JP4095207B2 - Filling toner container with toner - Google Patents

Description

【００３５】
上式において、「粒子投影像の周囲長」とは、二値化された粒子像のエッジ点を結んで得られる輪郭部の長さであり、「相当円の周囲長」とは、二値化された粒子像と同じ面積を有する円の外周の長さである。
【００３６】
トナーの平均円形度が０．９５０未満の場合には、トナー表面上で外添剤が偏在しやくなり、結果として、画像濃度が不安定になり易く、トナーの平均円形度が０．９９５を超える場合には、トナー表面上に外添剤が保持されにくくなり、結果として帯電が不均一になりカブリが発生しやすくなる。
【００３７】
トナーは、円形度の０．９５０未満の粒子を２〜４０個数％、好ましくは３〜３０個数％含有している。
【００３８】
円形度０．９５０未満の粒子の含有量が２個数％未満の場合には、トナーが最密充填され易くなり、結果として充填時の排出性の制御が困難になりやすくなる。
【００３９】
円形度０．９５０未満の粒子の含有量が４０個数％を超える場合には、トナーの流動性が低下し、細線再現性が低下の如き画像劣化を生じやすくなる。
【００４０】
本発明においては、特に懸濁重合方法が、製造されるトナー粒子の粒度分布がシャープになり、且つ離型剤としてのワックスを多量にトナー粒子中に含有させることができることから好ましい。更に一旦得られた重合トナー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も本発明に好適に利用することができる。
【００４１】
本発明のトナーは、重合方法を用いて製造されたトナー粒子を含有する場合においては、以下の如き製造方法によって具体的にトナー粒子を製造することが可能である。単量体中に低軟化点物質からなる離型剤、着色剤、荷電制御剤及び重合開始剤その他の添加剤を加え、ホモジナイザー、超音波分散機によって均一に溶融又は分散せしめた単量体系を、分散安定剤を含有する水相中に通常の撹拌機またはホモミキサー及びホモジナイザーの如き分散機により分散せしめる。好ましくは単量体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撹拌時間を調整し、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。
【００４２】
このとき、分散安定剤の種類や量、撹拌能力、水相のｐＨ及び重合温度により、円形度分布をコントロールすることができる。
【００４３】
本発明において、トナーの円相当径の円形度分布は、フロー式粒子像分析装置ＦＰＩＡ−１０００（東亜医用電子社製）を用いて以下の通り測定される。
【００４４】
測定は、フィルターを通して微細なごみを取り除き、その結果として１０^-3ｃｍ³の水中に測定範囲（例えば、円相当径０．６０μｍ以上１５９．２１μｍ未満）の粒子数が２０個以下のイオン交換水に界面活性剤（好ましくは和光純薬製コンタミノン）を０．１〜０．５重量％加えて調製した溶液約１０ｍｌ（２０℃）に、測定試料を約０．０２ｇ加えて均一に分散させて調製した。分散させる手段としては、株式会社エスエムテー社製の超音波分散機ＵＨ−５０（振動子は５φのチタン合金チップ）を用いた。分散時間は５分間以上とし、その際、分散媒の温度が４０℃以上にならないように適宜冷却した。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粒度分布及び円形度分布を測定する。
【００４５】
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。
【００４６】
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次元画像の面積から、同一の面積を有する円の直径を円相当径として算出する。更に、それぞれの粒子の２次元画像と同一面積を持つ円（相当円）の周囲長をそれぞれの粒子の２次元画像の周囲長で割って、それぞれの粒子の円形度を算出する。
【００４７】
結果（頻度％及び累積％）は、表１に示す通り、０．０６〜４００μｍの範囲を２２６チャンネル（１オクターブに対し３０チャンネルに分割）に分割して得ることができる。実際の測定では、円相当径が０．６０μｍ以上１５９．２１μｍ未満の範囲で粒子の測定を行う。
【００４８】
【表１】

＊）粒径範囲の上限は、その数値を含まず、「未満」を表わす。
【００４９】
特開平９−３０４９６８号公報には、トナーの重量平均粒径と篩の目開き比の関係が示されているが、本発明の如きトナーとして球形トナーを使用した際の外添剤の脱離を抑制し、長期にわたって安定に外添剤をトナー粒子上に付着させる点に関してはまったく記載されておらず、本発明とは異なるものである。
【００５０】
同様に、特開平７−３１１４７７号公報等には、トナーの篩装置として本発明の実施例で用いたターボスクリーナーの構成が、さらに、特開平１０−０４３６８８号公報等には、本発明の実施例で用いた超音波篩の使用が示されているが、いずれにおいてもトナー形状と外添剤の付着状態には言及しておらず、本発明とは異なるものである。
【００５１】
本発明においては、トナーの個数平均粒径が２〜８μｍであることも一つの特徴である。トナーの個数平均粒径が２μｍより小さい場合には、トナーの充填操作時に定量的に排出することが難しくなり、結果としてトナー容器からの溢れ・飛散等が生じやすくなる。一方、８μｍを超えると、微細な潜像に対する現像再現性が低下する。
【００５２】
本発明における外添剤としては、一般的に外添剤として広く知られている有機あるいは無機の微粒子を用いることが可能である。具体的には無機微粒子としては例えば金属酸化物（酸化アルミニウム、酸化チタン、チタン酸ストロンチウム、酸化セリウム、酸化マグネシウム、酸化クロム、酸化錫、酸化亜鉛など）・窒化物（窒化ケイ素など）・炭化物（炭化ケイ素など）・金属塩（硫酸カルシウム、硫酸バリウム、炭酸カルシウムなど）・脂肪酸金属塩（ステアリン酸亜鉛、ステアリン酸カルシウムなど）・カーボンブラック・シリカなどを用いることが出来る。また、有機微粒子としては、例えば乳化重合法やスプレードライ法による、スチレン、アクリル酸、メチルメタクリレート、ブチルアクリレート、２−エチルヘキシルアクリレートの如きトナー用結着樹脂に用いられるモノマー成分の単独重合体あるいは共重合体を用いることが出来る。
【００５３】
また、必要に応じてこれら微粒子を複数種併用することも可能である。
【００５４】
特に本発明においては、外添剤として、それ自身帯電能の小さい酸化チタン、酸化アルミニウム及びそれらのシリカ処理微粒子等を使用した場合に好適である。すなわち、上述の帯電能の小さい外添剤は、従来外添剤として広く使用されている帯電能の高いシリカ微粒子と比較してトナー粒子表面との静電付着力が小さく、粗粒子分離工程であるスクリーンに通過させる際、トナー粒子から遊離気味となる。しかしながら、本発明においては、次工程で充填工程をとるので、遊離が長期にわたって抑制されるようになる。
【００５５】
本発明のトナーに使用される外添剤としては、流動性付与の点から、その重量平均粒径が１０〜４００ｎｍ、好ましくは１０〜１００ｎｍであることが好ましい。４００ｎｍより大きいと、流動性不良によるトナー帯電が不均一となり、結果としてトナー飛散やカブリ等が生じてしまう。一方、１０ｎｍより小さいと、トナー表面に埋め込まれやすくなり、トナー劣化が早く生じてしまい、耐久性が低下してしまい好ましくない。
【００５６】
さらに、トナー粒子上で一次粒子又は二次粒子の状態で存在している上述の外添剤（Ａ）と、粒子が複数個合一することにより生成された非球形状無機微粉体（Ｂ）とを有することが、より好ましい。
【００５７】
すなわち、外添剤（Ａ）は、トナー粒子表面上に適度に付着することにより、トナー粒子表面の電荷を均一化させて、トナーの帯電量分布をシャープにし、且つトナーの流動性を向上させるように作用し、非球形状無機微粉体（Ｂ）は、トナー粒子のスペーサーとして機能することにより、外添剤（Ａ）のトナー粒子の埋設を抑制するように作用するものである。
【００５８】
一般に、表面に凹凸が少なく球形に近いトナー粒子は、キャリア粒子の如きトナーに摩擦帯電電荷を付与するための部材と接触した場合に、トナー粒子表面に外添されている外添剤の逃げる場所が少なく、トナー粒子表面に埋設され易く、トナー劣化が生じ易い。
【００５９】
しかしながら、本発明のトナーは、上述した通り平均円形度が０．９５０〜０．９９５であり、円形度０．９５０未満の粒子の含有量が２〜４０個数％である球形に近いトナーであるが、外添剤（Ａ）と非球形状無機微粉体（Ｂ）とをトナー粒子上に有していることから、外添剤（Ａ）のトナー粒子表面への埋設を有効に抑制するものである。
【００６０】
本発明に用いられる非球形状無機微粉体（Ｂ）は、トナー粒子上の形状係数ＳＦ−１が１５０より大きく、好ましくは１９０より大きく、更に好ましくは２００より大きいことが、外添剤（Ａ）のトナー粒子表面への埋設抑制の点で良い。
【００６１】
非球形状無機微粉体（Ｂ）の形状係数ＳＦ−１が１５０以下の場合には、トナー粒子表面に非球形状無機微粉体（Ｂ）自体が埋設し易くなることから、外添剤（Ａ）の埋設抑制効果が低下する。
【００６２】
非球形状無機微粉体（Ｂ）のトナー粒子上の形状係数ＳＦ−１の測定は、ＦＥ−ＳＥＭによる１０万倍の拡大倍率で行う。
【００６３】
本発明における形状係数を示すＳＦ−１とは、日立製作所ＦＥ−ＳＥＭ（Ｓ−８００）を用い粒子像を１００個無作為にサンプリングし、その画像情報はインターフェースを介してニコレ社製画像解析装置（Ｌｕｚｅｘ３）に導入し解析を行い、下式より算出した値を定義した。
【００６４】
【数２】

（式中、ＭＸＬＮＧは画像上測定粒子の絶対最大長を示し、ＡＲＥＡは測定粒子の投影面積を示す。）
【００６５】
非球形状無機微粉体（Ｂ）は、トナー粒子上の平均長径が好ましくは１２０乃至６００ｎｍ、より好ましくは１３０乃至５００ｎｍであることが良い。
【００６６】
非球形状無機微粉体（Ｂ）の平均長径が１２０ｎｍ未満の場合には、外添剤（Ａ）のトナー表面への埋め込みを抑制するスペーサー効果が小さく、結果として、トナーの現像性／転写性が低下し画像濃度が低下しやすくなり、６００ｎｍを超える場合には、上述のスペーサー効果は期待できるものの、トナー表面から遊離しやすくなり、結果として感光体の削れ、傷等が発生しやすくなる。
【００６７】
本発明に係るトナーは、通常、結着樹脂及び着色剤を主成分とする。
【００６８】
本発明に係るトナーの結着樹脂としては、ポリスチレン、ポリビニルトルエンの如きスチレン及びその置換体の単重合体；スチレン−プロピレン共重合体、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−アクリル酸メチル共重合体、スチレン−アクリル酸エチル共重合体、スチレン−アクリル酸ブチル共重合体、スチレン−アクリル酸オクチル共重合体、スチレン−アクリル酸ジメチルアミノエチル共重合体、スチレン−メタクリル酸メチル共重合体、スチレン−メタクリル酸エチル共重合体、スチレン−メタクリル酸ブチル共重合体、スチレン−メタクリル酸ジメチルアミノエチル共重合体、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−マレイン酸共重合体、スチレン−マレイン酸エステル共重合体の如きスチレン系共重合体；ポリメチルメタクリレート、ポリブチルメタクリレート、ポリ酢酸ビニル、ポリエチレン、ポリプロピレン、ポリビニルブチラール、ポリアクリル酸樹脂、ロジン、変性ロジン、テルペン樹脂、フェノール樹脂、脂肪族又は脂環族炭化水素樹脂、芳香族系石油樹脂、パラフィンワックス、カルナバワックスなどが挙げられる。これらは、単独あるいは混合して使用できる。
【００６９】
本発明に係るトナーに用いられる着色剤は、黒色着色剤としてカーボンブラック，磁性体，以下に示すイエロー／マゼンタ／シアン着色剤を用い各色に調色されたものが利用される。
【００７０】
イエロー着色剤としては、縮合アゾ化合物，イソインドリノン化合物，アンスラキノン化合物，アゾ金属錯体，メチン化合物，アリルアミド化合物に代表される化合物が用いられる。具体的には、Ｃ．Ｉ．ピグメントイエロー１２、１３、１４、１５、１７、６２、７４、８３、９３、９４、９５、１０９、１１０、１１１、１２８、１２９、１４７、１６８、１８０、ソルベントイエロー１６２、１６３等が好適に用いられる。
【００７１】
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．ピグメントレット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。
【００７２】
本発明に用いられる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、１５：２、１５：３、１５：４、６０、６２、６６等が特に好適に利用できる。
【００７３】
これらの着色剤は、単独又は混合し更には固溶体の状態で用いることができる。
【００７４】
本発明の着色剤は、カラートナーの場合、色相角，彩度，明度，耐候性，ＯＨＰ透明性，トナー中への分散性の点から選択される。該着色剤の添加量は、樹脂１００重量部に対し１〜２０重量部添加して用いられる。
【００７５】
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重量部に対し４０〜１５０重量部添加して用いられる。
【００７６】
本発明のトナーには、必要に応じて荷電制御剤を用いることができる。
【００７７】
本発明に用いられる荷電制御剤としては、公知のものが利用できるが、カラートナーの場合は、特に、無色でトナーの帯電スピードが速く且つ一定の帯電量を安定して維持できる荷電制御剤が好ましい。
【００７８】
具体的化合物としては、ネガ系としてサリチル酸，ナフトエ酸，ダイカルボン酸，それらの誘導体の金属化合物、スルホン酸，カルボン酸を側鎖に持つ高分子型化合物、ホウ素化合物、尿素化合物、ケイ素化合物、カリークスアレーン等が利用でき、ポジ系として四級アンモニウム塩、該四級アンモニウム塩を側鎖に有する高分子型化合物、グアニジン化合物、イミダゾール化合物等が好ましく用いられる。
【００７９】
該荷電制御剤は樹脂１００重量部に対し０．５〜１０重量部が好ましい。しかしながら本発明において荷電制御剤の添加は必須ではなく、二成分現像方法を用いた場合においては、キャリアとの摩擦帯電を利用し、非磁性一成分ブレードコーティング現像方法を用いた場合においてもブレード部材やスリーブ部材との摩擦帯電を積極的に利用することでトナー中に必ずしも荷電制御剤を含む必要はない。
【００８０】
本発明のトナーには、必要に応じて低軟化点物質、いわゆるワックスを用いることができる。
【００８１】
本発明のトナーに用いられる低軟化点物質としては、パラフィンワックス、ポリオレフィンワックス、マイクロクリスタリンワックス、フィッシャートロピッシュワックスの如きポリメチレンワックス、アミドワックス、高級脂肪酸、長鎖アルコール、エステルワックス及びこれらのグラフト化合物、ブロック化合物の如き誘導体が挙げられ、これらは低分子量成分が除去されたＤＳＣ吸熱曲線の最大吸熱ピークがシャープなものが好ましい。
【００８２】
好ましく用いられるワックスとしては、炭素数１５〜１００個の直鎖状のアルキルアルコール、直鎖状脂肪酸、直鎖状酸アミド、直鎖状エステルあるいは、モンタン系誘導体が挙げられる。また、これらワックスから液状脂肪酸の如き不純物を予め除去してあるものも好ましい。
【００８３】
さらに、好ましく用いられるワックスは、アルキレンを高圧下でラジカル重合あるいは低圧下でチーグラー触媒またはその他の触媒を用いて重合した低分子量のアルキレンポリマー；高分子量のアルキレンポリマーを熱分解して得られるアルキレンポリマー；アルキレンを重合する際に副生する低分子量アルキレンポリマーを分離精製したもの；一酸化炭素及び水素からなる合成ガスからアーゲ法により得られる炭化水素ポリマーの蒸留残分から、あるいは、蒸留残を水素添加して得られる合成炭化水素から、特定の成分を抽出分別したポリメチレンワックスが挙げられる。これらワックスには酸化防止剤が添加されていても良い。
【００８４】
本発明に使用される低軟化点物質は、ＤＳＣ吸熱曲線において、４０〜９０℃（さらに好ましくは４５〜８５℃）の領域に吸熱メインピークを有することが好ましい。さらに、吸熱メインピークは、半値幅が１０℃以内（より好ましくは５℃以内）であるシャープメルト性の低軟化点物質が好ましい。特に、低軟化点物質が炭素数１５〜４５個の長鎖アルキルアルコールと、炭素数１５〜４５個の長鎖アルキルカルボン酸とのエステル化合物を主成分とするエステルワックスが好ましい。
【００８５】
重合法によりトナー粒子を製造する方法としては、重合性単量体中に離型剤，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・超音波分散機等によって均一に溶解又は分散せしめた単量体組成物を、分散安定剤を含有する水相中で、ホモミキサー等により分散せしめる。単量体組成物からなる液滴が所望のトナー粒子のサイズが得られた段階で、造粒を停止する。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、所定の分子量分布を得る目的で、重合反応後半に昇温しても良く、更に、未反応の重合性単量体、副生成物等を除去するために反応後半、又は、反応終了後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、通常単量体組成物１００重量部に対して水３００〜３０００重量部を分散媒として使用するのが好ましい。
【００８６】
上記の重合法でトナー粒子を製造する際の分散安定剤の種類及び量、撹拌条件、水層のｐＨ及び重合条件、添加剤の分子量をコントロールすることにより、トナー粒子の形状係数を調整することができる。
【００８７】
本発明において、懸濁重合法によってトナー粒子を得る場合、係る重合性単量体としては、スチレン，ｏ（ｍ−、ｐ−）−メチルスチレン，ｍ（ｐ−）−エチルスチレン等のスチレン系単量体；（メタ）アクリル酸メチル，（メタ）アクリル酸エチル，（メタ）アクリル酸プロピル，（メタ）アクリル酸ブチル，（メタ）アクリル酸オクチル，（メタ）アクリル酸ドデシル，（メタ）アクリル酸ステアリル，（メタ）アクリル酸ベヘニル，（メタ）アクリル酸２−エチルヘキシル，（メタ）アクリル酸ジメチルアミノエチル，（メタ）アクリル酸ジエチルアミノエチル等の（メタ）アクリル酸エステル系単量体；ブタジエン，イソプレン，シクロヘキセン，（メタ）アクリロニトリル，アクリル酸アミド等のエン系単量体が好ましく用いられる。これらは、単独または一般的には出版物ポリマーハンドブック第２版ＩＩＩ−Ｐｌ３９〜１９２（Ｊｏｈｎ Ｗｉｌｅｙ＆Ｓｏｎｓ社製）に記載の理論ガラス転移温度（Ｔｇ）が、４０〜８０℃を示すように単量体を適宜混合し用いられる。理論ガラス転移温度が４０℃未満の場合には、トナーの保存安定性や現像剤の耐久安定性の面から問題が生じ、一方８０℃を超える場合は定着点の上昇をもたらし、特にフルカラートナーの場合においては各色トナーの混色が不十分となり色再現性に乏しく、更にＯＨＰ画像の透明性を著しく低下させ高画質の面から好ましくない。
【００８８】
また、懸濁重合法を用いてトナー粒子を得る方法においては、重合単量体の重合反応を阻害無く行わせしめるという観点から、極性樹脂を同時に添加するが特に好ましい。本発明に用いられる極性樹脂としては、スチレンと（メタ）アクリル酸の共重合体，マレイン酸共重合体，ポリエステル樹脂，エポキシ樹脂が好ましく用いられる。該極性樹脂は、単量体と反応しうる不飽和基を分子中に含まないものが特に好ましい。
【００８９】
本発明で使用される重合開始剤として、例えば、２，２’−アゾビス−（２，４−ジメチルバレロニトリル）、２，２’−アゾビスイソブチロニトリル、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、アゾビスイソブチロニトリル等のアゾ系重合開始剤；ベンゾイルペルオキシド、メチルエチルケトンペルオキシド、ジイソプロピルペルオキシカーボネート、クメンヒドロペルオキシド、２，４−ジクロロベンゾイルペルオキシド、ラウロイルペルオキシド等の過酸化物系重合開始剤が用いられる。
【００９０】
トナーの重量平均粒径及びはコールターカウンターＴＡ−ＩＩ型あるいはコールターマルチサイザー（コールター社製）等種々の方法で測定可能であるが、本発明においてはコールターカウンターマルチサイザーＴＡ−ＩＩ型（コールター社製）を用い、個数分布、体積分布を出力するインターフェイス（日科機製）及びＰＣ９８０１パーソナルコンピューター（ＮＥＣ製）を接続し、電解液は１級塩化ナトリウムを用いて１％ＮａＣｌ水溶液を調製する。たとえば、ＩＳＯＴＯＮ Ｒ−ＩＩ（コールターサイエンティフィックジャパン社製）が使用できる。測定法としては、前記電解水溶液１００〜１５０ｍｌ中に分散剤として界面活性剤、好ましくはアルキルベンゼンスルフォン酸塩を０．１〜５ｍｌ加え、更に測定試料を２〜２０ｍｇ加える。試料を懸濁した電解液は超音波分散器で約１〜３分間分散処理を行ない前記コールターカウンターマルチサイザー型によりアパーチャーとして１００μｍアパーチャーを用いて、２μｍ以上のトナーの体積、個数を測定して体積分布と個数分布とを算出した。それから、本発明に係わる体積分布から求めた体積基準の重量平均粒径（Ｄ４：各チャンネルの中央値をチャンネルの代表値とする）を求めた。
【００９１】
【実施例】
以下、発明を実施例により具体的に説明するがこれは本発明をなんら限定するものではない。「部」は「重量部」を意味する。
【００９２】
＜実施例１＞
イオン交換水７００部に、０．１Ｍ−Ｎａ₃ＰＯ₄水溶液４５０部を投入し、５０℃に加温した後、ＴＫ式ホモミキサー（特殊機化工業製）を用いて、１０，０００ｒｐｍにて撹拌した。これに１．０Ｍ−ＣａＣｌ₂水溶液７０部を添加し、さらに塩酸を添加し、リン酸カルシウム化合物を含むｐＨ６．０の水系媒体を得た。
【００９３】
一方、

上記処方を６０℃に加温し、ＴＫ式ホモミキサー（特殊機化工業製）を用いて、９０００ｒｐｍにて均一に溶解、分散した。これに、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）５部を溶解し、重合性単量体組成物を調製した。
【００９４】
前記水系媒体中に上記重合性単量体組成物を投入し、６０℃，Ｎ₂雰囲気下において、ＴＫ式ホモミキサーにて８０００ｒｐｍで撹拌し、重合性単量体組成物を造粒した。
【００９５】
その後、パドル撹拌翼で撹拌しつつ、５時間後、昇温速度４０℃／Ｈｒ．で８０℃に昇温し５時間反応させた。重合反応終了後、減圧下で残存モノマーを留去し、冷却後、塩酸を加えリン酸カルシウム塩を溶解させた後、ろ過、水洗、乾燥をして、個数平均粒径６．２μｍの着色トナー粒子を得た。
【００９６】
このトナー粒子１００部に対し、個数平均粒径が３０ｎｍでありシランカップリング剤で表面処理した酸化チタン微粉体を０．７部、個数平均粒径が３５ｎｍでありカップリング剤で表面処理したシリカ微粉体を０．７部加えた後、三井鉱山社製ヘンシェルミキサーを用い、均一に撹拌して下記の分級装置１で粗粉を除去しトナー１を得た。
【００９７】
分級装置１：
図２に示すように、弾性体のボール１６として、直径６．５ｍｍのポリウレタン製のボールを７個使用し、スクリーン１１としては目開きＢが４６μｍのポリエチレン製を使用した（Ｂ／ａ＝７．４２）。
【００９８】
このトナーを、図１に示す装置により、丸筒のトナーカートリッジＮｏ．１に充填した。このとき充填率０．４１ｇ／ｍｌであった。
【００９９】
図３には、スパイラル状スクリュー部分の拡大図を示す。図３のうち、Ｄはスクリューケーシングの内径、δはスクリュー部の最外縁部とスクリューケーシングの内壁とのクリアランス、ｒは回転数、Ｗはスクリュー部のピッチ長である。設定したそれぞれの値を表２に示す。
【０１００】
【表２】

【０１０１】
上記の懸濁重合シアントナー１のトナー粒子上に存在する酸化チタン微粉末（１）の形状係数ＳＦ−１は１１５であり、同様のシリカ微粉末（１）の形状係数ＳＦ−１は１８０であった。
【０１０２】
この懸濁重合シアントナー１のコールターカウンターによる個数平均粒径は６．２μｍであり、フロー式粒子像分析装置による円形度分布において、平均円形度は０．９８５であり、円形度０．９５０未満のトナー粒子が１０個数％であった。
【０１０３】
上記懸濁重合シアントナー１と下記の現像用キャリアＩとをトナー濃度８％で混合して二成分系シアン現像剤（１）を作製した。
【０１０４】
（現像用キャリアＩの製造）
水媒体中にフェノール／ホルムアルデヒドモノマー（５０：５０）を混合分散した後、モノマー重量に対して、イソプロポキシトリイソステアロイルチターネートで表面処理した０．２５μｍのマグネタイト粒子６００部、０．６μｍのヘマタイト粒子４００部を均一に分散させ、アンモニアを適宜添加しつつ、モノマーを重合させ、磁性粒子内包球状磁性樹脂キャリア芯材（平均粒径３３μｍ，飽和磁化３８Ａｍ²／ｋｇ）を得た。
【０１０５】
このキャリア芯材に、
【０１０６】
【数３】

【０１０７】
一方、トルエン２０部、ブタノール２０部、水２０部及び氷４０部を四つ口フラスコにとり、撹拌しながらＣＨ₃ＳｉＣ１₃ １５モルと（ＣＨ₃）₂ＳｉＣｌ₂１０モルとの混合物４０部及び触媒を加え、更に３０分間撹拌した後、６０℃で１時間縮合反応を行った。その後シロキサンを水で十分に洗浄し、トルエン−メチルエチルケトン−ブタノール混合溶媒に溶解して固型分１０％のシリコーンワニスを調製した。
【０１０８】
このシリコーンワニスに、シロキサン固型分１００部に対してイオン交換水２０部、下記式（１）で示す硬化剤２．０部、下記式（２）で示されるアミノシランカップリング剤１．０部、下記式（３）で示されるシランカップリング剤５．０部を同時添加し、キャリア被覆溶液Ｉを作製した。
【０１０９】
【数４】

【０１１０】
このキャリア被覆溶液Ｉを塗布機（岡田精工社製：スピラコーター）により、前述の表面改質を行ったキャリア芯材１００部に、樹脂コート量が０．５部となるように塗布し、コートキャリアＩ（現像用キャリアＩ）を得た。
【０１１１】
この現像用キャリアＩは、以下の測定法による体積の低抗値が４×１０¹³Ω・ｃｍであり、保磁力が５５エルステッドであった。
【０１１２】
体積抵抗値の測定
体積抵抗値は、図７に示すセルを用いて測定した。すなわち、セルＡにサンプル１４３を充填し、該充填サンプル１４３に接するように下部電極１４１及び上部電極１４２を配し、該電極間に１０００Ｖの直流電圧を印加し、その時流れる電流を電流計で測定することにより求めた。尚、１４４は絶縁物である。測定条件は、充填されたサンプル１４３のセルとの接触面積Ｓ＝２ｃｍ²，厚みｄ＝３ｍｍ，上部電極の荷重１５ｋｇ重とする。
【０１１３】
磁気特性の測定
装置は、ＢＨＵ−６０型磁化測定装置（理研測定製）を用いる。測定試料は約１．０ｇ秤量し内径７ｍｍφ，高さ１０ｍｍのセルにつめ、前記の装置にセットする。測定は印加磁場を徐々に加え最大１０００エルステッドまで変化させる。次いで印加磁場を減少せしめ、最終的に記録紙上に試料のヒステリシスカーブを得る。これより、飽和磁化，残留磁化，保磁力を求める。
【０１１４】
上記の二成分系現像剤（１）を、図５に示す画像形成装置の第１の画像形成ユニットＰａにおける現像器６３ａに投入し、丸筒のシアントナーカートリッジ（５９ａ）をトナーホッパー６５ａに装着して、現像器６３ａ中の二成分系現像剤（１）のトナー濃度が７％〜９％を維持するように、図示されないインダクタンス検知トナー濃度検知手段を用いてトナー濃度をコントロールし、トナーホッパー６５ａからトナー送り部材６６ａを介して現像器６３ａに懸濁重合トナー１を補給しながら、２３℃／６５％ＲＨ下でシアン単色での３万枚の連続複写を行なった。
【０１１５】
上記の画像形成装置の第１の画像形成ユニットＰａにおいて、感光ドラム６１ａとしては、下記の感光体Ｎｏ．１を用い、一次帯電器６２ａとしては、下記の磁気ブラシ帯電器Ｎｏ．１を用い、感光ドラム６１ａ移動方向に対して、磁気ブラシ帯電器をカウンター方向に１２０％でのスピードで回転させて、−７００Ｖの直流成分に１ｋＨｚ，１．２ｋＶｐｐの交流電圧を重畳させた帯電バイアス電圧を印加しながら感光体ドラム６１ａを−７００Ｖに一次帯電する構成とした。
【０１１６】
更に、第１の画像形成ユニットＰａは、転写部と帯電部との間及び帯電部と現像部との間に感光ドラム６１ａの表面に当接して、転写工程後に感光ドラム６１ａの表面上に存在する転写残トナーを除去回収するためのクリーニングユニットを有しておらず、転写工程後に感光ドラム６１ａの表面上に存在する転写残トナーを現像器６３ａが現像時に二成分系現像剤の磁気ブラシを用いて除去回収する現像同時クリーニング方式を行なう構成とした。現像器６３ａにおける現像時には、現像コントラスト２５０Ｖ、カブリとり反転コントラスト−１５０Ｖに設定し、図７に示す非連続の交流電圧を現像スリーブに印加しながら現像を行なった。
【０１１７】
（感光体Ｎｏ．１）
感光体Ｎｏ．１は負帯電用の有機光導電物質を用いたＯＰＣ感光体であり、φ３０ｍｍのアルミニウム製のシリンダー上に下記の機能層を５層設ける。
【０１１８】
第１層は導電層であり、アルミニウムシリンダーの欠陥をならすため、またレーザ露光の反射によるモアレの発生を防止するために設けられている厚さ約２０μｍの導電性粒子分散樹脂層である。
【０１１９】
第２層は正電荷注入防止層（下引き層）であり、アルミニウム基体から注入された正電荷が感光体表面に帯電された負電荷を打ち消すのを防止する役割を果し、６−６６−６１０−１２−ナイロンとメトキシメチル化ナイロンによって１０⁶Ω・ｃｍ程度に抵抗調整された厚さ約１μｍの中抵抗層である。
【０１２０】
第３層は電荷発生層であり、ジスアゾ系の顔料を樹脂に分散した厚さ約０．３μｍの層であり、レーザ露光を受けることによって正負の電荷対を発生する。
【０１２１】
第４層は電荷輸送層であり、ポリカーボネート樹脂にヒドラジンを分散したものであり、Ｐ型半導体である。従って、感光体表面に帯電された負電荷はこの層を移動することはできず、電荷発生層で発生した正電荷のみを感光体表面に輸送することができる。
【０１２２】
第５層は電荷注入層であり、光硬化性のアクリル樹脂にＳｎＯ₂超微粒子、更に帯電部材と感光体との接触時間を増加させて、均一な帯電を行うために粒径約０．２５μｍの４フッ化エチレン樹脂粒子を分散したものである。具体的には、酸素欠損型の低抵抗化した粒径約０．０３μｍのＳｎＯ₂粒子を樹脂１００重量部に対して１６０重量部、更に４フッ化エチレン樹脂粒子を３０重量部、分散剤を１．２重量部分散したものである。
【０１２３】
これによって感光体Ｎｏ．１の表面層の体積抵抗値は、電荷輸送層単体の場合３×１０⁵Ω・ｃｍだったのに比べ、８×１０¹¹Ω・ｃｍにまで低下している。
【０１２４】
（磁気ブラシ帯電器Ｎｏ．１）
ＭｇＯ ５部，ＭｎＯ ８部，ＳｒＯ ４部，Ｆｅ₂Ｏ₃ ８３部をそれぞれ微粒化し、水を添加混合して造粒し、酸素濃度を調整しながら１３００℃にて焼成し、粒度を調整し、平均粒径２８μｍのフェライトキャリア芯材（飽和磁化が６３Ａｍ²／ｋｇ，保磁力が５５エルステッド）を得た。
【０１２５】
上記キャリア芯材に、イソプロポキシトリイソステアロイルチタネート１０部をヘキサン９９部／水１部に混合させたものを、０．１部となるように表面処理してさらに、
【０１２６】
【数５】

【０１２７】
現像用キャリアＩの体積抵抗値と同じ方法で測定したこの磁性粒子ａの体積低抗値は、４×１０⁷Ω・ｃｍであり、加熱減量は０．１５部であった。
【０１２８】
磁気ブラシ帯電器Ｎｏ．１は、上記磁性粒子ａを内部にマグネットロールを内包する導電性非磁性スリーブの表面に磁気拘束させて磁気ブラシを形成させたものであり、帯電時には、マグネットロールが固定で導電性非磁性スリーブが回転する構成である。
【０１２９】
上記の３万枚の連続複写試験において、初期画像のベタ均一性、３万枚耐久後のカブリ、初期画像と３万枚耐久後画像との画像濃度差による耐久性、初期及び３万枚耐久後における転写性について評価した。更に、低湿下（１０℃／１０％ＲＨ）と高湿下（４０℃／８０％ＲＨ）の環境下に１ケ月放置したトナーを２３℃／６５％ＲＨ（ＮＮ）下で画出しを行い、保存安定性について評価した。
【０１３０】
評価結果は、表３に示す通り、画像濃度も安定で、カブリ、転写性も問題なく、非常に良好な結果が得られた。
【０１３１】
ベタ均一性
反射濃度計ＲＤ９１８（マクベス社製）で測定される画像濃度が１．５である直径２０ｍｍの円を５箇所設けたオリジナル原稿を複写し、画像部の画像濃度を反射濃度計ＲＤ９１８で測定し、その際の最大値と最小値との差を求めた。
【０１３２】
画像濃度
反射濃度計ＲＤ９１８（マクベス社製）で測定される画像濃度が１．５である直径２０ｍｍの円を設けたオリジナル原稿を複写し、画像部の画像濃度を反射濃度計ＲＤ９１８で測定した。
【０１３３】
カブリ量
画像形成後の非画像部（白地部）を１０点測定した反射濃度の最悪値（Ｄｓ）から画像形成前の用紙を１０点測定した反射濃度の平均値（Ｄｒ）を引いた値（Ｄｒ−Ｄｓ）をカブリ量とする。
【０１３４】
反射濃度の測定は、反射式濃度計（ＴＯＫＹＯ ＤＥＮＳＨＯＫＵ ＣＯ，ＬＴＤ社製ＲＥＦＬＥＣＴＯＭＥＴＥＲ ＭＯＤＥＬ ＴＣ−６ＤＳ）を用いた。
【０１３５】
カブリ量１．２％以下は実質的にカブリの無い良好な画像であり、カブリ量が１．５％を超えるとカブリの目立つ不鮮明な画像である。
【０１３６】
ベタ白抜け
前述の２０ｍｍの５箇所の画像部で１００μｍ程度以上の白抜けの個数を算出する。５個以下であれば実質上問題のない良好な画像であるが、１０個を超えると品位の劣化した画像となる。
【０１３７】
＜実施例２＞
実施例１において、分級装置のスクリーンとして目開きＢが７４μｍ（Ｂ／ａ＝１１．９）のポリエチレン製を使用する以外は同様にしてトナーカートリッジＮｏ．２を作製し、画出しを行ったところ、若干ベタ白抜けの品位が低下したものの実用上まったく問題のないレベルであった。このとき充填率は０．４２ｇ／ｍｌであった。これは、Ｂ／ａが大きくなったので、粗粒除去が若干不足したためと推測される。
【０１３８】
＜実施例３＞
実施例１において、分級装置のスクリーンとして目開きが３５μｍ（Ｂ／ａ＝５．６５）のポリエチレン製を使用する以外は同様にしてトナーカートリッジＮｏ．３を作製し、画出しを行ったところ、４０℃／８０％ＲＨ下で放置した際に若干カブリが悪化したものの実用上問題ないレベルであった。このとき充填率は０．４０ｇ／ｍｌであった。これは、スクリーンの目開きが小さいため、トナー粒子から外添剤が遊離気味となり、放置安定性が若干低下したためと推測される。
【０１３９】
＜比較例１＞

【０１４０】
上記原料をヘンシェルミキサーにより、予備混合を行い、二軸押出し式混練機により溶融混練し、冷却後ハンマーミルを用いて約１〜２ｍｍ程度に粗粉砕し、次いでエアージェット方式による微粉砕機で微粉砕した。更に得られた微粉砕物を分級したトナー粒子を使用する以外は同様にしてトナーカートリッジＮｏ．４を作製したところ、充填率が０．２８ｇ／ｍｌと小さく、さらに充填しようとするとトナー容器から溢れてしまい、生産性が非常に悪化した。これは、トナー形状が不定形であったために、トナーが詰まりにくかったためと推測される。このトナーの個数平均粒径は６．１μｍ、平均円形度は０．９３２、円形度０．９５０未満のトナー粒子が４３個数％であった。
【０１４１】
＜比較例２＞
比較例１において、トナー粒子を湯浴下で球状化処理する以外は同様にしてトナーカートリッジＮｏ．５を作製し、画出しを行ったところ、１万枚時点でカブリが悪化したので評価を中止した。これは、トナーが球状すぎたので、外添剤が脱離してしまい、トナーの帯電が不均一になったためと推測される。このトナーの個数平均粒径ａは５．９μｍ、Ｂ／ａ＝８．００、平均円形度は０．９９６、円形度０．９５０未満のトナー粒子が１．３個数％であった。充填率は０．４３ｇ／ｍｌであった。
【０１４２】
＜比較例３＞
実施例１において、分級装置のスクリーンとして目開きが１０４μｍ（Ｂ／ａ＝１６．８）のポリエチレン製を使用する以外は同様にしてトナーカートリッジＮｏ．７を作製し、画出しを行ったところ、ベタ白抜けの品位が初期から悪化したので評価を中止した。これは、Ｂ／ａが大きいために、粗粒除去が不十分であったためと推測される。このときの充填率は０．４１ｇ／ｍｌであり、個数平均粒径、平均円形度等は実施例１と同じであった。
【０１４３】
＜比較例４＞
実施例１において、分級装置のスクリーンとして目開きが２８μｍ（Ｂ／ａ＝４．３１）のポリエチレン製を使用する以外は同様にしてトナーカートリッジＮｏ．８を作製しようとしたところ、スクリーンの目詰りが激しく、生産性が著しく低下し、充填率の評価は困難であった。さらに、このトナーで画出しを行ったところ、初期からカブリ品位が悪化したので評価を中止した。これは、外添剤がスクリーン通過時にトナー粒子から脱離してしまったためと推測される。このときの個数平均粒径、平均円形度等は実施例１と同じであった。
【０１４４】
＜実施例４＞
実施例１において、無機微粉体（Ｂ）として、個数平均粒径が２８ｎｍであるカップリング剤処理シリカ微粉体に変える以外は同様にして充填率０．４５ｇ／ｍｌのトナーカートリッジＮｏ．９を作製し、画出しを行ったところ、３万枚時点で若干カブリ、ベタ均一性が悪化したものの、良好な結果が得られた。これは、このときのトナーの個数平均粒径、Ｂ／ａ、平均円形度等は実施例１と同じであったが、シリカ微粒子のＳＦ−１が１４１と若干小さく、耐久によってもう一方の外添剤の酸化チタン微粒子がトナー粒子に埋め込まれ気味になったためと推測される。
【０１４５】
＜実施例５＞
実施例１において、無機微粉体（Ａ）として、ＳＦ−１が１３８である平均粒径２５ｎｍのカップリング剤処理されたγ型アルミナを使用する以外は同様にして、充填率０．３８ｇ／ｍｌのトナーカートリッジＮｏ．１０を作製し、画出しを行ったところ、３万枚時点でベタ均一性が若干低下したものの、良好な結果が得られた。これは、このときのトナーの個数平均粒径、Ｂ／ａ、平均円形度等は実施例１と同じであったが、アルミナ微粒子のＳＦ−１が若干大きく、トナーの流動性付与がわずかに悪化したためと推測される。
【０１４６】
＜実施例６＞
無機微粉体（Ｂ）として、ＳＦ−１が１５８である平均粒径４０ｎｍのカップリング剤処理されたルチル型酸化チタンを使用する以外は同様にして充填率０．４２ｇ／ｍｌのトナーカートリッジＮｏ．１１を作製し、画出しを行ったところ、４０℃／８０％ＲＨ下の放置でカブリが若干悪化したものの、良好な結果が得られた。これは、このときのトナーの個数平均粒径、Ｂ／ａ、平均円形度等は実施例１と同じであったが、無機微粉体（Ｂ）の材質が酸化チタンであったために、トナー粒子との付着性が若干弱く、高湿下での保存で遊離気味になってしまったためと推測される。
【０１４７】
＜実施例７＞
実施例１において、酸化チタン微粉体を１．５重量部に増やす以外は同様にして、充填率０．５２ｇ／ｍｌのトナーカートリッジＮｏ．６を作製し、画出しを行ったところ、１万枚時点でベタ均一性が悪化したものの実用上許容レベルであった。これは、トナー充填率が高いので、トナーカートリッジから均一な排出が達成されずに、現像器内でトナー濃度にムラが生じたためと推測される。このトナーの個数平均粒径、Ｂ／ａ、平均円形度等は、実施例１と同じであった。
【０１４８】
＜実施例８＞
実施例１において、分級装置として、図４に示すジャイロシフターを使用し、目開き４６μｍのスチレン製のスクリーン３１に図示しない超音波振動子を取り付けて、目詰まりを防止しながら、トナーは３２から粗粒は３３から排出するように作製する以外は同様にしてトナーカートリッジＮｏ．１２を作製し、画出しを行ったところ、良好な結果が得られた。
【０１４９】
＜実施例９＞
（マゼンタトナーカートリッジの製造例）
・スチレン １７０部
・２−エチルヘキシルアクリレート ３０部
・キナクリドン顔料 １５部
・ジ−ターシャリブチルサリチル酸Ｃｒ化合物 ３部
・飽和ポリエステル １０部
（酸価１０ｍｇＫＯＨ／ｇ、ピーク分子量９，１００）
・エステルワックス ４０部
（Ｍｗ：４５０、Ｍｎ：４００、Ｍｗ／Ｍｎ：１．２５、融点７０℃、
粘度：６．５ｍＰａ・ｓ、ビッカース硬度：１．１、ＳＰ値：８．６）
【０１５０】
上記処方を実施例１と同様にして重合性単量体組成物を調製し、実施例１で調製した水系媒体中に投入し、以下同様の工程を経てマゼンタトナーカートリッジＮｏ．１３を得た。このトナーの個数平均粒径は６．１μｍ、Ｂ／ａ＝７．５４、平均円形度０．９８６、円形度０．９５０未満のトナー粒子９％、トナー充填率０．４２ｇ／ｍｌであった。
【０１５１】
（ブラックトナーカートリッジの製造例）
・スチレン １７０部
・２−エチルヘキシルアクリレート ３０部
・カーボンブラック １５部
・ジ−ターシャリブチルサリチル酸Ｃｒ化合物 ３部
・飽和ポリエステル １０部
（酸価１０ｍｇＫＯＨ／ｇ、ピーク分子量９，１００）
・エステルワックス ４０部
（Ｍｗ：５００、Ｍｎ：４００、Ｍｗ／Ｍｎ：１．２５、融点７０℃、
粘度：６．５ｍＰａ・ｓ、ビッカース硬度：１．１、ＳＰ値：８．６）
【０１５２】
上記処方を実施例１と同様にして重合性単量体組成物を調製し、実施例１で調製した水系媒体中に投入し、以下同様の工程を経てブラックトナーカートリッジＮｏ．１４を得た。このトナーの個数平均粒径は６．０μｍ、Ｂ／ａ＝７．６７、平均円形度０．９８６、円形度０．９５０未満のトナー粒子１０％、トナー充填率０．４１ｇ／ｍｌであった。
【０１５３】
（イエロートナーカートリッジの製造例）
・スチレン １７０部
・ｎ−ブチルアクリレート ３０部
・Ｃ．Ｉ．ピグメントイエロー９３ １５部
・ジ−ターシャリブチルサリチル酸Ｃｒ化合物 ３部
・飽和ポリエステル １０部
（酸価１０ｍｇＫＯＨ／ｇ、ピーク分子量９，１００）
・ジエステルワックス ４０部
（Ｍｗ：４８０、Ｍｎ：４１０、Ｍｗ／Ｍｎ：１．１７、融点７３℃、
粘度：１０．５ｍＰａ・ｓ、ビッカース硬度：１．０、ＳＰ値：９．１）
【０１５４】
上記処方を実施例１と同様にして重合性単量体組成物を調製し、その後、実施例１で調製した水系媒体中に投入し、６０℃，Ｎ₂雰囲気下において、クレアミキサーにて１２，０００ｒｐｍで１０分間撹拌し、重合性単量体組成物を造粒した。その後、水系媒体をパドル撹拌翼で撹拌しつつ、８０℃で昇温し、１０時間の重合反応を行った。
【０１５５】
重合反応終了後、冷却し、塩酸を加えリン酸カルシウムを溶解させた後、濾過、水洗、乾燥をして、イエロートナーカートリッジＮｏ．１５を得た。このトナーの個数平均粒径は６．３μｍ、Ｂ／ａ＝７．３０、平均円形度０．９８４、円形度０．９５０未満のトナー粒子１３％、トナー充填率０．４１ｇ／ｍｌであった。
【０１５６】
上記イエロートナー、マゼンタトナー及びブラックトナーを使用し、実施例１と同じキャリアを使用して、イエロー現像剤、マゼンタ現像剤及びブラック現像剤を作製した。
【０１５７】
図５の画像形成装置を使用し、ユニットＰａの６３ａにイエロー現像剤、５９ａにイエロートナーカートリッジを使用し、以下、Ｐｂユニットにマゼンタ現像剤／マゼンタトナーカートリッジを、ユニットＰｃに実施例１で使用したシアン現像剤／シアントナーカートリッジを、ユニットＰｄにブラック現像剤／ブラックトナーカートリッジを使用して、実施例１と同様にしてフルカラー画像耐久評価を１万枚行ったところ、実施例１同様良好な結果が得られた。
【０１５８】
【表３】

【０１５９】
【発明の効果】
本発明によれば、トナーの外添剤の遊離及び再凝集を起こすことなくトナーを簡便にトナーカートリッジに充填することが可能で、耐久による画像品位も向上させることができる。
【図面の簡単な説明】
【図１】本発明に用いた装置の概略図である。
【図２】本発明に用いた分級装置の概略図である。
【図３】充填装置のスパイラル状スクリュー部の拡大図を示す。
【図４】本発明に用いた分級装置の別の態様の概略図である。
【図５】本発明の画像形成方法を実施し得る好適な画像形成装置の例を示す概略図である。
【図６】実施例１で用いる交番電界を示す図である。
【図７】体積抵抗値を測定するのに用いる装置の説明図である。
【符号の説明】
５９ａ トナーカートリッジ
６０ａ 転写バイアス印加手段（接地していても良い）
６１ａ 感光体ドラム
６２ａ 一次帯電器
６３ａ 現像器
６４ａ 転写ブレード
６５ａ トナーホッパー
６６ａ 補給ローラ
６７ａ 露光装置
６８ 転写材担持体
６９ 分離帯電器
７０ 定着器
７１ 定着ローラ
７２ 加圧ローラ
７３ ウェッブ
７５，７６ 加熱手段
７８ 温度検知手段
７９ 転写ベルトクリーニング装置
８０ 駆動ローラ
８１ ベルト従動ローラ
８２ ベルト除電器
８３ レジストローラ
８４ 給紙ローラ
１０１ ホッパー
１０３ スパイラル状スクリュー
１０４ 排出口
１１２ 撹拌羽根[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a manufacturing method for filling a container with fine powder, and more particularly to a manufacturing method suitable for filling a container with toner used in an image forming apparatus.
[0002]
[Prior art]
In recent years, in image forming methods using electrophotographic technology such as copying machines and laser printers, further miniaturization of machines, longer life, lower energy consumption, higher definition of image quality, higher reproducibility, etc. have been demanded. It has been. As one method for achieving such a requirement, there is known a method for defining the average particle diameter and sphericity of toner particles as an electrostatic charge image developer.
[0003]
Various means have been reported as means for adjusting the average particle size and sphericity of the toner particles. For example, the conventional pulverized toner particles are dispersed in water and heated in a hot water bath method or passed through a hot air stream. There are a heat treatment method, a mechanical impact method in which mechanical energy is applied, and the like. Alternatively, a method of directly generating toner particles using a suspension polymerization method as described in JP-A-36-10231, JP-A-59-53856, and JP-A-59-61842. In addition, a water-based organic solvent that dissolves the monomer but does not dissolve the resulting polymer is used to perform direct polymerization to form toner particles, or directly polymerized in the presence of a water-soluble polar polymerization initiator. There are emulsion polymerization methods represented by the soap-free polymerization method for producing particles.
[0004]
In particular, when the toner particles are obtained by a so-called polymerization method, it is easy to adjust the average particle diameter and sphericity of the toner particles and to easily make the charging characteristics of the toner particles uniform. Therefore, it is possible to reduce so-called “fogging” in which poorly charged toner particles are scattered in the non-printing area, and to reduce the amount of waste toner.
[0005]
As a means for further improving the fluidity, charging characteristics, and environmental resistance of such toner particles, a method of appropriately adding various inorganic fine particles and organic fine particles to the toner particle surfaces is widely used. The fine particles are called external additives, and various types of external additives are used singly or in plural depending on their functions and effects. These external additives are present in the surface layer of the toner particles, so that their functions are best exhibited.
[0006]
However, the spherical toner is different from the conventional pulverized toner in the form of adhesion of the external additive on the surface of the toner particles. As a result, liberation of the external additive and accompanying re-aggregation of the external additive were liable to occur.
[0007]
As a result of detailed studies on this phenomenon, the present inventors
(1) When an external additive having a low charging ability is used (for example, titanium oxide, alumina, etc.)
(2) When an additive having a large dispersed particle size on the toner particles is used (silica of 100 nm or more, titanium oxide, alumina, organic resin particles, etc.)
(3) As a coarse particle removing step after external addition mixing, it was found that the problem occurred more remarkably when a mesh having a small mesh size was used.
[0008]
[Problems to be solved by the invention]
An object of the present invention is to provide a production method and a toner cartridge in which a toner is simply filled in a developing container without causing liberation and reaggregation of external additives.
[0009]
[Means for Solving the Problems]
As a result of detailed studies, the present inventors have found a method for easily filling toner into a developing container without causing the release and reaggregation of external additives, and a toner cartridge filled by the method according to the present invention. As a result, the present inventors have found that the image quality is improved as compared with a conventionally known method, and have reached the present invention.
[0011]
  IeThe present invention relates to a toner filling method in which a toner container having toner particles and an external additive and having a number average particle diameter a of 2 to 8 μm by a Coulter method is filled into a toner container through a spiral screw.
  The toner has an average circularity of 0.950 to 0.995 and 2 to 40 particles having a circularity of less than 0.950 in the circularity distribution of the particles measured by a flow particle image analyzer. Contains a number%,
  After dispersing the external additive on the toner particles, the coarse particles are separated and removed by passing through a screen having a mesh opening (B) of 5 ≦ B / a ≦ 15, and the filling rate is 0.3 to 0.5 g / ml. The present invention relates to a method for filling toner into a toner container, wherein the toner container is filled with toner.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
A schematic view of the apparatus used for filling according to the present invention is shown in FIG.
[0014]
The toner is put into the hopper 101, and the spiral screw 103 is rotated by the drive motor 111 to feed the toner downward. The toner passes through the gap between the spiral screw 103 and the screw casing 106 and is then discharged from the discharge port 104. In order to prevent toner flushing and eccentricity of the screw rotation shaft, the exhaust port 104 is provided with a star seat 105.
[0015]
When a toner container is placed under the discharge port 104 and the toner is filled in the toner container using the apparatus shown in FIG. 1, the toner can be filled in the developing container without excessive vibration of the toner particles. The external additives are less likely to be liberated and re-agglomerated, and the physical properties of the toner are not impaired.
[0016]
Further, when the toner in the developing container is filled with the method according to the present invention and the toner filled while applying vibration to the toner particles, the toner filled with the method according to the present invention has higher image characteristics. Became clear. This is considered to be because the adhesion state of the fine particles to the toner particle surface layer is more preferable in addition to the effect of preventing the external additive liberation / reaggregation described above.
[0017]
The improvement of the adhesion state of the fine particles described above is because the fine particles adhere to the toner particles by a pressure applied when a part of the toner particles passes through a minute gap, that is, a clearance between the outermost edge portion of the screw portion and the inner wall of the screw casing. This is considered to be achieved by adhering to the surface layer of the part.
[0018]
In the present invention, the inner diameter D of the screw casing is 12 to 130 mm, the clearance δ between the outermost edge of the screw portion and the inner wall of the screw casing is 0.05 to 3.0 mm, and the rotational speed r of the screw is 50. It is preferable that the pitch length W satisfies the following formula.
[0019]
0.1 × H <W <3.0 × H
(Where H is the outer diameter of the spiral screw, and H = D-2δ)
[0020]
More preferably, the inner diameter D of the screw casing is 15 to 100 mm, the clearance δ between the outermost edge of the screw portion and the inner wall of the screw casing is 0.10 to 2.5 mm, and the rotational speed r of the screw is 50 to It is preferably 1500 rpm and the pitch length W satisfies the following formula.
[0021]
0.3 × H <W <2.0 × H
[0022]
These parameters are considered to correlate with the adhesion state of fine particles having an average particle diameter of 1 to 1000 nm to the surface of the toner particles. That is, the inner diameter D of the screw casing is larger than 130 mm; or the clearance δ between the outermost edge of the screw portion and the inner wall of the screw casing is larger than 3.0 mm; or the rotational speed r of the screw is larger than 50 rpm. When the pitch length W is larger than 3.0 × H, the pressure applied to the toner particle surface layer becomes insufficient, and the fine particles are not preferably fixed to the toner particle surface layer. Further, the inner diameter D of the screw casing is smaller than 12 mm; or the clearance δ between the outermost edge of the screw portion and the inner wall of the screw casing is smaller than 0.05 mm; or the rotational speed r of the screw is smaller than 3000 rpm. Or when the pitch length W is smaller than 0.1 × H, the pressure applied to the toner particle surface layer becomes excessive, and the fine particles are fixedly embedded in the toner particle surface layer. A stable image cannot be supplied.
[0023]
The above-described effects are more prominent when a screen having a small screen opening after the addition, which is a configuration of the present invention, is used. That is, when a screen having a small mesh size is used, the toner particles are more likely to come into contact with the screen, and the external additive is easily released from the toner surface. However, in the present invention, it is presumed that the external additive is more preferably attached to the toner in order to pass the external additive slightly freed through the apparatus as shown in FIG.
[0024]
FIG. 2 is a schematic sectional view of a classifying apparatus suitable for the present invention. The blades 12 rotate at high speed inside the cylindrical screen 11. The toner supplied from the toner supply port 13 collides with the blades 12 to be agglomerated, collides with the screen 11 by centrifugal force, and toner having a particle size equal to or smaller than the mesh passes outside and passes through the toner collecting unit 14. After being collected, the coarse particles move inside the screen and are discharged from the coarse particle discharge port 15. Further, an elastic ball 16 is present inside the screen 11 and hits the inside of the screen 11 in accordance with the rotation of the blades to prevent clogging.
[0025]
The characteristic of the classifying device is that, first of all, toner aggregation is sufficiently solved by rotating blades. In the conventional classifying apparatus, rubber balls or the like are placed on the screen or the screen unit and solved by their movement. However, the ability is not sufficient and the throughput is reduced. In the above classifying apparatus, since aggregation is solved by blades rotating at high speed, it is possible to make the sufficiently dispersed toner collide with the screen.
[0026]
The second feature is that a strong centrifugal force is applied to the toner so as to pass through the screen. In the conventional apparatus, the toner is allowed to pass through the screen only by gravity. However, in the above-described apparatus, the toner can be given a stronger force to pass through the screen.
[0027]
The third feature is that an elastic ball inside the screen collides with the screen and gives a slight vibration to prevent clogging. Unlike brushes used in conventional gyro shifters, etc., it only gives the screen a slight vibration, and since it is a very small and sufficient amount, it does not damage the screen and No change in opening occurs. Further, since an elastic ball is used, fragments are not mixed in the toner.
[0028]
For example, the blade used in the classifying device may have a plurality of plate-like ones attached to the rotating shaft, and the rotational speed is generally in the range of 500 to 2000 rpm. As the screen to be used, all known materials can be used, but those made of a resin such as polyester are preferable because they give a slight vibration with an elastic ball. The ball of the elastic body to be used is a general ball such as urethane having a diameter of several millimeters, and about 10 pieces exhibit a sufficient effect.
[0029]
As described above, in the classifying apparatus preferably used in the present invention as disclosed in Japanese Patent Laid-Open No. 5-293443, etc., when the toner aggregation is disentangled, and further when passing through the screen, the external additive is free. Therefore, a stable adhesion state is achieved again with the above-described filling device.
[0030]
As the screen used in the production method of the present invention, any conventionally known materials can be used, but those made of a resin such as polyester are particularly preferred because they give the screen a slight vibration with an elastic ball. preferable. The elastic balls are general balls such as polyurethane having a diameter of several millimeters, and preferably about 10 balls exhibit a sufficient effect.
[0031]
In the present invention, the number average diameter a of the toner is 2 to 8 μm, and the screen aperture B satisfies the relationship of 5 ≦ B / a ≦ 15. Therefore, it is more effective when it is in the range of 7 ≦ B / a ≦ 10. When the screen aperture is B / a> 15, the effect of removing coarse particles is insufficient, and when B / a <5, the processing capacity is reduced and the liberation of external additives is promoted. Even if combined with it, it will not be possible to obtain a satisfactory product. Further, if a is less than 2 μm, the fluidity of the toner is lowered, the discharging property at the time of filling becomes unstable, and it becomes difficult to control the filling amount, and if a exceeds 8 μm, development reproduction for a fine latent image is performed. Sex is reduced.
[0032]
In the present invention, particles having an average circularity of 0.950 to 0.995 and a circularity of less than 0.950 in the circularity distribution of particles measured by a flow particle image analyzer of toner are used. It is also one feature that it contains 2 to 40% by number.
[0033]
Here, the “flow-type particle image analyzer” is a device that statistically performs image analysis of particle imaging, and the “average circularity” is an arithmetic average of the circularity obtained by the following equation using the device. Is calculated by
[0034]
[Expression 1]

[0035]
In the above equation, “perimeter of particle projection image” is the length of the contour obtained by connecting the edge points of the binarized particle image, and “perimeter of equivalent circle” is binary It is the length of the outer periphery of a circle having the same area as the converted particle image.
[0036]
When the average circularity of the toner is less than 0.950, the external additive tends to be unevenly distributed on the toner surface. As a result, the image density tends to become unstable, and the average circularity of the toner is 0.995. If it exceeds, the external additive is hardly held on the toner surface, and as a result, the charge becomes non-uniform and fog is likely to occur.
[0037]
The toner contains 2 to 40% by number, preferably 3 to 30% by number of particles having a circularity of less than 0.950.
[0038]
When the content of particles having a circularity of less than 0.950 is less than 2% by number, the toner is likely to be packed most closely, and as a result, it becomes difficult to control the discharge properties during filling.
[0039]
When the content of particles having a circularity of less than 0.950 exceeds 40% by number, the fluidity of the toner is lowered, and image deterioration such as a reduction in fine line reproducibility tends to occur.
[0040]
In the present invention, the suspension polymerization method is particularly preferable because the particle size distribution of the toner particles to be produced becomes sharp and a large amount of wax as a release agent can be contained in the toner particles. Further, a seed polymerization method in which a monomer is further adsorbed to the obtained polymerized toner particles and then polymerized using a polymerization initiator can be suitably used in the present invention.
[0041]
When the toner of the present invention contains toner particles produced using a polymerization method, the toner particles can be specifically produced by the following production method. Add a release agent, colorant, charge control agent, polymerization initiator and other additives consisting of a low softening point substance into the monomer, and a monomer system that is uniformly melted or dispersed by a homogenizer or ultrasonic disperser. Then, the mixture is dispersed in an aqueous phase containing a dispersion stabilizer by an ordinary stirrer or a disperser such as a homomixer and a homogenizer. Preferably, granulation is performed by adjusting the stirring speed and the stirring time so that the monomer droplets have a 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.
[0042]
At this time, the circularity distribution can be controlled by the type and amount of the dispersion stabilizer, the stirring ability, the pH of the aqueous phase and the polymerization temperature.
[0043]
In the present invention, the circularity distribution of the equivalent circle diameter of the toner is measured as follows using a flow type particle image analyzer FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.).
[0044]
The measurement removes fine debris through a filter and results in 10^-3cm^ThreeIn the water, a surfactant (preferably Wako Pure Chemicals Contaminone) is added to ion-exchanged water having a measurement range (for example, an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm) of 20 or less. About 0.02 g of the measurement sample was added to about 10 ml (20 ° C.) of the solution prepared by adding 0.5% by weight and dispersed uniformly. As a means for dispersing, an ultrasonic disperser UH-50 manufactured by SMT Co., Ltd. (vibrator is a 5φ titanium alloy chip) was used. The dispersion time was 5 minutes or more, and at that time, the dispersion medium was appropriately cooled so that the temperature of the dispersion medium did not exceed 40 ° C. Using the flow type particle image measuring apparatus, the particle size distribution and the circularity distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm are measured.
[0045]
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.
[0046]
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. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter. Further, the circularity of each particle is calculated by dividing the circumference of a circle (equivalent circle) having the same area as the two-dimensional image of each particle by the circumference of the two-dimensional image of each particle.
[0047]
As shown in Table 1, the results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels for one octave). In actual measurement, particles are measured in the range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm.
[0048]
[Table 1]

*) The upper limit of the particle size range does not include the numerical value and represents “less than”.
[0049]
Japanese Patent Application Laid-Open No. 9-304968 shows the relationship between the weight average particle diameter of the toner and the opening ratio of the sieve. The use of spherical toner as the toner of the present invention eliminates external additives. The point that the external additive is stably adhered to the toner particles over a long period of time is not described at all, which is different from the present invention.
[0050]
Similarly, Japanese Patent Application Laid-Open No. 7-311477 discloses a configuration of a turbo screener used as an example of the present invention as a toner sieving device. Further, Japanese Patent Application Laid-Open No. 10-043688 discloses the present invention. Although the use of the ultrasonic sieve used in the examples is shown, the toner shape and the adhesion state of the external additive are not mentioned in any case, and are different from the present invention.
[0051]
One feature of the present invention is that the toner has a number average particle diameter of 2 to 8 μm. When the number average particle diameter of the toner is smaller than 2 μm, it becomes difficult to quantitatively discharge the toner during the toner filling operation, and as a result, overflow or scattering from the toner container tends to occur. On the other hand, if it exceeds 8 μm, the development reproducibility for a fine latent image is lowered.
[0052]
As the external additive in the present invention, organic or inorganic fine particles generally known as external additives can be used. Specifically, examples of the inorganic fine particles include metal oxides (aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide, etc.), nitrides (silicon nitride, etc.), carbides ( Silicon carbide, etc.), metal salts (calcium sulfate, barium sulfate, calcium carbonate, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.), carbon black, silica, etc. can be used. Examples of the organic fine particles include a homopolymer or a copolymer of monomer components used in a binder resin for toner such as styrene, acrylic acid, methyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate by, for example, an emulsion polymerization method or a spray drying method. A polymer can be used.
[0053]
Further, a plurality of these fine particles can be used in combination as required.
[0054]
In particular, the present invention is suitable when titanium oxide, aluminum oxide, and silica-treated fine particles thereof having a small charging ability are used as external additives. That is, the above-mentioned external additive having a low charging ability has a smaller electrostatic adhesion force with the surface of the toner particles than the silica particles having a high charging ability that have been widely used as an external additive in the past. When passing through a certain screen, the toner particles become loose. However, in this invention, since a filling process is taken at the next process, liberation is suppressed over a long period of time.
[0055]
The external additive used in the toner of the present invention has a weight average particle diameter of 10 to 400 nm, preferably 10 to 100 nm, from the viewpoint of imparting fluidity. If it is larger than 400 nm, toner charging due to poor fluidity becomes non-uniform, resulting in toner scattering and fogging. On the other hand, if the thickness is smaller than 10 nm, the toner is likely to be embedded in the toner surface, toner deterioration occurs quickly, and durability is lowered, which is not preferable.
[0056]
Further, the non-spherical inorganic fine powder (B) produced by combining a plurality of particles with the above external additive (A) existing in the form of primary particles or secondary particles on the toner particles. It is more preferable to have.
[0057]
That is, the external additive (A) adheres appropriately on the surface of the toner particles, thereby uniformizing the charge on the surface of the toner particles, sharpening the toner charge amount distribution, and improving the fluidity of the toner. Thus, the non-spherical inorganic fine powder (B) functions as a spacer of the toner particles, thereby suppressing the embedding of the toner particles of the external additive (A).
[0058]
In general, toner particles with less irregularities on the surface and close to a spherical shape are places where external additives externally added to the surface of toner particles escape when they come into contact with a member such as carrier particles for imparting triboelectric charge to the toner. Are less likely to be embedded in the toner particle surface, and toner deterioration is likely to occur.
[0059]
However, the toner of the present invention is a nearly spherical toner having an average circularity of 0.950 to 0.995 and a content of particles having a circularity of less than 0.950 of 2 to 40% by number as described above. However, since the external additive (A) and the non-spherical inorganic fine powder (B) are contained on the toner particles, the embedding of the external additive (A) on the toner particle surface is effectively suppressed. It is.
[0060]
The non-spherical inorganic fine powder (B) used in the present invention has an external additive (A) having a shape factor SF-1 on the toner particles of greater than 150, preferably greater than 190, and more preferably greater than 200. ) In the toner particle surface.
[0061]
When the shape factor SF-1 of the non-spherical inorganic fine powder (B) is 150 or less, the non-spherical inorganic fine powder (B) itself is easily embedded in the toner particle surface. ) Burial suppression effect decreases.
[0062]
The shape factor SF-1 on the toner particles of the non-spherical inorganic fine powder (B) is measured at a magnification of 100,000 times by FE-SEM.
[0063]
In the present invention, SF-1 indicating the shape factor is 100 particle images randomly sampled using Hitachi FE-SEM (S-800), and the image information is image analysis apparatus manufactured by Nicole via the interface. (Luzex3) was introduced and analyzed, and the value calculated from the following equation was defined.
[0064]
[Expression 2]

(In the formula, MXLNG indicates the absolute maximum length of the measurement particle on the image, and AREA indicates the projected area of the measurement particle.)
[0065]
The non-spherical inorganic fine powder (B) preferably has an average major axis on the toner particles of 120 to 600 nm, more preferably 130 to 500 nm.
[0066]
When the average major axis of the non-spherical inorganic fine powder (B) is less than 120 nm, the spacer effect for suppressing the embedding of the external additive (A) on the toner surface is small, and as a result, the developability / transferability of the toner. When the thickness exceeds 600 nm, the spacer effect described above can be expected, but it is easily released from the toner surface, and as a result, the photoconductor is easily scraped and scratched.
[0067]
The toner according to the present invention usually contains a binder resin and a colorant as main components.
[0068]
As the binder resin of the toner according to the present invention, a homopolymer of styrene such as polystyrene and polyvinyltoluene and a substituted product thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer Styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene- Methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether Copolymer, styrene-vinyl Styrene copolymers such as methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate , Polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, paraffin wax, carnauba wax, etc. Is mentioned. These can be used alone or in combination.
[0069]
As the colorant used in the toner according to the present invention, a black colorant that is toned in each color using carbon black, a magnetic material, and the following yellow / magenta / cyan colorant is used.
[0070]
As the yellow colorant, compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, C.I. I. CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 168, 180, Solvent Yellow 162, 163, etc. are preferably used. It is done.
[0071]
As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigmentlets 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.
[0072]
As the cyan colorant used in the present invention, 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: 2, 15: 3, 15: 4, 60, 62, 66 and the like can be used particularly preferably.
[0073]
These colorants can be used alone or in combination and further in the form of a solid solution.
[0074]
In the case of a color toner, the colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by weight based on 100 parts by weight of the resin.
[0075]
When a magnetic material is used as the black colorant, 40 to 150 parts by weight are added to 100 parts by weight of the resin, unlike other colorants.
[0076]
In the toner of the present invention, a charge control agent can be used as necessary.
[0077]
As the charge control agent used in the present invention, known ones can be used. In the case of a color toner, in particular, a charge control agent that is colorless and has a high toner charging speed and can stably maintain a constant charge amount. preferable.
[0078]
Specific examples of the negative compounds include salicylic acid, naphthoic acid, dicarboxylic acid, metal compounds of their derivatives, polymer compounds having sulfonic acid and carboxylic acid in the side chain, boron compounds, urea compounds, silicon compounds, carbon compounds. Leaks arene can be used, and as a positive system, a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, an imidazole compound, and the like are preferably used.
[0079]
The charge control agent is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin. However, in the present invention, it is not essential to add a charge control agent. When a two-component development method is used, frictional charging with a carrier is utilized, and even when a nonmagnetic one-component blade coating development method is used, a blade member is used. In addition, it is not always necessary to include a charge control agent in the toner by actively using frictional charging with the sleeve member.
[0080]
In the toner of the present invention, a low softening point material, so-called wax, can be used as necessary.
[0081]
Examples of the low softening point substance used in the toner of the present invention include polymethylene waxes such as paraffin wax, polyolefin wax, microcrystalline wax, and Fischer tropish wax, amide wax, higher fatty acid, long chain alcohol, ester wax, and the like. Derivatives such as graft compounds and block compounds are exemplified, and those having a sharp maximum endothermic peak in the DSC endothermic curve from which low molecular weight components have been removed are preferred.
[0082]
Examples of the wax preferably used include linear alkyl alcohols having 15 to 100 carbon atoms, linear fatty acids, linear acid amides, linear esters, and montan derivatives. Further, those obtained by removing impurities such as liquid fatty acid from these waxes in advance are also preferred.
[0083]
Further, the wax preferably used is a low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or using a Ziegler catalyst or other catalyst under low pressure; an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer ; Separation and purification of low molecular weight alkylene polymer produced as a by-product during polymerization of alkylene; Hydrogenation of distillation residue of hydrocarbon polymer obtained by the age method from synthesis gas consisting of carbon monoxide and hydrogen, or hydrogenation of distillation residue And polymethylene wax obtained by extracting and fractionating specific components from the synthetic hydrocarbon obtained in this manner. These waxes may contain an antioxidant.
[0084]
The low softening point material used in the present invention preferably has an endothermic main peak in the region of 40 to 90 ° C. (more preferably 45 to 85 ° C.) in the DSC endothermic curve. Further, the endothermic main peak is preferably a sharp-melting low softening point material having a half-value width within 10 ° C. (more preferably within 5 ° C.). In particular, an ester wax having a low softening point substance mainly composed of an ester compound of a long-chain alkyl alcohol having 15 to 45 carbon atoms and a long-chain alkyl carboxylic acid having 15 to 45 carbon atoms is preferable.
[0085]
As a method for producing toner particles by a polymerization method, a release agent, a colorant, a charge control agent, a polymerization initiator and other additives are added to a polymerizable monomer, and the toner particles are uniformly distributed by a homogenizer, an ultrasonic disperser, or the like. The dissolved or dispersed monomer composition is dispersed with a homomixer or the like in an aqueous phase containing a dispersion stabilizer. The granulation is stopped when the droplets made of the 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, for the purpose of obtaining a predetermined molecular weight distribution, the temperature may be raised in the latter half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers, by-products, etc., in the latter half of the reaction or after the completion of the reaction. A part of the aqueous medium may be distilled off. After completion of the reaction, the produced toner particles are recovered by washing and filtration and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer composition.
[0086]
Adjusting the shape factor of the toner particles by controlling the type and amount of the dispersion stabilizer, the stirring conditions, the pH and polymerization conditions of the aqueous layer, and the molecular weight of the additive when the toner particles are produced by the above polymerization method. Can do.
[0087]
In the present invention, when toner particles are obtained by suspension polymerization, the polymerizable monomer may be styrene, such as styrene, o (m-, p-)-methylstyrene, m (p-)-ethylstyrene. Monomer; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid ester monomers such as stearyl acid, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate; butadiene, Enene monomers such as isoprene, cyclohexene, (meth) acrylonitrile, and acrylamide are preferably used. . These are monomers alone or generally such that the theoretical glass transition temperature (Tg) described in the publication Polymer Handbook 2nd edition III-Pl39-192 (John Wiley & Sons) shows 40-80 ° C. Are appropriately mixed and used. When the theoretical glass transition temperature is less than 40 ° C., there are problems in terms of storage stability of the toner and durability of the developer. On the other hand, when the temperature exceeds 80 ° C., the fixing point is increased. In some cases, the color toners are not sufficiently mixed, resulting in poor color reproducibility. Further, the transparency of the OHP image is remarkably lowered, which is not preferable from the viewpoint of high image quality.
[0088]
In addition, in the method of obtaining toner particles using the suspension polymerization method, it is particularly preferable to add a polar resin at the same time from the viewpoint of allowing the polymerization reaction of the polymerization monomer to be carried out without hindrance. As the polar resin used in the present invention, a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, a polyester resin, and an epoxy resin are preferably used. The polar resin is particularly preferably one containing no unsaturated group capable of reacting with the monomer in the molecule.
[0089]
Examples of the polymerization initiator used in the present invention include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, and 1,1′-azobis (cyclohexane). -1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo-based polymerization initiators such as azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, Peroxide-based polymerization initiators such as cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide are used.
[0090]
The weight average particle diameter of the toner and the toner can be measured by various methods such as Coulter Counter TA-II or Coulter Multisizer (Coulter). In the present invention, Coulter Counter Multisizer TA-II (Coulter) ) Is connected to an interface (manufactured by Nikka) and a PC 9801 personal computer (manufactured by NEC), and a 1% NaCl aqueous solution is prepared using first-grade sodium chloride. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant, preferably 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 electrolyte in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toners of 2 μm or more are measured using the Coulter counter multisizer type with a 100 μm aperture as the aperture. Distribution and number distribution were calculated. Then, a volume-based weight average particle diameter (D4: the median value of each channel is a representative value of the channel) obtained from the volume distribution according to the present invention was obtained.
[0091]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but this does not limit the present invention in any way. “Parts” means “parts by weight”.
[0092]
<Example 1>
To 700 parts of ion exchange water, 0.1M Na_ThreePO_FourAfter 450 parts of the aqueous solution was added and heated to 50 ° C., the mixture was stirred at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 1.0M-CaCl₂70 parts of an aqueous solution was added, and hydrochloric acid was further added to obtain an aqueous medium having a pH of 6.0 containing a calcium phosphate compound.
[0093]
on the other hand,

The above formulation was heated to 60 ° C., and uniformly dissolved and dispersed at 9000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). In this, 5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.
[0094]
The polymerizable monomer composition is charged into the aqueous medium, 60 ° C., N₂In an atmosphere, the mixture was stirred at 8000 rpm with a TK homomixer to granulate the polymerizable monomer composition.
[0095]
Thereafter, while stirring with a paddle stirring blade, after 5 hours, the heating rate was 40 ° C./Hr. The mixture was heated to 80 ° C. and reacted for 5 hours. After completion of the polymerization reaction, the residual monomer is distilled off under reduced pressure. After cooling, hydrochloric acid is added to dissolve the calcium phosphate salt, followed by filtration, washing with water, and drying to obtain colored toner particles having a number average particle diameter of 6.2 μm. Obtained.
[0096]
100 parts of the toner particles have a number average particle diameter of 30 nm, 0.7 parts of titanium oxide fine powder surface-treated with a silane coupling agent, and the number average particle diameter of 35 nm and silica surface-treated with a coupling agent. After adding 0.7 part of the fine powder, using a Henschel mixer manufactured by Mitsui Mining Co., Ltd., the mixture was stirred uniformly to remove the coarse powder with the following classifier 1 to obtain toner 1.
[0097]
Classification device 1:
As shown in FIG. 2, seven polyurethane balls having a diameter of 6.5 mm were used as the elastic balls 16, and polyethylene having an aperture B of 46 μm was used as the screen 11 (B / a = 7). .42).
[0098]
The toner is supplied to the toner cartridge No. of a round cylinder by the apparatus shown in FIG. 1 was filled. At this time, the filling rate was 0.41 g / ml.
[0099]
FIG. 3 shows an enlarged view of the spiral screw portion. In FIG. 3, D is the inner diameter of the screw casing, δ is the clearance between the outermost edge of the screw portion and the inner wall of the screw casing, r is the rotational speed, and W is the pitch length of the screw portion. Table 2 shows the set values.
[0100]
[Table 2]

[0101]
The shape factor SF-1 of the titanium oxide fine powder (1) present on the toner particles of the suspension polymerization cyan toner 1 is 115, and the shape factor SF-1 of the same silica fine powder (1) is 180. there were.
[0102]
This suspension polymerization cyan toner 1 has a number average particle diameter of 6.2 μm by Coulter counter, and in the circularity distribution by a flow type particle image analyzer, the average circularity is 0.985, and the circularity is less than 0.950. Of the toner particles was 10% by number.
[0103]
The suspension polymerization cyan toner 1 and the developing carrier I described below were mixed at a toner concentration of 8% to prepare a two-component cyan developer (1).
[0104]
(Manufacture of development carrier I)
After mixing and dispersing phenol / formaldehyde monomer (50:50) in an aqueous medium, 600 parts of 0.25 μm magnetite particles surface-treated with isopropoxy triisostearoyl titanate and 0.6 μm hematite based on the monomer weight While dispersing 400 parts of particles uniformly and adding ammonia appropriately, the monomer is polymerized, and the magnetic particle-containing spherical magnetic resin carrier core material (average particle size 33 μm, saturation magnetization 38 Am)²/ Kg).
[0105]
To this carrier core material,
[0106]
[Equation 3]

[0107]
Meanwhile, 20 parts of toluene, 20 parts of butanol, 20 parts of water and 40 parts of ice are placed in a four-necked flask and stirred with CH._ThreeSiC1_Three  15 mol and (CH_Three)₂SiCl₂40 parts of a mixture with 10 moles and a catalyst were added, and the mixture was further stirred for 30 minutes, and then subjected to a condensation reaction at 60 ° C. for 1 hour. Thereafter, the siloxane was thoroughly washed with water and dissolved in a toluene-methyl ethyl ketone-butanol mixed solvent to prepare a silicone varnish having a solid content of 10%.
[0108]
In this silicone varnish, 20 parts of ion-exchanged water with respect to 100 parts of siloxane solid, 2.0 parts of a curing agent represented by the following formula (1), 1.0 part of an aminosilane coupling agent represented by the following formula (2) Then, 5.0 parts of a silane coupling agent represented by the following formula (3) was simultaneously added to prepare a carrier coating solution I.
[0109]
[Expression 4]

[0110]
The carrier coating solution I was applied to 100 parts of the carrier core material subjected to the above-described surface modification by an applicator (Okada Seiko Co., Ltd .: Spiracoater), and the coating amount was 0.5 parts. Carrier I (developing carrier I) was obtained.
[0111]
This developing carrier I has a volume resistivity of 4 × 10 4 according to the following measurement method.¹³The coercive force was 55 Oersted.
[0112]
Measurement of volume resistance
The volume resistance value was measured using the cell shown in FIG. That is, the sample A is filled in the cell A, the lower electrode 141 and the upper electrode 142 are arranged so as to be in contact with the filled sample 143, a DC voltage of 1000 V is applied between the electrodes, and the current flowing at that time is measured with an ammeter. Was determined by Reference numeral 144 denotes an insulator. The measurement conditions were as follows: contact area S = 2 cm with the cell of the filled sample 143², Thickness d = 3 mm, upper electrode load 15 kg weight.
[0113]
Measuring magnetic properties
As the apparatus, a BHU-60 type magnetization measuring apparatus (manufactured by Riken Measurement) is used. About 1.0 g of the measurement sample is weighed and packed in a cell having an inner diameter of 7 mmφ and a height of 10 mm, and set in the above-mentioned apparatus. In the measurement, the applied magnetic field is gradually applied and changed up to 1000 oersted. Next, the applied magnetic field is decreased, and finally a hysteresis curve of the sample is obtained on the recording paper. From this, saturation magnetization, residual magnetization, and coercive force are obtained.
[0114]
The above two-component developer (1) is charged into the developing device 63a in the first image forming unit Pa of the image forming apparatus shown in FIG. 5, and a round cylindrical cyan toner cartridge (59a) is mounted on the toner hopper 65a. Then, the toner concentration is controlled using an inductance detection toner concentration detection means (not shown) so that the toner concentration of the two-component developer (1) in the developing device 63a is maintained at 7% to 9%, and the toner hopper While supplying the suspension polymerization toner 1 from 65a to the developing device 63a through the toner feeding member 66a, continuous copying of 30,000 sheets of cyan single color was performed at 23 ° C./65% RH.
[0115]
In the first image forming unit Pa of the image forming apparatus, the photosensitive drum 61a includes the following photosensitive member No. 1 and as the primary charger 62a, the following magnetic brush charger No. 1 is used. 1, the magnetic brush charger is rotated at a speed of 120% in the counter direction with respect to the moving direction of the photosensitive drum 61a, and charging is performed by superimposing an alternating voltage of 1 kHz and 1.2 kVpp on a direct current component of −700 V. The photosensitive drum 61a is primarily charged to -700 V while applying a bias voltage.
[0116]
Further, the first image forming unit Pa is in contact with the surface of the photosensitive drum 61a between the transfer unit and the charging unit and between the charging unit and the developing unit, and exists on the surface of the photosensitive drum 61a after the transfer process. There is no cleaning unit for removing and collecting the transfer residual toner, and the developing unit 63a uses a magnetic brush of a two-component developer when developing the transfer residual toner existing on the surface of the photosensitive drum 61a after the transfer process. It was set as the structure which performs the development simultaneous cleaning system which removes and collects using. During development in the developing device 63a, the development contrast was set to 250V, the fog removal inversion contrast was set to -150V, and development was performed while applying the discontinuous AC voltage shown in FIG. 7 to the development sleeve.
[0117]
(Photoreceptor No. 1)
Photoconductor No. Reference numeral 1 denotes an OPC photoconductor using an organic photoconductive material for negative charging, and five functional layers described below are provided on an aluminum cylinder having a diameter of 30 mm.
[0118]
The first layer is a conductive layer, and is a conductive particle-dispersed resin layer having a thickness of about 20 μm provided to smooth out defects in the aluminum cylinder and to prevent the occurrence of moire due to reflection of laser exposure.
[0119]
The second layer is a positive charge injection preventing layer (undercoat layer), and serves to prevent the positive charge injected from the aluminum substrate from canceling the negative charge charged on the surface of the photoreceptor. 10 by 610-12-nylon and methoxymethylated nylon⁶This is a medium resistance layer having a thickness of about 1 μm, the resistance of which is adjusted to about Ω · cm.
[0120]
The third layer is a charge generation layer, which is a layer having a thickness of about 0.3 μm in which a disazo pigment is dispersed in a resin, and generates positive and negative charge pairs upon receiving laser exposure.
[0121]
The fourth layer is a charge transport layer, which is obtained by dispersing hydrazine in a polycarbonate resin, and is a P-type semiconductor. Accordingly, negative charges charged on the surface of the photoreceptor cannot move through this layer, and only positive charges generated in the charge generation layer can be transported to the surface of the photoreceptor.
[0122]
The fifth layer is a charge injection layer and is made of SnO on a photocurable acrylic resin.₂Ultrafine particles, and further, tetrafluoroethylene resin particles having a particle size of about 0.25 μm are dispersed in order to increase the contact time between the charging member and the photosensitive member to perform uniform charging. Specifically, an oxygen-deficient SnO with a reduced resistance particle size of about 0.03 μm₂The particles are dispersed in an amount of 160 parts by weight with respect to 100 parts by weight of the resin, 30 parts by weight of tetrafluoroethylene resin particles, and 1.2 parts by weight of a dispersant.
[0123]
As a result, the photosensitive member No. The volume resistivity of the surface layer 1 is 3 × 10 in the case of the charge transport layer alone.^Five8 × 10 compared to Ω · cm¹¹It has dropped to Ω · cm.
[0124]
(Magnetic brush charger No. 1)
MgO 5 parts, MnO 8 parts, SrO 4 parts, Fe₂O_Three  83 parts were each atomized, granulated by adding water, mixed, fired at 1300 ° C. while adjusting the oxygen concentration, the particle size was adjusted, and the ferrite carrier core material having an average particle size of 28 μm (saturation magnetization of 63 Am)²/ Kg, the coercive force was 55 oersted).
[0125]
To the carrier core material, 10 parts of isopropoxy triisostearoyl titanate mixed with 99 parts of hexane / 1 part of water was subjected to a surface treatment to be 0.1 part,
[0126]
[Equation 5]

[0127]
The volume resistivity of the magnetic particles a measured by the same method as the volume resistivity of the developing carrier I is 4 × 10⁷The loss on heating was 0.15 part.
[0128]
Magnetic brush charger No. 1 is a magnetic brush formed by magnetically constraining the magnetic particles a on the surface of a conductive nonmagnetic sleeve containing a magnet roll, and the magnetic roll is fixed and a conductive nonmagnetic sleeve is fixed during charging. Is configured to rotate.
[0129]
In the above-described continuous copying test of 30,000 sheets, the uniformity of the initial image is solid, the fog after 30,000 sheets durability, the durability due to the image density difference between the initial image and the image after 30,000 sheets durability, the initial and 30,000 sheet durability Later transferability was evaluated. Further, the toner left for one month in the environment of low humidity (10 ° C / 10% RH) and high humidity (40 ° C / 80% RH) is imaged at 23 ° C / 65% RH (NN). The storage stability was evaluated.
[0130]
As shown in Table 3, the evaluation results were stable and the image density was stable, and there was no problem with fogging and transferability, and very good results were obtained.
[0131]
Solid uniformity
An original document provided with five circles with a diameter of 20 mm having an image density of 1.5 measured by a reflection densitometer RD918 (manufactured by Macbeth) was copied, and the image density of the image portion was measured by a reflection densitometer RD918. The difference between the maximum value and the minimum value at that time was obtained.
[0132]
Image density
An original document provided with a circle having a diameter of 20 mm with an image density of 1.5 measured by a reflection densitometer RD918 (manufactured by Macbeth) was copied, and the image density of the image portion was measured by a reflection densitometer RD918.
[0133]
Fog amount
A value (Dr−) obtained by subtracting the average value (Dr) of the reflection density obtained by measuring 10 points of the paper before image formation from the worst value (Ds) of the reflection density obtained by measuring 10 points of the non-image part (white background part) after the image formation. Ds) is the fog amount.
[0134]
The reflection density was measured using a reflection densitometer (TOKYO DENSHOKU CO, LTD, REFECTOMETER MODEL TC-6DS).
[0135]
A fog amount of 1.2% or less is a good image having substantially no fog, and if the fog amount exceeds 1.5%, the fog is conspicuous and unclear.
[0136]
Solid white
The number of white spots of about 100 μm or more is calculated in the above-mentioned five image portions of 20 mm. If it is 5 or less, it is a good image with substantially no problem, but if it exceeds 10, it becomes an image with degraded quality.
[0137]
<Example 2>
In Example 1, the toner cartridge No. 1 was similarly used except that a screen made of polyethylene having an aperture B of 74 μm (B / a = 11.9) was used as the screen of the classifier. 2 was produced and the image was printed out, but it was at a level where there was no practical problem at all, although the quality of the solid white was slightly reduced. At this time, the filling rate was 0.42 g / ml. This is presumed to be because the coarse particle removal was slightly insufficient because B / a became large.
[0138]
<Example 3>
In Example 1, the toner cartridge No. 1 was similarly used except that the screen of the classification device was made of polyethylene having an opening of 35 μm (B / a = 5.65). 3 was produced and imaged, and although it was slightly fogged when left at 40 ° C./80% RH, it was at a level of no practical problem. At this time, the filling rate was 0.40 g / ml. This is presumably because the screen has a small mesh opening, so that the external additive becomes loose from the toner particles and the storage stability is slightly lowered.
[0139]
<Comparative Example 1>

[0140]
The above raw materials are premixed with a Henschel mixer, melt-kneaded with a twin-screw extrusion kneader, cooled and roughly crushed to about 1 to 2 mm using a hammer mill, and then finely pulverized with an air jet type pulverizer. Crushed. Further, the toner cartridge No. 2 was similarly used except that toner particles obtained by classifying the obtained finely pulverized product were used. When No. 4 was produced, the filling rate was as small as 0.28 g / ml. When further filling was attempted, the toner container overflowed and the productivity was greatly deteriorated. This is presumably because the toner shape was indefinite and the toner was not easily clogged. The number average particle size of this toner was 6.1 μm, the average circularity was 0.932, and the number of toner particles having a circularity of less than 0.950 was 43% by number.
[0141]
<Comparative example 2>
In Comparative Example 1, the toner cartridge No. 1 was similarly prepared except that the toner particles were spheroidized in a hot water bath. 5 was produced and imaged, and the fog was deteriorated at the time of 10,000 sheets, so the evaluation was stopped. This is presumably because the toner was too spherical, so that the external additive was detached and the toner became non-uniformly charged. The number average particle diameter a of this toner was 5.9 μm, B / a = 8.00, the average circularity was 0.996, and the number of toner particles having a circularity of less than 0.950 was 1.3% by number. The filling rate was 0.43 g / ml.
[0142]
<Comparative Example 3>
In Example 1, the toner cartridge No. 1 was similarly used except that the screen of the classifying apparatus was made of polyethylene having an aperture of 104 μm (B / a = 16.8). 7 was produced and imaged, and the evaluation was stopped because the quality of solid white spots deteriorated from the beginning. This is presumably because the coarse particle removal was insufficient because B / a was large. The filling rate at this time was 0.41 g / ml, and the number average particle diameter, the average circularity and the like were the same as those in Example 1.
[0143]
<Comparative example 4>
In Example 1, the toner cartridge No. 1 was similarly used except that the screen of the classifying apparatus was made of polyethylene having an aperture of 28 μm (B / a = 4.31). As a result, the screen was severely clogged, the productivity was remarkably lowered, and the evaluation of the filling rate was difficult. Further, when the image was printed with this toner, the evaluation was stopped because the fog quality deteriorated from the beginning. This is presumably because the external additive was detached from the toner particles when passing through the screen. The number average particle diameter, average circularity, etc. at this time were the same as those in Example 1.
[0144]
<Example 4>
In Example 1, toner cartridge No. 1 having a filling rate of 0.45 g / ml was similarly used except that the inorganic fine powder (B) was changed to a coupling agent-treated silica fine powder having a number average particle diameter of 28 nm. 9 was produced and imaged, and good results were obtained although fog and solid uniformity were slightly deteriorated at the time of 30,000 sheets. The number average particle diameter, B / a, average circularity, and the like of the toner at this time were the same as those in Example 1, but the SF-1 of the silica fine particles was slightly small as 141, and the other outside was increased depending on the durability. This is presumably because the titanium oxide fine particles of the additive were embedded in the toner particles and became a little bit.
[0145]
<Example 5>
In Example 1, a filling rate of 0.38 g / ml was similarly obtained except that γ-type alumina treated with a coupling agent having an average particle diameter of 25 nm and SF-1 of 138 was used as the inorganic fine powder (A). Toner Cartridge No. 10 was produced and imaged, and good results were obtained although the solid uniformity slightly decreased at the time of 30,000 sheets. The number average particle diameter, B / a, average circularity, and the like of the toner at this time were the same as those in Example 1, but the SF-1 of the alumina fine particles was slightly large and the fluidity of the toner was slightly imparted. It is presumed that it deteriorated.
[0146]
<Example 6>
Toner cartridge No. 1 having a filling rate of 0.42 g / ml was used in the same manner except that rutile type titanium oxide treated with a coupling agent having an average particle size of 40 nm and SF-1 of 158 was used as the inorganic fine powder (B). No. 11 was produced and imaged, and good results were obtained although the fog slightly deteriorated when left at 40 ° C./80% RH. This is because the number average particle diameter, B / a, average circularity, and the like of the toner at this time were the same as those in Example 1, but the toner fine particles (B) were made of titanium oxide. This is presumably because it was slightly weakened and became loose when stored under high humidity.
[0147]
<Example 7>
In Example 1, a toner cartridge No. 1 having a filling rate of 0.52 g / ml was similarly prepared except that the titanium oxide fine powder was increased to 1.5 parts by weight. 6 was produced and imaged, and the solid uniformity deteriorated at the time of 10,000 sheets, but it was a practically acceptable level. This is presumably because the toner filling rate is high, so that uniform discharge from the toner cartridge is not achieved, and toner density is uneven in the developing device. The number average particle diameter, B / a, average circularity and the like of this toner were the same as those in Example 1.
[0148]
<Example 8>
In Example 1, the gyro shifter shown in FIG. 4 is used as a classification device, and an ultrasonic vibrator (not shown) is attached to a styrene screen 31 having an opening of 46 μm to prevent clogging. Coarse particles are prepared in the same manner except that the coarse particles are discharged from 33. When No. 12 was produced and imaged, good results were obtained.
[0149]
<Example 9>
(Magenta toner cartridge manufacturing example)
・ 170 parts of styrene
・ 30 parts of 2-ethylhexyl acrylate
・ Quinacridone pigment 15 parts
・ Di-tert-butylsalicylic acid Cr compound 3 parts
・ 10 parts of saturated polyester
(Acid value 10 mg KOH / g, peak molecular weight 9,100)
・ Ester wax 40 parts
(Mw: 450, Mn: 400, Mw / Mn: 1.25, melting point 70 ° C,
(Viscosity: 6.5 mPa · s, Vickers hardness: 1.1, SP value: 8.6)
[0150]
A polymerizable monomer composition was prepared in the same manner as in Example 1 and charged into the aqueous medium prepared in Example 1, and the magenta toner cartridge no. 13 was obtained. This toner had a number average particle size of 6.1 μm, B / a = 7.54, an average circularity of 0.986, a toner particle with a circularity of less than 0.950, 9%, and a toner filling rate of 0.42 g / ml. .
[0151]
(Black toner cartridge manufacturing example)
・ 170 parts of styrene
・ 30 parts of 2-ethylhexyl acrylate
・ 15 parts of carbon black
・ Di-tert-butylsalicylic acid Cr compound 3 parts
・ 10 parts of saturated polyester
(Acid value 10 mgKOH / g, peak molecular weight 9,100)
・ Ester wax 40 parts
(Mw: 500, Mn: 400, Mw / Mn: 1.25, melting point 70 ° C,
(Viscosity: 6.5 mPa · s, Vickers hardness: 1.1, SP value: 8.6)
[0152]
A polymerizable monomer composition was prepared in the same manner as in Example 1 and charged into the aqueous medium prepared in Example 1. The black toner cartridge no. 14 was obtained. This toner had a number average particle size of 6.0 μm, B / a = 7.67, an average circularity of 0.986, 10% of toner particles having a circularity of less than 0.950, and a toner filling rate of 0.41 g / ml. .
[0153]
(Example of manufacturing a yellow toner cartridge)
・ 170 parts of styrene
・ 30 parts of n-butyl acrylate
・ C. I. Pigment Yellow 93 15 parts
・ Di-tert-butylsalicylic acid Cr compound 3 parts
・ 10 parts of saturated polyester
(Acid value 10 mg KOH / g, peak molecular weight 9,100)
・ 40 parts diester wax
(Mw: 480, Mn: 410, Mw / Mn: 1.17, melting point 73 ° C.,
(Viscosity: 10.5 mPa · s, Vickers hardness: 1.0, SP value: 9.1)
[0154]
A polymerizable monomer composition was prepared in the same manner as in Example 1, and then charged into the aqueous medium prepared in Example 1, and the composition was 60 ° C., N₂Under an atmosphere, the polymerizable monomer composition was granulated by stirring for 10 minutes at 12,000 rpm with a CLEAR mixer. Then, the temperature of the aqueous medium was increased at 80 ° C. while stirring with a paddle stirring blade, and a polymerization reaction was performed for 10 hours.
[0155]
After completion of the polymerization reaction, the mixture was cooled, and hydrochloric acid was added to dissolve calcium phosphate, followed by filtration, washing with water and drying. 15 was obtained. This toner had a number average particle size of 6.3 μm, B / a = 7.30, an average circularity of 0.984, a toner particle having a circularity of less than 0.950, 13%, and a toner filling rate of 0.41 g / ml. .
[0156]
Using the yellow toner, magenta toner and black toner, the same carrier as in Example 1 was used to prepare a yellow developer, a magenta developer and a black developer.
[0157]
The image forming apparatus of FIG. 5 is used, a yellow developer is used for unit Pa 63a, a yellow toner cartridge is used for 59a, and a magenta developer / magenta toner cartridge is used for the Pb unit, and a unit Pc is used in the first embodiment. When the cyan developer / cyan toner cartridge was used and the black developer / black toner cartridge was used for the unit Pd, a full-color image durability evaluation was performed in the same manner as in Example 1, and the result was as good as in Example 1. Results were obtained.
[0158]
[Table 3]

[0159]
【The invention's effect】
According to the present invention, it is possible to easily fill the toner cartridge without causing the toner external additives to be released and re-aggregated, and the image quality due to durability can be improved.
[Brief description of the drawings]
FIG. 1 is a schematic view of an apparatus used in the present invention.
FIG. 2 is a schematic view of a classification device used in the present invention.
FIG. 3 shows an enlarged view of a spiral screw portion of the filling device.
FIG. 4 is a schematic view of another embodiment of the classification device used in the present invention.
FIG. 5 is a schematic view showing an example of a suitable image forming apparatus capable of carrying out the image forming method of the present invention.
6 is a diagram showing an alternating electric field used in Example 1. FIG.
FIG. 7 is an explanatory diagram of an apparatus used to measure a volume resistance value.
[Explanation of symbols]
59a toner cartridge
60a Transfer bias applying means (may be grounded)
61a Photosensitive drum
62a Primary charger
63a Developer
64a transfer blade
65a toner hopper
66a Supply roller
67a Exposure apparatus
68 Transfer material carrier
69 Separate charger
70 Fixing device
71 Fixing roller
72 Pressure roller
73 Web
75,76 Heating means
78 Temperature detection means
79 Transfer belt cleaning device
80 Drive roller
81 Belt driven roller
82 Belt static eliminator
83 Registration Roller
84 Paper feed roller
101 hopper
103 spiral screw
104 outlet
112 Stirring blade

Claims (3)

In a toner filling method in which a toner having a toner particle and an external additive and having a number average particle diameter a by a Coulter method of 2 to 8 μm is filled into a toner container via a spiral screw,
The toner has an average circularity of 0.950 to 0.995 and 2 to 40 particles having a circularity of less than 0.950 in the circularity distribution of particles measured by a flow particle image analyzer. Contains a number%,
After dispersing the external additive on the toner particles, the coarse particles are separated and removed by passing through a screen having a mesh opening (B) of 5 ≦ B / a ≦ 15, and the filling rate is 0.3 to 0.5 g / ml. A toner filling method for filling a toner container, wherein the toner container is filled with toner. The toner particles are produced by a polymerization method in which a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is subjected to suspension polymerization in an aqueous medium in the presence of a polymerization initiator. The method for filling a toner container according to claim 1 . The inner diameter D of the screw casing is 12 to 130 mm, the clearance δ between the outermost edge of the screw portion and the inner wall of the screw casing is 0.05 to 3.0 mm, and the rotational speed r of the screw is 50 to 3000 rpm. The method for filling toner into a toner container according to claim 1 or 2 , wherein the pitch length W satisfies the following formula.
0.1 × H <W <3.0 × H
(Where H is the outer diameter of the spiral screw, and H = D-2δ)

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