量が６×１０²、２．１×１０³、４×１０³、１．７５×１０⁴、５．１×１０⁴、１．１×１０⁵、３．９×１０⁵、８．６×１０⁵、２×１０⁶、４．４８×１０⁶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。
【０１２０】
（ＧＰＣによるワックス分子量の測定）
装置：ＧＰＣ−１５０Ｃ（ウォーターズ社）
カラム：ＧＭＨ−ＨＴ３０ｃｍ、２連（東ソー社製）
温度：１３５℃
溶媒：ｏ−ジクロロベンゼン（０．１質量％アイオノール添加）
流速：１．０ｍｌ／ｍｉｎ
試料：０．１５質量％のワックスを０．４ｍｌ注入
以上の条件で測定し、ワックスの分子量算出にあたっては単分散ポリスチレン標準試料により作成した分子量校正曲線を使用する。さらに、Ｍａｒｋ−Ｈｏｕｗｉｎｋ粘度式から導き出される換算式に基づいてポリエチレン換算することでワックスの分子量を算出する。
【０１２１】
＜トナー粒度分布の測定＞
本発明において、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（コールター社製）を用いて測定することができる。また、コールターマルチサイザー（コールター社製）を用いることも可能である。測定においては、電解液が使用されるが、この電解液には１％ＮａＣｌ水溶液が使用される。１％NaCl水溶液は、１級塩化ナトリウムを使用して調製しても良いし、また例えば、ＩＳＯＴＯＮ Ｒ−ＩＩ（コールターサイエンティフィックジャパン社製）等の市販品を使用しても良い。
【０１２２】
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ホン酸塩を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を超音波分散器で約１〜３分間分散処理し、前記測定装置により、アパーチャーとして１００μｍアパーチャーを用いて、２．００μｍ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、重量平均粒径（Ｄ４）（各チャンネルの中央値をチャンネル毎の代表値とする）を求める。
【０１２３】
チャンネルとしては、２．００〜２．５２μｍ；２．５２〜３．１７μｍ；３．１７〜４．００μｍ；４．００〜５．０４μｍ；５．０４〜６．３５μｍ；６．３５〜８．００μｍ；８．００〜１０．０８μｍ；１０．０８〜１２．７０μｍ；１２．７０〜１６．００μｍ；１６．００〜２０．２０μｍ；２０．２０〜２５．４０μｍ；２５．４０〜３２．００μｍ；３２．００〜４０．３０μｍの１３チャンネルを用いる。
【０１２４】
＜トナー及びワックス等における最大吸熱ピークの極大温度の測定＞
トナー及びワックスの最大吸熱ピークは、示差走査熱量計（ＤＳＣ測定装置）、ＤＳＣ−７（パーキンエルマー社製）やＤＳＣ２９２０（ＴＡインスツルメンツジャパン社製）を用いて測定することができる。測定方法は、ＡＳＴＭ Ｄ３４１８−８２に準ずる。
【０１２５】
測定試料は５〜２０ｍｇ、好ましくは１０ｍｇを精密に秤量する。それをアルミパン中に入れ、リファレンスとして空のアルミパンを用い、測定範囲３０〜２００℃の間で、１０℃／ｍｉｎの速度で以下の昇温及び降温条件によって昇温及び降温を行い、測定を行う。

【０１２６】
トナー及びワックスの最大吸熱ピークは、昇温IIの過程で、樹脂Ｔｇの吸熱ピーク以上の領域のベースラインからの高さが一番高いものを、若しくは樹脂Ｔｇの吸熱ピークが別の吸熱ピークと重なり判別し難い場合、その重なるピークの一番高いものを最大吸熱ピークとする。
【０１２７】
本発明に含まれる実施態様を以下に列挙する。
【０１２８】
［実施態様１］
結着樹脂、着色剤、及び離型剤を少なくとも含有する非磁性トナー粒子と、外添剤とを有する非磁性トナーにおいて、円相当径が３μｍ以上の非磁性トナーに含まれる粒子の平均円形度が０．９１５以上０．９６０以下であり、前記非磁性トナーを４５体積％メタノール水溶液に攪拌混合した混合液の紫外可視分光分析による波長６００ｎｍの光の透過率が１０乃至７０％であり、前記離型剤は、少なくともビニル系ユニットを有する炭化水素系ワックスを含むことを特徴とする非磁性トナー。
【０１２９】
［実施態様２］
前記非磁性トナーの重量平均粒径をＸ（μｍ）とし、円形度が０．９６０以上の非磁性トナーに含まれる粒子の個数基準累積値をＹ（％）としたときに、４≦Ｘ≦１１、及び−Ｘ＋２０≦Ｙ≦−Ｘ＋７０の関係を満足することを特徴とする実施態様１に記載の非磁性トナー。
【０１３０】
［実施態様３］
前記結着樹脂は、（ａ）ポリエステル樹脂、（ｂ）ポリエステルユニットとビニル系重合体ユニットを有しているハイブリッド樹脂、（ｃ）ハイブリッド樹脂とビニル系重合体との混合物、及び（ｄ）ポリエステル樹脂とビニル系重合体との混合物から選択される樹脂であることを特徴とする実施態様１又は２に記載の非磁性トナー。
【０１３１】
［実施態様４］
前記離型剤は、ゲルパーミエーションクロマトグラフィーによる分子量測定で二つのピークを有し、これらのピークのうちの高分子側のピークの面積をαとし、低分子側のピークの面積をβとしたときに、下記式（１）を満足することを特徴とする実施態様１乃至３のいずれか一つの態様に記載の非磁性トナー。
【０１３２】
【数９】
０．２≦β／（α＋β）≦０．９ （１）
【０１３３】
［実施態様５］
前記離型剤は、非磁性トナー粒子中の樹脂成分１００質量部に対して総量で１乃至１０質量部含有されていることを特徴とする実施態様１乃至４のいずれか一つの態様に記載の非磁性トナー。
【０１３４】
【実施例】
以下、本発明の具体的実施例について説明するが、本発明はこれらの実施例に限定されるものではない。
【０１３５】
（処理ワックスの製造法）
スチレンモノマー６００ｇに反応開始剤としてジクミルパーオキサイド１００ｇを添加した後、加熱溶融したパラフィンワックスＡ３３００ｇ中に攪拌しながら滴下し、４時間反応させ、離型剤１を得た。
【０１３６】
ビニル系モノマーの種類や比率、加熱温度等を変え、同様に離型剤２〜４を得た。得られた離型剤及び使用したワックスの組成及び物性を表１、表２に示す。
【０１３７】
【表１】

【０１３８】
【表２】

【０１３９】
（トナー製造法１）
表３に示す組成及び物性の樹脂、及び表４に示すトナー材料を表４に示す組成でヘンシェルミキサーにより十分予備混合を行い、混合物を二軸式押出機で溶融混練し、溶融混練物を冷却し、冷却物をハンマーミルを用いて粒径約１〜２ｍｍ程度に粗粉砕した。次いで、粗粉砕物をエアージェット方式による微粉砕機で微粉砕した。
【０１４０】
さらに、得られた微粉砕物を図２及び図３に示したような処理装置を用い、分級ロータの回転数を７３００ｒｐｍとして微粒子を除去しながら、分散ロータの回転数を５８００ｒｐｍ（回転周速を１３０ｍ／ｓｅｃ）として一回当たり４０秒間の表面処理を２０分間行った（原料供給口３より微粉砕物を投入し、４０秒間処理し、排出弁８を開けて処理品として取り出す操作を一回と数えた）。分散ロータ上部には角型のディスクを１０個設置し、ガイドリングと分散ロータ角型ディスクとの間隔を３０ｍｍとし、分散ロータとライナーとの間隔を５ｍｍとした。またブロワー風量を１４ｍ^３／ｍｉｎとし、ジャケットに通す冷媒の温度及び冷風温度Ｔ１を−２０℃とした。この状態で２０分間運転した結果、分級ロータ後方の温度Ｔ２は２７℃で安定しており、重量平均粒径６．８μｍのトナー樹脂粒子を得た。
【０１４１】
上記トナー樹脂粒子１００質量部に対して、針状チタン（テイカ社製 ＭＴ−１００Ｔ）１．５質量部を前記トナー樹脂粒子と混合してトナー１とした。さらにトナー１と、シリコーン樹脂で表面被覆した磁性マンガンマグネシウムフェライトキャリア粒子（平均粒径５０μｍ）とを、トナー濃度が６質量％になるように混合し、二成分系現像剤１とした。得られたトナーの物性を表５に示す。
【０１４２】
（トナー製造法２〜１８）
トナー材料、粉砕粒径、処理装置の条件を変えてトナー２〜１８および現像剤２〜１８を得た。得られたトナーの物性を表５に示す。
【０１４３】
【表３】

【０１４４】
【表４】

【０１４５】
【表５】

【０１４６】
＜実施例1＞
以下のようにしてトナー１及び現像剤１の評価を行った。
【０１４７】
＜定着可能温度幅の測定＞
カラー複写機ＣＬＣ１０００（キヤノン製）のオイル塗布機構を取り外し、さらに定着温度を自由に設定できるように前記カラー複写機を改造し、この改造機を用いて定着試験を行った。この試験では、画像面積比率は２５％に設定し、単位面積当たりのトナー載り量は０．７ｍｇ／ｃｍ²に設定した。
【０１４８】
前記の設定で、定着器の設定温度を１２０〜２１０℃迄の温度範囲で５℃おきに温度調節して、各々の温度で定着画像を出力し、得られた定着画像を４．９ｋＰａ（５０ｇ／ｃｍ²）の荷重をかけたシルボン紙で摺擦し、摺擦前後の濃度低下率が１０％以下となる定着温度を定着開始温度とした。また定着開始温度から更に設定温度を上げて行き、目視で高温オフセットの発生した温度をオフセット開始温度とした。また、定着開始温度からオフセット発生温度までの温度領域を定着可能温度幅とした。
【０１４９】
＜転写効率、飛び散り、カブリの評価＞
上記カラー複写機ＣＬＣ１０００の改造機を用いて常温環境下（N/N環境 ２３℃／６０％）で、画像面積比率２５％のオリジナル原稿を用いて、連続複写１万枚の試験を行った。
【０１５０】
転写率は、耐久前後の画像を現像、転写し、感光体上の転写前のトナー量（単位面積当たり）と、転写材上のトナー量（単位面積当たり）をそれぞれ測定し、下式により求めた。
【０１５１】
【数１０】
転写率(％)＝(転写材上のトナー量)／(感光体上の転写前のトナー量)×１００
【０１５２】
カブリは、白地部分の白色度をリフレクトメーター（東京電色社製）により測定し、白地部分の白色度と転写紙の白色度との差からカブリ濃度（％）を算出し、評価した。評価基準は次の通りである。
Ａ：非常に良好（０．５％未満）
Ｂ：良好（０．５％〜１．５％）
Ｃ：普通（１．５％〜２．５％）
Ｄ：やや悪い（２．５％〜３．５％）
Ｅ：悪い（３．５％以上）
【０１５３】
飛び散り性は、図４に示した「電」文字パターンを普通紙（７５ｇ／ｍ²）と厚紙（１０５ｇ／ｍ²と１３５ｇ／ｍ²）にプリントした際の文字周辺部へのトナー飛び散り（図５の状態）を目視で評価した。評価基準は次の通りである。
Ａ：目視で飛び散り無し。
Ｂ：ほとんど発生せず。
Ｃ：軽微な飛び散りが見られる。
Ｄ：若干の飛び散りが見られる。
Ｅ：顕著な飛び散りが見られる。
【０１５４】
結果を表６に示す。評価の結果、トナー１は、広い定着可能温度幅を有することがわかった。さらにトナー１は、１万枚後の画像形成においても非常に良好な転写性を示し、１万枚後の画像形成においても飛び散りやカブリを生じなかった。
【０１５５】
＜実施例２＞
実施例１と同様にしてトナー２及び現像剤２の評価を行った。
実施例２では実施例１に比べ、１万枚の耐久試験において飛び散りが若干生じたが問題ないレベルであった。転写性や定着性は非常に良好であった。結果を表６に示す。
【０１５６】
＜実施例３＞
実施例１と同様にしてトナー３及び現像剤３の評価を行った。
実施例３では実施例１に比べ、初期の転写効率が若干低くなったが、１万枚の耐久試験で転写効率は低下しなかった。飛び散り、カブリや定着性については非常に良好であった。結果を表６に示す。
【０１５７】
＜実施例４＞
実施例１と同様にしてトナー４及び現像剤４の評価を行った。
実施例４では実施例１に比べ、定着温度幅が若干狭くなったが、問題なく使用できるレベルであった。また、飛び散り、カブリや転写性については非常に良好であった。結果を表６に示す。
【０１５８】
＜実施例５＞
実施例１と同様にしてトナー５及び現像剤５の評価を行った。
実施例５では実施例１に比べ、１万枚の耐久試験においてカブリが若干生じたが問題ないレベルであった。初期の転写効率も若干低くなったが、耐久試験で転写効率は低下しなかった。定着性は非常に良好であった。結果を表６に示す。
【０１５９】
＜実施例６＞
実施例１と同様にしてトナー６及び現像剤６の評価を行った。
実施例６では実施例１に比べ、１万枚の耐久試験において飛び散りやカブリが若干生じたが問題ないレベルであった。また、定着性では定着温度幅が若干狭くなったが問題なく使用できるレベルであった。結果を表６に示す。
【０１６０】
＜実施例７＞
実施例１と同様にしてトナー７及び現像剤７の評価を行った。
実施例７では実施例１に比べ、初期の転写効率が若干下がり、１万枚の耐久試験において飛び散りが若干生じたが問題ないレベルであった。また、定着性では定着温度幅が若干狭くなったが問題なく使用できるレベルであった。結果を表６に示す。
【０１６１】
＜実施例８＞
実施例１と同様にしてトナー８及び現像剤８の評価を行った。
実施例８では実施例１に比べ、１万枚の耐久試験において飛び散りやカブリが若干生じたが問題ないレベルであった。また、定着性では定着温度幅が若干狭くなり、特に耐オフセット性が低下したが問題なく使用できるレベルであった。結果を表６に示す。
【０１６２】
＜実施例９＞
実施例１と同様にしてトナー９及び現像剤９の評価を行った。
実施例９では実施例１に比べ、１万枚の耐久試験において転写効率が低下し、飛び散りが生じやすくなったが使用可能レベルであった。また、定着性では定着温度幅が若干狭くなったが問題なく使用できるレベルであった。結果を表６に示す。
【０１６３】
＜実施例１０＞
実施例１と同様にしてトナー１０及び現像剤１０の評価を行った。
実施例１０では実施例１に比べ、転写効率が低く、１万枚の耐久試験において飛び散りやカブリが若干生じたが問題ないレベルであった。また、定着性では定着温度幅が若干狭くなり、特に低温定着性が悪くなったが使用可能レベルであった。結果を表６に示す。
【０１６４】
＜実施例１１＞
実施例１と同様にしてトナー１１及び現像剤１１の評価を行った。
実施例１１では実施例１に比べ、初期の転写効率が低く、１万枚の耐久試験において飛び散りやカブリが若干生じたが問題ないレベルであった。また、定着性では定着温度幅が狭くなったが使用可能レベルであった。結果を表６に示す。
【０１６５】
＜実施例１２＞
実施例１と同様にしてトナー１２及び現像剤１２の評価を行った。
実施例１２では実施例１に比べ、初期の転写効率が低く、１万枚の耐久試験において転写効率が若干低下した。また飛び散りやカブリが生じやすくなったが使用可能レベルであった。結果を表６に示す。
【０１６６】
＜実施例１３＞
Ｃ．Ｉ．ピグメントブルー１５：３に替えてＣ．Ｉ．ピグメントレッド５７：１を６質量部使用した以外はトナー製造法１と同様にして、マゼンタトナー１を得、マゼンタ現像剤１を得た。また、Ｃ．Ｉ．ピグメントブルー１５：３に替えてＣ．Ｉ．ピグメントイエロー７４を７質量部使用した以外はトナー製造法１と同様にして、イエロートナー１を得、イエロー現像剤１を得た。また、Ｃ．Ｉ．ピグメントブルー１５：３に替えてカーボンブラックを３部使用した以外はトナー製造法１と同様にして、ブラックトナー１を得、ブラック現像剤１を得た。
【０１６７】
得られたマゼンタ、イエロー、ブラックの各トナー及び各現像剤を実施例１と同様に評価した結果、これらのトナー及び現像剤は実施例１と同等に広い定着可能温度幅を有することがわかった。さらに１万枚後の耐久性も非常に良好な転写生を示し、飛び散りやカブリも発生しなかった。
【０１６８】
さらにシアントナー１及びシアン現像剤１（トナー製造法１で製造したトナー１及び現像剤１）、マゼンタトナー１及びマゼンタ現像剤１、イエロートナー１及びイエロー現像剤１、ブラックトナー１及びブラック現像剤１を用いて、上記カラー複写機ＣＬＣ１０００の改造機を用いて、常温環境下（Ｎ／Ｎ環境 ２３℃／６０％）、フルカラーモードでオリジナル原稿を用いた１万枚の耐久試験を実施した。その結果、耐久後もカブリや飛び散りも無く、非常に高精細なフルカラー画像を得ることができた。
【０１６９】
さらにシアントナー１、マゼンタトナー１、イエロートナー１、ブラックトナー１を用いて非磁性一成分の市販のフルカラー複写機（クリエイティブプロセッサー６６０、キヤノン製）用いて、常温環境下（Ｎ／Ｎ環境 ２３℃／６０％）、フルカラーモードでオリジナル原稿を用いた１万枚の耐久試験を実施した。その結果、耐久後もカブリや飛び散りも無く、非常に高精細なフルカラー画像を得ることができた。
【０１７０】
＜比較例１＞
実施例１と同様にしてトナー１３及び現像剤１３の評価を行った。
比較例１では、実施例１に比べ、１万枚の耐久試験において飛び散りが生じた。また、初期の転写効率が下がり、耐久試験後の転写効率の低下も見られた。さらに定着温度幅も狭くなった。結果を表６に示す。
【０１７１】
＜比較例２＞
実施例１と同様にしてトナー１４及び現像剤１４の評価を行った。
比較例２では、実施例１に比べ、１万枚の耐久試験において飛び散りが生じた。また、初期の転写効率が非常に下がり、耐久試験後の転写効率の低下も見られた。結果を表６に示す。
【０１７２】
＜比較例３＞
実施例１と同様にしてトナー１５及び現像剤１５の評価を行った。
比較例３では、実施例１に比べ、１万枚の耐久試験において、カブリがより多く生じ、特に飛び散りが非常に多く生じた。また、初期の転写効率が下がり、耐久試験後、転写効率が大きく低下した。結果を表６に示す。
【０１７３】
＜比較例４＞
実施例１と同様にしてトナー１６及び現像剤１６の評価を行った。
比較例４では、実施例１に比べ、１万枚の耐久試験において飛び散りやカブリがより多く生じた。また、初期の転写効率が非常に下がり、耐久試験後の転写効率の低下も見られた。また、定着可能温度領域が測定されなかった。結果を表６に示す。
【０１７４】
＜比較例５＞
実施例１と同様にしてトナー１７及び現像剤１７の評価を行った。
比較例５では、実施例１に比べ、１万枚の耐久試験において飛び散りやカブリが非常に多く生じた。また、初期の転写効率が下がり、耐久試験後の転写効率が非常に低下した。結果を表６に示す。
【０１７５】
＜比較例６＞
実施例１と同様にしてトナー１８及び現像剤１８の評価を行った。
比較例６では、実施例１に比べ、１万枚の耐久試験において飛び散りやカブリがより多く生じた。また、初期の転写効率が非常に下がり、耐久試験後の転写効率の低下も見られた。また、定着可能温度領域が測定されなかった。結果を表６に示す。
【０１７６】
【表６】

【０１７７】
【発明の効果】
本発明は、多量のオイルを塗布することなく、またはオイルを全く塗布することなく、低温定着性に優れ且つ耐高温オフセット性に優れたトナーを提供できる。また、本発明のトナーは、高い定着性や現像性を維持しながら、転写効率を向上させ、飛び散りを防止することができる。
【図面の簡単な説明】
【図１】本発明に使用される離型剤のＧＰＣ分子量分布曲線のピーク面積の分割方法を説明するための図である。
【図２】本発明のトナーを製造する際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一例の構成を示す概略的断面図である。
【図３】図２に示す分散ロータの上面図の一例を示す概略図である。
【図４】飛び散り評価用にプリントした文字「電」を示す図である。
【図５】図４に示す文字「電」をプリントしたときに文字周辺部へトナーが飛び散ったときの状態を示す図である。
【符号の説明】
1 分級ロータ
２ 微粉回収用排出口
３ 原料供給口
４ ライナ
５ 冷風導入口
６ 分散ロータ
７ 粉体排出口
８ 排出弁
９ ガイドリング
１０ 角型ディスク
１１ 第一の空間
１２ 第二の空間
１５ ケーシング[0001]
[Technical field to which the invention belongs]
The present invention relates to a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and a toner jet method, particularly a toner suitable for oilless heat roll fixing. The present invention relates to a color toner for developing an electrostatic image having excellent charge stability by continuous copying by controlling the amount of the release agent present on the surface of the toner particles and the toner shape using the agent.
[0002]
[Prior art]
In recent years, copying machines and printers have been pursued strictly for smaller size, lighter weight, higher speed, and higher reliability due to demands for space saving and energy saving, and are composed of simpler elements in various respects. It has become like this. As a result, the performance required for the toner becomes higher, and if the improvement in the performance of the toner cannot be achieved, the excellent functions of the apparatus configured as described above cannot be fully expressed.
[0003]
For example, various methods and apparatuses have been developed for fixing a toner image on a sheet such as paper. Conventionally, for the purpose of preventing toner from adhering to the surface of the fixing member, the surface of the fixing member is formed of a material excellent in releasability with respect to the toner, and further, offset is prevented on the surface, and fatigue of the roller surface is prevented. For this purpose, the roller surface is covered with a thin film of liquid having good releasability such as silicone oil. However, this method is extremely effective in preventing toner offset, but has a problem that the fixing device is complicated because an apparatus for supplying the liquid for preventing offset is necessary. . Further, the above-described method goes against the technical trend toward downsizing and weight reduction of the apparatus, and there are cases where silicone oil or the like evaporates due to heat and contaminates the inside of the machine. Therefore, instead of using a silicone oil supply device, instead of supplying an offset prevention liquid from the toner during heating, a method of adding a release agent such as low molecular weight polyethylene or low molecular weight polypropylene to the toner was proposed. Has been.
[0004]
Further, from the viewpoint of energy saving or the like, a heat fixing method in which a transfer material having an unfixed toner image is brought into close contact with a heating body through a film with a pressure member can be cited as one effective means. The heating method using a film is a method in which fixing is performed by allowing the toner image surface of a fixing sheet having a toner image to pass through the surface of a film formed of a material having releasability with respect to the toner while contacting the surface. It is. In this method, since the surface of the film and the toner image of the fixing sheet are in contact with each other, the thermal efficiency when fusing the toner image on the fixing sheet is extremely good, and the fixing can be performed quickly, Very good in photocopiers. However, in the above method, because of the kinking and durability of the film, a toner that cannot be fixed by applying pressure as much as heat roller fixing and can be sufficiently fixed even in a low pressure and low temperature state is required. Particularly in today's color image formation, it is important to fix a large amount of toner at a time in order to express colors by mixing colors.
[0005]
On the other hand, in full-color copying machines and printers, it is essential to achieve high transfer efficiency in order to obtain high-quality images. In the case of using a full-color copying machine that transfers a plurality of toner images after development, the amount of toner on the photosensitive member is increased as compared with the case of one-color black toner used in a black-and-white copying machine. It is difficult to improve transfer efficiency only by using.
[0006]
Therefore, in recent years, as one of the techniques for increasing the transfer efficiency, the toner shape has been made closer to a spherical shape. For example, polymerized toner such as suspension polymerization or emulsion polymerization, pulverized toner spheroidized in a solvent, spheroidized with hot air (see, for example, Patent Documents 1 and 2), or spherical with mechanical impact force. The method (for example, refer patent document 3) etc. are mentioned.
[0007]
Further, in recent years, as high-quality images and high-definition images are required, problems that have not been so conspicuous in the past have been highlighted. One of them is a problem called “scattering”. This occurs because the toner is transferred more than necessary to the image or character portion due to electrostatic attraction, and when that portion is thermocompression bonded on the recording material, the toner scatters to the edge portion and is fixed as it is. This is a phenomenon in which the edge portion and the boundary portion of the image are rough and rough, and the image quality is deteriorated. This is said to occur when the charge amount varies due to insufficient toner charge amount or excessive toner charge.
[0008]
When trying to achieve both of these technologies, that is, the use of a release agent and the spheroidization of a toner, for example, in a polymerized toner, the release agent is inevitably included, so if pressure cannot be applied at the time of fixing, release It tends to be difficult for the agent to come out on the toner surface, and the fixability tends to be slightly inferior. In addition, various conventional methods for making the pulverized toner into a sphere are very effective techniques for improving transfer efficiency, but the release agent tends to come out on the toner surface due to solvent, heat, etc. The durability against the deterioration of the agent and the contamination of the charging member tends to be weak, and further improvement has been demanded.
[0009]
Furthermore, there is a method (for example, see Patent Documents 4 and 5) that stabilizes charging and improves scattering by a combination of external additives, but further improvements have been demanded.
[0010]
[Patent Document 1]
Japanese Patent Laid-Open No. 11-295917
[Patent Document 2]
JP 2000-29241 A
[Patent Document 3]
Japanese Patent Laid-Open No. 7-181732
[Patent Document 4]
Japanese Patent Laid-Open No. 8-248673
[Patent Document 5]
JP 2002-23416 A
[0011]
[Problems to be solved by the invention]
An object of the present invention is to improve transfer efficiency and prevent scattering in a fixing system without applying a large amount of oil or without applying oil at all while maintaining high fixability and developability. And
[0012]
[Means for Solving the Problems]
The above-mentioned subject is achieved by the following composition. That is, the present invention contains at least a binder resin, a colorant, and a release agent. Non-magnetic Having toner particles and external additives Non-magnetic In the toner, the equivalent circle diameter is 3 μm or more. Non-magnetic The average circularity of the particles contained in the toner is 0.915 or more and 0.960 or less, Non-magnetic The mixture obtained by stirring and mixing the toner in a 45% by volume methanol aqueous solution has a light transmittance of 10 to 70% by UV-visible spectroscopic analysis, and the release agent is a hydrocarbon wax having at least a vinyl unit. Include Non-magnetic It relates to toner.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
In order to achieve high transfer efficiency, it is well known that a toner is mechanically impacted to be spheroidized. However, in a toner with a release agent added, the release agent is deposited on the surface of the toner particles due to mechanical impact during spheroidization, causing deterioration of external additives and contamination of the developing sleeve and charging member. However, developability may deteriorate. Therefore, in order to make it difficult for the release agent to deposit on the surface due to mechanical impact, the present inventors have intensively studied and as a result, it is very effective to use a hydrocarbon wax having a vinyl unit as the release agent. I found out. This is presumably because the release agent became difficult to come out on the surface of the toner particles due to the increased compatibility between the binder resin and the release agent. Furthermore, it has been found that the use of a hydrocarbon wax having a vinyl-based unit instead of a normal hydrocarbon-based wax as a release agent is more advantageous for stabilizing the charging of the toner. Although the reason for this is not clear, it is considered that the charging ability of the release agent itself used in the present invention is improved by having a vinyl-based unit as compared with a normal hydrocarbon-based wax.
[0014]
In the present invention, the transfer efficiency is improved by making the toner particles spherical, and the effect of imparting fluidity by the external additive is also increased. In addition, by improving the charging ability of the release agent, the variation in charging of the toner particles is reduced, and the scattering is improved.
[0015]
However, even if the compatibility between the binder resin and the release agent is improved, the release agent is deposited on the surface when a large mechanical impact is applied to the toner particles. The inventors have determined the degree of circularity of the toner particles and the amount of the release agent deposited on the surface of the toner particles to improve the transfer efficiency, the average degree of circularity of the toner, and 45% by volume of methanol. The inventors have found that it can be defined by the transmittance of light having a wavelength of 600 nm by ultraviolet-visible spectroscopic analysis of a mixed solution stirred and mixed in an aqueous solution, and have arrived at the present invention having the above-described configuration.
[0016]
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments of the present invention.
In the toner of the present invention, among the particles contained in the toner, the average circularity of particles having an equivalent circle diameter of 3 μm or more is 0.915 or more and 0.960 or less. The average circularity substantially represents the average circularity of the toner particles, and is preferably 0.920 to 0.955 from the viewpoint of realizing excellent transferability and charging stability.
[0017]
When the average circularity is less than 0.915, the effect of imparting fluidity by an external additive is reduced, so that the fluidity of the toner is reduced, the toner charge amount varies, and the transfer efficiency is reduced or scattered. Is likely to occur. On the other hand, when the average circularity is larger than 0.960, the triboelectric chargeability of the toner becomes insufficient and fogging is likely to occur. The average circularity can be adjusted by spheroidizing the toner particles.
[0018]
The toner of the present invention can adjust the circularity by using a specific processing device that brings the shape of toner particles close to a sphere. Such toner particle shape treatment can provide high transferability. However, in order to achieve both developability and fixability, the toner particles may exude onto the surface of the toner particles when spheroidizing. You must consider it.
[0019]
Examples of the device for spheroidizing toner particles include heat treatment devices such as surffusion (manufactured by Nippon Pneumatic Co., Ltd.) for hot-melting the particle surface and spheroidizing device (manufactured by Hosokawa Micron Co.). It is done. Alternatively, a hybridizer (made by Nara Machinery Co., Ltd.), a turbo mill (produced by Turbo Industry Co., Ltd.), a kryptron (produced by Kawasaki Heavy Industries Co., Ltd.), a mechano-fusion system (produced by Hosokawa Micron Co., Ltd.), etc. that spheroidizes the particle surface by mechanical impact treatment. . Among these, in the heat treatment apparatus, it is almost impossible to adjust the exudation of the release agent to the surface of the toner particles. In addition, even when using the above-described devices that spheroidize toner particles by mechanical impact, these devices have a degree for each device, but the system applies mechanical impact force to the toner particles while pulverizing the toner particles. Yes, even if the affinity with the binder resin is improved by using a specific release agent, the release agent tends to ooze out on the surface of the toner particles due to a new surface appearing during the spheronization process. .
[0020]
Therefore, an apparatus capable of performing spheroidization suitable for the toner of the present invention will be specifically described with reference to the drawings.
[0021]
FIG. 2 shows an example of a surface modification apparatus used in the present invention.
In the surface reforming apparatus shown in FIG. 3, the classification means for separating the casing 15, a jacket (not shown) through which cooling water or antifreeze liquid can be passed, and particles larger than a predetermined particle size and fine particles having a predetermined particle size or less. A classifying rotor 1, a dispersion rotor 6 which is a surface treatment means for applying a mechanical impact to the particles to treat the surface of the particles, and a predetermined interval with respect to the outer periphery of the dispersion rotor 6. Of the particles divided by the classification rotor 1, the guide ring 9 that is a guide means for guiding particles larger than a predetermined particle size among the particles divided by the classification rotor 1, and the particles divided by the classification rotor 1 The fine powder collection discharge port 2 is a discharge means for discharging fine particles having a predetermined particle size or less to the outside of the apparatus, and cold air introduction is a particle circulation means for sending particles whose surface is treated by the dispersion rotor 6 to the classification rotor 1. Mouth 5 and treatment A raw material supply port 3 for introducing the particles into the casing 15, and a closable powder discharge port 7 and the discharge valve 8 for discharging the treated surface particles from the casing 15 inside.
[0022]
The classification rotor 1 is a cylindrical rotor and is provided on one end face side in the casing 15. The fine powder collection outlet 2 is provided at one end of the casing 15 so as to discharge particles inside the classification rotor 1. The raw material supply port 3 is provided at the center of the peripheral surface of the casing 15. The cold air introduction port 5 is provided on the other end surface side of the peripheral surface of the casing 15. The powder discharge port 7 is provided at a position facing the raw material supply port 3 on the peripheral surface of the casing 15. The discharge valve 8 is a valve that freely opens and closes the powder discharge port 7.
[0023]
A dispersion rotor 6 and a liner 4 are provided between the cold air introduction port 5 and the raw material supply port 3 and the powder discharge port 7. The liner 4 is provided along the inner peripheral surface of the casing 15. As shown in FIG. 3, the dispersion rotor 6 includes a disk and a plurality of square disks 10 arranged along the normal line of the disk at the periphery of the disk. The dispersion rotor 6 is provided on the other end surface side of the casing 15 and is provided at a position where a predetermined interval is formed between the liner 4 and the square disk 10. A guide ring 9 is provided at the center of the casing 15. The guide ring 9 is a cylindrical body and is provided so as to extend from a position covering a part of the outer peripheral surface of the classification rotor 1 to the vicinity of the classification rotor 6. The guide ring 9 includes a first space 11 that is a space between the outer peripheral surface of the guide ring 9 and the inner peripheral surface of the casing 15 in the casing 15, and a second space that is a space inside the guide ring 9. A space 12 is formed.
[0024]
The dispersion rotor 6 may have a cylindrical pin instead of the square disk 10. In the present embodiment, the liner 4 is provided with a large number of grooves on the surface facing the square disk 10, but may have no grooves on the surface. Moreover, the installation direction of the classification rotor 1 may be vertical as shown in FIG. 1 or horizontal. Further, the number of classification rotors 1 may be single or multiple as shown in FIG.
[0025]
In the surface reforming apparatus configured as described above, when a certain amount of finely pulverized product is introduced from the raw material supply port 3 with the discharge valve 8 closed, the charged finely pulverized product is first blower (not shown). ) And classified by the classification rotor 1. At that time, the classified fine powder having a predetermined particle size or less passes through the peripheral surface of the classification rotor 1, is guided to the inside of the classification rotor 1, and is continuously discharged and removed out of the apparatus. Coarse powder having a predetermined particle diameter or more is applied to a circulating flow generated by the dispersion rotor 6 along the inner periphery (second space 12) of the guide ring 9 due to centrifugal force, and the gap between the square disk 10 and the liner 4 ( Hereinafter, it is also referred to as “surface modification zone”. The powder guided to the surface modification zone is subjected to a surface modification treatment by receiving a mechanical impact force between the dispersion rotor 6 and the liner 4. The surface-modified particles having undergone surface modification are transported to the classification rotor 1 along the outer periphery (first space 11) of the guide ring 9 on the cold air passing through the machine. Is discharged to the outside of the machine, and the coarse powder is circulated into the second space 12 again and repeatedly subjected to the surface modification action in the surface modification zone. As described above, in the surface modification apparatus of FIG. 2, the classification of particles by the classification rotor 1 and the treatment of the surface of the particles by the dispersion rotor 6 are repeated. After a certain period of time, the discharge valve 8 is opened and the surface modified particles are recovered from the discharge port 7.
[0026]
In such an apparatus, there is almost no exudation of the release agent due to heat, and the exudation of the release agent to the surface of the toner particles due to the emergence of a new surface as compared with the above-described system that gives a mechanical impact force. This is very preferable because it makes it easy to adjust the spheroidization of toner particles and the exudation of the release agent.
[0027]
The toner of the present invention has a weight average particle diameter of X (μm) and a number-based cumulative value of particles contained in toner having a circularity of 0.960 or more as Y (%), 4 ≦ X ≦ 11 And satisfying the relationship of −X + 20 ≦ Y ≦ −X + 70 is preferable in terms of improving toner developability and transfer efficiency. These formulas define the size of the toner and the ratio of the toner with high sphericity in the toner, and indicate the preferable ratio between the size of the toner and the sphericity for achieving both developability and transferability. Yes. Regarding developability, it is important to reduce contamination on the developing sleeve. In order to reduce contamination on the developing sleeve, it is preferable to lower the packing property, and the toner preferably has a large particle size or low sphericity. Conversely, with regard to transferability, the smaller the toner particle size, the better the dot reproducibility, and the higher the toner sphericity, the better the transfer efficiency and the prevention of scattering.
[0028]
Specifically, when the weight average particle size of the toner is less than 4.0 μm and the number-based cumulative value of particles having a circularity of 0.960 or more is greater than 66%, the toner packing property is improved, and thus the developing device. There is a possibility that the frictional force on the charging member is increased and the contamination of the developing sleeve by the release agent is promoted. When the toner has a weight average particle size of less than 4.0 μm and the number-based cumulative value of particles having a circularity of 0.960 or more is smaller than 16%, the transfer of the toner is insufficient and scattering is observed. Inferior images may be formed.
[0029]
Further, if the toner has a weight average particle size larger than 11.0 μm and the number-based cumulative value of the particles having a circularity of 0.960 or more is less than 9%, transferability is involved, so that the image quality is inferior, such as occurrence of scattering. Sometimes. When the weight average particle diameter of the toner is larger than 11.0 μm and the number-based cumulative value of the particles having a circularity of 0.960 or more is larger than 59%, the transferability of the toner is deteriorated and an image with inferior image quality is formed. In some cases, toner contamination on the developing sleeve may occur.
[0030]
The weight average particle diameter can be adjusted by, for example, classification of toner particles. Further, the number-based cumulative value can be measured by the particle image analyzer described above, and can be adjusted by, for example, spheroidizing conditions or mixing of toner particles having a known circularity.
[0031]
Next, measurement of the average circularity and the number-based cumulative value Y (%) of particles of 0.960 or more will be described.
[0032]
The equivalent circle diameter, circularity and frequency distribution of the toner are used as a simple method for quantitatively expressing the shape of the toner particles. In the present invention, the flow type particle image measuring device “FPIA-” is used. Model 2100 ”(Manufactured by Sysmex Corporation), and can be calculated using the following formula.
[0033]
[Expression 1]

[0034]
[Expression 2]

[0035]
Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the toner particle image. Define.
[0036]
In the present invention, the circularity is an index indicating the degree of unevenness of the toner particles, and is 1.000 when the toner particles are completely spherical. The more complicated the surface shape, the smaller the circularity.
[0037]
In the present invention, the circle-equivalent number average diameter D1 (μm) and the particle size standard deviation SDd, which mean the average value of the particle number frequency distribution based on the number of toners, are the particle size (central value) at the dividing point i of the particle size distribution. Is di, and the frequency is fi.
[0038]
[Equation 3]

[0039]
[Expression 4]

[0040]
In addition, the average circularity C and the circularity standard deviation SDc, which mean the average value of the circularity frequency distribution, can be obtained from the following equation when the circularity (center value) at the division point i of the particle size distribution is ci and the frequency is fci. Calculated.
[0041]
[Equation 5]

[0042]
[Formula 6]

[0043]
As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, and then further measurement is performed. Add 0.02 g of sample and disperse uniformly. As a means for dispersion, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios Co., Ltd.) is used, and dispersion treatment is performed for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more.
[0044]
To measure the shape of the toner particles, the flow type particle image measuring device is used, the concentration of the dispersion is readjusted so that the toner particle concentration at the time of measurement is 3000 to 10,000 / μl, and 1000 toner particles are obtained. Measure above. After the measurement, using this data, data of 3 μm or less is cut, and the number reference cumulative value Y (%) of 0.960 or more is obtained from the average circularity C or circularity frequency distribution of the toner particles.
[0045]
Further, the present invention defines the toner performance, specifically, the amount of the release agent on the surface of the toner as described above. The amount of the release agent in the vicinity of the toner surface can be grasped as a whole by measuring the transmittance in a 45 volume% methanol aqueous solution as a simple and accurate method. In this measurement method, the toner is forcibly dispersed once in a mixed solvent, and the characteristics of the amount of the release agent for each toner particle are easily obtained, and then the transmittance after a predetermined time is measured. It is possible to accurately grasp the amount of the release agent present in the entire toner. That is, when a large amount of hydrophobic release agent is present on the surface of the toner, it is difficult to disperse in the solvent and aggregates and precipitates, so that the transmittance is as high as 70%. On the contrary, if no release agent is present on the toner surface, the polyester unit of the binder resin that is hydrophilic occupies almost the surface, so that it is uniformly dispersed and the transmittance becomes a small value of less than 10%.
[0046]
In the toner of the present invention, the transmittance of light having a wavelength of 600 nm is 10 to 70% by ultraviolet-visible spectroscopic analysis of a mixed solution obtained by stirring and mixing a toner in a 45 volume% methanol aqueous solution. If the transmittance is within the above range, it indicates that the amount of the release agent on the surface of the toner particles is appropriate. The transmittance can be adjusted by the conditions and processing method of the spheroidizing treatment of the toner particles.
[0047]
The transmittance can be measured by the following operation. The immersion device and the spectrophotometer used for the measurement are not limited to the devices exemplified below.
[0048]
(1) Adjustment of toner dispersion
An aqueous solution having a volume mixing ratio of methanol: water of 45:55 is prepared. 10 ml of this aqueous solution is placed in a 30 ml sample bottle (Nippon Denka Glass: SV-30), 20 mg of toner is invaded on the liquid surface, and the bottle is covered. Then, it shakes at 150 rpm for 5 seconds with a Yayoi type shaker (model: YS-LD). At this time, the angle of shaking is such that the shaking column moves 15 degrees forward and 20 degrees backward, assuming that the vertical (vertical) of the shaker is 0 degree. The sample bottle is fixed to a fixing holder (with the sample bottle lid fixed on the extension of the center of the column) attached to the tip of the column. After removing the sample bottle, the dispersion after standing for 30 seconds is used as a measurement dispersion.
[0049]
(2) Transmittance measurement
The dispersion obtained in (1) is put into a 1 cm square quartz cell and the transmittance (%) at a wavelength of 600 nm of the dispersion after 10 minutes using a spectrophotometer MPS2000 (manufactured by Shimadzu Corporation) (see the following formula) ).
[0050]
[Expression 7]
Transmittance (%) = I / I ₀ × 100
(Where I is the incident light beam and I ₀ Is the transmitted light flux. )
[0051]
When the transmittance is 70% or more, it indicates that the amount of the release agent present on the surface of the toner particles is large, resulting in deterioration of toner fluidity, contamination of the developing sleeve and charging member, fogging, Toner scattering is likely to occur. Further, if the transmittance is less than 10%, the exudation of the release agent in the toner particles depends on the resin physical properties of the toner particle surface. Therefore, the use of a resin having a high melting point tends to reduce the hot offset ability. .
[0052]
Next, the release agent used in the present invention will be described.
As the release agent used in the present invention, a hydrocarbon wax having at least a vinyl unit can be used. Hydrocarbon waxes with vinyl units are compounds in which one or more of the hydrogens in the hydrocarbon wax are replaced and bonded, and vinyl monomers or vinyl copolymers are grafted onto the wax. Indicates what is being done. In the present invention, since the hydrocarbon wax having a vinyl unit has improved dispersibility in the toner, it is difficult for the wax to come out on the surface of the toner. It has been found that the surface treatment time for the conversion can be shortened.
[0053]
The details of the cause are not clear, but I thought it was probably as follows. Since the hydrocarbon wax having a vinyl unit is highly finely dispersed in the toner, the plasticity of the toner particles is improved and the surface is more effectively modified. As a result, the average circularity of the toner particles can be easily controlled, and the surface treatment can be performed in a short processing time, so that the amount of the release agent on the toner surface can be easily controlled.
[0054]
In the present invention, one type or two or more types of hydrocarbon waxes having vinyl units can be used, and hydrocarbon waxes having vinyl units and other types of waxes may be used in combination.
[0055]
A hydrocarbon wax having a vinyl unit can be produced by treating a hydrocarbon wax using a vinyl monomer in accordance with ordinary methods and conditions. Specifically, for example, a method using radiation or a method using a radical catalyst can be used, but a method using a radical catalyst is preferable.
[0056]
As the hydrocarbon wax, a hydrocarbon wax such as paraffin wax or polyolefin wax having a maximum endothermic peak maximum temperature of 60 to 110 ° C. can be preferably used, and paraffin hydrocarbon wax is particularly preferable. The maximum temperature of the maximum endothermic peak of the wax is measured with a differential scanning calorimeter (DSC measuring device). As the paraffin hydrocarbon wax, known paraffin wax, synthetic paraffin wax, microcrystalline wax, Fischer-Tropsch wax and the like can be used.
[0057]
Various vinyl monomers such as a styrene monomer and an unsaturated carboxylic acid monomer can be used as the vinyl monomer. First, examples of the styrene monomer include styrene, α-methyl styrene, vinyl toluene, isopropenyl toluene, p-methyl styrene, p-methoxy styrene, m-methyl styrene, and the like.
[0058]
Unsaturated carboxylic acid monomers include methyl acrylate, ethyl acrylate, butyl acrylate, acrylate-sec-butyl, isobutyl acrylate, propyl acrylate, isopropyl acrylate, 2-octyl acrylate, dodecyl acrylate , Stearyl acrylate, hexyl acrylate, isohexyl acrylate, phenyl acrylate, 2-chlorophenyl acrylate, diethylaminoethyl acrylate, 3-methoxybutyl acrylate, diethylene glycol ethoxylate acrylate, acrylic acid-2,2, Acrylic esters such as 2-trifluoroethyl, methyl methacrylate, ethyl methacrylate, methacrylate-n-butyl, methacrylate-sec-butyl, isobutyl methacrylate, propyl methacrylate Isopropyl methacrylate, 2-octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, hexyl methacrylate, decyl methacrylate, phenyl methacrylate, 2-chlorohexyl methacrylate, diethylaminoethyl methacrylate, 2-hexyl methacrylate Methacrylic acid esters such as ethyl and methacrylate-2,2,2-trifluoroethyl, and maleic acid such as ethyl maleate, propyl maleate, butyl maleate, diethyl maleate, dipropyl maleate and dibutyl maleate Examples thereof include acid esters, fumaric acid esters such as ethyl fumarate, butyl fumarate and dibutyl fumarate, and itaconic acid esters such as ethyl itaconate, diethyl itaconate and butyl itaconate.
[0059]
As radical catalysts, organic peroxides, organic peroxides such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxidebenzoate) hexyne-3 1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl -2,5-di (tert-butylperoxy) hexane, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octate, ter - butyl perpivalate, cumyl perpivalate and tert- butyl hydroperoxide diethyl acetate; other azo compounds such as azobisisobutyronitrile, and the like dimethyl azoisobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert- Dialkyl peroxides such as butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.
[0060]
The vinyl monomer may be one kind of monomer or two or more kinds of monomers, and is not limited to the kind or number of monomers. In the case of using a plurality of types of vinyl monomers, there is no limitation on the order in which the monomers are processed. Furthermore, in the present invention, a polymer of a vinyl monomer is also produced by the treatment. However, in the present invention, the presence or type of the polymer is not limited at all. The maximum temperature of the maximum endothermic peak of a hydrocarbon wax having a vinyl unit treated according to the present invention is generally not significantly different from that of a hydrocarbon wax before treatment.
[0061]
Mold release used in the present invention The agent is Gelper When there are two peaks in the molecular weight measurement by miation chromatography (GPC), the peak area on the polymer side of these peaks is α, and the peak area on the low molecule side is β, It is preferable to satisfy Formula (1). More preferably, 0.3 ≦ β / (α + β) ≦ 0.8.
[0062]
[Equation 8]
0.2 ≦ β / (α + β) ≦ 0.9 (1)
[0063]
The peak on the polymer side is a peak of a polymer of a wax having a vinyl unit and a vinyl monomer, and the peak on the low molecule side is a peak of a slightly reacted wax and an unreacted wax. This was judged from the result of GPC analysis of the untreated hydrocarbon wax, that the peak top position almost coincided with the low molecular side peak.
[0064]
In addition, the component obtained by extracting the peak component on the polymer side and the vinyl monomer used in the treatment are heated and mixed at a volume ratio of 1: 1, and until the extraction component and the vinyl monomer are phase-separated for a while. When left to stand and the volume ratio was confirmed, it remained almost 1: 1. From this, it was judged that the polymer of the vinyl monomer was very small.
[0065]
In the present invention, it is preferable that an unreacted wax is present from the viewpoint of fixability. In the case where there are three or more peaks, one of the lowest molecular component side among all peaks may be the low molecular side peak, and the sum of the remaining peak portions may be the polymer side peak. .
[0066]
When β / (α + β) is smaller than 0.2, the effect as a release agent becomes insufficient, and the fixability may not be sufficiently improved. If β / (α + β) is larger than 0.8, the dispersibility of the release agent on the surface of the toner particles tends to be slightly deteriorated.
[0067]
As shown in FIG. 1, the area α of the peak on the polymer side is a line drawn vertically from the valley of the GPC molecular weight distribution curve to the horizontal axis, the GPC molecular weight distribution curve, and an area divided by the horizontal axis, It is the area of the area including the peak on the polymer side. As shown in FIG. 1, the area β of the peak on the low molecule side is a line drawn vertically from the valley of the GPC molecular weight distribution curve to the horizontal axis, the GPC molecular weight distribution curve, and an area divided by the horizontal axis, It is the area of the area including the peak on the low molecule side.
[0068]
Moreover, when a shoulder is included in each peak, the said area is calculated | required as one peak including a shoulder.
[0069]
Further, the release agent used in the present invention is preferably contained in a total amount of 1 to 10 parts by weight, and preferably 3 to 8 parts by weight with respect to 100 parts by weight of the resin component in the toner particles. However, it is more preferable for achieving both excellent fixability and developability. When used in combination with other waxes, the total amount of each wax is the total amount of the release agent. When the content of the release agent is less than 1 part by mass, the low-temperature fixability and offset resistance of the toner may be deteriorated. When the content of the release agent is more than 10 parts by mass, scattering and Fog tends to occur, and transfer efficiency tends to decrease with durability.
[0070]
Next, the binder resin used in the present invention will be described.
As the binder resin that can be used in the present invention, commercially available resins can be used, but (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl copolymer unit, (c) Mixture of hybrid resin and vinyl copolymer, (d) Mixture of polyester resin and vinyl copolymer, (e) Mixture of hybrid resin and polyester resin, and (f) Polyester resin, hybrid resin and vinyl It is a resin selected from a mixture with a copolymer.
[0071]
When a polyester resin is used as the binder resin, a polyhydric alcohol and a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid ester, or the like can be used as a raw material monomer.
[0072]
Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Bisphenol A alkylene oxide adducts such as bis (4-hydroxyphenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.
[0073]
Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.
[0074]
As the polyvalent carboxylic acid component, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; Succinic acid substituted with 6 to 12 alkyl groups or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof;
[0075]
Among them, in particular, a bisphenol derivative represented by the following general formula (1) is used as a diol component, and a carboxylic acid component consisting of a divalent or higher carboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof (for example, fumaric acid). A polyester resin obtained by polycondensation using acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as an acid component is preferable because it has good charging characteristics as a color toner. .
[0076]
[Chemical 1]

[0077]
In the binder resin contained in the toner of the present invention, “hybrid resin” means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, it is a resin formed by a transesterification reaction between a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester, preferably a vinyl polymer. A graft copolymer (or block copolymer) having a trunk polymer and a polyester unit as a branch polymer.
[0078]
In the present invention, “polyester unit” refers to a portion derived from polyester, and “vinyl polymer unit” refers to a portion derived from a vinyl polymer. The polyester monomer constituting the polyester unit is a polyvalent carboxylic acid component and a polyhydric alcohol component, and the vinyl polymer unit is a monomer component having a vinyl group. A monomer having a vinyl group, or a polyhydric alcohol component and a monomer having a vinyl group are defined as “polyester unit” components.
[0079]
Vinyl monomers for producing vinyl polymer units include styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2, 4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn -Styrene such as dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene and derivatives thereof; ethylene, propylene, butylene, isobutylene Styrene unsaturated monoolefins such as butadiene, isoprene, etc. Unsaturated polyenes; vinyl halides such as vinyl chloride, vinyl chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, methacryl Propyl acetate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as: methyl acrylate, ethyl acrylate, propyl acrylate, acrylate-n-butyl, acrylate isobutyl, acrylate-n-octyl, acrylate Acrylic esters such as sil, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, Vinyl ketones such as vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; Vinyl naphthalenes; Acrylonitrile, methacrylonitrile, acrylamide And acrylic acid or methacrylic acid derivatives.
[0080]
In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester unsaturated dibasic acid half ester; dimethylmaleic acid, dimethyl fumaric acid unsaturated dibasic acid ester; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.
[0081]
Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.
[0082]
In the toner of the present invention, the vinyl polymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate and 1,3-butylene glycol. Examples include diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of the above compounds with methacrylate. The diacrylate compounds linked by an alkyl chain containing an ether bond include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, poly Examples include ethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate; di-linked by a chain containing an aromatic group and an ether bond. Examples of acrylate compounds include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and What replaced the acrylate of the above compound with the methacrylate is mentioned.
[0083]
Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallylcia Examples include nurate and triallyl trimellitate.
[0084]
In this invention, it is preferable that the monomer component which can react with the component of both resin units is included in any one or both of a vinyl-type polymer unit and a polyester unit. Examples of monomers that can react with the components of the vinyl polymer unit among the monomers constituting the polyester resin unit include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. It is done. Among the monomers constituting the vinyl polymer unit, those capable of reacting with the components of the polyester unit include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
[0085]
As a method of obtaining a reaction product of a vinyl polymer unit and a polyester unit, there is a polymer containing a monomer component capable of reacting with each of the vinyl polymer unit and the polyester unit listed above. A method obtained by carrying out the polymerization reaction of one or both resins is preferred.
[0086]
Examples of the polymerization initiator used in producing the vinyl polymer unit used in the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2,2′-azobis ( 2,4- Dimethylvaleronitrile), 2,2′-azobis ( 2- Methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone Ketone peroxides such as peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, Di-t-butyl peroxide, t-butylcumylpa -Oxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexa Noyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxide Oxycarbonate, di-methoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxy Seteto, t- butyl peroxy isobutyrate, t- butyl peroxyneodecanoate Eight, t- butyl peroxy -2- Ethyl hexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl Peroxy -2- Examples thereof include ethyl hexanoate, di-t-butyl peroxyhexahydroterephthalate, and di-t-butyl peroxyazelate.
[0087]
Examples of the production method capable of preparing the hybrid resin used in the toner of the present invention include the following production methods (1) to (6).
[0088]
(1) A method in which a vinyl polymer, a polyester resin, and a hybrid resin are blended after production, and the blended product is obtained by dissolving and swelling the resin component in an organic solvent (for example, xylene) and then distilling the organic solvent. Manufactured by. The hybrid resin is synthesized by separately producing a vinyl polymer and a polyester resin, then dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and performing a transesterification reaction by heating. The ester compound used can be used.
[0089]
(2) A method of producing a polyester unit and a hybrid resin component in the presence of a vinyl polymer unit in the presence of the vinyl polymer unit. The hybrid resin component is added as necessary to the reaction of a vinyl polymer unit (a vinyl monomer can be added if necessary) and a polyester monomer (polyhydric alcohol, polycarboxylic acid), and the unit and monomer as necessary. Produced by reaction with polyester. Also in this case, an organic solvent can be appropriately used.
[0090]
(3) A method for producing a vinyl polymer unit and a hybrid resin component in the presence of the polyester unit after the production. The hybrid resin component is produced by a reaction between a polyester unit (a polyester monomer can be added if necessary) and a vinyl monomer, and a reaction between the unit and the monomer and a vinyl polymer unit added as necessary. . Also in this case, an organic solvent can be appropriately used.
[0091]
(4) After the production of the vinyl polymer unit and the polyester unit, one or both of the vinyl monomer and the polyester monomer (polyhydric alcohol, polycarboxylic acid) were added in the presence of these polymer units, and added. A hybrid resin component can be produced by performing a polymerization reaction under conditions according to the monomer. Also in this case, an organic solvent can be appropriately used.
[0092]
(5) After producing the hybrid resin, either one or both of a vinyl monomer and a polyester monomer (polyhydric alcohol, polyvalent carboxylic acid) are added to perform either or both of addition polymerization and condensation polymerization reaction. As a result, a vinyl polymer unit and a polyester unit are produced. In this case, as the hybrid resin component, those produced by the production methods (2) to (4) can be used, and those produced by known production methods can be used as necessary. it can. Furthermore, an organic solvent can be used as appropriate.
[0093]
(6) A vinyl polymer unit, a polyester unit and a hybrid resin component are obtained by mixing vinyl monomers and polyester monomers (polyhydric alcohol, polycarboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reactions. Manufactured. Furthermore, an organic solvent can be used as appropriate.
[0094]
In the production methods (1) to (5), a plurality of polymer units having different molecular weights and different degrees of crosslinking can be used for the vinyl polymer unit and the polyester unit. The vinyl polymer or vinyl polymer unit in the present invention means a vinyl homopolymer or vinyl copolymer, a vinyl monopolymer unit or a vinyl copolymer unit.
[0095]
As the colorant used in the present invention, as the black colorant, a black colorant using carbon black, magnetic material, yellow, magenta, and cyan colorant is used. When a magnetic material is used as the black colorant, it is used by adding 30 to 200 parts by mass with respect to 100 parts by mass of the resin, unlike other colorants.
[0096]
Examples of the magnetic material include metal oxides containing elements such as iron, cobalt, nickel, copper, magnesium, manganese, aluminum, and silicon. Among them, those containing iron oxide as a main component, such as triiron tetroxide and γ-iron oxide, are preferable. Further, from the viewpoint of controlling the chargeability of the toner, other metal elements such as silicon element and aluminum element may be contained. The magnetic material has a BET specific surface area of 2 to 30 m by a nitrogen adsorption method. ² / G, especially 3 to 28m ² / G is preferable, and the Mohs hardness is preferably 5 to 7.
[0097]
The amount of magnetic material is 30 to 200 parts by mass, preferably 40 to 200 parts by mass, and more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the binder resin. If the amount is less than 30 parts by mass, coloring power is insufficient, or in a developing device that uses magnetic force for toner conveyance, the conveyance performance is insufficient and unevenness occurs in the developer layer on the developer carrier, and image unevenness tends to occur. In addition, there is a tendency that the image density is likely to decrease due to an increase in developer tribo. On the other hand, if it exceeds 200 parts by mass, there is a tendency that a problem arises in the fixing property.
[0098]
As the colorant when the toner of the present invention is used as a color toner, known dyes and pigments can be used.
[0099]
As a coloring pigment for magenta toner, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207.209, 238, C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.
[0100]
As the colorant, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.
[0101]
Examples of the magenta toner dye include C.I. I solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disperse thread 9; C.I. I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28 may be mentioned.
[0102]
Examples of the color pigment for cyan toner include C.I. I. Pigment blue 2, 3, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, and a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by the following formula.
[0103]
[Chemical 2]

[0104]
Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat yellow 1, 3, 20, etc. are mentioned.
[0105]
Examples of the coloring dye for yellow include C.I. I. Solvent Yellow 162 and the like, and it is also preferable to use a pigment and a dye together.
[0106]
The amount of the colorant used is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 12 parts by weight, and most preferably 3 to 10 parts by weight with respect to 100 parts by weight of the binder resin. is there.
[0107]
As the charge control agent contained in the toner in the present invention, known ones can be used, and in particular, an aromatic carboxylic acid metal compound that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount. Is preferred.
[0108]
Negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid in the side chain, boron compounds, urea compounds, silicon compounds, calixarenes, etc. Is available. As the positive charge control agent, a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, an imidazole compound, or the like can be used. The charge control agent may be added internally or externally to the toner particles. The addition amount of the charge control agent is preferably 0.2 to 10 parts by mass in total with respect to 100 parts by mass of the binder resin.
[0109]
An external additive is added to the toner of the present invention to improve fluidity. As the external additive, inorganic fine powders such as silicate fine powder, titanium oxide, and aluminum oxide are preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane coupling agent, silicone oil, or a mixture thereof.
[0110]
The external additive is usually used in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the toner particles. The present invention is very effective in non-magnetic one-component development and non-magnetic two-component development. When the toner particles are non-magnetic color toner particles for forming a full color image, it is preferable to use titanium oxide fine particles as an external additive. For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used.
[0111]
When the toner of the present invention is used for a two-component developer, the toner is used by mixing with a magnetic carrier. As the magnetic carrier, for example, surface oxidized or unoxidized iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, alloy particles thereof, oxide particles, ferrite and the like can be used.
[0112]
The coated carrier obtained by coating the surface of the magnetic carrier particles with a resin is particularly preferable in a developing method in which an AC bias is applied to the developing sleeve. Coating methods include a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the magnetic carrier particles, and a method in which the magnetic carrier particles and the coating material are mixed in a powder state. A conventionally known method can be applied.
[0113]
Examples of the coating material on the surface of the magnetic carrier particles include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These may be used alone or in plurality.
[0114]
The treatment amount of the coating material is preferably 0.1 to 30% by weight (preferably 0.5 to 20% by weight) with respect to the magnetic carrier particles. The average particle size of the magnetic carrier is preferably 10 to 100 μm, and more preferably 20 to 70 μm.
[0115]
When preparing a two-component developer by mixing the toner of the present invention and a magnetic carrier, good results are usually obtained when the mixing ratio is 2 to 15% by weight as the toner concentration in the developer. More preferably, it is 4 to 13% by weight.
[0116]
As a method for measuring the physical properties of the toner of the present invention, a suitable measurement method is shown below.
[0117]
<GPC measurement>
The molecular weight of the chromatogram by gel permeation chromatography (GPC) is measured under the following conditions.
[0118]
The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. About 50 to 200 μl of THF sample solution is injected and measured. An RI (refractive index) detector is used as the detector. As column, 10 ^Three ~ 2x10 ⁶ In order to accurately measure the molecular weight region, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, shodex GPC KF-801, 802, 803, 804, 805, 806, 807 manufactured by Showa Denko And a combination of μ-styragels 500, 103, 104, and 105 manufactured by Waters.
[0119]
In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts (retention time). Examples of standard polystyrene samples for preparing a calibration curve include those manufactured by Tosoh Corporation or Pressure Chemical Co. Made molecular weight 6 × 10 ² 2.1 × 10 ^Three 4 × 10 ^Three 1.75 × 10 ^Four 5.1 × 10 ^Four 1.1 × 10 ^Five 3.9 × 10 ^Five 8.6 × 10 ^Five 2 × 10 ⁶ 4.48 × 10 ⁶ It is appropriate to use at least about 10 standard polystyrene samples.
[0120]
(Measurement of wax molecular weight by GPC)
Apparatus: GPC-150C (Waters)
Column: GMH-HT 30 cm, 2 stations (manufactured by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% by mass ionol added)
Flow rate: 1.0 ml / min
Sample: 0.4 ml of 0.15 mass% wax was injected
The molecular weight calibration curve prepared with the monodisperse polystyrene standard sample is used for the measurement of the molecular weight of the wax under the above conditions. Furthermore, the molecular weight of the wax is calculated by converting to polyethylene based on a conversion formula derived from the Mark-Houwink viscosity formula.
[0121]
<Measurement of toner particle size distribution>
In the present invention, the average particle size and particle size distribution of the toner can be measured using a Coulter Counter TA-II type (manufactured by Coulter). It is also possible to use a Coulter Multisizer (manufactured by Coulter). In the measurement, an electrolytic solution is used, and a 1% NaCl aqueous solution is used for this electrolytic solution. The 1% NaCl aqueous solution may be prepared using primary sodium chloride, or commercially available products such as ISOTON R-II (manufactured by Coulter Scientific Japan) may be used.
[0122]
As a measuring 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 dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and the number of toner particles of 2.00 μm or more are measured and measured by the measuring apparatus using a 100 μm aperture as the aperture. The distribution and the number distribution are calculated to determine the weight average particle diameter (D4) (the median value of each channel is the representative value for each channel).
[0123]
As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00 μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00-40.30 μm are used.
[0124]
<Measurement of maximum temperature of maximum endothermic peak in toner and wax>
The maximum endothermic peak of toner and wax is a differential scanning calorimeter (DSC measuring device), DSC It can be measured using -7 (manufactured by Perkin Elmer) or DSC2920 (manufactured by TA Instruments Japan). The measuring method is based on ASTM D3418-82.
[0125]
The sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg. Put it in an aluminum pan, use an empty aluminum pan as a reference, and measure the temperature by raising and lowering the temperature within the measurement range of 30 to 200 ° C at the rate of 10 ° C / min. I do.

[0126]
The maximum endothermic peak of the toner and wax is the one having the highest height from the baseline in the region above the endothermic peak of the resin Tg in the process of temperature increase II, or the endothermic peak of the resin Tg is different from the endothermic peak. If it is difficult to discriminate overlap, the highest endothermic peak is taken as the maximum endothermic peak.
[0127]
Embodiments included in the present invention are listed below.
[0128]
[Embodiment 1]
Contains at least a binder resin, a colorant, and a release agent Non-magnetic Having toner particles and external additives Non-magnetic In the toner, the equivalent circle diameter is 3 μm or more. Non-magnetic Average circularity of particles contained in toner is 0.915 or more 0.960 And said Non-magnetic The mixture obtained by stirring and mixing a toner in a 45% by volume methanol aqueous solution has a light transmittance of 10 to 70% by UV-visible spectroscopic analysis, and the release agent is a hydrocarbon wax having at least a vinyl unit. It is characterized by including Non-magnetic toner.
[0129]
[Embodiment 2]
Above Non-magnetic The weight average particle diameter of the toner is X (μm) and the circularity is 0.960 or more. Non-magnetic The embodiment according to the first embodiment, wherein the relationship of 4 ≦ X ≦ 11 and −X + 20 ≦ Y ≦ −X + 70 is satisfied, where Y (%) is the number-based cumulative value of particles contained in the toner. Non-magnetic toner.
[0130]
[Embodiment 3]
The binder resin includes (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl polymer unit, (c) a mixture of the hybrid resin and the vinyl polymer, as well as (D) A polyester resin and a vinyl polymer From the mixture Embodiment 1 or 2, characterized in that it is a selected resin Non-magnetic toner.
[0131]
[Embodiment 4]
Said mold release The agent is Gelper There are two peaks in the molecular weight measurement by the migration chromatography, and when the area of the peak on the polymer side of these peaks is α and the area of the peak on the low molecule side is β, the following formula (1 The method according to any one of Embodiments 1 to 3, wherein: Non-magnetic toner.
[0132]
[Equation 9]
0.2 ≦ β / (α + β) ≦ 0.9 (1)
[0133]
[Embodiment 5]
The release agent is Non-magnetic 5. The toner according to any one of embodiments 1 to 4, wherein the resin component is contained in a total amount of 1 to 10 parts by mass with respect to 100 parts by mass of the resin component in the toner particles. Non-magnetic toner.
[0134]
【Example】
Specific examples of the present invention will be described below, but the present invention is not limited to these examples.
[0135]
(Processed wax production method)
After adding 100 g of dicumyl peroxide as a reaction initiator to 600 g of styrene monomer, it was dropped into 3300 g of heated and melted paraffin wax A while stirring and reacted for 4 hours to obtain a release agent 1.
[0136]
Release agents 2 to 4 were obtained in the same manner by changing the type and ratio of the vinyl monomer, the heating temperature, and the like. Tables 1 and 2 show the composition and physical properties of the obtained release agent and the wax used.
[0137]
[Table 1]

[0138]
[Table 2]

[0139]
(Toner Production Method 1)
The resin having the composition and physical properties shown in Table 3 and the toner material shown in Table 4 are sufficiently premixed by a Henschel mixer with the composition shown in Table 4, the mixture is melt-kneaded with a twin screw extruder, and the melt-kneaded product is cooled. The cooled product was coarsely pulverized to a particle size of about 1 to 2 mm using a hammer mill. Subsequently, the coarsely pulverized product was finely pulverized by an air jet type fine pulverizer.
[0140]
Further, the finely pulverized product obtained was processed using a processing apparatus as shown in FIGS. 2 and 3, and the rotational speed of the dispersing rotor was set to 5800 rpm (rotational peripheral speed was adjusted) while removing the fine particles by setting the rotational speed of the classification rotor to 7300 rpm. 130 m / sec) and surface treatment for 40 seconds per time was performed for 20 minutes (the finely pulverized product was charged from the raw material supply port 3 and treated for 40 seconds, Discharge valve The operation of opening 8 and taking it out as a processed product was counted once). Ten square disks were installed on the top of the dispersion rotor, the distance between the guide ring and the dispersion rotor square disk was 30 mm, and the distance between the dispersion rotor and the liner was 5 mm. Also, blower air volume is 14m ³ / Min, and the temperature of the refrigerant passing through the jacket and the cold air temperature T1 were set to -20 ° C. As a result of operating for 20 minutes in this state, the temperature T2 behind the classification rotor was stable at 27 ° C., and toner resin particles having a weight average particle diameter of 6.8 μm were obtained.
[0141]
With respect to 100 parts by mass of the toner resin particles, 1.5 parts by mass of acicular titanium (MT-100T manufactured by Teica) was mixed with the toner resin particles to obtain toner 1. Further, the toner 1 and magnetic manganese magnesium ferrite carrier particles (average particle diameter 50 μm) coated with a silicone resin were mixed so that the toner concentration was 6% by mass, whereby a two-component developer 1 was obtained. Table 5 shows the physical properties of the obtained toner.
[0142]
(Toner production method 2-18)
Toners 2 to 18 and developers 2 to 18 were obtained by changing the toner material, the pulverized particle size, and the conditions of the processing apparatus. Table 5 shows the physical properties of the obtained toner.
[0143]
[Table 3]

[0144]
[Table 4]

[0145]
[Table 5]

[0146]
<Example 1>
The toner 1 and the developer 1 were evaluated as follows.
[0147]
<Measurement of fixing temperature range>
The color application machine CLC1000 (made by Canon) was removed from the oil application mechanism, the color copy machine was remodeled so that the fixing temperature could be freely set, and a fixing test was performed using this remodeled machine. In this test, the image area ratio was set to 25%, and the applied toner amount per unit area was 0.7 mg / cm. ² Set to.
[0148]
With the above setting, the temperature of the fixing device is adjusted every 5 ° C. within a temperature range of 120 to 210 ° C., and a fixed image is output at each temperature. The obtained fixed image is 4.9 kPa (50 g). / Cm ² The fixing temperature at which the density reduction rate before and after the rubbing was 10% or less was determined as the fixing start temperature. Further, the set temperature was further raised from the fixing start temperature, and the temperature at which the high temperature offset occurred was determined as the offset start temperature. In addition, the temperature range from the fixing start temperature to the offset generation temperature is defined as a fixable temperature range.
[0149]
<Evaluation of transfer efficiency, scattering, and fog>
Using a modified machine of the color copier CLC1000, 10,000 copies of continuous copies were tested using an original document with an image area ratio of 25% under a normal temperature environment (N / N environment 23 ° C./60%).
[0150]
The transfer rate is obtained by developing and transferring the pre- and post-endurance images, measuring the amount of toner before transfer on the photoconductor (per unit area), and the amount of toner on the transfer material (per unit area), respectively, and calculating the transfer rate using the following formula: It was.
[0151]
[Expression 10]
Transfer rate (%) = (toner amount on transfer material) / (toner amount before transfer on photoconductor) × 100
[0152]
For the fog, the whiteness of the white background portion was measured with a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.), and the fog density (%) was calculated and evaluated from the difference between the whiteness of the white background portion and the whiteness of the transfer paper. The evaluation criteria are as follows.
A: Very good (less than 0.5%)
B: Good (0.5% to 1.5%)
C: Normal (1.5% to 2.5%)
D: Slightly bad (2.5% to 3.5%)
E: Bad (over 3.5%)
[0153]
The scattering property was determined by applying the “electric” character pattern shown in FIG. 4 to plain paper (75 g / m ² ) And cardboard (105 g / m ² And 135 g / m ² ) Was visually evaluated for toner scattering (state of FIG. 5) to the periphery of the character when printed. The evaluation criteria are as follows.
A: No scattering by visual inspection.
B: Almost no occurrence.
C: A slight scattering is seen.
D: Slight scattering is observed.
E: Significant scattering is observed.
[0154]
The results are shown in Table 6. As a result of the evaluation, it was found that the toner 1 has a wide fixable temperature range. Further, the toner 1 showed very good transferability even in image formation after 10,000 sheets, and no scattering or fogging occurred in image formation after 10,000 sheets.
[0155]
<Example 2>
In the same manner as in Example 1, toner 2 and developer 2 were evaluated.
In Example 2, compared with Example 1, although scattering occurred slightly in the endurance test of 10,000 sheets, it was a level with no problem. Transferability and fixability were very good. The results are shown in Table 6.
[0156]
<Example 3>
In the same manner as in Example 1, toner 3 and developer 3 were evaluated.
In Example 3, the initial transfer efficiency was slightly lower than that in Example 1, but the transfer efficiency did not decrease in the durability test for 10,000 sheets. Scattering, fogging and fixing properties were very good. The results are shown in Table 6.
[0157]
<Example 4>
In the same manner as in Example 1, toner 4 and developer 4 were evaluated.
In Example 4, although the fixing temperature range was slightly narrower than that in Example 1, it was at a level where it could be used without any problem. Further, scattering, fogging and transferability were very good. The results are shown in Table 6.
[0158]
<Example 5>
In the same manner as in Example 1, the toner 5 and the developer 5 were evaluated.
In Example 5, compared with Example 1, fogging occurred slightly in the endurance test for 10,000 sheets, but the level was satisfactory. Although the initial transfer efficiency was slightly lowered, the transfer efficiency did not decrease in the durability test. Fixability was very good. The results are shown in Table 6.
[0159]
<Example 6>
In the same manner as in Example 1, toner 6 and developer 6 were evaluated.
In Example 6, as compared with Example 1, scattering and fogging occurred slightly in the endurance test for 10,000 sheets, but the level was satisfactory. In terms of fixability, although the fixing temperature range was slightly narrow, it was at a level where it could be used without problems. The results are shown in Table 6.
[0160]
<Example 7>
In the same manner as in Example 1, the toner 7 and the developer 7 were evaluated.
In Example 7, the initial transfer efficiency was slightly lower than that in Example 1, and some scattering occurred in the endurance test for 10,000 sheets. In terms of fixability, although the fixing temperature range was slightly narrow, it was at a level where it could be used without problems. The results are shown in Table 6.
[0161]
<Example 8>
In the same manner as in Example 1, toner 8 and developer 8 were evaluated.
In Example 8, as compared with Example 1, scattering and fogging occurred slightly in the endurance test for 10,000 sheets, but the level was satisfactory. In terms of fixability, the fixing temperature range was slightly narrowed, and in particular, the anti-offset property was lowered, but it was at a level that could be used without any problem. The results are shown in Table 6.
[0162]
<Example 9>
In the same manner as in Example 1, toner 9 and developer 9 were evaluated.
In Example 9, compared with Example 1, the transfer efficiency was lowered in the endurance test for 10,000 sheets, and scattering was likely to occur, but it was at a usable level. In terms of fixability, although the fixing temperature range was slightly narrow, it was at a level where it could be used without problems. The results are shown in Table 6.
[0163]
<Example 10>
In the same manner as in Example 1, the toner 10 and the developer 10 were evaluated.
In Example 10, the transfer efficiency was lower than that in Example 1, and in the endurance test for 10,000 sheets, scattering and fogging occurred slightly, but the level was satisfactory. In terms of fixing performance, the fixing temperature range was slightly narrowed, and particularly low-temperature fixing performance was deteriorated, but it was at a usable level. The results are shown in Table 6.
[0164]
<Example 11>
In the same manner as in Example 1, the toner 11 and the developer 11 were evaluated.
In Example 11, compared with Example 1, the initial transfer efficiency was low, and in the endurance test for 10,000 sheets, scattering and fogging were slightly caused, but at a level with no problem. In terms of fixability, the fixing temperature range was narrow, but it was at a usable level. The results are shown in Table 6.
[0165]
<Example 12>
In the same manner as in Example 1, the toner 12 and the developer 12 were evaluated.
In Example 12, the initial transfer efficiency was lower than that in Example 1, and the transfer efficiency slightly decreased in the durability test for 10,000 sheets. Moreover, although it became easy to produce scattering and fog, it was a usable level. The results are shown in Table 6.
[0166]
<Example 13>
C. I. Pigment Blue 15: 3 instead of C.I. I. A magenta toner 1 was obtained and a magenta developer 1 was obtained in the same manner as in the toner production method 1 except that 6 parts by mass of Pigment Red 57: 1 was used. In addition, C.I. I. Pigment Blue 15: 3 instead of C.I. I. A yellow toner 1 was obtained and a yellow developer 1 was obtained in the same manner as in the toner production method 1 except that 7 parts by mass of Pigment Yellow 74 was used. In addition, C.I. I. Black toner 1 and black developer 1 were obtained in the same manner as in Toner Production Method 1 except that 3 parts of carbon black was used instead of Pigment Blue 15: 3.
[0167]
The obtained magenta, yellow, and black toners and developers were evaluated in the same manner as in Example 1. As a result, it was found that these toners and developers had a wide fixable temperature range as in Example 1. . Further, the durability after 10,000 sheets showed very good transfer, and no scattering or fogging occurred.
[0168]
Further, cyan toner 1 and cyan developer 1 (toner 1 and developer 1 produced by toner production method 1), magenta toner 1 and magenta developer 1, yellow toner 1 and yellow developer 1, black toner 1 and black developer 1 was used, and a durability test of 10,000 sheets using an original document in a full color mode was performed in a normal color environment (N / N environment 23 ° C./60%) using a modified machine of the color copier CLC1000. As a result, it was possible to obtain a very high-definition full-color image without fogging or scattering after endurance.
[0169]
Further, using a cyan toner 1, magenta toner 1, yellow toner 1 and black toner 1 and a non-magnetic one-component commercially available full color copier (Creative Processor 660, manufactured by Canon Inc.), in a normal temperature environment (N / N environment 23 ° C.). / 60%), a durability test of 10,000 sheets using an original document in a full color mode was performed. As a result, it was possible to obtain a very high-definition full-color image without fogging or scattering after endurance.
[0170]
<Comparative Example 1>
In the same manner as in Example 1, the toner 13 and the developer 13 were evaluated.
In Comparative Example 1, as compared with Example 1, scattering occurred in the durability test for 10,000 sheets. In addition, the initial transfer efficiency was lowered, and the transfer efficiency after the durability test was also lowered. Furthermore, the fixing temperature range was narrowed. The results are shown in Table 6.
[0171]
<Comparative example 2>
In the same manner as in Example 1, the toner 14 and the developer 14 were evaluated.
In Comparative Example 2, scattering occurred in the endurance test for 10,000 sheets as compared with Example 1. In addition, the initial transfer efficiency was greatly reduced, and a decrease in transfer efficiency after the durability test was also observed. The results are shown in Table 6.
[0172]
<Comparative Example 3>
In the same manner as in Example 1, the toner 15 and the developer 15 were evaluated.
In Comparative Example 3, as compared with Example 1, in the endurance test for 10,000 sheets, more fog was generated, and in particular, much scattering was generated. In addition, the initial transfer efficiency was lowered, and after the durability test, the transfer efficiency was greatly lowered. The results are shown in Table 6.
[0173]
<Comparative example 4>
In the same manner as in Example 1, the toner 16 and the developer 16 were evaluated.
In Comparative Example 4, more scattering and fogging occurred in the endurance test of 10,000 sheets compared to Example 1. In addition, the initial transfer efficiency was greatly reduced, and a decrease in transfer efficiency after the durability test was also observed. Also, the fixable temperature range was not measured. The results are shown in Table 6.
[0174]
<Comparative Example 5>
In the same manner as in Example 1, toner 17 and developer 17 were evaluated.
In Comparative Example 5, as compared with Example 1, splattering and fogging occurred in the endurance test of 10,000 sheets. In addition, the initial transfer efficiency was lowered, and the transfer efficiency after the durability test was extremely lowered. The results are shown in Table 6.
[0175]
<Comparative Example 6>
In the same manner as in Example 1, the toner 18 and the developer 18 were evaluated.
In Comparative Example 6, as compared with Example 1, more scattering and fogging occurred in the durability test of 10,000 sheets. In addition, the initial transfer efficiency was greatly reduced, and a decrease in transfer efficiency after the durability test was also observed. Also, the fixable temperature range was not measured. The results are shown in Table 6.
[0176]
[Table 6]

[0177]
【The invention's effect】
The present invention can provide a toner having excellent low-temperature fixability and high-temperature offset resistance without applying a large amount of oil or without applying any oil. The toner of the present invention can improve transfer efficiency and prevent scattering while maintaining high fixability and developability.
[Brief description of the drawings]
FIG. 1 is a diagram for explaining a method for dividing a peak area of a GPC molecular weight distribution curve of a release agent used in the present invention.
FIG. 2 is a schematic cross-sectional view showing an example of the structure of an example of a surface modification device used in a surface modification step when manufacturing the toner of the present invention.
FIG. 3 is a schematic view showing an example of a top view of the dispersion rotor shown in FIG. 2;
FIG. 4 is a diagram illustrating a character “Den” printed for scattering evaluation.
FIG. 5 is a diagram illustrating a state where toner is scattered around the character when the character “Den” shown in FIG. 4 is printed.
[Explanation of symbols]
1 classification rotor
2 Fine powder recovery outlet
3 Raw material supply port
4 liner
5 Cold air inlet
6 Distributed rotor
7 Powder outlet
8 Discharge valve
9 Guide ring
10 square disc
11 First space
12 Second space
15 casing

Claims (5)

In a non-magnetic toner having non -magnetic toner particles containing at least a binder resin, a colorant, and a release agent, and an external additive,
The average circularity of the particles contained in the non-magnetic toner having an equivalent circle diameter of 3 μm or more is 0.915 or more and 0.960 or less,
The transmittance of light having a wavelength of 600 nm by ultraviolet-visible spectroscopic analysis of a mixed solution obtained by stirring and mixing the nonmagnetic toner in a 45 volume% methanol aqueous solution is 10 to 70%,
The non-magnetic toner, wherein the release agent includes a hydrocarbon wax having at least a vinyl unit. When the weight average particle diameter of the nonmagnetic toner is X (μm) and the number-based cumulative value of particles contained in the nonmagnetic toner having a circularity of 0.960 or more is Y (%), 4 ≦ X ≦ The nonmagnetic toner according to claim 1, wherein a relationship of 11 and −X + 20 ≦ Y ≦ −X + 70 is satisfied. The binder resin includes (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl polymer unit, (c) a mixture of the hybrid resin and a vinyl polymer, and (d) a polyester. The nonmagnetic toner according to claim 1, wherein the toner is a resin selected from a mixture of a resin and a vinyl polymer. The releasing agent has two peaks in the molecular weight measurement by Gerupa permeation chromatography, and the area of the peak of the polymer side of these peaks alpha, the area of the peak of the low molecular side were the β 4. The non-magnetic toner according to claim 1, wherein the following formula (1) is satisfied.
0.2 ≦ β / (α + β) ≦ 0.9 (1) The releasing agent is not according to any one of claims 1 to 4, characterized in that it is contained 1 to 10 parts by weight in total with respect to 100 parts by mass of the resin component in the non-magnetic toner particles Magnetic toner.

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