JP4154078B2 - Image forming method - Google Patents

Description

【００４３】
【数２】

【００４４】
【数３】

【００４５】
なお、本発明で用いている測定装置である「ＦＰＩＡ−１０００」は、各粒子の円形度を算出後、平均円形度及び円形度標準偏差の算出に当たって、粒子を得られた円形度によって、円形度０．４〜１．０を６１分割したクラスに分け、分割点の中心値と頻度を用いて平均円形度及び円形度標準偏差の算出を行う算出法を用いている。しかしながら、この算出法で算出される平均円形度及び円形度標準偏差の各値と、上述した各粒子の円形度を直接用いる算出式によって算出される平均円形度及び円形度標準偏差の各値との誤差は、非常に少なく、実質的には無視できる程度であり、本発明においては、算出時間の短絡化や算出演算式の簡略化の如きデータの取り扱い上の理由で、上述した各粒子の円形度を直接用いる算出式の概念を利用し、一部変更したこのような算出法を用いても良い。
【００４６】
測定方法としては、ノニオン型界面活性剤約０．１ｍｇを溶解している水１０ｍｌにトナー約５ｍｇを分散させ分散液を調製し、超音波（２０ｋＨｚ、５０Ｗ）を分散液に５分間照射し、分散液濃度を５０００〜２００００個／μｌとして、上記フロー式粒子像測定装置を用い、０．６０μｍ以上１５９．２１μｍ未満の円相当径を有する粒子の円形度分布を測定する。
【００４７】
測定の概略は、東亜医用電子社（株）発行のＦＰＩＡ−１０００のカタログ（１９９５年６月版）、測定装置の操作マニアル及び特開平８−１３６４３９号公報に記載されているが、以下の通りである。
【００４８】
試料分散液は、フラットで扁平な透明フローセル（厚み約２００μｍ）の流路（流れ方向に沿って広がっている）を通過させる。フローセルの厚みに対して交差して通過する光路を形成するように、ストロボとＣＣＤカメラが、フローセルに対して、相互に反対側に位置するように装着される。試料分散液が流れている間に、ストロボ光がフローセルを流れている粒子の画像を得るために１／３０秒間隔で照射され、その結果、それぞれの粒子は、フローセルに平行な一定範囲を有する２次元画像として撮影される。それぞれの粒子の２次元画像の投影面積及び投影像の周囲長から上記の円形度算出式を用いてそれぞれの粒子の円形度を算出する。
【００４９】
本発明における「平均円形度」とは、トナー粒子の凹凸の度合いの指標であり、トナーが完全な球形の場合１．００を示し、トナー形状が複雑になるほど平均円形度は小さな値となる。
【００５０】
一般にトナー形状が不定形であるものは、トナー凸部、または、凹部での帯電均一性が低く、さらに、不定形であるために静電潜像担持体とトナーとの接触面積が増加することにより、トナー付着力が高くなり、結果として転写残トナーの増加を招く。
【００５１】
平均円形度が０．９５５より小さいということは、トナーは凹凸を有した不定形であるものが多く含まれていることを示し、転写効率が低下する。さらに平均円形度が０．９５５より小さなトナーは表面に凹凸を有しているために、低結晶性または非晶性の芳香族化合物の金属錯化合物、金属塩、または、金属錯化合物と金属塩との混合物が、トナー表面に均一に存在することができなくなる。一方、平均円形度が大きくなりすぎるとトナーは実質球形であり、トナーの表面積が小さくなり良好な帯電性が得られ難くなることから、平均円形度の上限は、０．９９０であることが特に好ましい。さらにトナーの円形度標準偏差が０．０４０より大きいということは、トナー形状にばらつきが多いことを示し、トナーの均一な帯電が困難となり、転写効率の低下が生じ易くなる。
【００５２】
本発明に用いるトナーは高画質化のため、微少な潜像ドットを忠実に再現するために、トナーの重量平均径は４乃至９μｍであることが好ましい。重量平均径が４乃至９μｍのトナー粒子においては、文字やライン画像の飛び散りが生じにくく、画像の輪郭部分、特に文字画像やラインパターンの現像での再現性が良好になる。
【００５３】
ここで粒度分布については、種々の方法によって測定できるが、本発明においてはコールターカウンタを用いて測定を実施した。即ち測定装置としては、コールターカウンタＴＡ−ＩＩ型あるいはコールターマルチサイザー（コールター社製）を用いる。電解液は、１級塩化ナトリウムを用いて、約１％ＮａＣｌ水溶液を調製する。例えばＩＳＯＴＯＮ−ＩＩ（コールター社製）が使用できる。測定方法としては、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は、超音波分散器で約１〜３分間分散処理を行い、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、トナーの体積、個数を測定して体積分布と個数分布を算出した。それから本発明に係る体積分布から求めた重量基準の重量平均粒径を求めた。
【００５４】
チャンネルとしては、２．００〜２．５２μｍ未満；２．５２〜３．１７μｍ未満；３．１７〜４．００μｍ未満；４．００〜５．０４μｍ未満；５．０４〜６．３５μｍ未満；６．３５〜８．００μｍ未満；８．００〜１０．０８μｍ未満；１０．０８〜１２．７０μｍ未満；１２．７０〜１６．００μｍ未満；１６．００〜２０．２０μｍ未満；２０．２０〜２５．４０μｍ未満；２５．４０〜３２．００μｍ未満；３２．００〜４０．３０μｍ未満の１３チャンネルを用いる。
【００５５】
本発明に用いるトナーのガラス転移点（Ｔｇ）は、定着性や保存性の点から好ましくは５０℃〜７５℃、より好ましくは５２℃〜７０℃であることが良い。ガラス転移点が４５℃より低いとブロッキングを起こしやすくなり、保存性に問題が発生する。また、耐久時のストレスにも弱く、トナー劣化等を生じやすく好ましくない。また、ガラス転移点が７０℃より高いと定着性が悪化し、多様なマテリアルに対応することが困難となり、好ましくない。
【００５６】
トナーのガラス転移点の測定には例えば、パーキンエルマー社製ＤＳＣ−７の様な高精度の内熱式入力補償型の示差走査熱量計で測定を行う。測定方法は、ＡＳＴＭＤ３４１８−８に準じて行う。本発明においては、試料を１回昇温させ前履歴をとった後、急冷し、再度昇温速度１０℃／ｍｉｎ、温度３０〜２００℃の範囲で昇温させた時に測定されるＤＳＣ曲線を用いる。
【００５７】
本発明に使用されるトナーの結着樹脂は、ポリスチレン；ポリ−ｐ−クロルスチレン、ポリビニルトルエンの如きスチレン置換体の単重合体；スチレン−ｐ−クロルスチレン共重合体、スチレン−ビニルトルエン共重合体、スチレン−ビニルナフタリン共重合体、スチレン−アクリル酸エステル共重合体、スチレン−メタクリル酸エステル共重合体、スチレン−α−クロルメタクリル酸メチル共重合体、スチレン−アクリロニトリル共重合体、スチレン−ビニルメチルエーテル共重合体、スチレン−ビニルエチルエーテル共重合体、スチレン−ビニルメチルケトン共重合体、スチレン−ブタジエン共重合体、スチレン−イソプレン共重合体、スチレン−アクリロニトリル−インデン共重合体の如きスチレン系共重合体；ポリ塩化ビニル、フェノール樹脂、天然変性フェノール樹脂、天然樹脂変性マレイン酸樹脂、アクリル樹脂、メタクリル樹脂、ポリ酢酸ビニール、シリコーン樹脂、ポリエステル樹脂、ポリウレタン、ポリアミド樹脂、フラン樹脂、エポキシ樹脂、キシレン樹脂、ポリビニルブチラール、テルペン樹脂、クマロンインデン樹脂、石油系樹脂等が使用できる。好ましい結着樹脂としては、スチレン系重合体もしくはポリエステル樹脂が挙げられる。
【００５８】
スチレン系共重合体のスチレンモノマーに対するコモノマーとしては、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸ドデシル、アクリル酸オクチル、アクリル酸−２−エチルヘキシル、アクリル酸フェニル、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸オクチル、アクリロニトリル、メタクリロニトリル、アクリルアミドのような二重結合を有するモノカルボン酸もしくはその置換体；マレイン酸、マレイン酸ブチル、マレイン酸メチル、マレイン酸ジメチルのような二重結合を有するジカルボン酸及びその置換体；塩化ビニル、酢酸ビニル、安息香酸ビニルのようなビニルエステル類；エチレン、プロピレン、ブチレンのようなエチレン系オレフィン類；ビニルメチルケトン、ビニルヘキシルケトンのようなビニルケトン類；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ようなビニルエーテル類；等のビニル単量体が挙げられる。これらは、単独もしくは組み合わせて用いられる。
【００５９】
結着樹脂の架橋剤としては、２個以上の重合可能な二重結合を有する化合物が用いられる。例えば、ジビニルベンゼン、ジビニルナフタレンのような芳香族ジビニル化合物；エチレングリコールジアクリレート、エチレングリコールジメタクリレート、１，３−ブタンジオールジメタクリレートのような二重結合を２個有するカルボン酸エステル；ジビニルアニリン、ジビニルエーテル、ジビニルスルフィド、ジビニルスルホンの如きジビニル化合物；３個以上のビニル基を有する化合物；が挙げられる。これらは単独もしくは混合して使用される。架橋剤の添加量としては、重合性単量体１００重量部に対して０．００１〜１０重量部が好ましい。
【００６０】
定着時の定着部材からの離型性の向上、定着性の向上の点から次のような低軟化点物質をトナー粒子中に含有させることも好ましい。パラフィンワックス及びその誘導体，マイクロクリスタリンワックス及びその誘導体，フィッシャートロプシュワックス及びその誘導体，ポリオレフィンワックス及びその誘導体，カルナバワックス及びその誘導体である。誘導体には酸化物や、ビニル系モノマーとのブロック共重合体，グラフト変性物が挙げられる。その他、長鎖アルコール，長鎖脂肪酸，酸アミド，エステルワックス，ケトン，硬化ヒマシ油及びその誘導体，植物系ワックス，動物系ワックス，鉱物系ワックス，ペトロラクタム等も場合により使用しても良い。
【００６１】
低軟化点物質としては、ＡＳＴＭ Ｄ３４１８−８に準拠して測定されたＤＳＣ曲線における吸熱メインピーク値が５５〜１２０℃、好ましくは６０〜９０℃、より好ましくは６０〜８５℃の値を示す低軟化点物質が好ましく、特に、ＤＳＣ曲線の接線離脱温度が４０℃以上の低軟化点物質がより好ましい。吸熱メインピークが５５℃未満であると、低軟化点物質の自己凝集力が弱いために、トナー粒子の内部又は中心部を構成しづらく、トナー粒子の製造時にトナー粒子表面に低軟化点物質が析出し、現像特性に悪影響を与えやすい。更に接線離脱温度が４０℃未満になると、トナー粒子の強度が低下し、耐久試験時の現像特性の低下を招きやすい。得られる定着画像も、低軟化点物質の融点が低いことに起因して、べた付いた感じの画像になりやすい。一方、吸熱メインピークが１２０℃を超えると、定着時に低軟化点物質がしみ出しにくく、低温定着性が低下する。更に、直接重合方法によりトナー粒子を生成する場合、重合性単量体組成物中への溶解性が低下し、水系媒体中での重合性単量体組成物のトナー粒径サイズヘの液滴の造粒中に低軟化点物質が析出し、造粒が困難となり好ましくない。
【００６２】
低軟化点物質は、トナーの結着樹脂１００重量部に対して２乃至４０重量部、より好ましくは５乃至３５重量部配合するのが良い。
【００６３】
低軟化点物質の配合量が下限より少ないとオフセット防止効果が低下しやすく、上限を超えると、耐ブロッキング効果が低下し、耐オフセット効果にも悪影響を与えやすく、ドラム融着、スリーブ融着を起こしやすく、特に重合トナー製法の場合には粒度分布の広いトナーが生成する傾向にあり好ましくない。
【００６４】
本発明に用いられる着色剤としてはカーボンブラック、磁性体、以下に示すイエロー／マゼンタ／シアンの各着色剤が好適に用いられる。
【００６５】
イエロー着色剤としては、縮合アゾ化合物、イソインドリノン化合物、アンスラキノン化合物、アゾ金属錯化合物、メチン化合物、アリルアミド化合物に代表される化合物が用いられる。具体的には、Ｃ．Ｉ．ピグメントイエロー１２、１３、１４、１５、１７、６２、７４、８３、９３、９４、９５、９７、１０９、１１０、１１１、１２０、１２７、１２８、１２９、１４７、１６８、１７４、１７６、１８０、１８１、１９１等が好適に用いられる。
【００６６】
マゼンタ着色剤としては、縮合アゾ化合物、ジケトピロロピロール化合物、アンスラキノン、キナクリドン化合物、塩基染料レーキ化合物、ナフトール化合物、ベンズイミダゾロン化合物、チオインジゴ化合物、ペリレン化合物が用いられる。具体的には、Ｃ．Ｉ．ピグメントレッド２、３、５、６、７、２３、４８：２、４８：３、４８：４、５７：１、８１：１、１２２、１４４、１４６、１６６、１６９、１７７、１８４、１８５、２０２、２０６、２２０、２２１、２５４が特に好ましい。
【００６７】
シアン着色剤としては、銅フタロシアニン化合物及びその誘導体、アンスラキノン化合物、塩基染料レーキ化合物等が利用できる。具体的には、Ｃ．Ｉ．ピグメントブルー１、７、１５、１５：１、１５、１５：２、１５：３、１５：４、６０、６２、６６等が特に好適に利用できる。
【００６８】
これらの着色剤は、単独または混合し更には固溶体の状態で用いることができる。本発明の着色剤は、色相角，彩度，明度，耐候性，ＯＨＰフィルム上の透明性，トナー粒子中への分散性の点から選択される。該着色剤の添加量は、結着樹脂１００重量部当り２〜２０重量部が一般に用いられる。
【００６９】
黒色着色剤として磁性体を用いた場合には、他の着色剤と異なり、樹脂１００重量部当り４０〜１５０重量部が一般に用いられる。
【００７０】
さらに本発明のトナーは更に磁性材料を含有させ磁性トナーとしても使用しうる。この場合、磁性材料は着色剤の役割をかねることもできる。本発明において、磁性トナー中に含まれる磁性体としては、マグネタイト、ヘマタイト、フェライト等の如き酸化鉄；鉄、コバルト、ニッケルのような金属或いはこれらの金属のアルミニウム、コバルト、銅、鉛、マグネシウム、スズ、亜鉛、アンチモン、ベリリウム、ビスマス、カドミウム、カルシウム、マンガン、セレン、チタン、タングステン、バナジウムのような金属の合金及びその混合物が挙げられる。
【００７１】
本発明に用いられる磁性体は、より好ましくは、表面改質された磁性体が好ましく、重合法トナーに用いる場合には、重合阻害のない物質である表面改質剤により、疎水化処理を施したものであれば、どんなものでも良く、このような表面改質剤としては、例えばシランカップリング剤、チタンカップリング剤等を挙げることができる。これらの磁性体は平均粒径が１μｍ以下、好ましくは０．１〜０．５μｍのものが好ましい。
【００７２】
本発明の画像形成方法に関わるトナーにおいては、現像性、流動性及び耐久性の向上のために、上記金属化合物が表面に存在しているトナー粒子に微粒子を添加することが好ましく、粒径の異なる２種類以上の微粒子を添加することがより好ましい。これは粒径の小さな微粒子（以後「小粒径微粒子」と略す）が流動性を付与し、粒径の大きな微粒子（以後「大粒径微粒子」と略す）は所謂スペーサー粒子として働き、耐久によるトナー劣化を防ぐためである。そのため、大粒径微粒子の一次粒径が０．０３μｍ未満であると、大粒径微粒子がトナーに埋め込まれてしまい、スペーサー粒子としての役割を果たしにくく、また、０．８μｍを超えると大粒径微粒子はトナーに付着せずに遊離しやすくなり、上記効果が薄れ好ましくない。従って、大粒径微粒子の一次粒径は、０．０３μｍ乃至０．８μｍであることが好ましく、小粒径微粒子の一次粒径は、５ｎｍ（０．００５μｍ）乃至２０ｎｍ（０．０２μｍ）であることが好ましい。小粒径微粒子の一次粒径が２０ｎｍを超える場合には、トナーの流動性が充分に高くなり難く、５ｎｍ未満の場合には、トナー粒子表面の微細な凹凸に埋もれてしまい、帯電性及び流動性の調整が充分に行われ難い。
【００７３】
これら微粒子としては、シリカ微粉体、酸化チタン、アルミナ微粉体、樹脂微粒子等が挙げられ、トナー粒子１００重量部に対して小粒径微粒子と大粒径微粒子との合計量で０．０１〜８重量部、好ましくは０．１〜５重量部使用するのが良い。
【００７４】
小粒径微粒子の添加量（Ｓ）と大粒径微粒子の添加量（Ｌ）との比が、好ましくはＳ：Ｌ＝１：０．１〜３．５であり、より好ましくはＳ：Ｌ＝１：０．１〜３．０である。
【００７５】
本発明で用いられる微粒子は、必要に応じ、疎水化、帯電性コントロールの目的でシリコーンワニス、各種変性シリコーンワニス、シリコーンオイル、各種変性シリコーンオイル、シランカップリング剤、官能基を有するシランカップリング剤、その他の有機ケイ素化合物の如き処理剤で処理されていることも好ましい。
【００７６】
なお、本発明に用いる微粒子の平均粒径の求め方は、まず、微粒子を電子顕微鏡、あるいは、透過電子顕微鏡にて、１万倍から１０万倍の倍率で観察し、写真を撮る。そして画像上の１ｎｍ以上の微粒子を対象にして、一次粒径であると確認できるものについて、１００個無作為にサンプリングし、その像から粒径を求め、平均する。
【００７７】
他の添加剤としては、テフロン、ステアリン酸亜鉛、ポリフッ化ビニリデンの如き滑剤（中でもポリフッ化ビニリデンが好ましい）；酸化セリウム、炭化ケイ素、チタン酸ストロンチウムの如き研磨剤（中でもチタン酸ストロンチウムが好ましい）；ケーキング防止剤；カーボンブラック、酸化亜鉛、酸化アンチモン、酸化スズの如き導電性付与剤等が挙げられる。
【００７８】
このような微粒子の添加方法としては、ヘンシェルミキサーの如き混合機により、混合・撹拌することにより行うが、上記金属化合物とトナー粒子とを混合・撹拌した後で、これら微粒子を添加混合することが好ましい。これは、上記金属化合物と上記微粒子とを同時にトナー粒子と添加混合する場合、及び上記微粒子をトナー粒子と混合後に、上記金属化合物を添加混合する場合には、上記微粒子がトナー粒子表面に付着してしまうことから、上記金属化合物がトナー粒子表面に存在・被覆することが困難となるためである。さらにトナー粒子表層に存在できない該化合物は遊離してしまい、帯電部材を汚染し、カブリの増加、画質の低下を招き好ましくない。
【００７９】
次に本発明に用いられるトナーを製造するための方法について説明する。本発明に用いられるトナーは、粉砕トナー製法及び重合トナー製法を用いて製造することが可能である。
【００８０】
本発明において、粉砕トナーの製造方法は結着樹脂、ワックス、着色剤としての顔料、染料、又は磁性体、その他の添加剤をヘンシェルミキサー、ボールミルの如き混合器により十分混合してから加熱ロール、ニーダー、エクストルーダーの如き熱混練機を用いて溶融混練して樹脂を溶融せしめた中に顔料、染料又は磁性体を分散又は溶解せしめ、冷却固化後、粉砕、分級を行なってトナーを得ることが出来る。分級工程においては生産効率上、多分割分級機を用いることが好ましい。
【００８１】
このような粉砕法により得られるトナーは平均円形度が０．９５５未満であり、この場合、粉砕法で得られたトナー粒子を、水中に分散させ加熱する湯浴法、熱気流中を通過させる熱処理法、機械的エネルギーを付与して処理する機械的衝撃法などによりトナーの表面改質を行い、平均円形度を上げることが好ましい。表面改質の装置としては公知のもの全てを用いることが出来るが、具体的にはメカノフュージョン、Ｉ式ミル、ハイブリタイザー、及び特開平１０−９４７３４号公報に記載の装置等が挙げられる。
【００８２】
本発明において、重合トナーの製造方法は、特公昭５６−１３９４５号公報等に記載のディスク又は多流体ノズルを用い溶融混合物を空気中に霧化し球状トナーを得る方法や、特公昭３６−１０２３１号公報，特開昭５９−５３８５６号公報，特開昭５９−６１８４２号公報に述べられている懸濁重合方法を用いて直接トナーを生成する方法や、単量体には可溶で得られる重合体が不溶な水系有機溶剤を用い直接トナーを生成する分散重合方法又は水溶性極性重合開始剤存在下で直接重合しトナーを生成するソープフリー重合方法に代表される乳化重合方法や、予め一次極性乳化粒子を作った後、反対電荷を有する極性粒子を加えて会合させるヘテロ凝集法等を用いてトナー粒子を製造することが可能である。特には懸濁重合方法によるトナー粒子の生成が好ましい。さらに一旦得られた重合粒子に更に単量体を吸着せしめた後、重合開始剤を用い重合せしめるシード重合方法によるトナー粒子も本発明に好適に利用することができる。
【００８３】
本発明のトナー粒子の製造に重合方法を用いる場合においては、以下の如き方法によってトナー粒子を製造することが可能である。重合性単量体中に低軟化物質からなる離型剤，着色剤，荷電制御剤，重合開始剤その他の添加剤を加え、ホモジナイザー，超音波分散機の如き分散機によって均一に溶解又は分散せしめた重合性単量体組成物を、分散安定剤を含有する水相中に通常の撹拌機，ホモミキサー又はホモジナイザーにより分散せしめる。好ましくは重合性単量体組成物の液滴が所望のトナー粒子のサイズを有するように撹拌速度及び時間を調整し、造粒する。その後は分散安定剤の作用により、粒子状態が維持され、且つ粒子の沈降が防止される程度の撹拌を行えば良い。重合温度は４０℃以上、一般的には５０〜９０℃の温度に設定して重合を行う。また、反応後半に昇温しても良く、さらに、トナー定着時の臭いの原因等となる未反応の重合性単量体、副生成物等を除去する為に反応後半、または反応終了時に一部水系媒体を留去しても良い。反応終了後生成したトナー粒子を洗浄、ろ過により回収し、乾燥する。懸濁重合法においては、通常単量体系１００重量部に対して水３００〜３０００重量部を分散剤として使用することが好ましい。
【００８４】
本発明のトナーを重合方法で製造する際に用いられる重合性単量体としては、ラジカル重合が可能なビニル系重合性単量体が用いられる。該ビニル系重合性単量体としては、単官能性重合性単量体或いは多官能性重合性単量体を使用することができる。
【００８５】
単官能性重合性単量体としては、スチレン、α−メチルスチレン、β−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、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−フェニルスチレンの如きスチレン系重合性単量体；メチルアクリレート、エチルアクリレート、ｎ−プロピルアクリレート、ｉｓｏ−プロピルアクリレート、ｎ−ブチルアクリレート、ｉｓｏ−ブチルアクリレート、ｔｅｒｔ−ブチルアクリレート、ｎ−アミルアクリレート、ｎ−ヘキシルアクリレート、２−エチルヘキシルアクリレート、ｎ−オクチルアクリレート、ｎ−ノニルアクリレート、シクロヘキシルアクリレート、ベンジルアクリレート、ジメチルフォスフェートエチルアクリレート、ジブチルフォスフェートエチルアクリレート、２−ベンゾイルオキシエチルアクリレートの如きアクリル系重合性単量体；メチルメタクリレート、エチルメタクリレート、ｎ−プロピルメタクリレート、ｉｓｏ−プロピルメタクリレート、ｎ−ブチルメタクリレート、ｉｓｏ−ブチルメタクリレート、ｔｅｒｔ−ブチルメタクリレート、ｎ−アミルメタクリレート、ｎ−ヘキシルメタクリレート、２−エチルヘキシルメタクリレート、ｎ−オクチルメタクリレート、ｎ−ノニルメタクリレート、ジエチルフォスフェートエチルメタクリレート、ジブチルフォスフェートエチルメタクリレートの如きメタクリル系重合性単量体；メチレン脂肪族モノカルボン酸エステル類；酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、安息香酸ビニル、ギ酸ビニルの如きビニルエステル類；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、ビニルイソプロピルケトンの如きビニルケトン類が挙げられる。
【００８６】
多官能性重合性単量体としては、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、トリプロピレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、２，２’−ビス［４−（アクリロキシ・ジエトキシ）フェニル］プロパン、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、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、１，３−ブチレングリコールジメタクリレート、１，６−ヘキサンジオールジメタクリレート、ネオペンチルグリコールジメタクリレート、ポリプロピレングリコールジメタクリレート、２，２’−ビス［４−（メタクリロキシ・ジエトキシ）フェニル］プロパン、２，２’−ビス［４−（メタクリロキシ・ポリエトキシ）フェニル］プロパン、トリメチロールプロパントリメタクリレート、テトラメチロールメタンテトラメタクリレート、ジビニルベンゼン、ジビニルナフタリン、ジビニルエーテル等が挙げられる。
【００８７】
本発明において、前記単官能性重合性単量体を単独あるいは２種以上組み合わせて、また、単官能性重合性単量体と多官能性重合性単量体を組み合わせて使用することができる。また、前記多官能性重合性単量体を架橋剤として使用することも可能である。
【００８８】
上記した重合性単量体の重合の際に用いられる重合開始剤としては、油溶性開始剤及び／又は水溶性開始剤が用いられる。例えば、油溶性開始剤としては、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス−２，４−ジメチルバレロニトリル、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、２，２’−アゾビス−４−メトキシ−２，４−ジメチルバレロニトリルの如きアゾ化合物；アセチルシクロヘキシルスルホニルパーオキサイド、ジイソプロピルパーオキシカーボネート、デカノニルパーオキサイド、ラウロイルパーオキサイド、ステアロイルパーオキサイド、プロピオニルパーオキサイド、アセチルパーオキサイド、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ベンゾイルパーオキサイド、ｔ−ブチルパーオキシイソブチレート、シクロヘキサノンパーオキサイド、メチルエチルケトンパーオキサイド、ジクミルパーオキサイド、ｔ−ブチルヒドロパーオキサイド、ジ−ｔ−ブチルパーオキサイド、クメンヒドロパーオキサイドの如きパーオキサイド系開始剤が挙げられる。
【００８９】
水溶性開始剤としては、過硫酸アンモニウム、過硫酸カリウム、２，２’−アゾビス（Ｎ，Ｎ’−ジメチレンイソブチロアミジン）塩酸塩、２，２’−アゾビス（２−アミノジノプロパン）塩酸塩、アゾビス（イソブチルアミジン）塩酸塩、２，２’−アゾビスイソブチロニトリルスルホン酸ナトリウム、硫酸第一鉄又は過酸化水素が挙げられる。
【００９０】
重合開始剤は重合性単量体１００重量部に対して０．５〜２０重量部の添加量が好ましく、単独又は併用しても良い。
【００９１】
本発明において、重合法トナーを製造する際に用いる分散剤として例えば無機系酸化物として、リン酸三カルシウム，リン酸マグネシウム，リン酸アルミニウム，リン酸亜鉛，炭酸カルシウム，炭酸マグネシウム，水酸化カルシウム，水酸化マグネシウム，水酸化アルミニウム，メタケイ酸カルシウム，硫酸カルシウム，硫酸バリウム，ベントナイト，シリカ，アルミナ等が挙げられる。有機系化合物としては例えばポリビニルアルコール，ゼラチン，メチセルロース，メチルヒドロキシプロピルセルロース，エチルセルロース，カルボキシメチルセルロースのナトリウム塩，デンプン等が使用されてる。これら分散剤は、重合性単量体１００重量部に対して０．２〜２．０重量部を使用することが好ましい。
【００９２】
これら分散剤は、市販のものをそのまま用いても良いが、細かい均一な粒度を有する分散粒子を得るために、分散媒体中にて高速撹拌下にて該無機化合物を生成させることも出来る。例えば、リン酸三カルシウムの場合、高速撹拌下において、リン酸ナトリウム水溶液と塩化カルシウム水溶液を混合することで懸濁重合方法に好ましい分散剤を得ることが出来る。これら分散剤の微細化のため０．００１〜０．１重量％の界面活性剤を併用しても良い。具体的には市販のノニオン，アニオン，カチオン型の界面活性剤が利用できる。例えばドデシル硫酸ナトリウム，テトラデシル硫酸ナトリウム，ペンタデシル硫酸ナトリウム，オクチル硫酸ナトリウム，オレイン酸ナトリウム，ラウリル酸ナトリウム，ステアリン酸カリウム，オレイン酸カルシウム等が好ましく用いられる。
【００９３】
本発明の画像形成方法においては、種々の帯電方法を用いることができるが、帯電部材を感光体に当接させる接触帯電法も好適に使用される。その場合、一般のトナーを使った場合、クリーニングの後の残トナーが後工程である接触帯電部材に付着すると、帯電不良を引き起こし、画像上に帯電ムラが発生する。従って、帯電手段が感光体に接することのないコロナ放電等に比べて、カブリおよび残トナーの量は、より少なく、付着し難くする必要がある。従って、接触帯電法において用いられるトナーには、現像性が高く且つカブリの少ないという良好な帯電特性が求められる。さらには、高転写性を有していることが求められる。すなわち、接触帯電法においては、低結晶性または非晶性の芳香族化合物の金属塩、金属錯化合物、または、金属塩と金属錯化合物の混合物がトナー粒子表面に存在していることが重要であり、さらには円形度を厳密に規定したトナーを用いる必要がある。
【００９４】
本発明の画像形成方法における現像工程の条件としては、トナー担持体と感光体表面が接触していることが必須であり、より好ましくは反転現像方法を用いるということである。
【００９５】
トナー担持体としては、弾性ローラを用い、弾性ローラ表面等にトナーをコーティングし、これを感光体表面と接触させる方法も用いられる。この場合、トナーを介して感光体と感光体表面に対向する弾性ローラ間に働く電界によって現像されるので、弾性ローラ表面あるいは、表面近傍が電位をもち、感光体表面とトナー担持体表面の狭い間隙で電界を有する必要性がある。このため、弾性ローラの弾性ゴムが中抵抗領域に抵抗制御されて感光体表面との導通を防ぎつつ電界を保つか、または導電性ローラの表面層に薄層の絶縁層を設ける方法も利用できる。さらには、導電性ローラ上に感光体表面に対向する側を絶縁性物質により被覆した導電性樹脂スリーブあるいは、絶縁性スリーブで感光体に対向しない側に導電層を設けた構成も可能である。また、トナー担持体として剛体ローラを用い、感光体をベルトの如きフレキシブルな物とした構成も可能である。トナー担持体としての現像ローラの抵抗としては１０²〜１０⁹Ω・ｃｍの範囲が好ましい。
【００９６】
トナー担持体の表面形状としては、その表面粗度Ｒａ（μｍ）を０．２〜３．０となるように設定すると、高画質及び高耐久性を両立できる。表面粗度Ｒａはトナー搬送能力及びトナー帯電能力と相関する。トナー担持体の表面粗度Ｒａが３．０を超えると、トナー担持体上のトナー層の薄層化が困難となるばかりか、トナーの帯電性が改善されないので画質の向上は望めない。３．０以下にすることでトナー担持体表面のトナーの搬送能力を抑制し、トナー担持体上のトナー層を薄層化すると共に、トナー担持体とトナーの接触回数が多くなるため、トナーの帯電性も改善されるので相乗的に画質が向上する。一方、表面粗度Ｒａが０．２よりも小さくなると、トナーコート量の制御が難しくなる。
【００９７】
トナー担持体上にコートされるトナー量は、０．２〜３．０ｍｇ／ｃｍ²であることが好ましい。
【００９８】
本発明において、トナー担持体の表面粗度Ｒａは、ＪＩＳ表面粗さ「ＪＩＳ Ｂ ０６０１」に基づき、表面粗さ測定器（サーフコーダＳＥ−３０Ｈ、株式会社小坂研究所社製）を用いて測定される中心線平均粗さに相当する。具体的には、粗さ曲線からその中心線の方向に測定長さａとして２．５ｍｍの部分を抜き取り、この抜き取り部分の中心線をＸ軸、縦倍率の方向をＹ軸、粗さ曲線をｙ＝ｆ（ｘ）で表したとき、次式によって求められる値をミクロメートル（μｍ）で表したものを言う。
【００９９】
【数４】

【０１００】
本発明の画像形成方法においては、トナー担持体は感光体の周速同方向に回転していてもよいし、逆方向に回転していてもよい。その回転が同方向である場合、トナー担持体の周速を感光体の周速に対し１．０５〜３．０倍となるように設定することが好ましい。
【０１０１】
トナー担持体の周速が、感光体の周速に対し１．０５倍未満であると、感光体上のトナーの受ける撹拌効果が不十分となり、良好な画像品質が望めない。また、ベタ黒画像等、広い面積にわたって多くのトナー量を必要とする画像を現像する場合、静電潜像へのトナー供給量が不足し画像濃度が薄くなる。周速比が高まれば高まるほど、現像部位に供給されるトナーの量は多く、潜像に対しトナーの脱着頻度が多くなり、不要な部分は回収され必要な部分には付与されるという繰り返しにより、潜像に忠実な画像が得られる。但し、逆に周速比が３．０を超える場合には、上記の如きトナーの過剰な帯電によって引き起こされる種々の問題（トナーの過度なチャージアップによる画像濃度低下等）の他に、機械的ストレスによるトナーの劣化やトナー担持体へのトナー固着が発生、促進され、好ましくない。
【０１０２】
感光体としては、ａ−Ｓｅ、ＣｄＳ、ＺｎＯ₂、ＯＰＣ、ａ−Ｓｉの様な光導電絶縁物質層を持つ感光ドラムもしくは感光ベルトが好適に使用される。
【０１０３】
ＯＰＣ感光体における有機系感光層の結着樹脂は、ポリカーボネート樹脂、ポリエステル樹脂、アクリル系樹脂が特に転写性やクリーニング性がよく、クリーニング不良、感光体へのトナーの融着及び外添剤のフィルミングが起こりにくく、好ましい。
【０１０４】
次に本発明の画像形成方法を図３及び図４を参照しながら以下に説明する。
【０１０５】
図３において、１４０は現像装置、１００は感光体、１２７は紙などの被転写体（転写材）、１１４は転写部材、１２６は定着用加圧ローラー、１２８は定着用加熱ローラー、１１７は感光体１００に接触して直接帯電を行う一次帯電部材を示す。一次帯電部材１１７には、感光体１００表面を一様に帯電するようにバイアス電源１３１が接続されている。
【０１０６】
現像装置１４０はトナー１４２を収容しており、感光体１００と接触して矢印方向に回転するトナー担持体１０４を具備する。さらに、トナー量規制及び帯電付与のための現像ブレード１４３，トナー１４２をトナー担持体１０４に付着させ、かつトナー担持体１０４との摩擦でトナーヘの帯電付与を行うため矢印方向に回転する塗布ローラ１４１も備えている。トナー担持体１０４には現像バイアス電源１３３が接続されている。塗布ローラ１４１にもバイアス電源１３２が接続されており、負帯電性トナーを使用する場合は現像バイアスよりも負側に、正帯電性トナーを使用する場合は現像バイアスよりも正側に電圧が設定される。
【０１０７】
転写部材１１４には感光体１００と反対極性の転写バイアス電源１３４が接続されている。
【０１０８】
ここで、感光体１００とトナー担持体１０４の接触部分における回転方向の長さ、いわゆる現像ニップ幅は０．２ｍｍ以上８．０ｍｍ以下が好ましい。０．２ｍｍ未満では現像量が不足して満足な画像濃度が得られず、転写残トナーの回収も不十分となる。８．０ｍｍを超えてしまうと、トナーの供給量が過剰となり、カブリ抑制が悪化しやすく、また、感光体１００の摩耗にも悪影響を及ぼす。
【０１０９】
トナー担持体１０４としては、表面に弾性層を有する、いわゆる弾性ローラが好ましく用いられる。
【０１１０】
使用される弾性層の材料の硬度としては、２０〜６５度（アスカＣ）のものが好適に使用される。
【０１１１】
また、トナー担持体１０４の抵抗としては、体積抵抗値で１０²〜１０⁹Ω・ｃｍ程度の範囲が好ましい。１０²Ω・ｃｍよりも低い場合、例えば感光体１００の表面にピンホール等がある場合、過電流が流れる恐れがある。反対に１０⁹Ω・ｃｍよりも高い場合は、摩擦帯電によるトナーのチャージアップが起こりやすく、画像濃度の低下を招きやすい。
【０１１２】
トナー担持体１０４上のトナーコート量は、０．ｌｍｇ／ｃｍ²以上２．０ｍｇ／ｃｍ²以下が好ましい。０．ｌｍｇ／ｃｍ²よりも少ないと十分な画像濃度が得にくく、２．０ｍｇ／ｃｍ²よりも多くなると個々のトナー粒子全てを均一に摩擦帯電することが難しくなり、カブリ抑制の悪化の要因となる。さらに、０．２ｍｇ／ｃｍ²以上１．２ｍｇ／ｃｍ²以下がより好ましい。
【０１１３】
トナーコート量は現像ブレード１４３により制御されるが、この現像ブレード１４３はトナー層を介してトナー担持体１０４に接触している。この時の接触圧は、５ｇ／ｃｍ以上５０ｇ／ｃｍ以下が好ましい範囲である。５ｇ／ｃｍよりも小さいとトナーコート量の制御に加え均一な摩擦帯電も難しくなり、カブリ抑制の悪化等の原因となる。一方、５０ｇ／ｃｍよりも大きくなるとトナー粒子が過剰な負荷を受けるため、粒子の変形や現像ブレード１４３あるいはトナー担持体１０４へのトナーの融着等が発生しやすくなり、好ましくない。
【０１１４】
トナーコート量の規制部材としては、トナーを圧接塗布するための弾性ブレード以外にも、金属ブレードあるいはローラ等を用いても良い。
【０１１５】
弾性の規制部材には、所望の極性にトナーを帯電させるのに適した摩擦帯電系列の材質を選択することが好ましく、シリコーンゴム、ウレタンゴム、ＮＢＲの如きゴム弾性体、ポリエチレンテレフタレートの如き合成樹脂弾性体、ステンレス、銅、リン青銅の如き金属弾性体が使用できる。また、それらの複合体であっても良い。
【０１１６】
また、弾性の規制部材とトナー担持体に耐久性が要求される場合には、金属弾性体に樹脂やゴムをスリーブ当接部に当たるように貼り合わせたり、コーティング塗布したものが好ましい。
【０１１７】
更に、弾性の規制部材中に有機物や無機物を添加してもよく、溶融混合させても良いし、分散させても良い。例えば、金属酸化物、金属粉、セラミックス、炭素同素体、ウィスカー、無機繊維、染料、顔料、界面活性剤などを添加することにより、トナーの帯電性をコントロールできる。特に、弾性体がゴムや樹脂等の成型体の場合には、シリカ、アルミナ、チタニア、酸化錫、酸化ジルコニア、酸化亜鉛等の金属酸化物微粉末、カーボンブラック、一般にトナーに用いられる荷電制御剤等を含有させることも好ましい。
【０１１８】
またさらに、規制部材に直流電場及び／または交流電場を印加することによっても、トナーヘのほぐし作用のため、均一薄層塗布性、均一帯電性がより向上し、充分な画像濃度の達成及び良質の画像を得ることができる。
【０１１９】
図３において、一次帯電部材１１７は矢印方向に回転する感光体１００を一様に帯電する。
【０１２０】
ここで用いている一次帯電部材は、中心の芯金１１７ｂとその外周を形成した導電性弾性層１１７ａとを基本構成とする帯電ローラである。帯電ローラ１１７は、静電潜像担持体一面に押圧力を持って当接され、感光体１００の回転に伴い従動回転する。
【０１２１】
帯電ローラ１１７を用いたときの好ましいプロセス条件としては、ローラの当接圧が５〜５００ｇ／ｃｍであり、印加電圧としては直流電圧あるいは直流電圧に交流電圧を重畳したもの等が用いられ、特に限定されないが、本発明においては直流電圧のみの印加電圧が好適に用いられ、この場合の電圧値としては±０．２〜±５ｋＶの範囲で使用される。
【０１２２】
この他の帯電手段としては、帯電ブレードを用いる方法や、導電性ブラシを用いる方法がある。これらの接触帯電手段は、非接触のコロナ帯電に比べて、高電圧が不必要になったり、オゾンの発生が低減するといった効果がある。接触帯電手段としての帯電ローラおよび帯電ブレードの材質としては、導電性ゴムが好ましく、その表面に離型性被膜を設けても良い。離型性被膜としては、ナイロン系樹脂、ＰＶＤＦ（ポリフッ化ビニリデン）、ＰＶＤＣ（ポリ塩化ビニリデン）などが適用可能である。
【０１２３】
一次帯電工程に次いで、発光素子１２１からの露光１２３によって感光体１００上に情報信号に応じた静電潜像を形成し、トナー担持体１０４と当接する位置においてトナーにより静電潜像を現像し可視像化する。さらに、本発明の画像形成方法において、特に感光体上にデジタル潜像を形成した現像システムと組み合わせることで、潜像を乱さないためにドット潜像に対して忠実に現像することが可能となる。次に、該可視像を転写部材１１４により被転写体１２７上に転写する。転写を感光体１００の表面は、クリーニング装置１１３により清掃される。なお、クリーニング装置１１３はトナーの転写効率が高い場合は無くてもよく、この場合は、現像時あるいは現像後の空白時に、直流あるいは交流成分のバイアスを印加し、現像と感光体上の残余トナーを回収できるように制御を行う。次に、転写トナー１２９は被転写体１２７と共に定着用加圧ローラー１２６と定着用加圧ローラー１２８の間を通過して定着され、永久画像を得る。なお、加熱加圧定着手段としては、ここに示したハロゲンヒーター等の発熱体を内蔵した加熱ローラーとこれと押圧力をもって圧接された弾性体の加圧ローラーを基本構成とする熱ローラー方式以外に、フィルムを介してヒーターにより加熱定着する方式も用いられる。
【０１２４】
一方、転写されずに感光体１００上に残った転写残トナーは、感光体１００と一次帯電部材１１７の間を通過して、再び現像ニップ部に到達し、トナー担持体１０４によって現像器１４０内に回収される。
【０１２５】
次に、中間転写ベルトを用いた画像形成方法について図５を用いて説明する。
【０１２６】
図５は、電子写真プロセスを利用したカラー画像形成装置（複写機あるいはレーザービームプリンター）の概略的説明図である。
【０１２７】
１は第１の画像担持体としてのドラム状の電子写真感光体であり、矢印の方向に所定の周速度（プロセススピード）で回転駆動される。
【０１２８】
感光ドラム１は回転過程で、一次帯電器２により所定の極性・電位に一様に帯電処理され、次いで不図示の像露光手段３による露光を受ける。このようにして目的のカラー画像の第１の色成分像（例えばイエロー色成分像）に対応した静電潜像が形成される。
【０１２９】
次いで、その静電潜像が第１の現像器（イエロー色現像器４１）により第１色であるイエロー成分像に現像される。この時第２〜第４の現像器、即ちマゼンタ現像器４２、シアン色現像器４３、およびブラック色現像器４４は作動しておらず、感光ドラム１には作用していないので、上記第１色のイエロー成分画像は上記第２〜第４の現像器による影響を受けない。
【０１３０】
中間転写ベルト２０は矢印の方向に回転駆動される。
【０１３１】
感光体１上に形成された上記第１色のイエロー成分像が、感光体１と中間転写ベルト２０とのニップ部を通過する過程で、一次転写ローラ６２を介してバイアス電源２９から中間転写ベルト２０に印加される一次転写バイアスによって形成される電界により、中間転写ベルト２０の外周面に順次転写（一次転写）されていく。
【０１３２】
中間転写ベルト２０に対応する第１色のイエロートナー画像の転写を終えた感光ドラム１の表面は、クリーニング装置１３により清掃される。
【０１３３】
以下、同様に第２色のマゼンタトナー画像、第３色のシアントナー画像、第４色のブラックトナー画像が順次中間転写ベルト２０上に重ね合わせて転写され、目的のカラー画像に対応した合成カラートナー画像が形成される。
【０１３４】
６３は二次転写ローラで、二次転写対向ローラ６４に対応し平行に軸受させて中間転写ベルト２０の下面部に離間可能な状態に配設してある。
【０１３５】
トナー画像を感光ドラム１から中間転写ベルト２０へ転写するための一次転写バイアスは、トナーとは逆極性でバイアス電源２９から印加される。その印加電圧は例えば＋１００Ｖ〜＋２ｋＶの範囲である。
【０１３６】
感光ドラム１から中間転写ベルト２０への第１〜第３色のトナー画像の一次転写工程において、二次転写ローラ６３及び転写残トナー帯電部材５２は中間転写ベルト２０から離間することも可能である。
【０１３７】
中間転写ベルト２０上に転写されたフルカラー画像は、二次転写ローラ６３が中間転写ベルト２０に当接され、給紙ローラ１１から中間転写ベルト２０と二次転写ローラ６３との当接部分に所定のタイミングで第２の画像担持体である転写材Ｐが給送され、二次転写バイアスがバイアス電源２８から二次転写ローラ６３に印加されることにより転写材Ｐに二次転写される。トナー画像が転写された転写材Ｐは、定着器１５へ導入され加熱定着される。
【０１３８】
転写材Ｐへの画像転写終了後、中間転写ベルト２０には転写残トナークリーニング装置５０が当接され、中間転写ベルト２０の表面が清掃される。
【０１３９】
転写材Ｐへの画像転写終了後、中間転写ベルト２０には転写残トナー帯電部材５２が当接され、感光ドラム１とは逆極性のバイアスを印加することにより、転写材Ｐに転写されずに中間転写ベルト２０上に残留しているトナー（転写残トナー）に感光ドラム１と逆極性の電荷が付与される。
【０１４０】
前記転写残トナーは、感光ドラム１との当接部およびその近傍において感光ドラム１に静電的に転写されることにより、中間転写ベルト２０がクリーニングされる。
【０１４１】
【実施例】
以下、実施例をもって本発明を説明するが、これらは本発明をなんら制限するものではない。
【０１４２】
トナーの製造例１
高速撹拌装置ＴＫ−ホモミキサーを備えた２リットル用四つ口フラスコ中に、イオン交換水９１０重量部と０．１モル／リットル−Ｎａ₃ＰＯ₄水溶液４５０重量部を添加し、回転数を１５０００ｒｐｍに調整し、６０℃に加温せしめた。ここに１．０モル／リットル−ＣａＣｌ₂水溶液６８重量部を徐々に添加し微小な難水溶性分散剤Ｃａ₃（ＰＯ₄）₂を含む分散媒系を調製した。
・スチレン単量体 １６０重量部
・ｎ−ブチルアクリレート単量体 ４０重量部
・カーボンブラック ４重量部
・離型剤 ８重量部
・スチレン−ブタジエン共重合体樹脂 １０重量部
・結晶性のアゾ系鉄錯化合物Ａ ４重量部
上記混合物をアトライターを用い３時間分散させた後、重合開始剤である２，２’−アゾビス（２，４−ジメチルバレロニトリル）４重量部を添加した分散物（重合性単量体組成物）を、前記分散媒中に投入し回転数を維持しつつ１０分間造粒した。その後高速撹拌器からプロペラ撹拌羽根に撹拌器を変え、２００ｒｐｍ，６０℃で５時間重合を行い、その後内温を８０℃に昇温させ５時間重合を継続した。
【０１４３】
重合終了後スラリーを冷却し、希塩酸を添加し分散剤を除去せしめた。
【０１４４】
更に洗浄し乾燥を行うことで重量平均粒径が７．３μｍであり、平均円形度が０．９８１であり、円形度標準偏差が０．０２６の黒色粒子（トナー粒子）１を得た。
【０１４５】
得られたトナー粒子１ １００重量部に対して、非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂを０．１重量部加え、ヘンシェルミキサーにて撹拌羽根の周速を５０ｍ／ｓｅｃとし、温度４５℃未満で５分間混合した後、平均粒径が１０ｎｍの疎水化処理シリカ１．５重量部と、平均粒径が０．５μｍの樹脂（ポリメチルメタクリレート）微粒子０．５重量部を外添しトナーＡを得た。得られたトナーＡは、重量平均粒径が７．３μｍであり、平均円形度が０．９８１であり、円形度標準偏差が０．０２６であった。
【０１４６】
非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂを０．１重量部加え、ヘンシェルミキサーにて５分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行うと、トナー粒子表面の非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂは、粒状態ではなく、均一にトナー粒子表面を被覆していることが確認された。
【０１４７】
上記のジアルキルサリチル酸のアルミニウム錯化合物Ｂは、Ａｌ₂（ＳＯ₄）₃水溶液に、ジアルキルサリチル酸のアルカリ水溶液をＡｌ₂（ＳＯ₄）₃ １モルに対してジアルキルサリチル酸が２．６モルとなるように添加し、撹拌して反応させ、反応物を濾別、温水、洗浄、乾燥することにより得られたものである。
【０１４８】
このジアルキルサリチル酸のアルミニウム錯化合物Ｂは、Ｘ線回折測定において、測定角２θが６乃至４０ｄｅｇｒｅｅの範囲に、測定強度が１００００ｃｐｓ以上であり、且つ半値半幅が０．３ｄｅｇｒｅｅ以下であるピークを有していないことを確認した。
【０１４９】
また、アゾ系鉄錯化合物Ａは、Ｘ線回折測定において、測定強度が最大のピークとして、２θ＝１３．６ｄｅｇｒｅｅに測定強度が１５０００ｃｐｓであり、半値半幅＝０．１３のピークを有しており、結晶性物質であることを確認した。
【０１５０】
トナーの製造例２
高速撹拌装置ＴＫ−ホモミキサーを備えた２リットル用四つ口フラスコ中に、イオン交換水９１０重量部と０．１モル／リットル−Ｎａ₃ＰＯ₄水溶液４５０重量部を添加し、回転数を１５０００ｒｐｍに調整し、６０℃に加温せしめた。ここに１．０モル／リットル−ＣａＣｌ₂水溶液６８重量部を徐々に添加し微小な難水溶性分散剤Ｃａ₃（ＰＯ₄）₂を含む分散媒系を調製した。
・スチレン単量体 １６０重量部
・ｎ−ブチルアクリレート単量体 ４０重量部
・カーボンブラック ４重量部
・離型剤 ８重量部
・ポリエステル樹脂 ４重量部
・結晶性のアゾ系クロム錯化合物Ｃ ４重量部
上記混合物をアトライターを用い３時間分散させた後、重合開始剤である２，２’−アゾビス（２，４−ジメチルバレロニトリル）４重量部を添加した分散物（重合性単量体組成物）を、前記分散媒中に投入し回転数を維持しつつ１０分間造粒した。その後高速撹拌器からプロペラ撹拌羽根に撹拌器を変え、２００ｒｐｍ，６０℃で５時間重合を行ない、その後内温を８０℃に昇温させ５時間重合を継続した。
【０１５１】
重合終了後スラリーを冷却し、希塩酸を添加し分散剤を除去せしめた。
【０１５２】
更に洗浄し乾燥を行うことで重量平均粒径が７．６μｍであり、平均円形度が０．９８２であり、円形度標準偏差が０．０２５の黒色粒子（トナー粒子）２を得た。
【０１５３】
得られたトナー粒子２ １００重量部に対して、非晶性のジアルキルサリチル酸のジルコニウム錯化合物Ｄを０．３重量部加え、ヘンシェルミキサーにて撹拌羽根の周速を３５ｍ／ｓｅｃとし、温度４５℃未満で９分間混合した後、平均粒径が１０ｎｍの疎水化処理シリカ１．５重量部と、平均粒径が０．５μｍの樹脂微粒子０．５重量部を外添しトナーＢを得た。得られたトナーＢの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１５４】
非晶性のジアルキルサリチル酸のジルコニウム錯化合物Ｄを０．３重量部加え、ヘンシェルミキサーにて９分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行うと、トナー粒子表面の非晶性のジアルキルサリチル酸のジルコニウム錯化合物Ｄは、粒状態ではなく、均一にトナー粒子表面を被覆していることが確認された。
【０１５５】
このジアルキルサリチル酸のジルコニウム錯化合物Ｄは、Ｘ線回折測定において、測定角２θが６乃至４０ｄｅｇｒｅｅの範囲に、測定強度が１００００ｃｐｓ以上であり、且つ半値半幅が０．３ｄｅｇｒｅｅ以下であるピークを有していないことを確認した。
【０１５６】
また、アゾ系クロム錯化合物Ｃは、図２に示すように、Ｘ線回折測定において、測定強度が最大のピークとして、２θ＝８．７２ｄｅｇｒｅｅに測定強度が４１０００ｃｐｓであり、半値半幅＝０．１４のピークを有しており、結晶性物質であることを確認した。
【０１５７】
トナーの製造例３
トナーの製造例１において、外部添加した非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂに代えて、非晶性のジアルキルサリチル酸のジルコニウム錯化合物Ｄを用いたことを除いては全てトナーの製造例１と同様にしてトナーＣを得た。得られたトナーＣの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１５８】
非晶性のジアルキルサリチル酸のジルコニウム錯化合物Ｄを０．１重量部加え、ヘンシェルミキサーにて５分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行うと、トナー粒子表面の非晶性のジアルキルサリチル酸のジルコニウム錯化合物Ｄは、粒状態ではなく、均一にトナー粒子表面を被覆していることが確認された。
【０１５９】
トナーの製造例４
トナーの製造例１において、外部添加した非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂの添加量を０．０１重量部に変えたことを除いては全てトナーの製造例１と同様にしてトナーＤを得た。得られたトナーＤの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１６０】
非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂを０．０１重量部加え、ヘンシェルミキサーにて５分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行うと、トナー粒子表面の非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂは、粒状態ではなく、均一にトナー粒子表面を被覆していることが確認された。
【０１６１】
トナーの製造例５
トナーの製造例１において、外部添加した非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂの添加量を０．００５重量部に変えたことを除いては全てトナーの製造例１と同様にしてトナーＥを得た。得られたトナーＥの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１６２】
非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂを０．００５重量部加え、ヘンシェルミキサーにて５分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行うと、トナー粒子表面の非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂは、粒状態ではなく、均一にトナー粒子表面を被覆していることが確認された。
【０１６３】
トナーの製造例６
トナーの製造例１において、外部添加した非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂの添加量を０．５重量部に変えたことを除いては全てトナーの製造例１と同様にしてトナーＦを得た。得られたトナーＦの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１６４】
非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂを０．５重量部加え、ヘンシェルミキサーにて５分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行うと、トナー粒子表面の非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂは、粒状態ではなく、均一にトナー粒子表面を被覆していることが確認された。
【０１６５】
トナーの製造例７
トナーの製造例１において、外部添加した非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂの添加量を０．７重量部に変えたことを除いては全てトナーの製造例１と同様にしてトナーＧを得た。得られたトナーＧの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１６６】
非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂを０．７重量部加え、ヘンシェルミキサーにて５分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行うと、トナー粒子表面の非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂは、粒状態ではなく、均一にトナー粒子表面を被覆していることが確認された。
【０１６７】
トナーの製造例８
・ポリエステル樹脂 １００重量部
・カーボンブラック ４重量部
・離型剤 ４重量部
・非晶性のジアルキルサリチル酸のジルコニウム錯化合物Ｄ ６重量部
上記物質をヘンシェルミキサーにより十分予備混合を行い、二軸押出混練機により約１４０℃の温度で溶融混練し、冷却後ハンマーミルを用いて約１〜２ｍｍ程度に粗粉砕し、ついでエアージェット方式による微粉砕機で微粉砕した。さらに得られた微粉砕物を分級して、重量平均径が８．４μｍ、平均円形度が０．９５２、円形度標準偏差が０．０４５の黒色粒子３を得た。
【０１６８】
得られた黒色粒子３をハイブリタイザーを用い、４０００ｒｐｍで３分間表面処理を行い、平均円形度が０．９６３であり、円形度標準偏差が０．０３６の黒色粒子（トナー粒子）４を得た。
【０１６９】
得られたトナー粒子４ １００重量部に対し、非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂを０．１重量部加え、ヘンシェルミキサーにて撹拌羽根の周速を５０ｍ／ｓｅｃとし、温度４５℃未満で５分間混合した後、平均粒径が１２ｎｍの疎水化処理シリカ１．０重量部と、平均粒径が０．５μｍの樹脂微粒子０．３重量部を外添しトナーＨを得た。得られたトナーＨの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１７０】
非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂを０．１重量部加え、ヘンシェルミキサーにて５分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行うと、トナー粒子表面の非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂは、粒状態ではなく、均一にトナー粒子表面を被覆していることが確認された。
【０１７１】
トナーの製造例９
トナーの製造例１において、外部添加した樹脂微粒子の平均粒径を１．０μｍに変更したことを除いては全てトナーの製造例１と同様にしてトナーＩを得た。得られたトナーＩの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１７２】
トナーの製造例１０
トナーの製造例１において、平均粒径が０．５μｍの樹脂微粒子を外添しないことを除いては全てトナーの製造例１と同様にしてトナーＪを得た。得られたトナーＪの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１７３】
トナーの製造例１１
トナーの製造例２において、トナー粒子２の製造時に、結晶性のアゾ系クロム錯化合物Ｃを添加しなかったことを除いては全てトナーの製造例２と同様にしてトナー粒子５を製造し、同様にしてトナーＫを得た。得られたトナーＫの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１７４】
非晶性のジアルキルサリチル酸のジルコニウム錯化合物Ｄを０．３重量部加え、ヘンシェルミキサーにて９分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行うと、トナー粒子表面の非晶性のジアルキルサリチル酸のジルコニウム錯化合物Ｄは、粒状態ではなく、均一にトナー粒子表面を被覆していることが確認された。
【０１７５】
トナーの製造例１２
トナーの製造例２において、外部添加した非晶性のジアルキルサリチル酸のジルコニウム錯化合物Ｄを非晶性のジアルキルサリチル酸のクロム錯化合物Ｅに変更したことを除いては全てトナーの製造例２と同様としてトナーＬを得た。得られたトナーＬの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１７６】
非晶性のジアルキルサリチル酸のクロム錯化合物Ｅを０．３重量部加え、ヘンシェルミキサーにて９分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行ったところ、非晶性のジアルキルサリチル酸のクロム錯化合物Ｅは、粒状態ではなく、トナー粒子表面を被覆しているものの、非被覆部が点在していることが確認された。
【０１７７】
このジアルキルサリチル酸のクロム錯化合物Ｅは、図１に示すように、Ｘ線回折測定において、測定角２θが６乃至４０ｄｅｇｒｅｅの範囲に、２θ＝１４．３２ｄｅｇｒｅｅに測定強度４３００ｃｐｓのピークが測定され、このピークは、半値半幅が約４であり、よって、測定角２θが６乃至４０ｄｅｇｒｅｅの範囲に、測定強度が１００００ｃｐｓ以上であり、且つ半値半幅が０．３ｄｅｇｒｅｅ以下であるピークを有していないことを確認した。
【０１７８】
トナーの製造例１３
トナーの製造例２で得られたトナー粒子２ １００重量部に対し、非晶性のジアルキルサリチル酸のクロム錯化合物Ｅを０．３重量部、平均粒径が１０ｎｍの疎水化処理シリカを１．５重量部、平均粒径が０．５μｍの樹脂微粒子を０．５重量部それぞれ同時にヘンシェルミキサーにて撹拌羽根の周速を３５ｍ／ｓｅｃとし、温度４５℃未満で９分間混合することにより外添し、トナーＭを得た。得られたトナーＭの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１７９】
外添後のトナーを１万倍及び３万倍でＳＥＭ観察を行ったところ、非晶性のジアルキルサリチル酸のクロム錯化合物Ｅの一部はトナー粒子表面を被覆しており、一部は遊離していた。
【０１８０】
トナーの製造例１４
高速撹拌装置ＴＫ−ホモミキサーを備えた２リットル用四つ口フラスコ中に、イオン交換水９１０重量部と０．１モル／リットル−Ｎａ₃ＰＯ₄水溶液４５０重量部を添加し、回転数を１２０００ｒｐｍに調整し、６０℃に加温せしめた。ここに１．０モル／リットル−ＣａＣｌ₂水溶液６８重量部を徐々に添加し微小な難水溶性分散剤Ｃａ₃（ＰＯ₄）₂を含む分散媒系を調製した。
・スチレン単量体 １６０重量部
・ｎ−ブチルアクリレート単量体 ４０重量部
・イエロー顔料（Ｃ．Ｉ．ピグメントイエロー１７） ２０重量部
・離型剤 ３０重量部
・ポリエステル樹脂 ２０重量部
・非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂ ２重量部
上記混合物をアトライターを用い３時間分散させた後、重合開始剤である２，２’−アゾビス（２，４−ジメチルバレロニトリル）４重量部を添加した分散物（重合性単量体組成物）を、前記分散媒中に投入し回転数を維持しつつ１０分間造粒した。その後高速撹拌器からプロペラ撹拌羽根に撹拌器を変え、２００ｒｐｍ，６０℃で５時間重合を行い、その後内温を８０℃に昇温させ５時間重合を継続した。
【０１８１】
重合終了後スラリーを冷却し、希塩酸を添加し分散剤を除去せしめた。
【０１８２】
更に洗浄し乾燥を行うことで重量平均粒径が７．２μｍであり、平均円形度が０．９７９であり、円形度標準偏差が０．０３０のイエローの着色粒子（トナー粒子）６を得た。
【０１８３】
得られたイエローのトナー粒子６ １００重量部に対して、非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂを０．０５重量部加え、ヘンシェルミキサーにて撹拌羽根の周速を５０ｍ／ｓｅｃとし、温度４５℃未満で５分間混合した後、平均粒径が１０ｎｍの疎水化処理シリカ１．５重量部と、平均粒径が０．０４μｍの疎水化処理シリカ０．５重量部を外添しトナーＮを得た。得られたトナーＮの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１８４】
非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂを０．０５重量部加え、ヘンシェルミキサーにて５分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行うと、トナー粒子表面の非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂは、粒状態ではなく、均一にトナー粒子表面を被覆していることが確認された。
【０１８５】
トナーの比較製造例１
トナーの製造例２において、外部添加の非晶性のジアルキルサリチル酸のジルコニウム錯化合物Ｄを添加しなかったことを除いては全てトナーの製造例２と同様にしてトナーＯを得た。得られたトナーＯの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１８６】
トナーの比較製造例２
トナーの製造例２で得られたトナー粒子２ １００重量部に対し、結晶性のアルキルサリチル酸の亜鉛錯化合物Ｆを０．３重量部添加し、ヘンシェルミキサーにて撹拌羽根の周速を３５ｍ／ｓｅｃとし、温度４５℃未満で９分間混合した後、平均粒径が１０ｎｍの疎水化処理シリカ１．５重量部と、平均粒径が０．５μｍの樹脂微粒子０．５重量部を外添しトナーＰを得た。得られたトナーＰの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１８７】
結晶性のアルキルサリチル酸の亜鉛錯化合物Ｆを０．３重量部加え、ヘンシェルミキサーにて９分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行ったところ、トナー粒子表面に結晶性のアルキルサリチル酸の亜鉛錯化合物Ｆが不均一に埋め込められており、結晶性のアルキルサリチル酸の亜鉛錯化合物Ｆがトナー表面を被覆していないことが確認された。
【０１８８】
なお、アルキルサリチル酸の亜鉛錯化合物Ｆは、Ｘ線回折測定において、測定強度が最大のピークとして、２θ＝６．５８ｄｅｇｒｅｅに測定強度が８００００ｃｐｓであり、半値半幅＝０．２１のピークを有しており、結晶性物質であることを確認した。
【０１８９】
トナーの比較製造例３
トナーの製造例２で得られたトナー粒子２ １００重量部に対し、結晶性のアゾ系クロム錯化合物Ｃを０．３重量部添加し、ヘンシェルミキサーにて撹拌羽根の周速を３５ｍ／ｓｅｃとし、温度４５℃未満で９分間混合した後、平均粒径が１０ｎｍの疎水化処理シリカ１．５重量部と、平均粒径が０．５μｍの樹脂微粒子０．５重量部を外添しトナーＱを得た。得られたトナーＱの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１９０】
結晶性のアゾ系クロム錯化合物Ｃを０．３重量部加え、ヘンシェルミキサーにて５分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行ったところ、トナー粒子表面に結晶性のアゾ系クロム錯化合物Ｃが不均一に埋め込められており、結晶性のアゾ系クロム錯化合物Ｃがトナー粒子表面を被覆していないことが確認された。
【０１９１】
トナーの比較製造例４
トナーの製造例１１において、外部添加した非晶性のジアルキルサリチル酸のジルコニウム錯化合物Ｄの代わりに結晶性のアゾ系クロム錯化合物Ｃを０．３重量部添加したこと以外は全てトナーの製造例１１と同様にしてトナーＲを得た。得られたトナーＲの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１９２】
結晶性のアゾ系クロム錯化合物Ｃを０．３重量部加え、ヘンシェルミキサーにて９分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行ったところ、トナー粒子表面に結晶性のアゾ系クロム錯化合物Ｃが不均一に埋め込められており、結晶性のアゾ系クロム錯化合物Ｃがトナー粒子表面を被覆していないことが確認された。
【０１９３】
トナーの比較製造例５
トナー粒子として、トナーの製造例８で得られた黒色粒子３ １００重量部に対し、非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂを０．１重量部加え、ヘンシェルミキサーにて撹拌羽根の周速を５０ｍ／ｓｅｃとし、温度４５℃未満で５分間混合した後、平均粒径が１２ｎｍの疎水化処理シリカ１．０重量部と、平均粒径が０．５μｍの樹脂微粒子０．３重量部を外添しトナーＳを得た。得られたトナーＳの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１９４】
非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂを０．１重量部加え、ヘンシェルミキサーにて５分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行うと、非晶性のジアルキルサリチル酸のアルミニウム錯化合物Ｂがトナー粒子の凹部を被覆していないことが確認された。
【０１９５】
トナーの比較製造例６
トナーの製造例１４で得られたイエローのトナー粒子６ １００重量部に対し、結晶性のアルキルサリチル酸の亜鉛錯化合物Ｆを０．０５重量部添加し、ヘンシェルミキサーにて撹拌羽根の周速を５０ｍ／ｓｅｃとし、温度４５℃未満で５分間混合した後、平均粒径が１０ｎｍの疎水化処理シリカ１．５重量部と、平均粒径が０．５μｍの樹脂微粒子０．５重量部を外添しトナーＴを得た。得られたトナーＴの重量平均粒径、平均円形度及び円形度標準偏差を表１に示す。
【０１９６】
結晶性のアルキルサリチル酸の亜鉛錯化合物Ｆを０．０５重量部加え、ヘンシェルミキサーにて５分間混合した後のトナー粒子を１万倍及び３万倍でＳＥＭ観察を行ったところ、トナー粒子表面に結晶性のアルキルサリチル酸の亜鉛錯化合物Ｆが不均一に埋め込められており、結晶性のアルキルサリチル酸の亜鉛錯化合物Ｆがトナー粒子表面を被覆していないことが確認された。
【０１９７】
【表１】

【０１９８】
［実施例１〜８、参考例１〜５及び比較例１〜５］
図３および４のような構成を有する電子写真装置として６００ｄｐｉレーザービームプリンタ（キヤノン製：ＬＢＰ−８６０）を用意した。プロセススピードは、６０ｍｍ／ｓに改造してある。
【０１９９】
この装置の帯電方式をゴムローラを当接して行う直接帯電とし、印加電圧を直流成分（−１２００Ｖ）とした。
【０２００】
次に、プロセスカートリッジにおける現像部分を改造した。トナー供給体であるステンレススリーブの代わりに、カーボンブラックを分散したシリコーンゴムからなる中抵抗ゴムローラ（１６φ、硬度ＡＳＫＥＲ Ｃ４５度、抵抗１０⁵Ω・ｃｍ）をトナー担持体とし、感光体に当接した。この時の現像ニップ幅は約３ｍｍとなるようにした。該トナー担持体の回転周速は、感光体との接触部分において同方向であり、該感光体回転周速に対し１４０％となるように駆動する。
【０２０１】
ここで用いる感光体としては、３０φ，２５４ｍｍのＡｌシリンダーを基体としたもので、これに、以下に示すような構成の層を順次浸漬塗布により積層して、感光体を作製した。
（１）導電性被覆層：酸化錫及び酸化チタンの粉末をフェノール樹脂に分散したものを主体とする。膜厚１５μｍ。
（２）下引き層：変性ナイロン、及び共重合ナイロンを主体とする。膜厚０．６μｍ。
（３）電荷発生層：長波長域に吸収を持つチタニルフタロシアニン顔料をブチラール樹脂に分散したものを主体とする。膜厚０．６μｍ。
（４）電荷輸送層：ホール搬送性トリフェニルアミン化合物をポリカーボネート樹脂（オストワルド粘度法による分子量２万）に８：１０の重量比で溶解したものを主体とする。膜厚２０μｍ。
【０２０２】
トナー担持体にトナーを塗布する手段として、現像器内に発泡ウレタンゴムからなる塗布ローラを設け、該トナー担持体に当接させた。塗布ローラには、約−５５０Ｖの電圧を印加する。さらに、該トナー担持体上トナーのコート層制御のために樹脂をコートしたステンレス製ブレードを、トナー担持体との接触圧が線圧約２０ｇ／ｃｍとなるように取付けた。概略を図４に示す。また、現像時の印加電圧をＤＣ成分（−４５０Ｖ）のみとした。
【０２０３】
これらのプロセスカートリッジの改造に適合するよう電子写真装置に以下のように改造及びプロセス条件設定を行った。
【０２０４】
改造された装置はローラ帯電器（直流のみを印加）を用い像担持体を一様に帯電する。帯電に次いで、レーザー光で画像部分を露光することにより静電潜像を形成し、トナーにより可視画像とした後に、電圧を＋７００Ｖ印加したローラによりトナー像を転写材に転写するプロセスを持つ。概略を図３に示した。
【０２０５】
また、感光体帯電電位は、暗部電位を−５８０Ｖとし、明部電位を−１５０Ｖとした。転写材としては、７５ｇ／ｍ²の紙を用いた。
【０２０６】
トナーＡ〜Ｍ及びトナーＯ〜Ｓを用いて、上記画像形成装置により常温常湿環境下（２３℃，６５％ＲＨ）において７０００枚の画出し試験を行った。なお、耐久性評価は以下のように評価した。
【０２０７】
＜転写効率＞
転写効率は、ベタ黒画像転写後の感光体上の転写残トナーをマイラーテープによりテーピングしてはぎ取り、紙上に貼ったもののマクベス濃度の値をＣ、転写後定着前のトナーの載った紙上にマイラーテープを貼ったもののマクベス濃度をＤ、未使用の紙上に貼ったマイラーテープのマクベス濃度をＥとしたとき、近似的に以下の式で計算した。
【０２０８】
【数５】

【０２０９】
転写効率は、以下の基準で評価を行った。
◎：転写効率が９６％以上
○：転写効率が９２％から９５％
△：転写効率が８８％から９１％
×：転写効率が８７％以下
【０２１０】
＜画質＞
画質の判断基準は以下の通りである。
◎：非常に良好。
○：わずかにがさついているものの、良好な画像。
△：がさついているものの、実用上問題の無いレベル。
×：がさつきがひどい。
【０２１１】
＜カブリ＞
紙上カブリの測定は、反射濃度計（東京電色社製のＲＥＦＬＥＣＴＯＭＥＴＥＲ ＭＯＤＥＬ ＴＣ−６ＤＳ）を使用して測定し、黒トナー画像では、Ｇｒｅｅｎフィルターを使用し、後述する実施例１５におけるイエロートナー画像ではｂｌｕｅフィルターを使用し、下記式より算出した。数値が小さい程、カブリが少ない。
【０２１２】
カブリ（反射率）（％）＝〔標準紙の反射率（％）〕−〔サンプルの白地部の反射率（％）〕
【０２１３】
なお、カブリの評価は、ベタ白画像を初期から７０００枚の連続画出し試験時に１０００枚ごとに画像を形成した紙をサンプリングし、サンプリングした画像についてカブリの測定を行う。カブリの測定は、画像の４隅と中央部の５ケ所について測定を行い、５点の平均値を紙上カブリとする。
【０２１４】
画出し初期のカブリの評価基準は、以下の通りである。
◎：カブリの平均が３％以下
○：カブリの平均が５％以下
△：カブリの平均が５％を超える
×：測定点全てにおいてカブリが５％を超える
【０２１５】
画出し耐久後のカブリの評価基準は、以下の通りである。
◎：耐久全般でカブリが３％以下
○：耐久全般でカブリが５％以下
△：耐久中に一時的にカブリが５％を超えることがある
×：耐久の半分以上でカブリが５％を超える
【０２１６】
評価結果を表２に示す。
【０２１７】
【表２】

【０２１８】
［実施例９］
上記の実施例１〜８及び参考例１〜５の評価方法で用いた画像形成装置のプロセスカートリッジのクリーニングブレードを取り外して、トナーＡを用いて画出し試験を行った。評価結果を下記表３に示す。
【０２１９】
【表３】

【０２２０】
［実施例１０及び比較例６］
図５に示す構成を有する、フルカラー画像形成装置であるＬＢＰ−２０４０を接触現像を行うよう改造を行い、トナーＮ及びＴを用いて常温常湿環境下（２３℃，６５％ＲＨ）において３０００枚の画出し試験を行った。評価結果を下記表４に示す。
【０２２１】
評価項目は実施例１〜８及び参考例１〜５と同様であるが、転写効率については、感光体から中間転写体への転写を一次転写、中間転写体から紙上への転写を二次転写とし、ベタ黒画像転写後の感光体上の転写残トナーをマイラーテープによりテーピングしてはぎ取ったもののマクベス濃度の値をＦ、二次転写前の中間転写体上にマイラーテープを貼ったもののマクベス濃度をＧ、中間転写体上の二次転写残トナーをマイラーテープによりテーピングしてはぎ取ったもののマクベス濃度の値をＨ、二次転写後定着前のトナーの載った紙上にマイラーテープを貼ったもののマクベス濃度をＩ、未使用の紙上に貼ったもののマクベス濃度をＥとしたとき、近似的に以下の式で計算した。
【０２２２】
【数６】

【０２２３】
【表４】

【０２２４】
【発明の効果】
本発明によれば、上記の如き低結晶性または非晶性の芳香族化合物の金属塩、金属錯体、または、金属塩と金属錯体の混合物がトナー粒子表面に存在していることを特徴とするトナーを用いることにより、接触現像方法において耐久後でも転写効率が高く、カブリの少ない高品位な画像が得られる。
【図面の簡単な説明】
【図１】非晶性の芳香族化合物の金属錯体のＸ線回折チャートである。
【図２】結晶性の芳香族化合物の金属錯体のＸ線回折チャートである。
【図３】本発明が適用されうる画像形成装置の概略説明図である。
【図４】図３に示す画像形成装置の現像装置の概略説明図である。
【図５】本発明が適用されうる中間転写体を用いたフルカラー画像形成装置の概略説明図である。
【符号の説明】
１ 感光ドラム
２ 一次帯電器
３ 像露光手段
１０ 転写材ガイド
１１ 給紙ローラ
１３ 感光ドラムのクリーニング装置
１５ 定着器
２０ 中間転写ベルト
２６ バイアス電源
２８ バイアス電源
２９ バイアス電源
４１ イエロー色現像装置
４２ マゼンタ色現像装置
４３ シアン色現像装置
４４ ブラック色現像装置
５０ 中間転写体のクリーニング装置
５２ 転写残トナー帯電部材
６２ 一次転写ローラ
６３ 二次転写ローラ
６４ 二次転写対向ローラ
６５ 中間転写ベルト支持ローラ
６６ 中間転写ベルト支持ローラ
１００ 感光体
１０４ トナー担持体
１１３ クリーニング装置
１１４ 転写手段
１１７ 帯電器
１２３ レーザー光又はアナログ光
１２６ 加圧定着手段
１２８ 加熱定着手段
１３１、１３２、１３３、１３４ バイアス印加手段
１４０ 現像装置
１４１ 塗布ローラ
１４２ トナー
１４３ 弾性ブレード[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an image forming method used in a recording method using an electrophotographic method, an electrostatic recording method, a magnetic recording method, a toner jet method, or the like.
[0002]
[Prior art]
Conventionally, a number of methods are known as electrophotographic methods. In general, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the electric latent image is converted into a toner. The image is developed with a visible image, and if necessary, the toner image is transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material by heat or pressure to obtain a fixed image. is there. At this time, the toner remaining on the photoreceptor without being transferred to the transfer material after the transfer is cleaned by various methods.
[0003]
As a method for visualizing an electric latent image, a cascade development method, a magnetic brush development method, a nonmagnetic one-component development method, and a pressure development method are known. Furthermore, a magnetic one-component developing method is also used in which a magnetic toner is used and a rotating sleeve having a magnetic pole at the center is used to fly between the photosensitive member and the sleeve by an electric field.
[0004]
The one-component developing method does not require carrier particles such as glass beads or iron powder as in the two-component method, and therefore the developing device itself can be reduced in size and weight. Furthermore, since the two-component development method needs to keep the toner concentration in the carrier constant, a device for detecting the toner concentration and supplying a necessary amount of toner is required. Therefore, the developing device is also large and heavy here. Since such a device is not necessary in the one-component development method, it is preferable because it can be made small and light.
[0005]
In recent years, a so-called contact one-component developing method has been proposed in which development is carried out by using a semiconductive developing roller or a developing roller having a dielectric layer formed on the surface thereof and pressing the photosensitive member surface layer.
[0006]
In the one-component development method, if the photosensitive member and the toner carrier have a distance, the electric force lines concentrate on the edge portion of the electrostatic latent image on the photosensitive member, and the toner is developed along the electric force lines. Image quality is likely to deteriorate due to an edge effect in which toner is biased and developed at the edge portion of the image.
[0007]
This edge effect is prevented by bringing the photosensitive member and the toner carrier very close to each other, but the gap between the photosensitive member and the toner carrier is mechanically set, that is, the gap is larger than the thickness of the toner layer on the toner carrier. Is difficult to set small.
[0008]
Therefore, the edge effect is prevented by using a contact one-component developing method in which the toner carrying member is pressed against the photosensitive member for development. However, if the toner carrier surface moving speed is the same as the photosensitive member surface moving speed, a satisfactory image cannot be obtained when the latent image on the photosensitive member is visualized. Therefore, in the contact one-component developing method, by making a difference in the toner carrier surface moving speed with respect to the photosensitive member surface moving speed, a part of the toner on the toner carrier is made to the latent image on the photosensitive member surface. It is developed and some other toner is stripped off, resulting in a developed image without edge effects that is very faithful to the latent image.
[0009]
In such a contact one-component development method, it is essential to rub the surface of the photosensitive member with toner and a toner carrier. For this reason, toner deterioration occurs due to long-term use, and toner fluidity and charging uniformity are reduced. This is undesirable because fog increases and transfer efficiency decreases. In addition, due to the decrease in transfer efficiency, the reproducibility of fine dots decreases, resulting in image quality degradation.
[0010]
Japan Hardcopy '89 Proceedings, pages 25 to 28, discusses a contact-type one-component non-magnetic development system. However, this durability is not mentioned.
[0011]
FUJITSU Sci. Tech. J. et al. , 28, 4, pp. 473-480 (December 992) reports an outline of a printer using a one-component contact development method. However, its durability characteristics are not sufficient and there is room for further improvement.
[0012]
In order to reduce fog and improve transfer efficiency, JP-A-6-222609 and JP-A-8-036316 describe a toner having a prescribed amount of external additive and two types of external additives having different average particle diameters. Although a technique relating to a one-component contact development method using a toner externally added with toner is disclosed, the transfer efficiency after endurance is still not sufficient.
[0013]
Japanese Patent Application Laid-Open No. 9-127720 and Japanese Patent Application Laid-Open No. 9-190006 disclose a method for externally adding a metal salt compound. However, the level is still insufficient.
[0014]
In JP-A-10-97095 (corresponding EP 822456A1), by defining a circularity distribution in particles having a particle diameter of 3 μm or more in a toner having one or more endothermic peaks in a differential thermal analysis in a temperature region of 120 ° C. It is disclosed to suppress toner retransfer.
[0015]
In EP 886187A1, a fine dot is faithfully observed because the average particle diameter and shape factor on the toner particles of an external additive possessed by a toner having a specific circularity distribution and a specific weight average particle diameter are within a specific range. It is described that a reproducible high-quality image is obtained, the mechanical stress in the developing device is high, and toner deterioration hardly occurs.
[0016]
However, the above-mentioned two prior arts have a point to be further improved in terms of improving transfer efficiency and suppressing fogging when contact development is performed.
[0017]
[Problems to be solved by the invention]
An object of the present invention is to provide an image forming method that is excellent in durability, has no fog, has high transfer efficiency, and provides a high-resolution and high-definition image.
[0018]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that the above-described problems can be solved by the following image forming method, and have completed the present invention.
[0019]
  That is, the present invention includes a charging step for charging an electrostatic charge image carrier, an exposure step for forming an electrostatic latent image on the electrostatic image carrier by exposure, and an electrostatic latent image on the electrostatic image carrier. An image forming method comprising at least a development step of developing an image and a toner coated on a toner carrying member in contact with each other, and a transfer step of transferring the toner image to a transfer material,
  The toner has toner particles containing at least a binder resin, a colorant, and a release agent, and has an average circularity of 0.955 or more.
The toner is obtained by mixing and stirring the aluminum complex compound of dialkyl salicylic acid and the toner particles, and further adding fine particles to the outside, and the aluminum complex compound of dialkyl salicylic acid is formed on the toner particle surface. , Without being embedded, it is no longer in a granular state,
  The aluminum complex compound of the dialkyl salicylic acid isIn X-ray diffraction, there is no peak having a measurement intensity of 10000 cps or more and a half width at half maximum of 0.3 degrees or less in a measurement angle 2θ range of 6 to 40 degrees.NoCrystallinityofCompoundAnd Al ₂ (SO _Four ) _Three Alkaline aqueous solution of dialkyl salicylic acid in the aqueous solution, Al ₂ (SO _Four ) _Three Dialkyl salicylic acid added at a ratio of 2.1 to 3.0 moles per mole and obtained by reactionThe present invention relates to an image forming method.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
As a result of intensive studies by the present inventors, in a toner having toner particles containing at least a binder resin, a colorant, and a release agent, the average circularity of the toner is 0.955 or more, and X-ray diffraction is performed. In the range of 6 to 40 degrees of measurement angle 2θ, a metal complex compound of a low crystalline or amorphous aromatic compound having no peak with a measured intensity of 10,000 cps or more and a half width at half maximum of 0.3 degrees or less It has been found that by allowing the metal salt or a mixture of both to exist on the surface of the toner particles, high transfer efficiency can be maintained over a long period of time, and voids and fog can be reduced.
[0021]
When the metal compound such as a metal salt of an aromatic compound or a metal complex compound is low crystalline or amorphous, the metal compound itself can be stretched by applying a force such as shearing force. By mixing the metal compound particles and the toner particles by the method described later, the metal compound existing on the toner particle surface can be present in a state where the toner particle surface is uniformly coated. Further, the metal compound has a charge control function, and the toner compound can be quickly charged and a sufficient charge amount can be obtained when the metal compound uniformly exists (more preferably, coats) the surface of the toner particles. Therefore, the toner charge amount distribution becomes uniform even in a state where the fluidity of the toner is poor after the endurance. Further, since the metal compound is present in a state where the surface of the toner particles is uniformly coated, it becomes difficult to embed the external additive, and toner deterioration hardly occurs. Therefore, it is considered that an image having high transfer efficiency and no fogging can be obtained even after the endurance due to the synergistic effect of these actions.
[0022]
In the present invention, the term “coating” refers to a metal salt of an aromatic compound, a metal complex compound, or a mixture of a metal salt and a metal complex compound on the surface of toner particles in SEM observation at a magnification of 10,000 to 30,000. Is defined as a state in which it can be confirmed that the particles are not embedded in the toner particles and are not in the granular state.
[0023]
On the other hand, when a metal compound such as a metal salt of an aromatic compound or a metal complex compound is a crystalline substance, transfer efficiency cannot be obtained because a sufficient charge amount cannot be obtained or a uniform charge amount distribution cannot be obtained. Decrease.
[0024]
The reason for this is not clear, but is thought to be due to the following reasons.
[0025]
Generally, the activity of the crystal is considered to be high at the defect portion of the crystal lattice, and it is considered that the generation of electric charges occurs in the metal compound at places with high activity such as corners and edges of the crystal. However, when the metal compound is a crystalline substance, in combination with a toner having a smooth surface with an average circularity of 0.955 or more, the metal compound is hard because it is a crystal, and toner particles are not stretched. It will be embedded in. For this reason, it is considered that the exposure of the highly active site of the metal compound is reduced and a sufficient charge amount cannot be obtained.
[0026]
Further, in the case of a crystalline substance, even if the addition amount is increased, the metal compound is embedded in the toner particles non-uniformly and cannot be present uniformly on the toner particle surface. Further, when the crystal is large, it cannot be embedded in the toner particles. Therefore, the above effect cannot be obtained, and the transfer efficiency is lowered after the endurance.
[0027]
In the present invention, “amorphous or low crystallinity” means that the measured intensity is 10000 cps (count per second) or more and the half width at half maximum is 0.3 degrees or less as shown in FIG. This is a state having no peak, and is clearly different from the diffraction pattern (FIG. 2) of the metal complex compound of the crystalline aromatic compound. In general, in X-ray diffraction measurement, a crystalline substance shows a specific diffraction peak depending on the crystal plane spacing depending on Bragg's diffraction conditions, and the diffraction intensity depends on the crystal state and crystallinity. A substance that does not have a peak with a measured line diffraction intensity of 10000 cps or more and a half width at half maximum of 0.3 degrees or less can be considered as an amorphous or low crystalline substance. In the actual measurement, the influence of the direct beam is large in the range where the measurement angle 2θ is less than 6 degrees, and the measurement intensity decreases as the measurement angle 2θ increases. Therefore, in the range where 2θ exceeds 40 degrees, the measurement intensity is small. In the range, it is not preferable to make a crystal or non-crystal judgment. The “half width at half maximum” means a width that is ½ of the peak width (full width at half maximum) at ½ measurement intensity of the peak top measurement intensity (cps).
[0028]
For the measurement of X-ray diffraction according to the present invention, for example, an X-ray diffractometer MXP18 manufactured by Mac Science Co., Ltd. is used, and measurement is performed under the following conditions using CuKα rays.
[0029]
X-ray tube: Cu
Tube voltage: 50 kV
Tube current: 300mA
Scanning method: 2θ / θ scan
Scan speed: 2 deg. / Min
Sampling interval: 0.02 deg.
Divergent slit: 0.50 deg.
Scattering slit: 0.50 deg.
Receiving slit: 0.3mm
[0030]
In addition, the metal salt of an aromatic compound, a metal complex compound, or a mixture of a metal salt and a metal complex compound is about 12 mg / cm on a glass plate.²The measurement is carried out after the surface is made free of irregularities.
[0031]
The amount of the aromatic metal complex compound, metal salt, or mixture of both present on the toner particle surface is 0.01 to 0.5 parts by weight, more preferably 0.01 to 0 parts per 100 parts by weight of the toner particles. .3 parts by weight is preferred. If the amount is less than 0.01 parts by weight, it is difficult to uniformly exist on the toner surface, resulting in a decrease in transfer efficiency after endurance. This increases the proportion of the material that is present and causes contamination of the charging member. Further, by internally adding a metal complex compound of an aromatic compound, a metal salt, or a mixture of both to the toner, the toner is more uniformly charged, and the transfer efficiency after the endurance is unlikely to decrease. The amount of internal addition is preferably 0.05 to 5 parts by weight per 100 parts by weight of the binder resin. When the amount of internal addition is less than 0.05 parts by weight, such effects are reduced. On the other hand, when the amount exceeds 5 parts by weight, the fixing property is inferior. Particularly in color toners, the transparency of OHT is reduced, the color complex of the aromatic metal complex, the metal salt, or a mixture of both. A color shift occurs, which is not preferable.
[0032]
The metal complex compound or metal salt of the aromatic compound added internally may be different from or the same as the compound existing on the toner surface, and may be crystalline or amorphous.
[0033]
In addition, as a metal complex compound, a metal complex or a metal complex salt is mentioned.
[0034]
In the present invention, all known metal complexes or metal salts of aromatic compounds to be added can be used, for example, aromatic hydroxycarboxylic acids such as oxycarboxylic acids, aromatic mono- and polycarboxylic acid-based metal compounds. And aromatic monoazo metal compounds. Among these, a metal complex compound of an oxycarboxylic acid compound, a metal salt, or a mixture of both, particularly when the central metal is aluminum or zirconium, more preferably aluminum, transfer efficiency is unlikely to decrease. Although the reason for this is not clear, it is considered that the aluminum or zirconium compound of oxycarboxylic acid improves the chargeability of the toner, provides a large charge amount, and provides good toner coverage. Yes.
[0035]
As an example of producing a metal complex compound or metal salt of a low crystalline or amorphous aromatic compound used in the present invention, a method for producing an aluminum complex compound of amorphous dialkylsalicylic acid preferably used in the present invention is illustrated. To do.
[0036]
Al₂(SO_Four)_ThreeIt is possible to produce an aluminum complex compound of dialkyl salicylic acid by adding and stirring an aqueous alkali solution of dialkyl salicylic acid to the aqueous solution, filtering the reaction product, washing and drying. In the present invention, it is necessary that the aluminum complex compound of the dialkyl salicylic acid to be produced has low crystallinity or amorphousness.₂(SO_Four)_Three  By reacting dialkyl salicylic acid with respect to 1 mol, preferably 2.1 to 3.0 mol, more preferably 2.2 to 2.8 mol, the remaining amount of unreacted substances is suppressed and low crystalline or non-crystalline A compound having crystallinity can be produced.
[0037]
The average particle diameter of the primary particles of the metal complex compound or metal salt of the low crystalline or non-crystalline aromatic compound used in the present invention is preferably 0.7 μm or less, more preferably 0.05 to 0.50 μm. It is good to be.
[0038]
The average particle size of the primary particles of the metal complex compound or metal salt of the low crystalline or non-crystalline aromatic compound is measured with a transmission electron microscope (TEM) by 30,000 times to 70,000 times. Take a picture by observing at magnification. Then, for particles that can be confirmed to be primary particles with particles of 0.01 μm or more on the image being measured, 50 samples are randomly sampled, the particle diameter of each image is measured, and the number average value is calculated. The average particle size of the primary particles.
[0039]
As a method of coating the toner surface with a metal salt of an aromatic compound, a metal complex compound, or a mixture of a metal salt and a metal complex compound, the compound and colored particles (toner) are mixed and stirred using a mechanical impact force. To do. As a method for applying a mechanical impact force, all known methods can be used. Specifically, a mechanofusion system (Hosokawa Micron Co., Ltd.), which is a mixing device applying a dry mechanochemical method, is used at the exit of an acceleration tube. I-type jet mill which is a crusher provided with a collision member, a hybridizer (manufactured by Nara Machinery Co., Ltd.) which is a mixing device having a rotor and a liner, a crushing rotor is rotated at high speed, a rotor collides with particles, and particles collide with each other Treatment with a turbo mill (Turbo Kogyo Co., Ltd.) that generates slag, a Henschel mixer (Mitsui Miike Chemical Co., Ltd.), which is a mixer having high-speed stirring blades, and the like.
[0040]
That is, even when the metal compound and toner particles are mixed and stirred at a low share or low speed, the metal compound is released from the toner particles. On the other hand, when the metal compound and the toner particles are mixed and stirred at a high shear rate or at a high speed, adhesion and coating of the metal compound to the toner particles occur rapidly, and it becomes difficult to uniformly coat the entire toner particles. For this reason, in order to make the metal compound uniformly exist on the surface of the toner particles, it is preferable to use a Henschel mixer, the peripheral speed of the stirring blade is 30 to 80 m / sec, and the mixing time is 1 to 10 minutes. Moreover, in order to prevent generation | occurrence | production of a coarse grain, it is preferable that the temperature at the time of mixing and stirring shall be 50 degrees C or less.
[0041]
The toner used in the present invention has an average circularity of 0.955 or more, preferably 0.955 to 0.990, more preferably 0.960 to 0.990, and still more preferably 0.960 to 0.960. It is preferably 0.985, and the circularity standard deviation is preferably less than 0.040. The average circularity in the present invention is used as a simple method for quantitatively expressing the shape of particles, and in the present invention, measurement is performed using a flow type particle image analyzer FPIA-1000 manufactured by Toa Medical Electronics, The circularity of the measured particles is obtained by the following equation (1), and the value obtained by dividing the total circularity of all particles measured by the total number of particles as defined by the following equation (2) is defined as the average circularity. To do.
[0042]
[Expression 1]

[0043]
[Expression 2]

[0044]
[Equation 3]

[0045]
In addition, “FPIA-1000”, which is a measuring apparatus used in the present invention, calculates the circularity of each particle, and then calculates the average circularity and the circularity standard deviation. The degree 0.4 to 1.0 is divided into 61 classes, and a calculation method is used in which the average circularity and the circularity standard deviation are calculated using the center value and frequency of the dividing points. However, each value of the average circularity and the circularity standard deviation calculated by this calculation method, and each value of the average circularity and the circularity standard deviation calculated by the calculation formula that directly uses the circularity of each particle described above, In the present invention, the error of each of the above-mentioned particles is reduced due to data handling reasons such as a short calculation time and a simplified calculation formula. Such a calculation method that is partially changed by using the concept of a calculation formula that directly uses the circularity may be used.
[0046]
As a measurement method, about 5 mg of toner is dispersed in 10 ml of water in which about 0.1 mg of a nonionic surfactant is dissolved to prepare a dispersion, and ultrasonic waves (20 kHz, 50 W) are irradiated to the dispersion for 5 minutes. The circularity distribution of particles having a circle-equivalent diameter of 0.60 μm or more and less than 159.21 μm is measured using the above flow type particle image measurement apparatus at a dispersion concentration of 5000 to 20000 / μl.
[0047]
The outline of the measurement is described in the catalog (June 1995 edition) of FPIA-1000 published by Toa Medical Electronics Co., Ltd., the operation manual of the measuring apparatus, and JP-A-8-136439. It is.
[0048]
The sample dispersion is passed through a flat and flat transparent flow cell (thickness: about 200 μm) flow path (spread along the flow direction). The strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other so as to form an optical path that passes through the thickness of the flow cell. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. The circularity of each particle is calculated from the projected area of the two-dimensional image of each particle and the perimeter of the projected image using the above circularity calculation formula.
[0049]
The “average circularity” in the present invention is an index of the degree of unevenness of toner particles, and indicates 1.00 when the toner is perfectly spherical, and the average circularity becomes smaller as the toner shape becomes more complicated.
[0050]
In general, toner with an irregular shape has low charging uniformity at the convex or concave portions of the toner, and furthermore, because of the irregular shape, the contact area between the electrostatic latent image carrier and the toner increases. As a result, the toner adhesion becomes high, resulting in an increase in the residual toner.
[0051]
An average circularity of less than 0.955 indicates that the toner contains a lot of irregular shapes having irregularities, and the transfer efficiency is lowered. Further, since the toner having an average circularity of less than 0.955 has irregularities on the surface, the metal complex compound, metal salt, or metal complex compound and metal salt of a low crystalline or amorphous aromatic compound is used. Cannot be uniformly present on the toner surface. On the other hand, if the average circularity is too large, the toner is substantially spherical, and the surface area of the toner becomes small, making it difficult to obtain good chargeability. Therefore, the upper limit of the average circularity is particularly 0.990. preferable. Further, the fact that the standard deviation of the circularity of the toner is larger than 0.040 indicates that there are many variations in the toner shape, and it becomes difficult to uniformly charge the toner and the transfer efficiency tends to be lowered.
[0052]
The toner used in the present invention preferably has a weight average diameter of 4 to 9 μm to faithfully reproduce minute latent image dots in order to improve image quality. In toner particles having a weight average diameter of 4 to 9 μm, characters and line images are less likely to scatter, and the reproducibility of image contours, particularly character images and line patterns, is improved.
[0053]
Here, the particle size distribution can be measured by various methods, but in the present invention, measurement was performed using a Coulter counter. That is, a Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter, Inc.) is used as a measuring device. As the electrolyte, first grade sodium chloride is used to prepare an approximately 1% NaCl aqueous solution. For example, ISOTON-II (manufactured by Coulter) can be used. 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 subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toners are measured by using the measuring apparatus with a 100 μm aperture as the aperture. Distribution was calculated. Then, the weight-based weight average particle diameter determined from the volume distribution according to the present invention was determined.
[0054]
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Use 13 channels less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm.
[0055]
The glass transition point (Tg) of the toner used in the present invention is preferably 50 ° C. to 75 ° C., more preferably 52 ° C. to 70 ° C., from the viewpoint of fixability and storage stability. When the glass transition point is lower than 45 ° C., blocking tends to occur, and a problem occurs in storage stability. Further, it is weak against endurance stress, and is liable to cause toner deterioration and the like. On the other hand, if the glass transition point is higher than 70 ° C., the fixability deteriorates and it becomes difficult to deal with various materials, which is not preferable.
[0056]
To measure the glass transition point of the toner, for example, a high-accuracy internal heat input compensation type differential scanning calorimeter such as DSC-7 manufactured by Perkin Elmer is used. The measurement method is performed according to ASTM D3418-8. In the present invention, the DSC curve measured when the sample is heated once and then the previous history is taken, rapidly cooled, and heated again at a temperature rising rate of 10 ° C./min and a temperature of 30 to 200 ° C. is used. .
[0057]
The binder resin of the toner used in the present invention includes polystyrene; a homopolymer of a styrene substitution product such as poly-p-chlorostyrene and polyvinyltoluene; a styrene-p-chlorostyrene copolymer, and a styrene-vinyltoluene copolymer. Polymer, styrene-vinyl naphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl Styrene such as methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Copolymer; Polyvinyl chloride, Fe Resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene Resin, coumarone indene resin, petroleum resin, etc. can be used. Preferred binder resins include styrenic polymers or polyester resins.
[0058]
As a comonomer for the styrene monomer of the styrenic copolymer, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, Monocarboxylic acid having a double bond such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide or a substituted product thereof; maleic acid, butyl maleate, methyl maleate, Dicarboxylic acids having a double bond such as dimethyl maleate and its substitutes; Vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; Ethylene-based olefins such as ethylene, propylene and butylene S; vinyl methyl ketone, vinyl ketones such as vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl ethers such as vinyl isobutyl ether; vinyl monomers can be mentioned. These may be used alone or in combination.
[0059]
As the crosslinking agent for the binder resin, a compound having two or more polymerizable double bonds is used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline; And divinyl compounds such as divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups. These may be used alone or in combination. The addition amount of the crosslinking agent is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the polymerizable monomer.
[0060]
From the viewpoint of improving the releasability from the fixing member at the time of fixing and improving the fixing property, it is also preferable to contain the following low softening point substance in the toner particles. Paraffin wax and derivatives thereof, microcrystalline wax and derivatives thereof, Fischer-Tropsch wax and derivatives thereof, polyolefin wax and derivatives thereof, carnauba wax and derivatives thereof. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. In addition, long-chain alcohols, long-chain fatty acids, acid amides, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant-based waxes, animal-based waxes, mineral-based waxes, petrolactams and the like may be used in some cases.
[0061]
As a low softening point substance, a low endothermic main peak value in a DSC curve measured according to ASTM D3418-8 is 55 to 120 ° C, preferably 60 to 90 ° C, more preferably 60 to 85 ° C. A softening point material is preferable, and in particular, a low softening point material having a DSC curve tangential separation temperature of 40 ° C. or higher is more preferable. When the endothermic main peak is less than 55 ° C., the low softening point substance has a weak self-cohesive force, so that it is difficult to form the inside or the center of the toner particle. It tends to deposit and adversely affect development characteristics. Further, when the tangential separation temperature is less than 40 ° C., the strength of the toner particles decreases, and the development characteristics during the durability test tend to be deteriorated. The obtained fixed image also tends to be a sticky image due to the low melting point of the low softening point substance. On the other hand, if the endothermic main peak exceeds 120 ° C., the low softening point substance is difficult to ooze out during fixing, and the low-temperature fixability is lowered. Further, when the toner particles are produced by the direct polymerization method, the solubility in the polymerizable monomer composition is lowered, and the droplets of the polymerizable monomer composition to the toner particle size in an aqueous medium are reduced. A low softening point substance precipitates during granulation, and granulation becomes difficult, which is not preferable.
[0062]
The low softening point substance may be blended in an amount of 2 to 40 parts by weight, more preferably 5 to 35 parts by weight, based on 100 parts by weight of the toner binder resin.
[0063]
When the blending amount of the low softening point material is less than the lower limit, the effect of preventing offset tends to be lowered, and when the upper limit is exceeded, the anti-blocking effect is lowered and the anti-offset effect is easily adversely affected. In particular, in the case of a polymerized toner manufacturing method, a toner having a wide particle size distribution tends to be generated, which is not preferable.
[0064]
As the colorant used in the present invention, carbon black, a magnetic material, and the following yellow / magenta / cyan colorants are preferably used.
[0065]
As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex compounds, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 168, 174, 176, 180, 181 and 191 are preferably used.
[0066]
As the magenta colorant, a condensed azo compound, diketopyrrolopyrrole compound, anthraquinone, quinacridone compound, basic dye lake compound, naphthol compound, benzimidazolone compound, thioindigo compound, and perylene compound are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 are particularly preferred.
[0067]
As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like can be used particularly preferably.
[0068]
These colorants can be used alone or mixed and further used in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, transparency on the OHP film, and dispersibility in the toner particles. The amount of the colorant added is generally 2 to 20 parts by weight per 100 parts by weight of the binder resin.
[0069]
When a magnetic material is used as the black colorant, 40 to 150 parts by weight per 100 parts by weight of the resin is generally used, unlike other colorants.
[0070]
Furthermore, the toner of the present invention may further contain a magnetic material and be used as a magnetic toner. In this case, the magnetic material can also serve as a colorant. In the present invention, the magnetic substance contained in the magnetic toner includes iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, nickel, and aluminum, cobalt, copper, lead, magnesium of these metals, Examples include alloys of metals such as tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.
[0071]
The magnetic material used in the present invention is more preferably a surface-modified magnetic material. When used in a polymerization toner, the magnetic material is subjected to a hydrophobizing treatment with a surface modifier that is a substance that does not inhibit polymerization. Any surface modifier may be used, and examples of such a surface modifier include silane coupling agents and titanium coupling agents. These magnetic materials have an average particle diameter of 1 μm or less, preferably 0.1 to 0.5 μm.
[0072]
In the toner relating to the image forming method of the present invention, in order to improve developability, fluidity and durability, it is preferable to add fine particles to the toner particles having the metal compound on the surface. It is more preferable to add two or more different kinds of fine particles. This is because fine particles with a small particle size (hereinafter abbreviated as “small particle size”) impart fluidity, and fine particles with a large particle size (hereinafter abbreviated as “large particle size”) act as so-called spacer particles, depending on durability. This is to prevent toner deterioration. Therefore, if the primary particle size of the large particle size is less than 0.03 μm, the large particle size particle is embedded in the toner, making it difficult to serve as a spacer particle. Fine particles are not preferable because they do not adhere to the toner and are easily released, and the above effect is reduced. Therefore, the primary particle size of the large particle size is preferably 0.03 μm to 0.8 μm, and the primary particle size of the small particle size particle is 5 nm (0.005 μm) to 20 nm (0.02 μm). It is preferable. When the primary particle size of the small particle size exceeds 20 nm, the fluidity of the toner is not sufficiently high, and when the particle size is less than 5 nm, the toner particles are buried in fine irregularities on the surface of the toner particle, so It is difficult to adjust the sex sufficiently.
[0073]
Examples of these fine particles include silica fine powder, titanium oxide, alumina fine powder, resin fine particles, and the like. The total amount of small particle size particles and large particle size particles is 0.01 to 8 with respect to 100 parts by weight of toner particles. Part by weight, preferably 0.1 to 5 parts by weight is used.
[0074]
The ratio of the addition amount (S) of the small particle size fine particles and the addition amount (L) of the large particle size fine particles is preferably S: L = 1: 0.1 to 3.5, more preferably S: L. = 1: 0.1 to 3.0.
[0075]
The fine particles used in the present invention, if necessary, for the purpose of hydrophobization and charge control, silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, and silane coupling agents having functional groups In addition, it is also preferable to treat with other treating agents such as organosilicon compounds.
[0076]
The average particle diameter of the fine particles used in the present invention is determined by first observing the fine particles with an electron microscope or a transmission electron microscope at a magnification of 10,000 to 100,000 times and taking a photograph. Then, with respect to fine particles of 1 nm or more on the image, 100 particles that can be confirmed to have a primary particle diameter are sampled randomly, and the particle diameter is obtained from the image and averaged.
[0077]
Other additives include lubricants such as Teflon, zinc stearate, and polyvinylidene fluoride (especially polyvinylidene fluoride is preferred); abrasives such as cerium oxide, silicon carbide, and strontium titanate (especially strontium titanate is preferred); Anti-caking agent; conductivity imparting agents such as carbon black, zinc oxide, antimony oxide and tin oxide.
[0078]
Such fine particles are added by mixing and stirring with a mixer such as a Henschel mixer. After mixing and stirring the metal compound and toner particles, the fine particles may be added and mixed. preferable. This is because when the metal compound and the fine particles are added and mixed with toner particles at the same time, and when the metal compound is added and mixed after mixing the fine particles with the toner particles, the fine particles adhere to the surface of the toner particles. For this reason, it is difficult for the metal compound to be present and coated on the surface of the toner particles. Further, the compound which cannot be present on the surface layer of the toner particles is liberated, contaminating the charging member, causing an increase in fog and a decrease in image quality, which is not preferable.
[0079]
Next, a method for producing the toner used in the present invention will be described. The toner used in the present invention can be manufactured using a pulverized toner manufacturing method and a polymerized toner manufacturing method.
[0080]
In the present invention, the method for producing the pulverized toner includes a binder resin, a wax, a pigment as a colorant, a dye, or a magnetic material, and other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, A toner can be obtained by dispersing or dissolving a pigment, dye or magnetic substance in a melted and kneaded resin using a thermal kneader such as a kneader or an extruder, and dispersing or dissolving the pigment, dye or magnetic substance, cooling and solidifying, and then pulverizing and classifying. I can do it. In the classification step, it is preferable to use a multi-division classifier in terms of production efficiency.
[0081]
The toner obtained by such a pulverization method has an average circularity of less than 0.955. In this case, the toner particles obtained by the pulverization method are dispersed in water and heated in a hot water bath method or passed through a hot air stream. It is preferable to increase the average circularity by modifying the surface of the toner by a heat treatment method, a mechanical impact method in which mechanical energy is applied, or the like. As the apparatus for surface modification, all known apparatuses can be used. Specific examples include mechanofusion, I-type mill, hybridizer, and apparatus described in JP-A-10-94734.
[0082]
In the present invention, a polymerized toner is produced by a method described in Japanese Examined Patent Publication No. 56-13945 or the like using a disk or a multi-fluid nozzle to atomize the molten mixture into the air to obtain a spherical toner, or Japanese Examined Patent Publication No. 36-10231. JP-A-59-53856, JP-A-59-61842, a method for directly producing toner using a suspension polymerization method, An emulsion polymerization method represented by a dispersion polymerization method in which a toner is directly generated using an aqueous organic solvent in which the coalescence is insoluble or a soap-free polymerization method in which a toner is formed by direct polymerization in the presence of a water-soluble polar polymerization initiator, After making the emulsified particles, it is possible to produce toner particles using a hetero-aggregation method in which polar particles having opposite charges are added and associated. In particular, toner particles are preferably produced by a suspension polymerization method. Furthermore, toner particles obtained by a seed polymerization method in which a monomer is further adsorbed to the obtained polymer particles and then polymerized using a polymerization initiator can also be suitably used in the present invention.
[0083]
When the polymerization method is used for the production of the toner particles of the present invention, the toner particles can be produced by the following method. Add a release agent, colorant, charge control agent, polymerization initiator and other additives consisting of a low softening substance into the polymerizable monomer, and dissolve or disperse it uniformly with a disperser such as a homogenizer or an ultrasonic disperser. The polymerizable monomer composition thus obtained is dispersed in an aqueous phase containing a dispersion stabilizer by a usual stirrer, homomixer or homogenizer. Preferably, granulation is performed by adjusting the stirring speed and time so that the droplets of the polymerizable monomer composition have the desired toner particle size. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. Polymerization is carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. In addition, the temperature may be raised in the second half of the reaction, and in order to remove unreacted polymerizable monomers and by-products that cause odor at the time of toner fixing, the temperature is increased in the second half of the reaction or at the end of the reaction. The partial aqueous medium may be distilled off. After completion of the reaction, the toner particles produced are collected by washing, filtration, and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersant with respect to 100 parts by weight of the monomer system.
[0084]
As the polymerizable monomer used when the toner of the present invention is produced by the polymerization method, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.
[0085]
Monofunctional polymerizable monomers include styrene, α-methyl styrene, β-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p A styrenic polymerizable monomer such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n -Hexyl acrylate, 2-ethylhexyl acrylate Acrylic polymerizable monomers such as relate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl Methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl Methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic polymerizable monomers such as methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl ethyl ether, Examples include vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.
[0086]
As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2'-bis [4- (acryloxy-diethoxy) phenyl] propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis [4- (methacryloxy-diethoxy) phenyl] propane, Examples include 2,2′-bis [4- (methacryloxy / polyethoxy) phenyl] propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like.
[0087]
In the present invention, the above-mentioned monofunctional polymerizable monomers can be used alone or in combination of two or more, or a monofunctional polymerizable monomer and a polyfunctional polymerizable monomer can be used in combination. Moreover, it is also possible to use the said polyfunctional polymerizable monomer as a crosslinking agent.
[0088]
As the polymerization initiator used in the polymerization of the polymerizable monomer described above, an oil-soluble initiator and / or a water-soluble initiator is used. For example, as the oil-soluble initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) Azo compounds such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropylperoxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide Oxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumylper Kisaido, t- butyl hydroperoxide, di -t- butyl peroxide, include peroxide initiators such as cumene hydroperoxide.
[0089]
Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloric acid Salts, sodium azobis (isobutylamidine) hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.
[0090]
The polymerization initiator is preferably added in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer, and may be used alone or in combination.
[0091]
In the present invention, as a dispersant used when producing a polymerization toner, for example, as an inorganic oxide, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, Examples thereof include magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. As the organic compound, for example, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, starch and the like are used. These dispersants are preferably used in an amount of 0.2 to 2.0 parts by weight based on 100 parts by weight of the polymerizable monomer.
[0092]
Commercially available dispersants may be used as they are, but in order to obtain dispersed particles having a fine and uniform particle size, the inorganic compound can also be produced in a dispersion medium under high-speed stirring. For example, in the case of tricalcium phosphate, a preferred dispersant for the suspension polymerization method can be obtained by mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution under high-speed stirring. In order to refine these dispersants, 0.001 to 0.1% by weight of a surfactant may be used in combination. Specifically, commercially available nonionic, anionic and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like are preferably used.
[0093]
In the image forming method of the present invention, various charging methods can be used, but a contact charging method in which a charging member is brought into contact with the photosensitive member is also preferably used. In this case, when a general toner is used, if the residual toner after cleaning adheres to a contact charging member which is a subsequent process, charging failure occurs and charging unevenness occurs on the image. Therefore, compared with corona discharge in which the charging means does not come into contact with the photoreceptor, the amount of fog and residual toner is smaller and it is necessary to make it difficult to adhere. Therefore, the toner used in the contact charging method is required to have good charging characteristics such as high developability and low fog. Furthermore, it is required to have high transferability. That is, in the contact charging method, it is important that a metal salt of a low crystalline or amorphous aromatic compound, a metal complex compound, or a mixture of a metal salt and a metal complex compound is present on the toner particle surface. In addition, it is necessary to use a toner whose circularity is strictly defined.
[0094]
As a condition of the developing step in the image forming method of the present invention, it is essential that the toner carrying member and the surface of the photosensitive member are in contact with each other, and more preferably, a reversal developing method is used.
[0095]
As the toner carrier, an elastic roller is used, and the surface of the elastic roller or the like is coated with toner and brought into contact with the surface of the photoreceptor. In this case, since development is performed by an electric field acting between the photosensitive member and the elastic roller facing the surface of the photosensitive member via toner, the surface of the elastic roller or the vicinity of the surface has a potential, and the surface of the photosensitive member and the surface of the toner carrying member are narrow. There is a need to have an electric field in the gap. For this reason, it is possible to use a method in which the elastic rubber of the elastic roller is resistance controlled to the middle resistance region to keep the electric field while preventing conduction with the surface of the photoreceptor, or a method of providing a thin insulating layer on the surface layer of the conductive roller. . Further, a conductive resin sleeve in which the side facing the surface of the photoreceptor is covered with an insulating material on the conductive roller, or a conductive layer is provided on the side not facing the photoreceptor with the insulating sleeve is also possible. Further, a configuration in which a rigid roller is used as the toner carrying member and the photosensitive member is a flexible material such as a belt is possible. The resistance of the developing roller as the toner carrier is 10²-10⁹A range of Ω · cm is preferred.
[0096]
As the surface shape of the toner carrier, when the surface roughness Ra (μm) is set to 0.2 to 3.0, both high image quality and high durability can be achieved. The surface roughness Ra correlates with the toner conveying ability and the toner charging ability. When the surface roughness Ra of the toner carrier exceeds 3.0, it is difficult not only to make the toner layer on the toner carrier thin, but also the chargeability of the toner is not improved, so that no improvement in image quality can be expected. By setting it to 3.0 or less, the toner carrying ability on the surface of the toner carrier is suppressed, the toner layer on the toner carrier is thinned, and the number of contact between the toner carrier and the toner is increased. Since the charging property is also improved, the image quality is synergistically improved. On the other hand, when the surface roughness Ra is smaller than 0.2, it becomes difficult to control the toner coat amount.
[0097]
The amount of toner coated on the toner carrier is 0.2 to 3.0 mg / cm.²It is preferable that
[0098]
In the present invention, the surface roughness Ra of the toner carrier is measured using a surface roughness measuring instrument (Surfcoder SE-30H, manufactured by Kosaka Laboratory Co., Ltd.) based on JIS surface roughness “JIS B 0601”. This corresponds to the centerline average roughness. Specifically, a 2.5 mm portion as the measurement length a is extracted from the roughness curve in the direction of the center line, the center line of this extraction portion is the X axis, the direction of the vertical magnification is the Y axis, and the roughness curve is When expressed by y = f (x), it means a value obtained by the following formula expressed in micrometers (μm).
[0099]
[Expression 4]

[0100]
In the image forming method of the present invention, the toner carrier may be rotated in the same direction as the circumferential speed of the photosensitive member, or may be rotated in the opposite direction. When the rotation is in the same direction, it is preferable to set the peripheral speed of the toner carrier to be 1.05 to 3.0 times the peripheral speed of the photosensitive member.
[0101]
When the peripheral speed of the toner carrier is less than 1.05 times the peripheral speed of the photoreceptor, the stirring effect received by the toner on the photoreceptor is insufficient, and good image quality cannot be expected. In addition, when developing an image that requires a large amount of toner over a wide area, such as a solid black image, the amount of toner supplied to the electrostatic latent image is insufficient and the image density becomes low. The higher the peripheral speed ratio, the more toner is supplied to the development site, the more frequent the toner is desorbed from the latent image, and the unnecessary parts are collected and applied to the necessary parts. An image faithful to the latent image can be obtained. However, when the peripheral speed ratio exceeds 3.0, on the other hand, in addition to various problems caused by excessive charging of the toner as described above (image density reduction due to excessive charging of the toner, etc.), mechanical Deterioration of toner due to stress and toner adhesion to the toner carrier are generated and promoted, which is not preferable.
[0102]
As a photoreceptor, a-Se, CdS, ZnO₂A photosensitive drum or photosensitive belt having a photoconductive insulating material layer such as OPC and a-Si is preferably used.
[0103]
As the binder resin of the organic photosensitive layer in the OPC photoreceptor, polycarbonate resin, polyester resin, and acrylic resin are particularly good in transferability and cleaning properties, poor cleaning, toner fusion to the photoreceptor, and external additive fill. It is preferable because it does not easily cause ming.
[0104]
Next, the image forming method of the present invention will be described below with reference to FIGS.
[0105]
In FIG. 3, 140 is a developing device, 100 is a photosensitive member, 127 is a transfer target (transfer material) such as paper, 114 is a transfer member, 126 is a fixing pressure roller, 128 is a fixing heating roller, and 117 is photosensitive. 1 shows a primary charging member that contacts a body 100 and performs direct charging. A bias power supply 131 is connected to the primary charging member 117 so as to uniformly charge the surface of the photoreceptor 100.
[0106]
The developing device 140 contains toner 142 and includes a toner carrier 104 that contacts the photoconductor 100 and rotates in the direction of the arrow. Further, a developing blade 143 and a toner 142 for toner amount regulation and charging are attached to the toner carrier 104, and a coating roller 141 that rotates in the direction of the arrow in order to charge the toner by friction with the toner carrier 104. It also has. A developing bias power supply 133 is connected to the toner carrier 104. A bias power source 132 is also connected to the application roller 141, and a voltage is set on the negative side of the developing bias when negatively charged toner is used, and on the positive side of the developing bias when positively charged toner is used. Is done.
[0107]
A transfer bias power supply 134 having a polarity opposite to that of the photoconductor 100 is connected to the transfer member 114.
[0108]
Here, the length in the rotation direction, that is, the so-called development nip width at the contact portion between the photoconductor 100 and the toner carrier 104 is preferably 0.2 mm or more and 8.0 mm or less. If the thickness is less than 0.2 mm, the development amount is insufficient and a satisfactory image density cannot be obtained, and the transfer residual toner is not sufficiently collected. If it exceeds 8.0 mm, the amount of toner supplied becomes excessive, fog suppression is likely to deteriorate, and the wear of the photoconductor 100 is also adversely affected.
[0109]
As the toner carrier 104, a so-called elastic roller having an elastic layer on the surface is preferably used.
[0110]
As the hardness of the material of the elastic layer used, a hardness of 20 to 65 degrees (Asuka C) is preferably used.
[0111]
The resistance of the toner carrier 104 is 10 in terms of volume resistance.²-10⁹A range of about Ω · cm is preferable. 10²If it is lower than Ω · cm, for example, if there is a pinhole or the like on the surface of the photoreceptor 100, an overcurrent may flow. Conversely, 10⁹When it is higher than Ω · cm, the toner is likely to be charged up due to frictional charging, and the image density is likely to be lowered.
[0112]
The toner coat amount on the toner carrier 104 is 0. lmg / cm²2.0 mg / cm or more²The following is preferred. 0. lmg / cm²If it is less, it is difficult to obtain a sufficient image density, and 2.0 mg / cm²If it exceeds the upper limit, it becomes difficult to uniformly triboelectrically charge all the individual toner particles, which causes deterioration of fog suppression. Furthermore, 0.2 mg / cm²1.2 mg / cm or more²The following is more preferable.
[0113]
The toner coating amount is controlled by the developing blade 143, and the developing blade 143 is in contact with the toner carrier 104 through the toner layer. The contact pressure at this time is preferably in the range of 5 g / cm to 50 g / cm. If it is less than 5 g / cm, in addition to controlling the toner coating amount, uniform frictional charging becomes difficult, which causes deterioration of fog suppression. On the other hand, if it exceeds 50 g / cm, the toner particles are subjected to an excessive load, so that the deformation of the particles and the fusion of the toner to the developing blade 143 or the toner carrier 104 are likely to occur.
[0114]
As the toner coating amount regulating member, a metal blade, a roller, or the like may be used in addition to the elastic blade for press-contacting the toner.
[0115]
For the elastic regulating member, it is preferable to select a frictional charging material suitable for charging the toner to a desired polarity. A rubber elastic body such as silicone rubber, urethane rubber or NBR, or a synthetic resin such as polyethylene terephthalate. A metal elastic body such as an elastic body, stainless steel, copper, or phosphor bronze can be used. Moreover, those composites may be sufficient.
[0116]
Further, when durability is required for the elastic regulating member and the toner carrying member, it is preferable that the metal elastic member is bonded or coated with a resin or rubber so as to contact the sleeve contact portion.
[0117]
Furthermore, an organic substance or an inorganic substance may be added to the elastic regulating member, and it may be melt-mixed or dispersed. For example, the chargeability of the toner can be controlled by adding a metal oxide, metal powder, ceramics, carbon allotrope, whisker, inorganic fiber, dye, pigment, surfactant or the like. In particular, when the elastic body is a molded body such as rubber or resin, fine metal oxide powders such as silica, alumina, titania, tin oxide, zirconia, and zinc oxide, carbon black, and a charge control agent generally used for toners Etc. are also preferably contained.
[0118]
Furthermore, by applying a DC electric field and / or an AC electric field to the regulating member, the uniform thin layer coating property and the uniform charging property are further improved due to the loosening action on the toner, and sufficient image density can be achieved and a good quality can be achieved. An image can be obtained.
[0119]
In FIG. 3, the primary charging member 117 uniformly charges the photoreceptor 100 rotating in the direction of the arrow.
[0120]
The primary charging member used here is a charging roller that basically includes a central core metal 117b and a conductive elastic layer 117a that forms the outer periphery thereof. The charging roller 117 is brought into contact with the entire surface of the electrostatic latent image carrier with a pressing force, and is driven to rotate as the photosensitive member 100 rotates.
[0121]
As a preferable process condition when the charging roller 117 is used, the contact pressure of the roller is 5 to 500 g / cm, and the applied voltage is a DC voltage or a DC voltage superposed with an AC voltage. Although not limited, in the present invention, an applied voltage of only a DC voltage is preferably used, and a voltage value in this case is used in a range of ± 0.2 to ± 5 kV.
[0122]
Other charging means include a method using a charging blade and a method using a conductive brush. These contact charging means have an effect that a high voltage is unnecessary and generation of ozone is reduced as compared with non-contact corona charging. The material of the charging roller and charging blade as the contact charging means is preferably conductive rubber, and a release coating may be provided on the surface thereof. As the releasable coating, nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride), and the like are applicable.
[0123]
Subsequent to the primary charging step, an electrostatic latent image corresponding to the information signal is formed on the photoconductor 100 by exposure 123 from the light emitting element 121, and the electrostatic latent image is developed with toner at a position in contact with the toner carrier 104. Visualize. Furthermore, in the image forming method of the present invention, particularly in combination with a developing system in which a digital latent image is formed on a photoreceptor, it becomes possible to develop the dot latent image faithfully without disturbing the latent image. . Next, the visible image is transferred onto the transfer target 127 by the transfer member 114. The surface of the photoconductor 100 for transfer is cleaned by a cleaning device 113. The cleaning device 113 may be omitted if the toner transfer efficiency is high. In this case, a bias of a direct current or alternating current component is applied at the time of development or at the time of blanking after development, and the residual toner on the development and the photosensitive member. Control is performed so that it can be recovered. Next, the transfer toner 129 passes through the fixing pressure roller 126 and the fixing pressure roller 128 together with the transfer target 127 and is fixed to obtain a permanent image. In addition to the heat roller system, the heating and pressure fixing means includes a heating roller having a built-in heating element such as a halogen heater and an elastic pressure roller pressed against the heating roller with a pressing force. A system in which heat is fixed by a heater through a film is also used.
[0124]
On the other hand, the untransferred toner remaining on the photoconductor 100 without being transferred passes between the photoconductor 100 and the primary charging member 117, reaches the developing nip again, and is contained in the developing device 140 by the toner carrier 104. To be recovered.
[0125]
Next, an image forming method using the intermediate transfer belt will be described with reference to FIG.
[0126]
FIG. 5 is a schematic explanatory diagram of a color image forming apparatus (a copying machine or a laser beam printer) using an electrophotographic process.
[0127]
Reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member as a first image carrier, which is rotationally driven in the direction of an arrow at a predetermined peripheral speed (process speed).
[0128]
In the rotating process, the photosensitive drum 1 is uniformly charged to a predetermined polarity and potential by the primary charger 2, and then subjected to exposure by an image exposure means 3 (not shown). In this way, an electrostatic latent image corresponding to the first color component image (for example, yellow color component image) of the target color image is formed.
[0129]
Next, the electrostatic latent image is developed into a yellow component image which is the first color by the first developing device (yellow color developing device 41). At this time, the second to fourth developing units, that is, the magenta developing unit 42, the cyan developing unit 43, and the black developing unit 44 are not operated and do not act on the photosensitive drum 1. The yellow component image of the color is not affected by the second to fourth developing units.
[0130]
The intermediate transfer belt 20 is driven to rotate in the direction of the arrow.
[0131]
In the process in which the yellow component image of the first color formed on the photoreceptor 1 passes through the nip portion between the photoreceptor 1 and the intermediate transfer belt 20, the intermediate transfer belt is supplied from the bias power supply 29 via the primary transfer roller 62. The image is sequentially transferred (primary transfer) to the outer peripheral surface of the intermediate transfer belt 20 by an electric field formed by a primary transfer bias applied to the belt 20.
[0132]
The surface of the photosensitive drum 1 after the transfer of the first color yellow toner image corresponding to the intermediate transfer belt 20 is cleaned by the cleaning device 13.
[0133]
Thereafter, similarly, a second color magenta toner image, a third color cyan toner image, and a fourth color black toner image are sequentially superimposed and transferred onto the intermediate transfer belt 20, and a composite color corresponding to the target color image is obtained. A toner image is formed.
[0134]
Reference numeral 63 denotes a secondary transfer roller, which is supported in parallel with the secondary transfer counter roller 64 and arranged in a state in which it can be separated from the lower surface of the intermediate transfer belt 20.
[0135]
A primary transfer bias for transferring the toner image from the photosensitive drum 1 to the intermediate transfer belt 20 is applied from a bias power source 29 with a polarity opposite to that of the toner. The applied voltage is, for example, in the range of +100 V to +2 kV.
[0136]
In the primary transfer process of the first to third color toner images from the photosensitive drum 1 to the intermediate transfer belt 20, the secondary transfer roller 63 and the untransferred toner charging member 52 can be separated from the intermediate transfer belt 20. .
[0137]
The full-color image transferred onto the intermediate transfer belt 20 is contacted by the secondary transfer roller 63 with the intermediate transfer belt 20 and a predetermined portion of the paper feed roller 11 is contacted with the intermediate transfer belt 20 and the secondary transfer roller 63. At this time, the transfer material P as the second image carrier is fed, and the secondary transfer bias is applied from the bias power supply 28 to the secondary transfer roller 63 to be secondarily transferred to the transfer material P. The transfer material P onto which the toner image has been transferred is introduced into the fixing device 15 and is heated and fixed.
[0138]
After the image transfer to the transfer material P is completed, the transfer residual toner cleaning device 50 is brought into contact with the intermediate transfer belt 20 to clean the surface of the intermediate transfer belt 20.
[0139]
After the image transfer to the transfer material P is completed, the transfer residual toner charging member 52 is brought into contact with the intermediate transfer belt 20 and is not transferred to the transfer material P by applying a bias having a polarity opposite to that of the photosensitive drum 1. Electric charge having a polarity opposite to that of the photosensitive drum 1 is applied to the toner (transfer residual toner) remaining on the intermediate transfer belt 20.
[0140]
The transfer residual toner is electrostatically transferred to the photosensitive drum 1 at and near the contact portion with the photosensitive drum 1, whereby the intermediate transfer belt 20 is cleaned.
[0141]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention, these do not limit this invention at all.
[0142]
Toner production example 1
In a 4 liter flask for 2 liters equipped with a high-speed stirring device TK-homomixer, 910 parts by weight of ion-exchanged water and 0.1 mol / liter-Na_ThreePO_Four450 parts by weight of an aqueous solution was added, the rotational speed was adjusted to 15000 rpm, and the mixture was heated to 60 ° C. Here 1.0 mol / liter-CaCl₂Gradual addition of 68 parts by weight of aqueous solution to form a slightly water-insoluble dispersant Ca_Three(PO_Four)₂A dispersion medium system containing was prepared.
・ 160 parts by weight of styrene monomer
・ 40 parts by weight of n-butyl acrylate monomer
・ Carbon black 4 parts by weight
・ 8 parts by weight of release agent
・ Styrene-butadiene copolymer resin 10 parts by weight
・ 4 parts by weight of crystalline azo-based iron complex compound A
After the mixture was dispersed for 3 hours using an attritor, a dispersion in which 4 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added (polymerizable monomer composition) ) In the dispersion medium and granulated for 10 minutes while maintaining the rotation speed. Then, the stirrer was changed from a high-speed stirrer to a propeller stirring blade, polymerization was performed at 200 rpm and 60 ° C. for 5 hours, and then the internal temperature was raised to 80 ° C. and polymerization was continued for 5 hours.
[0143]
After completion of the polymerization, the slurry was cooled and diluted hydrochloric acid was added to remove the dispersant.
[0144]
By further washing and drying, black particles (toner particles) 1 having a weight average particle diameter of 7.3 μm, an average circularity of 0.981, and a circularity standard deviation of 0.026 were obtained.
[0145]
0.1 part by weight of an aluminum complex compound B of amorphous dialkylsalicylic acid is added to 100 parts by weight of the obtained toner particles 1, and the peripheral speed of the stirring blade is set to 50 m / sec using a Henschel mixer, and the temperature is 45 ° C. After mixing for less than 5 minutes, 1.5 parts by weight of hydrophobized silica having an average particle diameter of 10 nm and 0.5 parts by weight of resin (polymethyl methacrylate) fine particles having an average particle diameter of 0.5 μm are externally added to the toner. A was obtained. The obtained toner A had a weight average particle diameter of 7.3 μm, an average circularity of 0.981, and a circularity standard deviation of 0.026.
[0146]
When SEM observation of the toner particles after adding 0.1 parts by weight of amorphous dialkylsalicylic acid aluminum complex compound B and mixing for 5 minutes with a Henschel mixer at 10,000 times and 30,000 times, It was confirmed that the aluminum complex compound B of amorphous dialkylsalicylic acid uniformly coats the toner particle surface, not in a granular state.
[0147]
The above-mentioned aluminum complex compound B of dialkyl salicylic acid is Al₂(SO_Four)_ThreeAlkaline aqueous solution of dialkyl salicylic acid is added to the aqueous solution.₂(SO_Four)_Three  It was obtained by adding dialkyl salicylic acid to 2.6 mol with respect to 1 mol, reacting with stirring, and separating the reaction product by filtration, warm water, washing and drying.
[0148]
The aluminum complex compound B of dialkyl salicylic acid has a peak with a measurement angle of 2θ in the range of 6 to 40 degrees and a measured intensity of 10,000 cps or more and a half width at half maximum of 0.3 degrees or less in the X-ray diffraction measurement. Confirmed that there is no.
[0149]
In addition, the azo-based iron complex compound A has a peak of maximum intensity in X-ray diffraction measurement, a measurement intensity of 15000 cps at 2θ = 13.6 degrees, and a half-width at half maximum = 0.13. It was confirmed to be a crystalline substance.
[0150]
Toner Production Example 2
In a 4 liter flask for 2 liters equipped with a high-speed stirring device TK-homomixer, 910 parts by weight of ion-exchanged water and 0.1 mol / liter-Na_ThreePO_Four450 parts by weight of an aqueous solution was added, the rotational speed was adjusted to 15000 rpm, and the mixture was heated to 60 ° C. Here 1.0 mol / liter-CaCl₂Gradual addition of 68 parts by weight of aqueous solution to form a slightly water-insoluble dispersant Ca_Three(PO_Four)₂A dispersion medium system containing was prepared.
・ 160 parts by weight of styrene monomer
・ 40 parts by weight of n-butyl acrylate monomer
・ Carbon black 4 parts by weight
・ 8 parts by weight of release agent
・ 4 parts by weight of polyester resin
・ Crystalline azo-based chromium complex compound C 4 parts by weight
After the mixture was dispersed for 3 hours using an attritor, a dispersion in which 4 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added (polymerizable monomer composition) ) In the dispersion medium and granulated for 10 minutes while maintaining the rotation speed. Thereafter, the stirrer was changed from a high-speed stirrer to a propeller stirring blade, polymerization was carried out at 200 rpm and 60 ° C. for 5 hours, and then the internal temperature was raised to 80 ° C. and polymerization was continued for 5 hours.
[0151]
After completion of the polymerization, the slurry was cooled and diluted hydrochloric acid was added to remove the dispersant.
[0152]
By further washing and drying, black particles (toner particles) 2 having a weight average particle diameter of 7.6 μm, an average circularity of 0.982 and a circularity standard deviation of 0.025 were obtained.
[0153]
0.3 parts by weight of amorphous dialkyl salicylic acid zirconium complex compound D is added to 100 parts by weight of the obtained toner particles 2, and the peripheral speed of the stirring blade is set to 35 m / sec with a Henschel mixer, and the temperature is 45 ° C. After mixing for less than 9 minutes, 1.5 parts by weight of hydrophobized silica having an average particle diameter of 10 nm and 0.5 parts by weight of resin fine particles having an average particle diameter of 0.5 μm were externally added to obtain toner B. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner B.
[0154]
SEM observation of the toner particles after adding 0.3 parts by weight of amorphous dialkyl salicylic acid zirconium complex compound D and mixing for 9 minutes with a Henschel mixer at 10,000 times and 30,000 times It was confirmed that the zirconium complex compound D of amorphous dialkyl salicylic acid uniformly coats the toner particle surfaces, not in the granular state.
[0155]
The zirconium complex D of dialkyl salicylic acid has a peak having a measurement intensity of 10,000 cps or more and a half width at half maximum of 0.3 degrees or less in a measurement angle 2θ range of 6 to 40 degrees in X-ray diffraction measurement. Confirmed that there is no.
[0156]
In addition, as shown in FIG. 2, the azo-based chromium complex compound C has a maximum measurement intensity peak in X-ray diffraction measurement of 2θ = 8.72 degrees, a measurement intensity of 41000 cps, and a half-value half width = 0.14. It was confirmed that it was a crystalline substance.
[0157]
Toner Production Example 3
In toner production example 1, toner production example 1 is used except that an amorphous dialkyl salicylic acid aluminum complex compound B is used instead of an externally added amorphous dialkyl salicylic acid aluminum complex compound D. In the same manner as above, Toner C was obtained. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner C.
[0158]
When SEM observation of the toner particles after adding 0.1 parts by weight of amorphous dialkyl salicylic acid zirconium complex compound D and mixing for 5 minutes with a Henschel mixer at 10,000 times and 30,000 times, It was confirmed that the zirconium complex compound D of amorphous dialkyl salicylic acid uniformly coats the toner particle surfaces, not in the granular state.
[0159]
Toner Production Example 4
In Toner Production Example 1, toner D was prepared in the same manner as in Toner Production Example 1 except that the addition amount of the externally added amorphous dialkyl salicylic acid aluminum complex compound B was changed to 0.01 parts by weight. Got. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner D.
[0160]
When SEM observation of the toner particles after adding 0.01 parts by weight of amorphous dialkylsalicylic acid aluminum complex compound B and mixing for 5 minutes with a Henschel mixer at 10,000 times and 30,000 times, It was confirmed that the aluminum complex compound B of amorphous dialkylsalicylic acid uniformly coats the toner particle surface, not in a granular state.
[0161]
Toner Production Example 5
In Toner Production Example 1, toner E was prepared in the same manner as in Toner Production Example 1, except that the addition amount of the externally added amorphous dialkyl salicylic acid aluminum complex compound B was changed to 0.005 parts by weight. Got. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner E.
[0162]
When SEM observation of the toner particles after adding 0.005 parts by weight of amorphous dialkyl salicylic acid aluminum complex compound B and mixing for 5 minutes with a Henschel mixer at 10,000 times and 30,000 times, It was confirmed that the aluminum complex compound B of amorphous dialkylsalicylic acid uniformly coats the toner particle surface, not in a granular state.
[0163]
Toner Production Example 6
In the toner production example 1, the toner F was the same as the toner production example 1 except that the addition amount of the externally added amorphous dialkyl salicylic acid aluminum complex compound B was changed to 0.5 parts by weight. Got. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner F.
[0164]
After adding 0.5 parts by weight of amorphous dialkyl salicylic acid aluminum complex compound B and mixing the toner particles for 5 minutes with a Henschel mixer, the SEM observation of the toner particles at 10,000 times and 30,000 times revealed that It was confirmed that the aluminum complex compound B of amorphous dialkylsalicylic acid uniformly coats the toner particle surface, not in a granular state.
[0165]
Toner Production Example 7
Toner G is the same as Toner Production Example 1 except that the amount of externally added amorphous dialkyl salicylic acid aluminum complex compound B in the toner production example 1 is changed to 0.7 parts by weight. Got. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner G.
[0166]
SEM observation of the toner particles after adding 0.7 parts by weight of amorphous dialkyl salicylic acid aluminum complex compound B and mixing for 5 minutes with a Henschel mixer at 10,000 and 30,000 times reveals that the surface of the toner particles It was confirmed that the aluminum complex compound B of amorphous dialkylsalicylic acid uniformly coats the toner particle surface, not in a granular state.
[0167]
Toner Production Example 8
・ 100 parts by weight of polyester resin
・ Carbon black 4 parts by weight
・ 4 parts by weight of release agent
・ Amorphous dialkyl salicylic acid zirconium complex D 6 parts by weight
The above materials are sufficiently premixed with a Henschel mixer, melt-kneaded at a temperature of about 140 ° C. with a twin-screw extruder kneader, cooled and roughly crushed to about 1 to 2 mm using a hammer mill, and then air-jet type It was pulverized with a pulverizer. Further, the obtained finely pulverized product was classified to obtain black particles 3 having a weight average diameter of 8.4 μm, an average circularity of 0.952, and a circularity standard deviation of 0.045.
[0168]
The obtained black particles 3 were subjected to a surface treatment at 4000 rpm for 3 minutes using a hybridizer to obtain black particles (toner particles) 4 having an average circularity of 0.963 and a circularity standard deviation of 0.036. .
[0169]
0.1 part by weight of amorphous dialkyl salicylic acid aluminum complex compound B is added to 100 parts by weight of the toner particles 4 obtained, and the peripheral speed of the stirring blade is set to 50 m / sec with a Henschel mixer, and the temperature is less than 45 ° C. Then, 1.0 part by weight of hydrophobized silica having an average particle diameter of 12 nm and 0.3 part by weight of resin fine particles having an average particle diameter of 0.5 μm were externally added to obtain toner H. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner H.
[0170]
When SEM observation of the toner particles after adding 0.1 parts by weight of amorphous dialkylsalicylic acid aluminum complex compound B and mixing for 5 minutes with a Henschel mixer at 10,000 times and 30,000 times, It was confirmed that the aluminum complex compound B of amorphous dialkylsalicylic acid uniformly coats the toner particle surface, not in a granular state.
[0171]
Toner Production Example 9
In Toner Production Example 1, Toner I was obtained in the same manner as in Toner Production Example 1 except that the average particle size of the externally added resin fine particles was changed to 1.0 μm. Table 1 shows the weight average particle diameter, average circularity and circularity standard deviation of the obtained toner I.
[0172]
Toner Production Example 10
In Toner Production Example 1, Toner J was obtained in the same manner as in Toner Production Example 1 except that resin fine particles having an average particle size of 0.5 μm were not externally added. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner J.
[0173]
Toner Production Example 11
In Toner Production Example 2, toner particles 5 were produced in the same manner as in Toner Production Example 2 except that the crystalline azo-chromium complex C was not added when the toner particles 2 were produced. In the same manner, Toner K was obtained. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner K.
[0174]
SEM observation of the toner particles after adding 0.3 parts by weight of amorphous dialkyl salicylic acid zirconium complex compound D and mixing for 9 minutes with a Henschel mixer at 10,000 times and 30,000 times It was confirmed that the zirconium complex compound D of amorphous dialkyl salicylic acid uniformly coats the toner particle surfaces, not in the granular state.
[0175]
Toner Production Example 12
In toner production example 2, all the same as toner production example 2 except that the externally added zirconium complex D of amorphous dialkyl salicylic acid was changed to chromium complex E of amorphous dialkyl salicylic acid. Toner L was obtained. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner L.
[0176]
After adding 0.3 part by weight of the chromium complex compound E of amorphous dialkyl salicylic acid and mixing for 9 minutes with a Henschel mixer, the toner particles were observed with SEM at 10,000 times and 30,000 times. It was confirmed that the chromium complex compound E of dialkyl salicylic acid was not in a granular state but coated the toner particle surface, but was scattered with non-coated portions.
[0177]
As shown in FIG. 1, this dialkyl salicylic acid chromium complex E has a peak of a measurement intensity of 4300 cps at a measurement angle 2θ of 6 to 40 degrees and a measurement angle 2θ of 14.32 degrees, as shown in FIG. The peak has a half width at half maximum of about 4, and therefore does not have a peak with a measured angle 2θ in the range of 6 to 40 degrees, a measured intensity of 10,000 cps or more, and a half width at half maximum of 0.3 degrees or less. confirmed.
[0178]
Toner Production Example 13
To 100 parts by weight of toner particles 2 obtained in Toner Production Example 2, 0.3 parts by weight of amorphous dialkyl salicylic acid chromium complex compound E and 1.5 parts of hydrophobized silica having an average particle diameter of 10 nm are used. Part by weight, and 0.5 parts by weight of resin fine particles with an average particle size of 0.5 μm are added at the same time with a Henschel mixer at a peripheral speed of the stirring blade of 35 m / sec and mixed for 9 minutes at a temperature of less than 45 ° C. Toner M was obtained. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner M.
[0179]
When the SEM observation of the toner after the external addition was performed at 10,000 times and 30,000 times, a part of the chromium complex compound E of amorphous dialkyl salicylic acid covered the toner particle surface, and a part was released. It was.
[0180]
Toner Production Example 14
In a 4 liter flask for 2 liters equipped with a high-speed stirring device TK-homomixer, 910 parts by weight of ion-exchanged water and 0.1 mol / liter-Na_ThreePO_Four450 parts by weight of an aqueous solution was added, the rotational speed was adjusted to 12000 rpm, and the mixture was heated to 60 ° C. Here 1.0 mol / liter-CaCl₂Gradual addition of 68 parts by weight of aqueous solution to form a slightly water-insoluble dispersant Ca_Three(PO_Four)₂A dispersion medium system containing was prepared.
・ 160 parts by weight of styrene monomer
・ 40 parts by weight of n-butyl acrylate monomer
・ Yellow pigment (CI Pigment Yellow 17) 20 parts by weight
・ 30 parts by weight of release agent
・ 20 parts by weight of polyester resin
Amorphous dialkyl salicylic acid aluminum complex compound B 2 parts by weight
After the mixture was dispersed for 3 hours using an attritor, a dispersion in which 4 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added (polymerizable monomer composition) ) In the dispersion medium and granulated for 10 minutes while maintaining the rotation speed. Then, the stirrer was changed from a high-speed stirrer to a propeller stirring blade, polymerization was performed at 200 rpm and 60 ° C. for 5 hours, and then the internal temperature was raised to 80 ° C. and polymerization was continued for 5 hours.
[0181]
After completion of the polymerization, the slurry was cooled and diluted hydrochloric acid was added to remove the dispersant.
[0182]
By further washing and drying, yellow colored particles (toner particles) 6 having a weight average particle diameter of 7.2 μm, an average circularity of 0.979, and a circularity standard deviation of 0.030 were obtained. .
[0183]
To 100 parts by weight of the obtained yellow toner particles 6, 0.05 part by weight of amorphous dialkyl salicylic acid aluminum complex compound B was added, and the peripheral speed of the stirring blade was adjusted to 50 m / sec with a Henschel mixer, and the temperature After mixing for 5 minutes at less than 45 ° C., 1.5 parts by weight of hydrophobized silica having an average particle size of 10 nm and 0.5 parts by weight of hydrophobized silica having an average particle size of 0.04 μm are externally added to toner N. Got. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner N.
[0184]
When SEM observation of the toner particles after adding 0.05 parts by weight of amorphous dialkyl salicylic acid aluminum complex compound B and mixing for 5 minutes with a Henschel mixer at 10,000 times and 30,000 times, It was confirmed that the aluminum complex compound B of amorphous dialkylsalicylic acid uniformly coats the toner particle surface, not in a granular state.
[0185]
Comparative toner production example 1
Toner O was obtained in the same manner as in Toner Production Example 2 except that the externally added amorphous dialkyl salicylic acid zirconium complex compound D was not added. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner O.
[0186]
Toner Comparative Production Example 2
0.3 parts by weight of a crystalline alkylsalicylic acid zinc complex compound F is added to 100 parts by weight of toner particles 2 obtained in Toner Production Example 2, and the peripheral speed of the stirring blade is set to 35 m / sec using a Henschel mixer. After mixing for 9 minutes at a temperature of less than 45 ° C., 1.5 parts by weight of hydrophobized silica having an average particle diameter of 10 nm and 0.5 parts by weight of resin fine particles having an average particle diameter of 0.5 μm are externally added to the toner. P was obtained. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner P.
[0187]
When 0.3 parts by weight of crystalline alkylsalicylic acid zinc complex compound F was added and mixed for 9 minutes with a Henschel mixer, the toner particles were observed at 10,000 and 30,000 times by SEM. It was confirmed that the zinc complex compound F of crystalline alkyl salicylic acid was embedded unevenly, and the zinc complex compound F of crystalline alkyl salicylic acid did not cover the toner surface.
[0188]
In addition, the zinc complex compound F of alkyl salicylic acid has a peak with a maximum measured intensity of 2θ = 6.58 degrees, a measured intensity of 80000 cps, and a half width at half maximum = 0.21 in X-ray diffraction measurement. It was confirmed that it was a crystalline substance.
[0189]
Comparative toner production example 3
0.3 parts by weight of crystalline azo-based chromium complex compound C is added to 100 parts by weight of toner particles 2 obtained in Toner Production Example 2, and the peripheral speed of the stirring blade is set to 35 m / sec using a Henschel mixer. After mixing at a temperature of less than 45 ° C. for 9 minutes, 1.5 parts by weight of hydrophobized silica having an average particle diameter of 10 nm and 0.5 parts by weight of resin fine particles having an average particle diameter of 0.5 μm are externally added to the toner Q. Got. Table 1 shows the weight average particle diameter, average circularity and circularity standard deviation of the obtained toner Q.
[0190]
SEM observation of the toner particles after adding 0.3 parts by weight of crystalline azo-chromium complex compound C and mixing for 5 minutes with a Henschel mixer was performed at 10,000 and 30,000 times. It was confirmed that the crystalline azo-chromium complex compound C was embedded unevenly, and the crystalline azo-chromium complex compound C did not cover the toner particle surface.
[0191]
Toner Comparative Production Example 4
In Toner Production Example 11, all of the toner production examples 11 except that 0.3 parts by weight of crystalline azo-based chromium complex compound C was added in place of the externally added amorphous dialkyl salicylic acid zirconium complex compound D. A toner R was obtained in the same manner as above. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner R.
[0192]
SEM observation of the toner particles after adding 0.3 parts by weight of crystalline azo-chromium complex compound C and mixing for 9 minutes with a Henschel mixer was performed at 10,000 and 30,000 times. It was confirmed that the crystalline azo-chromium complex compound C was embedded unevenly, and the crystalline azo-chromium complex compound C did not cover the toner particle surface.
[0193]
Comparative toner production example 5
As toner particles, 0.1 part by weight of an aluminum complex compound B of amorphous dialkyl salicylic acid is added to 100 parts by weight of the black particles 3 obtained in Toner Production Example 8, and the peripheral speed of the stirring blade is increased by a Henschel mixer. Was mixed at a temperature of less than 45 ° C. for 5 minutes, and then 1.0 part by weight of hydrophobized silica having an average particle diameter of 12 nm and 0.3 part by weight of resin fine particles having an average particle diameter of 0.5 μm were added. Externally added toner S was obtained. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner S.
[0194]
When SEM observation of the toner particles after adding 0.1 parts by weight of amorphous dialkyl salicylic acid aluminum complex compound B and mixing for 5 minutes with a Henschel mixer at 10,000 times and 30,000 times, It was confirmed that the aluminum complex compound B of dialkyl salicylic acid did not cover the concave portions of the toner particles.
[0195]
Comparative toner production example 6
0.05 parts by weight of a crystalline alkylsalicylic acid zinc complex compound F is added to 100 parts by weight of the yellow toner particles 6 obtained in Toner Production Example 14, and the peripheral speed of the stirring blade is set to 50 m with a Henschel mixer. After mixing for 5 minutes at a temperature of less than 45 ° C., 1.5 parts by weight of hydrophobized silica having an average particle diameter of 10 nm and 0.5 parts by weight of resin fine particles having an average particle diameter of 0.5 μm are externally added. The toner T was obtained. Table 1 shows the weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner T.
[0196]
SEM observation of the toner particles after adding 0.05 parts by weight of crystalline alkylsalicylic acid zinc complex compound F and mixing for 5 minutes with a Henschel mixer was performed at 10,000 and 30,000 times. It was confirmed that the zinc complex compound F of crystalline alkylsalicylic acid was embedded unevenly, and the zinc complex compound F of crystalline alkylsalicylic acid did not cover the toner particle surface.
[0197]
[Table 1]

[0198]
  [Examples 1 to8, Reference Examples 1-5And Comparative Examples 1 to 5]
  A 600 dpi laser beam printer (manufactured by Canon: LBP-860) was prepared as an electrophotographic apparatus having the configuration shown in FIGS. The process speed is modified to 60 mm / s.
[0199]
The charging method of this apparatus was direct charging performed by contacting a rubber roller, and the applied voltage was a DC component (-1200 V).
[0200]
Next, the development part in the process cartridge was modified. Instead of a stainless steel sleeve as a toner supply body, a medium resistance rubber roller (16φ, hardness ASKER C45 degree, resistance 10 made of silicone rubber dispersed with carbon black)^Five(Ω · cm) was used as a toner carrier, and was in contact with the photoreceptor. The developing nip width at this time was set to about 3 mm. The rotation speed of the toner carrier is the same in the contact portion with the photoconductor, and is driven to be 140% of the rotation speed of the photoconductor.
[0201]
The photoconductor used here was a 30φ, 254 mm Al cylinder as a substrate, and layers having the following constitution were sequentially laminated by dip coating to produce a photoconductor.
(1) Conductive coating layer: Mainly composed of a powder of tin oxide and titanium oxide dispersed in a phenolic resin. Film thickness 15 μm.
(2) Undercoat layer: Mainly composed of modified nylon and copolymer nylon. Film thickness 0.6 μm.
(3) Charge generation layer: Mainly composed of a titanyl phthalocyanine pigment having absorption in a long wavelength region dispersed in a butyral resin. Film thickness 0.6 μm.
(4) Charge transport layer: Mainly composed of a hole transportable triphenylamine compound dissolved in a polycarbonate resin (molecular weight 20,000 by Ostwald viscosity method) at a weight ratio of 8:10. Film thickness 20 μm.
[0202]
As a means for applying the toner to the toner carrier, an application roller made of urethane foam rubber was provided in the developing device and brought into contact with the toner carrier. A voltage of about −550 V is applied to the application roller. Further, a stainless steel blade coated with resin for controlling the coat layer of the toner on the toner carrier was attached so that the contact pressure with the toner carrier was about 20 g / cm. The outline is shown in FIG. In addition, the applied voltage at the time of development was only a DC component (−450 V).
[0203]
The electrophotographic apparatus was remodeled and process conditions were set as follows in order to conform to the remodeling of these process cartridges.
[0204]
The modified device uses a roller charger (applying only direct current) to uniformly charge the image carrier. Subsequent to charging, an image portion is exposed with a laser beam to form an electrostatic latent image, and a visible image is formed with toner, and then the toner image is transferred to a transfer material by a roller to which a voltage of +700 V is applied. The outline is shown in FIG.
[0205]
The photosensitive member charging potential was -580V for the dark portion potential and -150V for the bright portion potential. As a transfer material, 75 g / m²Paper was used.
[0206]
Using the toners A to M and the toners O to S, the image forming test of 7000 sheets was performed by the image forming apparatus in a normal temperature and normal humidity environment (23 ° C., 65% RH). In addition, durability evaluation was evaluated as follows.
[0207]
<Transfer efficiency>
The transfer efficiency is determined by tapering the transfer residual toner on the photoconductor after the solid black image transfer with a Mylar tape and pasting it on the paper. The Macbeth density value is C, and the Mylar is applied on the paper with the toner after the fixing before the transfer. When the Macbeth concentration of the tape with the tape applied was D and the Macbeth concentration of the Mylar tape affixed on unused paper was E, it was approximately calculated by the following equation.
[0208]
[Equation 5]

[0209]
The transfer efficiency was evaluated according to the following criteria.
A: Transfer efficiency is 96% or more
○: Transfer efficiency is 92% to 95%
Δ: Transfer efficiency is 88% to 91%
X: Transfer efficiency is 87% or less
[0210]
<Image quality>
The criteria for determining the image quality are as follows.
A: Very good.
◯: Good image although slightly distorted.
Δ: A level where there is no problem in practical use although there is a slight difference.
X: The roughness is terrible.
[0211]
<Fog>
The fog on paper is measured using a reflection densitometer (REFLECTOMETER MODEL TC-6DS manufactured by Tokyo Denshoku Co., Ltd.). For a black toner image, a Green filter is used. For a yellow toner image in Example 15 to be described later, It calculated from the following formula using a blue filter. The smaller the value, the less fog.
[0212]
Fog (reflectance) (%) = [reflectance of standard paper (%)] − [reflectance of white background of sample (%)]
[0213]
The evaluation of fog is performed by sampling the paper on which the solid white image is formed every 1000 sheets from the initial stage during the continuous image output test of 7000 sheets, and measuring the fog for the sampled image. The fog is measured at the five corners of the four corners and the center of the image, and the average value of the five points is defined as fog on paper.
[0214]
The evaluation standard of fog at the initial stage of image drawing is as follows.
A: The average fog is 3% or less.
○: The average fog is 5% or less
Δ: fogging average exceeds 5%
X: Fog exceeds 5% at all measurement points
[0215]
The evaluation criteria of fog after image endurance are as follows.
◎: fog is 3% or less in general durability
○: fog is 5% or less in general durability
Δ: fog may temporarily exceed 5% during endurance
×: More than half of durability and fog exceeds 5%
[0216]
The evaluation results are shown in Table 2.
[0217]
[Table 2]

[0218]
  [Example9]
  Examples 1 to above8 and Reference Examples 1-5The image forming test was performed using the toner A after removing the cleaning blade of the process cartridge of the image forming apparatus used in the evaluation method. The evaluation results are shown in Table 3 below.
[0219]
[Table 3]

[0220]
  [Example10And Comparative Example 6]
  The LBP-2040, which is a full-color image forming apparatus having the configuration shown in FIG. 5, was modified to perform contact development, and 3000 sheets were used in a normal temperature and humidity environment (23 ° C., 65% RH) using toners N and T. An image output test was conducted. The evaluation results are shown in Table 4 below.
[0221]
  Evaluation items are Examples 1 to8 and Reference Examples 1-5As for transfer efficiency, the transfer from the photosensitive member to the intermediate transfer member is the primary transfer, and the transfer from the intermediate transfer member to the paper is the secondary transfer. The value of the Macbeth density of the toner taped and removed by Mylar tape is F, the Macbeth density of the Mylar tape pasted on the intermediate transfer body before the secondary transfer is G, and the secondary transfer residual toner on the intermediate transfer body is Macbeth density value of tape taped and removed by Mylar tape, H, Macbeth density of Mylar tape pasted on paper with toner before fixing after secondary transfer I, Macbeth density of paper pasted on unused paper When E is E, it is approximately calculated by the following equation.
[0222]
[Formula 6]

[0223]
[Table 4]

[0224]
【The invention's effect】
According to the present invention, a metal salt, a metal complex, or a mixture of a metal salt and a metal complex of the low crystalline or amorphous aromatic compound as described above is present on the toner particle surface. By using the toner, a high-quality image with high transfer efficiency and little fogging can be obtained even after endurance in the contact development method.
[Brief description of the drawings]
FIG. 1 is an X-ray diffraction chart of a metal complex of an amorphous aromatic compound.
FIG. 2 is an X-ray diffraction chart of a metal complex of a crystalline aromatic compound.
FIG. 3 is a schematic explanatory diagram of an image forming apparatus to which the present invention can be applied.
4 is a schematic explanatory diagram of a developing device of the image forming apparatus shown in FIG.
FIG. 5 is a schematic explanatory diagram of a full-color image forming apparatus using an intermediate transfer member to which the present invention can be applied.
[Explanation of symbols]
1 Photosensitive drum
2 Primary charger
3 Image exposure means
10 Transfer material guide
11 Paper feed roller
13 Photosensitive drum cleaning device
15 Fixing device
20 Intermediate transfer belt
26 Bias power supply
28 Bias power supply
29 Bias power supply
41 Yellow color developing device
42 Magenta color developing device
43 Cyan developing device
44 Black color developing device
50 Cleaning device for intermediate transfer member
52 Transfer residual toner charging member
62 Primary transfer roller
63 Secondary transfer roller
64 Secondary transfer counter roller
65 Intermediate transfer belt support roller
66 Intermediate transfer belt support roller
100 photoconductor
104 Toner carrier
113 Cleaning device
114 Transfer means
117 Charger
123 Laser light or analog light
126 Pressure fixing means
128 Heat fixing means
131, 132, 133, 134 Bias applying means
140 Developer
141 Application roller
142 Toner
143 Elastic blade

Claims (11)

A charging step for charging the electrostatic image carrier, an exposure step for forming an electrostatic latent image on the electrostatic image carrier by exposure, an electrostatic latent image on the electrostatic image carrier and a toner carrier An image forming method comprising at least a development step of developing while contacting a coated toner, and a transfer step of transferring the toner image to a transfer material,
The toner has toner particles containing at least a binder resin, a colorant, and a release agent, and has an average circularity of 0.955 or more.
The toner is obtained by mixing and stirring the aluminum complex compound of dialkyl salicylic acid and the toner particles, and further adding fine particles to the outside, and the aluminum complex compound of dialkyl salicylic acid is formed on the toner particle surface. , Without being embedded, it is no longer in a granular state,
Aluminum complex compound of the dialkyl salicylic acid, in a range of measurement angles 2θ of 6 to 40degree in X-ray diffraction, the measured intensity is not less than 10000 cps, and half width at half maximum that have the following peaks 0.3degree torquecontrol-crystalline A dialkyl salicylic acid alkaline aqueous solution is added to an Al ₂ (SO ₄ ) ₃ aqueous solution at a ratio of 2.1 to 3.0 mol of dialkyl salicylic acid per 1 mol of Al ₂ (SO ₄ ) _3. An image forming method characterized by being obtained by reacting . Aluminum complex compound of dialkyl salicylic acid of the non-crystalline The image forming method according to claim 1, characterized in that is present in the toner particles 100 parts by weight per 0.01 to 0.5 part by weight toner particle surfaces . Aluminum complex compound of dialkyl salicylic acid of the non-crystalline The image forming method according to claim 1, characterized in that is present in the toner particles 100 parts by weight per 0.01 to 0.3 part by weight toner particle surfaces .   The image according to any one of claims 1 to 3, wherein the toner particles further contain a metal complex compound, a metal salt of an aromatic compound, or a mixture of a metal complex compound and a metal salt. Forming method. Metal complex compounds of aromatic compounds, metal salts or a mixture of metal complex compound and metal salt are contained in the binder resin per 100 parts by weight of 0.05 to 5 parts by weight the toner particles, the non-crystalline 2. The image forming method according to claim 1, wherein the aluminum complex compound of dialkyl salicylic acid is present on the toner particle surface in an amount of 0.01 to 0.5 parts by weight per 100 parts by weight of the toner particles. The image forming method according to any one of claims 1 to 5 average circularity of the toner is characterized in that it is a 0.955 to 0.990. The image forming method according to any one of claims 1 to 5 average circularity of the toner is characterized in that it is a .960-.985. The image forming method according to any one of claims 1 to 7 circularity standard deviation of the toner is equal to or less than 0.040. Microparticles, image forming method according to any one of claims 1 to 8, characterized in that it has two or more different particulate average particle sizes. 10. The image forming method according to claim 9 , wherein an average particle size of at least one kind of fine particles is 0.03 to 0.8 μm. The charging step, the charging member is brought into contact with the electrostatic image bearing member, a voltage is applied to from the charging member outside to any one of claims 1 to 10, characterized in that charging the electrostatic image bearing member The image forming method described.

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