JP2004333682A - Developer carrier and developing apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developer carrier and a developing apparatus constituted so that developer can have a stable and high charge even in the case of repeatedly forming images, the developer is prevented from firmly sticking to a sleeve and the developer is hardly melt-stuck and hardly soiled. <P>SOLUTION: The developer carrier is provided with at least a substrate and a resin layer formed on the substrate surface, the resin layer is formed of resin composite containing at least aminosilane coupling agent, and binder resin used for the resin layer is provided with a copolymer containing vinyl polymerizable monomer and vinyl monomer containing nitrogen. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

〔但し、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４は水素原子あるいは炭素数１〜４の飽和炭化水素基を示し、ｎは１〜４の整数を示す。〕
【００３４】
本発明に用いられる４級アンモニウム基含有ビニルモノマーとしては、メチルメタクリレートと共重合可能なものであれば特にその構造は限定されるものではないが、より好ましい４級アンモニウム基含有ビニルモノマーとしては、下記一般式（２）に示される４級アンモニウム基含有ビニルモノマーがある。
【外４】

〔式中、Ｒ_５は、水素原子又はメチル基を示し、Ｒ_６は、炭素数１〜４のアルキレン基を示し、Ｒ_７〜Ｒ_９は、メチル基、エチル基又はプロピル基を示し、Ｘ_１は、−ＣＯＯ−又は−ＣＯＮＨ−を示し、Ａ⁻は、Ｃｌ⁻，（１／２）ＳＯ_４ ^２−の如きアニオンを示す。〕
【００３５】
本発明の樹脂バインダーに添加するアミノシランカップリング剤としては、一般に公知のものが使用可能である。例としては、アミノプロピルトリメトキシシラン、アミノプロピルトリエトキシシラン、ジメチルアミノプロピルトリメトキシシラン、ジエチルアミノプロピルトリメトキシシラン、ジプロピルアミノプロピルトリメトキシシラン、ジブチルアミノプロピルトリメトキシシラン、モノブチルアミノプロピルトリメトキシシラン、ジオクチルアミノプロピルトリメトキシシラン、ジブチルアミノプロピルジメトキシシラン、ジブチルアミノプロピルモノメトキシシラン、ジメチルアミノフェニルトリメトキシシラン、トリメトキシシリル−γ−プロピルフェニルアミン、トリメトキシシリル−γ−プロピルベンジルアミン、トリメトキシシリル−γ−プロピルピヘリジン、トリメトキシシリル−γ−プロピルモルホリン、トリメトキシシリル−γ−プロピルイミダゾール等がある。これらの処理剤は１種あるいは２種以上混合物あるいは併用や多重処理して用いられる。アミノシランカップリング剤の樹脂バインダーに対する添加量は、樹脂１００部に対して１〜１００部とすることが好ましく、１〜５０部であることがより好ましい。１部未満ではアミノシランカップリング剤添加による帯電付与性・表面離型性・潤滑性の向上がほとんど確認されず、１００部を超えると被膜強度の低下を招きやすい。
【００３６】
本発明の樹脂層に添加し、樹脂層に導電性を付与する材料としては、一般に公知の導電性微粉末が挙げられる。例えば、銅、ニッケル、銀、アルミニウム等の金属あるいは合金の粉体、酸化アンチモン、酸化インジウム、酸化スズ、酸化チタン等の金属酸化物、カーボンファイバー、カーボンブラック、グラファイト等の炭素系導電剤等々が挙げられる。導電性微粉末の添加量は、その現像システムにより異なるが、例えば、体積固有抵抗が１×１０^−２Ω・ｃｍ〜１×１０^５Ω・ｃｍの範囲になるように添加することが好ましい。カーボンブラック、とりわけ導電性のアモルファスカーボンは特に電気伝導性に優れ、他に比べ、少ない量の添加で導電性を付与することができ、添加量のコントロールによりある程度任意の抵抗値を得ることができるので、好適に用いられる。本発明の樹脂層中には潤滑性粉末を含有させることも好ましい。このような潤滑性粉末の例としては、二硫化モリブデン、窒化硼素、雲母、グラファイト、フッ化グラファイト、銀−セレン化ニオブ、塩化カルシウム−グラファイト、滑石、テフロン（登録商標）、ＰＶＤＦ等のフッ素化重合体、ステアリン酸亜鉛、ステアリン酸マグネシウム、ステアリン酸アルミニウム、パルミチン酸亜鉛等の脂肪酸金属塩等々が挙げられる。なかでもグラファイトは、潤滑性とともに導電性も有することから好ましく用いられる。本発明の樹脂層を得る方法としては、例えば、各成分を溶剤中に分散混合して塗料化し、前記基体上に塗工することにより得ることが可能である。各成分の分散混合には、サンドミル、ペイントシェーカー、ダイノミル、パールミル等のビーズを利用した公知の分散装置が好適に利用可能である。また塗工方法としては、ディッピング法、スプレー法、ロールコート法等、公知の方法が適用可能である。この被膜層の表面粗さはＪＩＳ中心線平均粗さ（Ｒａ）で０．３〜３．５μｍの範囲にあることが好ましい。Ｒａが０．３μｍ未満ではトナー担持体上のトナーが鏡映力により現像剤担持体表面に不動層を作ってしまい、トナーへの帯電付与が現像性が不充分となり、ムラ、飛び散り、濃度薄などの画像不良が発生する。Ｒａが３．５μｍを超えると、トナー担持体上のトナーコート層の規制が不十分となり、画像の均一性が不十分となったり、帯電不十分のための画像濃度薄となったりする。より好ましい範囲は現像剤層厚の規制方法により異なるが、いずれの形態による上記範囲にあることが好ましい。
【００３７】
また、現像剤担持体の樹脂被覆層の構成として、前述した添加物質に加えて、粒径が０．３〜３０μｍの球状粒子を被覆樹脂層中に分散させることで、表面粗さを安定化させ、現像剤担持体上のトナーコート量を最適化することが可能である。該球状粒子は、現像剤担持体の被覆層表面に均一な表面粗度を保持させると同時に、被覆層表面が摩耗した場合でも被覆層の表面粗度の変化が少なく、且つトナー汚染やトナー融着を発生しにくくする効果がある。
【００３８】
本発明に使用される球状粒子としては、個数平均径が０．３〜３０μｍ、好ましくは２〜２０μｍである。球状粒子の個数平均粒径が０．３μｍ未満では表面に均一な粗さを付与する効果と帯電性能を高める効果が少なく、現像剤への迅速且つ均一な帯電が不十分となると共に、被覆層の摩耗によるトナーのチャージアップ、トナー汚染及びトナー融着が発生し、ゴーストの悪化、画像濃度低下を生じやすくなるため好ましくない。個数平均粒径が３０μｍを超える場合には、被覆層表面の粗さが大きくなり過ぎ、トナーの帯電が十分に行われにくくなってしまうと共に、被覆層の機械的強度が低下してしまうため好ましくない。
【００３９】
さらに好ましくは、球状粒子の真密度は、３ｇ／ｃｍ^３以下、好ましくは２．７ｇ／ｃｍ^３以下、より好ましくは０．９〜２．３ｇ／ｃｍ^３であることが良い。即ち、球状粒子の真密度が３ｇ／ｃｍ^３を超える場合には、被覆層中での球状粒子の分散性が不十分となる為、被覆層表面に均一な粗さを付与しにくくなる。また、塗料の保存安定性が良くないため、ここでも均一表面凹凸を有する摩擦帯電付与部材表面が得にくくなる。球状粒子の真密度が０．９ｇ／ｃｍ^３より小さい場合にも、被覆層中での球状粒子の分散性及び保存安定性が不十分となる。
【００４０】
本発明に於いて、球状粒子における球状とは、粒子の長径／短径の比が１．０〜１．５程度の物を意味しており、本発明において好ましくは、長径／短径の比が１．０〜１．２の粒子を使用することが良い。球状粒子の長径／短径の比が１．５を超える場合には、被覆層表面粗さの不均一化が発生し、トナーの迅速且つ均一な帯電化及び導電性被覆層の強度の点で好ましくない。
【００４１】
本発明に用いられる球状粒子は、公知の球状粒子が使用可能である。例えば、球状の樹脂粒子、球状の金属酸化物粒子、球状の炭素化物粒子などがある。球状の粒子としては、例えば、懸濁重合、分散重合法等による球状の樹脂粒子などが用いられる。球状の樹脂粒子は、より少ない添加量で好適な表面粗さが得られ、更に均一な表面形状が得られやすい。この様な球状粒子としては、ポリアクリレート、ポリメタクリレート等のアクリル系樹脂粒子、ナイロン等のポリアミド系樹脂粒子、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂粒子、シリコーン系樹脂粒子、フェノール系樹脂粒子、ポリウレタン系樹脂粒子、スチレン系樹脂粒子、ベンゾグアナミン粒子、等々が挙げられる。粉砕法により得られた樹脂粒子を熱的にあるいは物理的な球形化処理を行ってから用いてもよい。
【００４２】
また、該球状粒子の表面に無機物を付着させる、あるいは固着させて用いてもよい。この様な無機微粉体としては、ＳｉＯ_２，ＳｒＴｉＯ_３，ＣｅＯ_２、ＣｒＯ，Ａｌ_２Ｏ_３，ＺｎＯ，ＭｇＯの如き酸化物、Ｓｉ_３Ｎ_４の如き窒化物、ＳｉＣの如き炭化物、ＣａＳＯ_４，ＢａＳＯ_４，ＣａＣＯ_３の如き硫酸塩、炭酸塩、等々が挙げられる。このような無機微粉末は、カップリング剤により処理して用いても良い。
【００４３】
特に結着樹脂との密着性を向上させる目的、あるいは粒子に疎水性を与える、等々の目的では好ましく用いることが可能である。このようなカップリング剤としては、例えば、シランカップリング剤、チタンカップリング剤、ジルコアルミネートカップリング剤等がある。より具体的には、例えばシランカップリング剤としては、ヘキサメチルジシラザン、トリメチルシラン、トリメチルクロルシラン、トリメチルエトキシシラン、ジメチルジクロルシラン、メチルトリクロルシラン、アリルジメチルクロルシラン、アリルフェニルジクロルシラン、ベンジルジメチルクロルシラン、ブロムメチルジメチルクロルシラン、α−クロルエチルトリクロルシラン、β−クロルエチルトリクロルシラン、クロルメチルジメチルクロルシラン、トリオルガノシリルメルカプタン、トリメチルシリルメルカプタン、トリオルガノシリルアクリレート、ビニルジメチルアセトキシシラン、ジメチルジエトキシシラン、ジメチルジメトキシシラン、ジフェニルジエトキシシラン、ヘキサメチルジシロキサン、１，３−ジビニルテトラメチルジシロキサン、１，３−ジフェニルテトラメチルジシロキサン及び１分子当たり２から１２個のシロキサン単位を有し末端に位置する単位にそれぞれ１個宛の硅素原子に結合した水酸基を含有したジメチルポリシロキサン等が挙げられる。このように球状樹脂粒子表面に対して無機微粉末で処理することにより、被覆層中への分散性、被覆層表面の均一性、被覆層の耐汚染性、トナーへの帯電付与性、被覆層の耐摩耗性等を向上させることができる。
【００４４】
また、本発明に使用する球状粒子は、導電性であることがより好ましい。即ち、球状粒子に導電性を持たせることによって、その導電性のゆえに粒子表面にチャージが蓄積しにくく、トナー付着の軽減やトナーの帯電付与性を向上させることができるからである。本発明において、球状粒子の導電性としては、体積抵抗値が１０^６Ω・ｃｍ以下、より好ましくは１０^−３〜１０^６Ω・ｃｍの粒子であることが好ましい。本発明において、球状粒子の体積抵抗が１０^６Ω・ｃｍを超えると、摩耗によって被覆層表面に球状粒子が露出し部分的に絶縁性となるために、これが核となりトナーの汚染や融着が発生しやすくなるとともに、迅速且つ均一な帯電が行われにくくなるため、好ましくない。
【００４５】
本発明で用いられる導電性球状粒子を得る方法としては、以下に述べる様な方法が好ましいが必ずしもこれらに限定されるものではない。本発明に用いられる特に好ましい導電性球状粒子を得る方法としては、例えば、球状の樹脂粒子やメソカーボンマイクロビーズを焼成することにより炭素化及び／又は黒鉛化して、低濃度且つ良導電性の球状炭素粒子を得る方法が挙げられる。そして、球状の樹脂粒子に用いられる樹脂としては、例えば、フェノール樹脂、ナフタレン樹脂、フラン樹脂、キシレン樹脂、ジビニルベンゼン重合体、スチレン−ジビニルベンゼン共重合体、ポリアクリロニトリルが挙げられる。又、メソカーボンマイクロビーズは、通常、中ピッチを加熱焼成していく過程で生成する球状結晶を多量のタール、中油、キノリン等の溶剤で洗浄することによって製造することができる。
【００４６】
より好ましい導電性球状粒子を得る方法としては、フェノール樹脂、ナフタレン樹脂、フラン樹脂、キシレン樹脂、ジビニルベンゼン重合体、スチレン−ジビニルベンゼン共重合体、ポリアクリロニトリル等の球状粒子表面に、メカノケミカル法によってバルクメソフェーズピッチを被覆し、被覆された粒子を酸化性雰囲気下で熱処理した後に焼成して炭素化及び／又は黒鉛化し、導電性の球状炭素粒子を得る方法が挙げられる。
【００４７】
上記した方法で得られる導電性の球状炭素粒子は、いずれの方法でも、焼成条件を変化させることによって得られる球状炭素粒子の導電性をある程度は制御することが可能であり、本発明において好ましく使用される。又、上記の方法で得られる球状炭素粒子は、場合によっては、更に導電性を高める為に導電性球状粒子の真密度が３ｇ／ｃｍ^３を超えない程度の範囲で、導電性の金属及び／又は金属酸化物のめっきを施していてもよい。
【００４８】
本発明で用いられる導電性球状粒子を得る他の方法としては、球状の樹脂粒子からなる芯粒子に対して、芯粒子の粒径よりも小さい導電性微粒子を適当な配合比で機械的に混合することによって、ファンデルワールス力及び静電気力の作用により芯粒子の周囲に均一に導電性微粒子を付着させた後、例えば、機械的衝撃力を付与することによって生ずる局部的温度上昇により芯粒子表面を軟化させ、芯粒子表面に導電性微粒子を成膜して導電化処理した球状樹脂粒子を得る方法が挙げられる。
【００４９】
上記の芯粒子には、有機化合物からなる真密度の小さい球形の樹脂粒子を使用することが好ましく、樹脂としては、例えば、ＰＭＭＡ、アクリル樹脂、ポリブタジエン樹脂、ポリスチレン樹脂、ポリエチレン、ポリプロピレン、ポリブタジエン、又はこれらの共重合体、ベンゾグアナミン樹脂、フェノール樹脂、ポリアミド樹脂、ナイロン、フッ素系樹脂、シリコーン樹脂、エポキシ系樹脂、ポリエステル樹脂が挙げられる。芯粒子（母粒子）の表面に成膜する際に使用される導電性微粒子（小粒子）としては、導電性微粒子被膜を均一に設けるために、小粒子の粒径が母粒子の粒径の１／８以下のものを使用するのが好ましい。
【００５０】
本発明に用いられる導電性球状粒子を得る他の方法としては、球状樹脂粒子中に導電性微粒子を均一に分散させることにより、導電性微粒子が分散された導電性球状粒子を得る方法が挙げられる。球状樹脂粒子中に導電性微粒子を均一に分散させる方法としては、例えば、結着樹脂と導電性微粒子とを混練して導電性微粒子を分散させた後、冷却固化し、所定の粒径に粉砕し、機械的処理及び熱的処理により球形化して導電性球状粒子を得る方法、又は、重合性単量体中に重合開始剤、導電性微粒子及びその他の添加剤を加え、分散機によって均一に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に撹拌機によって所定の粒子径になる様に懸濁させて重合を行い、導電性微粒子が分散された球状粒子を得る方法が挙げられる。
【００５１】
これらの方法で得られた導電性微粒子が分散された導電性球状粒子においても、前記した芯粒子よりも小さい粒径の導電性微粒子と適当な配合比で機械的に混合して、ファンデルワールス力及び静電気力の作用により導電性球状粒子の周囲に均一に導電性微粒子を付着させた後、例えば、機械的衝撃力を付与することにより生ずる局部的温度上昇により導電性球状粒子の表面を軟化させ、該表面に導電性微粒子を成膜して、更に導電性を高めて使用してもよい。
【００５２】
本発明における表面粗さの測定は、小坂研究所製表面粗度計ＳＥ−３３００Ｈを用い、測定条件としては、カットオフ０．８ｍｍ、規定距離８．０ｍｍ、送り速度０．５ｍｍ／ｓｅｃ．にて１２箇所の測定値の平均をとった。
【００５３】
次に、トナーについて説明する。トナーは主として樹脂、離型剤、荷電制御剤、着色剤等を溶融混練し、固化した後粉砕し、しかる後分級などをして粒度分布をそろえた微粉体である。トナーに用いられる結着樹脂としては、一般に公知の樹脂が使用可能である。
【００５４】
例えば、スチレン、α−メチルスチレン、ｐ−クロルスチレンなどの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−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−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などの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、テンペル樹脂、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単独或いは混合して使用できる。
【００５５】
又、トナー中には顔料を含有することができる。例えば、カーボンブラック、ニグロシン染料、ランプ黒、スーダンブラックＳＭ、ファースト・イエローＧ、ベンジジン・イエロー、ピグメント・イエロー、インドファースト・オレンジ、イルガジン・レッド、パラニトロアニリン・レッド、トルイジン・レッド、カーミンＦＢ、パーマネント・ボルドーＦＲＲ、ピグメント・オレンジＲ、リソール・レッド２Ｇ、レーキ・レッドＣ、ローダミンＦＢ、ローダミンＢレーキ、メチル・バイオレッドＢレーキ、フタロシアニン・ブルー、ピグメント・ブルー、ブリリアント・グリーンＢ、フタロシアニングリーン、オイルイエローＧＧ、ザボン・ファーストイエローＣＧＧ、カヤセットＹ９６３、カヤセットＹＧ、ザボン・ファーストオレンジＲＲ、オイル・スカーレット、オラゾール・ブラウンＢ、ザボン・ファーストスカーレットＣＧ、オイルピンクＯＰ等が適用できる。
【００５６】
トナーを磁性トナーとして用いるために、トナーの中に磁性粉を含有せしめてもよい。このような磁性粉としては、磁場の中におかれて磁化される物質が用いられ、鉄、コバルト、ニッケル等の強磁性金属の粉末、又はマグネタイト、ヘマタイト、フェライト等の合金や化合物がある。この磁性粉の含有量はトナー重量に対して１５〜７０重量％が良い。
【００５７】
トナーに、定着時の離型性向上、定着性向上の目的で、ワックス類を含有させることができる。そのようなワックス類としては、パラフィンワックス及びその誘導体、マイクロクリスタンリンワックス及びその誘導体、フィッシャートロプッシュワックス及びその誘導体、ポリオレフィンワックス及びその誘導体、カルナバワックス及びその誘導体などで、誘導体には酸化物や、ビニル系モノマーとのブロック共重合物、グラフト変性物を含む。その他、アルコール、脂肪酸、酸アミド、エステル、ケトン、硬化ヒマシ油及びその誘導体、植物系ワックス、動物系ワックス、鉱物系ワックス、ペトロラクタム等も利用できる。
【００５８】
必要に応じて、トナーに荷電制御剤を含有させてもよい。荷電制御剤には、負荷電制御剤、正荷電制御剤がある。例えばトナーを負荷電性に制御するものとして下記物質がある。例えば有機金属錯体、キレート化合物が有効であり、モノアゾ金属錯体、アセチルアセトン金属錯体、芳香族ハイドロキシカルボン酸、芳香族ダイカルボン酸系の金属錯体がある。他には、芳香族ハイドロキシカルボン酸、芳香族モノ及びポリカルボン酸及びその金属塩、無水物、エステル類、ビスフェノール等のフェノール誘導体類などがある。また、トナーを正帯電させるための物質としては下記のようなものがある。ニグロシン及び脂肪酸金属塩等による変性物、トリブチルベンジルアンモニウム−１−ヒドロキシ−４−ナフトスルフォン酸塩、テトラブチルアンモニウムテトラフルオロボレート等の四級アンモニウム塩、及びこれらの類似体であるホスホニウム塩等のオニウム塩及びこれらのレーキ顔料、（レーキ化剤としては、りんタングステン酸、りんモリブデン酸、りんタングステンモリブデン酸、タンニン酸、ラウリン酸、没食子酸、フェリシアン化物、フェロシアン化物など）高級脂肪酸の金属塩；ジブチルスズオキサイド、ジオクチルスズオキサイド、ジシクロヘキシルスズオキサイド等のジオルガノスズオキサイド；ジブチルスズボレート、ジオクチルスズボレート、ジシクロヘキシルスズボレート等のジオルガノスズボレート類；グアニジン化合物、イミダゾール化合物。
【００５９】
トナーは必要に応じて、流動性改善等の目的で無機微粉末の如き粉末を外添して用いられる。このような微粉末としては、シリカ微粉末、アルミナ、チタニア、酸化ゲルマニウム、酸化ジルコニウム等の金属酸化物；炭化ケイ素、炭化チタン等の炭化物；及び窒化ケイ素、窒化ゲルマニウム等の窒化物等の無機微粉体が用いられる。これらの微粉体は、有機ケイ素化合物、チタンカップリング剤等で有機処理して用いることが可能である。例えば有機ケイ素化合物としては、ヘキサメチルジシラザン、トリメチルシラン、トリメチルクロルシラン、トリメチルエトキシシラン、ジメチルジクロルシラン、メチルトリクロルシラン、アリルジメチルクロルシラン、アリルフェニルジクロルシラン、ベンジルジメチルクロルシラン、ブロムメチルジメチルクロルシラン、α−クロルエチルトリクロルシラン、β−クロルエチルトリクロルシラン、クロルメチルジメチルクロルシラン、トリオルガノシリルメルカプタン、トリメチルシリルメルカプタン、トリオルガノシリルアクリレート、ビニルジメチルアセトキシシラン、ジメチルエトキシシラン、ジメチルジメトキシシラン、ジフェニルジエトキシシラン、ヘキサメチルジシロキサン、１，３−ジビニルテトラメチルジシロキサン、１，３−ジフェニルテトラメチルジシロキサン、及び１分子当たり２から１２個のシロキサン単位を有し末端に位置する単位にそれぞれ１個宛のＳｉに結合した水酸基を含有するジメチルポリシロキサン等がある。また、未処理の微粉体を窒素含有のシランカップリング剤で処理したものを用いてもよい。特にポジトナーの場合好ましい。そのような処理剤の例としては、アミノプロピルトリメトキシシラン、アミノプロピルトリエトキシシラン、ジメチルアミノプロピルトリメトキシシラン、ジエチルアミノプロピルトリメトキシシラン、ジプロピルアミノプロピルトリメトキシシラン、ジブチルアミノプロピルトリメトキシシラン、モノブチルアミノプロピルトリメトキシシラン、ジオクチルアミノプロピルトリメトキシシラン、ジブチルアミノプロピルジメトキシシラン、ジブチルアミノプロピルモノメトキシシラン、ジメチルアミノフェニルトリメトキシシラン、トリメトキシシリル−γ−プロピルフェニルアミン、トリメトキシシリル−γ−プロピルベンジルアミン、トリメトキシシリル−γ−プロピルピペリジン、トリメトキシシリル−γ−プロピルモルホリン、トリメトキシシリル−γ−プロピルイミダゾール、等がある。
【００６０】
上記シランカップリング剤により無機微粉体を処理する方法としては、例えば、１）スプレー法、２）有機溶媒法、３）水溶液法などがある。一般に、スプレー法による処理とは、ピグメントを撹拌しここにカップリング剤の水溶液あるいは溶媒液をスプレーし、この後水あるいは溶媒を１２０〜１３０℃程度で除去乾燥する方法である。また、有機溶媒法による処理とは、少量の水とともに加水分解用触媒を含む有機溶媒（アルコール、ベンゼン、ハロゲン化炭化水素等）にカップリング剤を溶解し、これにピグメントを浸漬した後、濾過或いは圧搾により固液分離を行い１２０〜１３０℃程度で乾燥させるものである。水溶液法とは０．５％程度のカップリング剤を、一定ｐＨの水あるいは水−溶媒中で加水分解させ、ここにピグメントを浸漬した後、同様に固液分離を行い乾燥するものである。
【００６１】
他の有機処理としてシリコーンオイルで処理された微粉体を用いることも可能である。好ましいシリコーンオイルとしては、２５℃における粘度がおよそ０．５〜１００００ｍｍ^２／ｓ、好ましくは１〜１０００ｍｍ^２／ｓのものが用いられ、例えばメチルハイドロジエンシリコーンオイル、ジメチルシリコーンオイル、フェニルメチルシリコーンオイル、クロルフェニルメチルシリコーンオイル、アルキル変性シリコーンオイル、脂肪酸変性シリコーンオイル、ポリオキシアルキレン変性シリコーンオイル、フッ素変性シリコーンオイルなどが挙げられる。また、側鎖に窒素原子を有するシリコーンオイルを用いても良い。特にポジトナーの場合は好ましい。シリコーンオイルによる処理は、例えば次のようにして行い得る。必要に応じて加熱しながら顔料を激しく撹乱しており、これに上記シリコーンオイル或いはその溶液をスプレーもしくは気化して吹き付けるか、又は顔料をスラリー状にしておき、これを撹拌しつつシリコーンオイル或いはその溶液を滴下することによって容易に処理できる。これらのシリコーンオイルは１種あるいは２種以上の混合物あるいは併用や多重処理して用いられる。また、シランカップリング剤による処理と併用しても構わない。このようなトナーは、種々の方法で、球形化処理、表面平滑化処理を施して用いると、転写性が良好となり好ましい。そのような方法としては、撹拌羽根またはブレードなど、及びライナーまたはケーシングなどを有する装置で、例えば、トナーをブレードとライナーの間の微小間隙を通過させる際に、機械的な力により表面を平滑化したりトナーを球形化したりする方法、温水中にトナーを懸濁させ球形化する方法、熱気流中にトナーを曝し、球形化する方法等がある。また、球状のトナーを作る方法としては、水中にトナー結着樹脂となる単量体を主成分とする混合物を懸濁させ、重合してトナー化する方法がある。一般的な方法としては、重合性単量体、着色剤、重合開始剤、さらに必要に応じて架橋剤、荷電制御剤、離型剤、その他の添加剤を均一に溶解または分散せしめて単量体組成物とした後、この単量体組成物を分散安定剤を含有する連続層、例えば水相中に適用な撹拌機を用いて適当な粒径に分散し、さらに重合反応を行わせ、所望の粒径を有する現像剤を得る方法である。
【００６２】
次に本発明の現像剤担持体を用いた現像装置及び装置ユニットについて説明例示する。
【００６３】
図１は、非磁性一成分現像剤を用いた場合に用いられる現像装置の構成の一例を模式的に示す。図１において、公知のプロセスにより形成された静電潜像を担持する像担持体、例えば電子写真感光ドラム１は、矢印Ｂ方向に回転される。現像剤担持体としての現像スリーブ８は、金属製円筒管（基体）６とその表面に形成される樹脂被膜層７から構成されている。非磁性一成分現像剤を用いるために金属製円筒管６の内部には磁石は内設されていない。金属製円筒管の替わりに円柱状部材を用いることもできる。現像器であるホッパー３中には非磁性一成分現像剤４を撹拌するための撹拌翼１０が設けられている。現像スリーブ８に現像剤４を供給し、かつ現像後の現像スリーブ８の表面に存在する現像剤４を剥ぎ取るための現像剤供給・剥ぎ取り部材１２が現像スリーブ８に当接している。現像剤供給・剥ぎ取り部材である供給・剥ぎ取りローラ１２が現像スリーブ８と同じ方向に回転することにより、供給・剥ぎ取りローラ１２の表面は、現像スリーブ８の表面とカウンター方向に移動することになり、ホッパー３から供給された非磁性トナーを有する一成分非磁性現像剤は、現像剤スリーブ８に供給され、現像スリーブ８が一成分現像剤４を担持して、矢印Ａ方向に回転することにより、現像スリーブ８と感光ドラム１とが対向した現像部Ｄに非磁性一成分現像剤４を搬送する。現像スリーブ８に担持されている一成分現像剤は、現像スリーブ８の表面に対して現像剤層を介して圧接する現像剤層厚規制部材１１により現像剤層厚が規定される。非磁性一成分現像剤４は現像スリーブ８との摩擦により、感光ドラム１上の静電潜像を現像可能な摩擦帯電電荷を得る。現像スリーブ８上に形成される非磁性一成分現像剤４の薄層の厚みは、現像部における現像スリーブ８と感光ドラム１との間の最小間隙Ｄよりも更に薄いものであることが好ましい。このような現像剤層により静電潜像を現像する非接触型現像装置に、本発明は特に有効である。しかし、現像部において現像剤層の厚みが現像スリーブ８と感光ドラム１との間の最小間隙Ｄ以上の厚みである接触型現像装置にも、本発明は適用することができる。説明の煩雑を避けるため、以下の説明では、非接触型現像装置を例にとって行う。
【００６４】
上記現像スリーブ８には、これに担持された非磁性トナーを有する一成分非磁性現像剤４を飛翔させるために、電源９により現像バイアス電圧が印加される。この現像バイアス電圧として直流電圧を使用するときは、静電潜像の画像部（非磁性現像剤４が付着して可視化される領域）の電位と背景部の電位との間の値の電圧が、現像スリーブ８に印加されることが好ましい。現像画像の濃度を高め或いは階調製を向上するために、現像スリーブ８に交番バイアス電圧を印加して、現像部に向きが交互に反転する振動電界を形成してもよい。この場合、上記画像部の電位と背景部の電位の間の値を有する直流電圧成分が重畳された交番バイアス電圧を現像スリーブ８に印加することが好ましい。高電位部と低電位部を有する静電潜像の高電位部に現像剤を付与させて可視化する所謂正規現像では、静電潜像の極性と逆極性に帯電する現像剤を使用する。静電潜像の低電位部にトナーを付着させて可視化する所謂反転現像では、現像剤は静電潜像の極性と同極性に帯電する現像剤を使用する。高電位と低電位というのは、絶対値による表現である。いずれにしても、非磁性一成分現像剤４は現像スリーブ８との摩擦により静電潜像を現像するための極性を帯電する。現像剤供給・剥ぎ取り部材としては、樹脂、ゴム、スポンジの如き弾性ローラ部材が好ましい。剥ぎ取り部材としては、弾性ローラに代えてベルト部材又はブラシ部材を用いることもできる。感光体１に現像移行されなかった現像剤を現像剤供給・剥ぎ取り部材１２により、一旦スリーブ表面から剥ぎ取ることにより、スリーブ上の不動の現像剤の発生を防いだり、現像剤の帯電を均一化する働きを有する。現像剤供給・剥ぎ取り部材として弾性ローラからなる供給・剥ぎ取りローラ１２を用いる場合には、供給・剥ぎ取りローラ１２の周速は、表面がカウンター方向に回転する場合、現像スリーブ８の周速１００％に対して、好ましくは２０〜１２０％、より好ましくは３０〜１００％であることが良い。供給・剥ぎ取りローラ１２の周速が２０％未満の場合には、現像剤の供給が不足し、ベタ画像の追従性が低下し、ゴースト画像の原因となり、１２０％を超える場合には、現像剤の供給量が多くなり現像剤層厚の規性不良や帯電量不足によるカブリの原因となり、さらにトナーにダメージを与えやすい、トナー劣化によるカブリやトナー融着の原因となり易い。供給・剥ぎ取りローラの回転方向が現像スリーブの表面と同（順）方向の場合には、供給ローラの周速は、スリーブ周速に対して、好ましくは１００〜３００％、より好ましくは１０１〜２００％であることが上記のトナー供給量の点で良い。供給・剥ぎ取りローラの回転方向は、現像スリーブの表面とカウンター方向に回転することが、剥ぎ貼り性及び供給性の点でより好ましい。現像スリーブ８に対する現像剤供給・剥ぎ取り部材１２の侵入量は、０．５〜２．５ｍｍであることが、現像剤の供給及び剥ぎ取り性の点で好ましい。現像剤供給・剥ぎ取り部材１２の侵入量が０．５ｍｍ未満の場合には、剥ぎ取り不足により、ゴーストが発生し易くなり、侵入量が２．５ｍｍを超える場合には、トナーのダメージが大きくなり、トナー劣化により融着やカブリの原因となり易い。
【００６５】
図１の現像装置では、現像スリーブ８上の非磁性一成分現像剤４の層厚を規制する部材として、ウレタンゴム、シリコーンゴムの如きゴム弾性を有する材料、或いはリン青銅、ステンレス銅の如き金属弾性を有する材料の弾性規制ブレード１１を使用し、この弾性規制ブレード１１を図１の現像装置では現像スリーブ８に回転方向と逆の姿勢で圧接させ、現像スリーブ８上に更に薄い現像剤層を形成することができる。この弾性規制ブレード１１としては、特に安定した規制力とトナーへの安定した（負）帯電付与性のためには、安定した加圧力の得られるリン青銅板表面にポリアミドエラストマー（ＰＡＥ）を貼り付けた構造のものを用いることが好ましい。ポリアミドエラストマー（ＰＡＥ）としては、例えばポリアミドとポリエーテルの共重合体が挙げられる。現像スリーブ８に対する現像剤層厚規制部材１１の当接圧力は、線圧５〜５０ｇ／ｃｍであることが、現像剤の規制を安定化させ、現像剤層厚を好適にさせることができる点で好ましい。現像剤層厚規制部材１１の当接圧力が線圧５ｇ／ｃｍ未満の場合には、現像剤の規制が弱くなり、カブリやトナーもれの原因となり、線圧５０ｇ／ｃｍを超える場合には、トナーへのダメージが大きくなり、トナー劣化やスリーブ及びブレードへの融着の原因となり易い。
【００６６】
本発明の現像剤担持体は、このような現像スリーブ８に対して、現像剤供給・剥ぎ取り部材１２及び現像剤層厚規制部材１１が圧接する装置に適用した場合に、特に有効である。すなわち、現像スリーブ８に対して、現像剤供給・剥ぎ取り部材１２及び現像剤層厚規制部材１１が圧接する場合には、現像スリーブ８の表面がこれらの圧接される部材によって摩耗や現像剤の融着がより生じ易い使用環境にあることから、本発明の多数枚耐久性に優れた樹脂被覆層を有する現像剤担持体による効果が有効に発現されることになる。
【００６７】
図２は、磁性一成分現像剤を用いた場合に用いられる現像装置の構成の一例を模式的に示す。図２において、公知のプロセスにより形成された静電潜像を担持する像担持体、例えば電子写真感光ドラム１は、矢印Ｂ方向に回転される。現像剤担持体としての現像スリーブ１８は、金属製円筒管（基体）１６とその表面に形成される樹脂被覆層１７から構成されている。現像容器としてのホッパー１３中には磁性一成分現像剤１４を撹拌するための撹拌翼２０が設けられている。ホッパー１３から供給された一成分磁性現像剤としての磁性トナー１４を担持して、矢印Ａ方向に回転することにより、現像スリーブ１８と感光ドラム１とが対向した現像部に磁性一成分現像剤１４を搬送する。現像スリーブ１８内には、磁性一成分現像剤１４を現像スリーブ１８上に磁気的に吸引保持するために、磁石１５が配置されている。磁性一成分現像剤１４は現像スリーブ１８との摩擦により、感光ドラム１上の静電潜像を現像可能な摩擦帯電電荷を得る。
【００６８】
図２の現像装置では、現像スリーブ１８上の磁性一成分現像剤１４の層厚を規制する部材として、ウレタンゴム、シリコーンゴムの如きゴム弾性を有する材料、或いはリン青銅、ステンレス銅の如き金属弾性を有する材料の弾性規制ブレード２１を使用し、この弾性規制ブレード２１を図２の現像装置では現像スリーブ１８に回転方向と逆の姿勢で圧接させ、現像スリーブ１８上に更に薄い現像剤層を形成することができる。
【００６９】
図３の現像装置では弾性規制ブレード２１を現像スリーブ１８に回転方向と同方向の姿勢で圧接させていることが特徴である。現像スリーブ１８上に形成される磁性一成分現像剤１４の薄層の厚みは、現像部における現像スリーブ１８と感光ドラム１との間の最小間隙Ｄよりも更に薄いものであることが好ましい。このような現像剤層により静電潜像を現像する非接触型現像装置に、本発明は特に有効である。しかし、現像部において現像剤層の厚みが現像スリーブ１８と感光ドラム１との間の最小間隙Ｄ以上の厚みである接触型現像装置にも、本発明は適用することができる。
【００７０】
説明の煩雑を避けるため、以下の説明では、非接触型現像装置を例にとって行う。
【００７１】
上記現像スリーブ１８には、これに担持された磁性トナーを有する一成分磁性現像剤１４を飛翔させるために、電源１９により現像バイアス電圧が印加される。この現像バイアス電圧として直流電圧を使用するときは、静電潜像の画像部（磁性一成分現像剤１４が付着して可視化される領域）の電位と背景部の電位との間の値の電圧が、現像スリーブ１８に印加されることが好ましい。現像画像の濃度を高め或いは階調性を向上するために、現像スリーブ１８に交番バイアス電圧を印加して、現像部に向きが交互に反転する振動電界を形成してもよい。この場合、上記画像部の電位と背景部の電位の間の値を有する直流電圧成分が重畳された交番バイアス電圧を現像スリーブ１８に印加することが好ましい。高電位部と低電位部を有する静電潜像の高電位部に現像剤を付着させて可視化する所謂正規現像では、静電潜像の極性と逆極性に帯電するトナーを使用する。静電潜像の低電位部に現像剤を付着させて可視化する所謂反転現像では、現像剤は静電潜像の極性と同極性に帯電する現像剤を使用する。高電位と低電位というのは、絶対値による表現である。いずれにしても、磁性一成分現像剤１４は現像スリーブ１８との摩擦により静電潜像を現像するための極性を帯電する。上記の現像装置を画像形成装置本体に対して着脱可能に装着する装置ユニットとして用いることが可能である。
【００７２】
図３を参照しながら、図１で例示した本発明の現像剤担持体を有する現像装置を使用した画像形成装置の一例について説明する。先ず、一次帯電手段としての接触（ローラ）帯電手段２９により静電潜像担持体としての感光ドラム１の表面を負極性に帯電し、レーザー光の露光２５によるイメージスキャニングによりデジタル潜像が感光ドラム１上に形成される。次に、現像剤層厚規制部材としての弾性規制ブレード１１を有し、現像剤担持体としての現像スリーブ８が具備されている現像装置によって、上記のデジタル潜像が、現像容器としてのホッパー３内の非磁性トナーを有する負帯電性一成分系現像剤４によって反転現像される。図３に示す様に、現像領域Ｄにおいて感光ドラム１の導電性基体は接地されており、現像スリーブ８にはバイアス印加手段９により交互バイアス、パルスバイアス及び／又は直流バイアスが印加されている。次に、被記録材Ｐが搬送されて転写部に来ると、転写手段としての接触（ローラ）転写手段２３により被記録材Ｐの背面（感光ドラム側と反対面）から電圧印加手段２４で帯電されることにより、感光ドラム１の表面上に形成されている現像画像が接触転写手段２３で被記録材Ｐ上へ転写される。次に、感光ドラム１から分離された被記録材Ｐは、定着手段としての加熱加圧ローラ定着器２７に搬送され、該定着器２７によって被記録材Ｐ上の現像画像の定着処理がなされる。転写工程後の感光ドラム１に残留する一成分系現像剤４は、クリーニングブレード２８ａを有するクリーニング手段２８で除去される。残留する一成分系現像剤４が少ない場合には、クリーニング工程を省くことも可能である。クリーニング後の感光ドラム１は、必要によりイレース露光２６により除電され、再度、一次帯電手段としての接触（ローラ）帯電手段２９による帯電工程から始まる上記工程が繰り返される。上記の一連の工程において、感光ドラム（即ち、静電潜像担持体）１は感光層及び導電性基体を有するものであり、矢印方向に動く。現像剤担持体である非磁性の円筒の現像スリーブ８は、現像領域Ｄにおいて感光ドラム１の表面と同方向に進む様に回転する。現像スリーブ８の表部には、供給ローラ１２が接触し、かつ現像スリーブ８の表面の移動方向と逆方向に表面が移動するように回転している。この供給ローラ１２の回転によって、ホッパー３内の一成分系現像剤４は、現像スリーブ８上に塗布されて担持され、且つ現像スリーブ８の表面との摩擦及び／又は非磁性トナー同士の摩擦によって、例えば、マイナスのトリボ電荷が与えられる。更に、弾性規制ブレード１１を現像剤層を介して現像スリーブ８を弾性的に押圧する様に設け、現像剤層の厚さを薄く（３０μｍ〜３００μｍ）且つ均一に規制して、現像領域Ｄにおける感光ドラム１と現像スリーブ８との間隙よりも薄い現像剤層を形成させる。現像スリーブ８の回転速度を調整することによって、現像スリーブ８の表面速度が感光ドラム１の表面の速度と実質的に等速、もしくはそれに近い速度となる様にする。現像領域Ｄにおいて、現像スリーブ８に現像バイアス電圧として、交流バイアス又はパルスバイアスをバイアス印加手段９により印加してもよい。この交流バイアスはｆが２００〜４，０００Ｈｚ、Ｖｐｐが５００〜３，０００Ｖであればよい。
【００７３】
現像領域Ｄにおける現像剤の移転に際し、感光ドラム１の表面の静電気力、及び交流バイアス又はパルスバイアスの如き現像バイアス電圧の作用によって、現像剤は静電潜像側に移転する。
【００７４】
一次帯電手段としては、以上の如く接触帯電手段として帯電ローラ２９を用いて説明したが、帯電ブレード、帯電ブラシの如き接触帯電手段でもよく、更に非接触のコロナ帯電手段でもよい。しかしながら、帯電によるオゾンの発生が少ない点で接触帯電手段の方が好ましい。
【００７５】
転写手段としては、以上の如く転写ローラ２３の如き接触転写手段を用いて説明したが、非接触のコロナ転写手段でもよい。しかしながら、こちらも転写によるオゾンの発生が少ない点で接触転写手段の方が好ましい。
【００７６】
本発明に於いて、装置ユニットは、図１乃至３に示す現像装置を画像形成装置本体（例えば、複写機、レーザービームプリンタ、ファクシミリ装置）に対して着脱可能に装置するものである。装置ユニットとしては、図１乃至３に示す現像装置に加えて、ドラム状の静電潜像保持体（感光ドラム）１、クリーニングブレード２８ａを有するクリーニング手段２８及び一次帯電手段としての接触（ローラ）帯電手段２９からなるグループから選択される１種以上の構成部材を一体に有していることも可能である。
【００７７】
本発明の画像形成方法をファクシミリのプリンタに適用する場合には、光像露光Ｌは受信データをプリントするための露光になる。図５はこの場合の一例をブロック図で示したものである。コントローラ３１は画像読取部４０とプリンタ３９を制御する。コントローラ３１の全体はＣＰＵ３７により制御されている。画像読取部からの読取データは、送信回路３３を通して相手局に送信される。相手局から受けたデータは受信回路３２を通してプリンタ３９に送られる。画像メモリには所定の画像データが記憶される。プリンタコントローラ３８はプリンタ３９を制御している。３４は電話である。回路３５から受信された画像（回線を介して接続されたリモート端末からの画像情報）は、受信回路３２で復調された後、ＣＰＵ３７は画像情報の複合処理を行い順次画像メモリ３６に格納される。そして、少なくとも１ページの画像がメモリ３６に格納されると、そのページの画像記録を行う。ＣＰＵ３７は、メモリ３６より１ページの画像情報を読み出しプリンタコントローラ３８に複合化された１ページの画像情報を送出する。プリンタコントローラ３８は、ＣＰＵ３７からの１ページの画像情報を受け取るとそのページの画像情報記録を行うべく、プリンタ３９を制御する。尚、ＣＰＵ３７は、プリンタ３９による記録中に、次のページの受信を行っている。以上の様に、画像の受信と記録が行われる。
【００７８】
（実施例）
以下に、実施例及び比較例を挙げて本発明をより具体的に説明する。表１に、実施例及び比較例で得られた摩擦帯電付与部材の構成をまとめて示した。
【００７９】

アミノシランカップリング剤（１）の構造を下記に示す。
【外５】

【００８０】
メチルメタクリレート−ジメチルアミノエチルメタクリレート共重合体Ａは、予めＭＥＫの一部に溶解させた。カーボンブラック、結晶性グラファイト、アミノシランカップリング剤を添加しガラスビーズを用いたサンドミルで分散した。さらにＭＥＫを添加して固形分濃度を３０％とした。分散終了後、ガラスビーズと分離して、室温にて粘度を測定したところ、７２ｍＰａ・ｓであった。この塗料を用いてスリーブの塗工を行った。両端をフランジ加工された、外径１６ｍｍφのアルミニウム製円柱状丸棒を回転台に立てて回転させ、両端部をマスキングしながらスプレーガンを一定速度で下降させ、丸棒表面に塗布することにより膜厚の均一な塗布スリーブを得た。これを乾燥炉にて１６０℃で３０分間乾燥硬化させ、スリーブ１とした。乾燥後の塗料の付着量は９０００ｍｇ／ｍ^２であった。表面粗さを測定したところ、中心線平均粗さＲａが０．６２μｍであった。
【００８１】
これとは別の丸棒にＯＨＰシートとアルミシートを巻き付け同様に塗工し、これらのシートを体積固有抵抗測定のサンプルとした（ＯＨＰシートで抵抗測定、アルミシートで塗工膜厚を測定する）。体積固有抵抗を測定したところ、４０．２Ω・ｃｍであった。体積固有抵抗値は三菱油化社製、ローレスターＡＰに４端子プローブを取付けて測定した（但し、体積抵抗の高めのサンプルについては、同社のハイレスターを用いた）。
【００８２】
次に、このスリーブ１を用い、図３に示す画像形成装置として、キヤノン社製のＬＢＰ−２２６０改造機を用いて画出しを行った。ＥＰ−８２カートリッジにこのスリーブを装着可能に加工し取付けた。シアントナーを用い、単色で３千枚までの耐久試験を行った。ＥＰ−８２カートリッジのスリーブ近傍の模式図を図１に示す。この評価に用いたトナーの製造例を下記に示す。
【００８３】
反応容器中のイオン交換水１００００部に０．１ｍｏｌ／Ｌ−Ｎａ_３ＰＯ_４水溶液重量部ならびに１ｍｏｌ／Ｌ−ＨＣｌ水溶液を８５重量部投入し、Ｎ_２パージしながら６５℃で６０分保温した。高速撹拌装置ＴＫ−ホモミキサーを用いて、１２０００ｒｐｍにて撹拌しながら、１．０ｍｏｌ／Ｌ−ＣａＣｌ_２水溶液６０重量部を一括投入し、ｐＨ＝６．５のリン酸カルシウム塩を含む水系媒体を調整した。
【００８４】

別容器中で上記材料を６５℃に保温し、ＴＫ式ホモミキサーを用いて１２０００ｒｐｍ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）４重量部を溶解し、重合性単量体組成物を調整した。
【００８５】
反応容器中の前記水系媒体中に上記重合性単量体組成物を投入し、６５℃、Ｎ_２パージ下において、ＴＫ式ホモミキサーを用いて１００００ｒｐｍで１０分間撹拌し、重合性単量体組成物を造粒した。その後、パドル撹拌翼で撹拌しつつ６５℃で６時間、さらに８５℃に昇温し、９時間反応させた後、８５℃で蒸留を行った。
【００８６】
重合反応終了後、反応容器を冷却し、塩酸を加えてＣａ_３（ＰＯ_４）_２を溶解し、濾過、水洗、乾燥をして、イエロートナー粒子を得た。上記イエロートナー粒子１００質量部に対して流動向上剤として、ヘキサメチルジシラザンで処理した疎水性シリカ微粉体（ＢＥＴ：２５０ｍ^２／ｇ）１．５質量部をヘンシェルミキサーで乾式混合して、本発明のトナーとした。
【００８７】
画出し評価は、２３℃／５％ＲＨの低湿環境下と、３０℃／８０％ＲＨの高湿環境下の２環境下にて行った。このときの画出し評価結果を表２に示す。
【００８８】
〔評価方法〕
評価は次のような事項について行った。
【００８９】
（１）画像濃度（５濃度、ベタ濃度）
５ｍｍ角黒及びベタ黒印字した際のページ内のポイント１０箇所について、反射濃度計ＲＤ９１８（マクベス社製）により反射濃度測定を行い、１０点の平均をとって画像濃度とした。
【００９０】
（２）トナー帯電量（Ｑ／Ｍ）
現像スリーブ上に担持されたトナーを、金属円筒管と円筒フィルターにより吸収捕集し、その時金属円筒管を通じてコンデンサーに蓄えられる電荷量Ｑを、及び捕集されるトナー重量Ｍから、単位重量あたりの電荷量Ｑ／Ｍ（ｍＣ／ｋｇ）を計算する。
【００９１】
（３）カブリ（紙カブリ）
ベタ白画像の反射率を測定し、更に未使用の転写紙の反射率を測定し（ベタ白画像の反射率の最悪値）−（未使用転写紙の反射率の最高値）をカブリ濃度とし、その数値で示す（ただし反射率の測定はランダムに１０回の測定を行った）。反射率はＴＣ−６ＤＳ（東京電色社製）で測定した。評価基準としては、１．５以下；ほとんどわからない。１．５〜２．５；注意深く見ないとわからない。２．５〜３．５；次第にカブリが認識できるようになる。４．０；実用レベル下限で一見してカブリが確認できる。５．０以上；かなり悪い。
【００９２】
（４）ドラム上カブリ（ドラムカブリ）
ベタ白画像時に、転写前のドラムに移行したトナーをマイラーテープで貼り取って回収し白紙に貼り付け反射濃度を測定し、白紙に貼り付けたマイラーテープの反射濃度との差をカブリ濃度とした。測定は上記と同じＴＣ−６ＤＳを用いた。
【００９３】
（５）ベタ白筋、白帯（白帯）
ベタ画像で、画像進行方向に白筋状または白帯状の濃度薄部分が発生する現象で、トナーの帯電が不十分で現像が均一に行われない場合や、トナー固着や融着が生じている場合に発生する。以下の評価基準に基づいて評価した。
【００９４】
（評価基準）
Ａ：全く見られない。
Ｂ：透かして見ると濃度薄が確認できる。
Ｃ：通常のベタ画像の目視でやや現認されるが、画像濃度差はほとんどない。
Ｄ：通常のベタ画像の目視で確認されるが、写真画像では認識しずらい程度。
Ｅ：通常のベタ画像の目視ではっきり現認される。写真などのハーフトーンでも現認される。
Ｆ：かなり濃度差のある画像。
【００９５】
（６）トナー飛散（飛散）
スリーブからのトナーの飛散状態を以下の評価基準に基づいて評価比較する。
【００９６】
Ａ：カートリッジのスリーブ近傍にも飛散がほとんどない。
Ｂ：カートリッジのスリーブ下のステージ部分に多少のトナー付着が見られる程度。
Ｃ：上記の汚染は多少見られるが、汚染が本体までには至らない。
Ｄ：上記の汚染は見られ、かつ汚染が本体に多少認められる。
Ｅ：飛散が本体にまで認められるが、スリーブからのトナーのボタ落ちはない。
Ｆ：スリーブ上にトナーがコートされない部分が発生し、その部分ではトナーがスリーブからボタ落ち（スリーブ下のステージに落ちたトナーが溜り、そこからトナーがこぼれる）している。
Ｇ：スリーブ上のかなりの部分からボタ落ちが発生している。
【００９７】
（７）コート層の削れ量（膜削れ）
塗工前のスリーブ（アルミニウム丸棒）の外径、塗工後の樹脂層を含めた外径をレーザー測長器にて測定（１０箇所の平均）しておき、耐久後の樹脂層を含めた外径をレーザー測長器にて測定し、（画出し前の樹脂層を含めた外径）−（耐久後の樹脂層を含めた外径）を削れ量として、μｍ単位で表す。
【００９８】
＜実施例２＞
【外６】

【００９９】
実施例１で用いたアミノシランカップリング剤（１）に替えて、上記アミノシランカップリング剤（２）を用いた以外は、実施例１と同様にしてスリーブ２を作製し、実施例１と同様の評価を行った。
【０１００】
＜実施例３＞
【外７】

【０１０１】
実施例１で用いたアミノシランカップリング剤（１）に替えて、上記アミノシランカップリング剤（３）を用いた以外は、実施例１と同様にしてスリーブ３を作製し、実施例１と同様の評価を行った。
【０１０２】
＜実施例４〜７＞
実施例１で用いた共重合体Ａに替えて、メチルメタクリレートとジメチルアミノエチルメタクリレートのモル比を変化させた共重合体Ｂ〜Ｅを用いた以外は、実施例１と同様にしてスリーブ４〜７を作製し、実施例１と同様の評価を行った。
【０１０３】
スリーブ４に使用した共重合体
メチルメタクリレート−ジメチルアミノエチルメタクリレート共重合体Ｂ（４０％ＭＥＫ溶液）
（モル比９９７：３、Ｍｗ＝１９０００、Ｍｎ＝５０００、Ｍｗ／Ｍｎ＝１．９）
スリーブ５に使用した共重合体
メチルメタクリレート−ジメチルアミノエチルメタクリレート共重合体Ｃ（４０％ＭＥＫ溶液）
（モル比９９９９：１、Ｍｗ＝２２０００、Ｍｎ＝９０００、Ｍｗ／Ｍｎ＝２．４）
スリーブ６に使用した共重合体
メチルメタクリレート−ジメチルアミノエチルメタクリレート共重合体Ｄ（４０％ＭＥＫ溶液）
（モル比８２：１８、Ｍｗ＝９９００、Ｍｎ＝４４００、Ｍｗ／Ｍｎ＝２．３）
スリーブ７に使用した共重合体
メチルメタクリレート−ジメチルアミノエチルメタクリレート共重合体Ｅ（４０％ＭＥＫ溶液）
（モル比７０：３０、Ｍｗ＝８５００、Ｍｎ＝２９００、Ｍｗ／Ｍｎ＝２．９）
【０１０４】
＜実施例８〜１３＞
実施例１で用いた共重合体Ａに替えて、共重合体の分子量を変化させた共重合体Ｆ〜Ｋを用いて、実施例１と同様にしてスリーブ８〜１３を作製し、実施例１と同様の評価を行った。
【０１０５】
スリーブ８に使用した共重合体
メチルメタクリレート−ジメチルアミノエチルメタクリレート共重合体Ｆ（４０％ＭＥＫ溶液）
（モル比９０：１０、Ｍｗ＝３７００、Ｍｎ＝２３００、Ｍｗ／Ｍｎ＝１．６）
スリーブ９に使用した共重合体
メチルメタクリレート−ジメチルアミノエチルメタクリレート共重合体Ｇ（４０％ＭＥＫ溶液）
（モル比９０：１０、Ｍｗ＝２５００、Ｍｎ＝１３００、Ｍｗ／Ｍｎ＝１．９）
スリーブ１０に使用した共重合体
メチルメタクリレート−ジメチルアミノエチルメタクリレート共重合体Ｈ（４０％ＭＥＫ溶液）
（モル比９０：１０、Ｍｗ＝４００００、Ｍｎ＝１９０００、Ｍｗ／Ｍｎ＝２．１）
スリーブ１１に使用した共重合体
メチルメタクリレート−ジメチルアミノエチルメタクリレート共重合体Ｉ（４０％ＭＥＫ溶液）
（モル比９０：１０、Ｍｗ＝５２５００、Ｍｎ＝２２２００、Ｍｗ／Ｍｎ＝２．４）
スリーブ１２に使用した共重合体
メチルメタクリレート−ジメチルアミノエチルメタクリレート共重合体Ｊ（４０％ＭＥＫ溶液）
（モル比９０：１０、Ｍｗ＝１２９００、Ｍｎ＝３９００、Ｍｗ／Ｍｎ＝３．３）
スリーブ１３に使用した共重合体
メチルメタクリレート−ジメチルアミノエチルメタクリレート共重合体Ｋ（４０％ＭＥＫ溶液）
（モル比９０：１０、Ｍｗ＝１２９００、Ｍｎ＝３２００、Ｍｗ／Ｍｎ＝４．０）
【０１０６】
＜実施例１４＞
実施例１で用いたアミノシランカップリング剤（１）の添加量を１５部とした以外は、実施例１と同様にしてスリーブ１４を作製し、実施例１と同様の評価を行った。
【０１０７】
＜実施例１５＞
実施例１で用いたアミノシランカップリング剤（１）の添加量を３０部とした以外は、実施例１と同様にしてスリーブ１５を作製し、実施例１と同様の評価を行った。
【０１０８】
＜実施例１６＞
実施例１で用いた共重合体Ａの添加量を２０部とし、アミノシランカップリング剤（１）の添加量を５部とした以外は、実施例１と同様にしてスリーブ１６を作製し、実施例１と同様の評価を行った。
【０１０９】
＜実施例１７＞
実施例１で用いた共重合体Ａの添加量を５０部とし、アミノシランカップリング剤（１）の添加量を１２．５部とした以外は、実施例１と同様にしてスリーブ１７を作製し、実施例１と同様の評価を行った。
【０１１０】
＜実施例１８＞
実施例１で用いた共重合体Ａの添加量を８０部とし、アミノシランカップリング剤（１）の添加量を２０部とした以外は、実施例１と同様にしてスリーブ１８を作製し、実施例１と同様の評価を行った。
【０１１１】
＜実施例１９〜２１＞
実施例１で用いた共重合体Ａのジメチルアミノエチルメタクリレートモノマーに替えて、ジエチルアミノエチルメタクリレートモノマー、ジブチルアミノエチルメタクリレートモノマー、ジメチルアミノスチレンモノマーをそれぞれ用い、メチルメタクリレートモノマーと共重合させた共重合体Ｌ〜Ｎを用いることを除いては、実施例１と同様にしてスリーブ１９〜２１を作製し、実施例１と同様の評価を行った。
【０１１２】
＜実施例２２〜２５＞
実施例１で用いた共重合体Ａのメチルメタクリレートモノマーに替えてアクリル酸、メタクリル酸、マレイン酸ブチル、スチレンをそれぞれ用い、ジメチルアミノエチルメタクリレートモノマーと共重合させた共重合体Ｏ〜Ｒを用いることを除いては、実施例１と同様にしてスリーブ２２〜２５を作製し、実施例１と同様の評価を行った。
【０１１３】
＜実施例２６〜２８＞
実施例１で用いた共重合体Ａに替えて、３元共重合体である下記共重合体Ｓ〜Ｕを用いて、実施例１と同様にしてスリーブ２６〜２８を作製し、実施例１と同様の評価を行った。
【０１１４】
スリーブ２６に使用した共重合体
メチルメタクリレート−ジメチルアミノエチルメタクリレート−アクリル酸共重合体Ｓ（４０％ＭＥＫ溶液）（モル比９０：５：５、Ｍｗ＝１１５００、Ｍｎ＝４８００、Ｍｗ／Ｍｎ＝２．４）
スリーブ２７に使用した共重合体
メチルメタクリレート−ジメチルアミノエチルメタクリレート−メタクリル酸共重合体Ｔ（４０％ＭＥＫ溶液）（モル比９０：５：５、Ｍｗ＝１２５００、Ｍｎ＝５７００、Ｍｗ／Ｍｎ＝２．２）
スリーブ２８に使用した共重合体
メチルメタクリレート−ジメチルアミノエチルメタクリレート−マレイン酸ブチル共重合体Ｕ（４０％ＭＥＫ溶液）（モル比９０：５：５、Ｍｗ＝１１９００、Ｍｎ＝４９００、Ｍｗ／Ｍｎ＝２．４）
【０１１５】
＜実施例２９＞
実施例１で用いた共重合体Ａのジメチルアミノエチルメタクリレートモノマーに替えて、下記４級アンモニウム基含有ビニルモノマー（１）を用い、メチルメタクリレートモノマーと共重合させた共重合体Ｖを用いて、実施例１と同様にしてスリーブ２９を作製し、実施例１と同様の評価を行った。
【外８】

【０１１６】
＜実施例３０＞
実施例２９で用いた共重合体Ｖに替えて、４級アンモニウム基含有ビニルモノマーを下記（２）に替えた共重合体Ｗを用いて、実施例２９と同様にスリーブ３０を作製し同様の評価を行った。
【外９】

【０１１７】
＜実施例３１＞
実施例２９で用いた共重合体Ｖに替えて、４級アンモニウム基含有ビニルモノマーを下記（３）に替えた共重合体Ｘを用いて、実施例２９と同様にスリーブ３１を作製し同様の評価を行った。
【外１０】

【０１１８】
＜実施例３２＞
実施例３１で用いたメチルメタクリレートモノマーに替えてスチレンモノマーを用いた共重合体Ｙを用いて、実施例３１と同様にスリーブ３２を作製し同様の評価を行った。
【０１１９】
（比較例１）
実施例３１において、メチルメタクリレートの単独重合体を用いたこと以外は、実施例３１と同様にスリーブＡを作製し同様の評価を行った。
【０１２０】
（比較例２）
比較例１で使用したメチルメタクリレートの単独重合体にアミノシランカップリング剤（１）を添加すること以外は、比較例１と同様にしてスリーブＢを作製し同様の評価を行った。
【０１２１】
（比較例３）
実施例１で使用した共重合体を用いた塗料に代えて、下記の組成のフェノール系塗料を用いた以外は、実施例１と同様にして、スリーブＣを作製した。塗料の乾燥硬化時間は、１５０℃、３０分とした。
【０１２２】
・フェノール樹脂中間体 １００重量部
・平均粒径３μｍの結晶性グラファイト ２５重量部
・メタノール ２５０重量部
得られたスリーブＣを用いて実施例１と同様の評価を行った。
【０１２３】
（比較例４）
実施例１で用いたアルミニウム円筒管の表面にガラスビーズ（ＦＧＢ＃３００）を用いてサンドブラスト処理を行った。このスリーブＤを用いて、実施例１と同様の評価を行った。
【０１２４】
（比較例５）
実施例１において、アミノシランカップリング剤（１）を添加しないこと以外は、実施例１と同様にスリーブＥを作製し同様の評価を行った。
【０１２５】
（比較例６）
実施例２５において、アミノシランカップリング剤（１）を添加しないこと以外は、実施例１と同様にスリーブＦを作製し同様の評価を行った。
【０１２６】
【表１】

【０１２７】
【表２】

【０１２８】
【表３】

【０１２９】
【発明の効果】
本発明によれば、現像剤担持体上の現像剤が、繰り返しの画出しにおいても、安定且つ適正な電荷を有し、均一でムラがなく、画像濃度低下やゴーストの発生のない、高品位の画像を得ることができる。特に、高画質、省エネルギーを目的として、粒径が小さく、低温定着材料を用いたトナーにおいても、樹脂被覆層へのトナー付着を軽減させ、更にはより帯電性あるいは現像性を向上させることにより、高精細高品位な画像を得ることができる。更に樹脂被覆層の耐摩耗性を確保し、かつ均一な樹脂層を形成することにより、長く安定した画像を得ることができる。
【図面の簡単な説明】
【図１】本発明の現像剤担持体を有する非磁性一成分現像方式の現像装置の一例を示す模式図である。
【図２】本発明の現像剤担持体を有する磁性一成分現像方式の現像装置の他の例を示す模式図である。
【図３】本発明の現像剤担持体を有する磁性一成分現像方式の現像装置の他の例を示す模式図である。
【図４】本発明の画像形成装置をファクシミリ装置のプリンタに適用した場合のブロック図を示す。
【符号の説明】
１ 電子写真感光ドラム（潜像担持体）
３ ホッパー
４ 非磁性トナー（現像剤）
６ 金属製円筒管（基体）
７ 樹脂被膜層
８ 現像スリーブ（現像剤担持体）
９ 電源
１０ トナー撹拌翼
１１ 弾性規制ブレード（現像剤層厚規制部材）
１２ 現像剤供給・剥ぎ取りローラ（現像剤供給・剥ぎ取り部材）
１３ ホッパー
１４ 磁性トナー（現像剤）
１５ 磁石
１６ 金属製円筒管（基体）
１７ 樹脂被膜層
１８ 現像スリーブ（現像剤担持体）
１９ 電源
２０ トナー撹拌翼
２１ 弾性規制ブレード（現像剤層厚規制部材）[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a developing device and a developing device for developing a latent image formed on an electrostatic latent image carrier used in electrophotography, electrostatic recording, magnetic recording and the like with a developer to visualize the latent image. The present invention relates to an agent carrier.
[0002]
[Prior art]
Conventionally, many methods have been known as electrophotography. In general, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is formed into a toner ( (Developer) to develop a visible image, transfer the toner image to a transfer material such as paper if necessary, and then fix the toner image on the transfer material by heat, pressure, etc. to obtain a copy It is.
[0003]
Development methods in electrophotography are mainly classified into a one-component development method and a two-component development method. In recent years, since it is necessary to reduce the size of a copying apparatus in order to reduce the weight and size of an electrophotographic apparatus, a developing apparatus using a one-component toner is often used.
[0004]
Unlike the two-component system, the one-component developing system does not require carrier particles such as glass beads and iron powder, so that the developing device itself can be reduced in size and weight. Further, in the two-component developing method, since it is necessary to keep the toner concentration in the developer 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. In the one-component developing system, such an apparatus is not necessary, so that the apparatus can be made small and light, which is preferable.
[0005]
For example, as a developing method using a one-component toner, an electrostatic latent image is formed on the surface of a photosensitive drum as an image carrier, friction between a developing sleeve as a developer carrier and toner particles, and / or a developing sleeve is formed. A positive or negative charge is applied to the toner particles due to friction between the toner particles and the developer regulating member that regulates the amount of toner applied above, and this toner is applied thinly on the developing sleeve so that the photosensitive drum and the developing sleeve face each other. Is transported to a developing area, and the toner flies and adheres to the electrostatic latent image on the surface of the photosensitive drum in the developing area to develop the latent image, and the electrostatic latent image is visualized as a toner image. In recent years, LED and LBP printers have become the mainstream in the market for printer devices, and the direction of technology has been changed to higher resolution, that is, 300, 400 dpi in the past, to 600, 800, 1200 dpi. Accordingly, higher definition is also required for the developing system. Also, the functions of the copiers have been advanced, and the digital copying machines are moving toward digitalization. In this direction, the method of forming an electrostatic charge image with a laser is the main method, so it is also proceeding in the direction of high resolution, and here too, a high resolution and high definition development method is required like a printer. JP-A-1-112253, JP-A-2-284158, and the like have proposed toners having a small particle diameter, and the toner particle diameter is proceeding in a further smaller direction.
[0006]
Further, as a developer carrying member used for development, for example, a metal, an alloy thereof or a compound thereof is molded into a cylindrical shape, and the surface thereof is treated by electrolysis, blasting, sanding or the like so as to have a predetermined surface roughness. Is used. However, in this case, the developer existing in the vicinity of the surface of the developer carrier in the developer layer formed on the surface of the developer carrier by the regulating member has a very high electric charge, and the reflection force on the surface of the carrier is reduced. The developer is intensely attracted, so that there is no chance of friction between the toner and the carrier, so that the developer cannot have a suitable charge (a so-called charge-up phenomenon).
[0007]
Further, for the purpose of improving the image quality, as described above, the average particle diameter of the developer is made smaller, and the regulation of the developer in the configuration of the developing device is further strengthened, so that the developer is thinned on the developer carrier. This tends to increase the physical load on the developer and the developer carrying member, so that the above-described charge-up phenomenon and sleeve ghost are more likely to occur. Under such circumstances, sufficient development and transfer are not performed, resulting in an image with image density unevenness and scattered characters.
[0008]
In order to prevent the generation of a developer having such an excessive charge and the strong adhesion of the developer, a film in which a conductive substance such as carbon graphite or a solid lubricant is dispersed in a resin is loaded with the developer. A method of forming on a body has been proposed in Japanese Patent Application Laid-Open No. 1-277265.
[0009]
However, in a developer having a further reduced particle size as described above, in order to prevent irregular coating of the developer on the developer carrying member, the content of the magnetic substance is increased, or the surface of the toner particles is charged. In some cases, a material that does not accumulate too much, or an external additive that causes the charge to leak, may be selected. In such a case, the rise of toner charging tends to be slow. Further, in recent years, a reduction in energy consumption of the copying machine and the LBP main body has been demanded again, and accordingly, in order to reduce energy required for fixing, low temperature fixing of a developer used has been actively studied. . As a method, there is a tendency that a Tg (glass transition point) of a developer is set to be relatively large, a low molecular weight component is added to a binder resin more, or a low melting point component such as wax is added more. . Under the influence of the influence, the developer which is likely to be fused to a sleeve or the like is increasing. Further, since the fixing property is prioritized, the toner is hardly charged, and the developing property may not be sufficiently secured.
[0010]
Therefore, it is necessary to further improve the charge-imparting property of the developer to the developer carrier, prevent the charge-up phenomenon, and make it difficult for the developer to fuse to the developer carrier. Furthermore, with the stricter regulation of the thickness of the developer layer, the recent increase in the number of times of use of the cartridge or the increase in capacity, there is a demand for sufficient abrasion resistance and uniformity of the resin layer.
[0011]
[Problems to be solved by the invention]
In order to solve the above-mentioned problems, a binder resin contained in a resin coating layer formed on the surface of a substrate was previously described in JP-A-11-125966 by combining a methyl methacrylate monomer (M) unit having a high mechanical strength with a developing unit. By providing a copolymer having a specific ratio of nitrogen-containing vinyl monomer (N) units having a high negative triboelectric charging property to the agent and having a specific weight average molecular weight (Mw), the charge imparting property is improved. Despite the further improvement, the developer that makes it difficult for the developer to fuse to the developer carrier, and has a high abrasion resistance of the resin coating layer, and has a good triboelectric charging property until after many sheets have been used. An agent carrier was proposed. In the present invention, the above-described problems can be solved by further improving the developer carrier in Japanese Patent Application Laid-Open No. H11-125966, and a developer carrier capable of coping with the trend toward higher image quality of electrophotography is provided. The purpose is to provide.
[0012]
That is, an object of the present invention is to provide a developer on a developer carrier that has a stable and appropriate charge even in repeated image formation, is uniform and has no unevenness, and does not cause a decrease in image density or generation of a ghost. It is another object of the present invention to provide a developer carrier capable of obtaining a high-quality image.
[0013]
Further, an object of the present invention is to improve the chargeability or developability even in a toner using a low-temperature fixing material with a small particle diameter for the purpose of high image quality and energy saving, and to reduce toner adhesion to a resin coating layer. Accordingly, it is an object of the present invention to provide a developer carrier capable of stably obtaining a high-definition, high-quality image for a long time.
[0014]
It is a further object of the present invention to provide a developer carrier capable of obtaining a long and stable high-quality image by ensuring the abrasion resistance of the resin coating layer and forming a more uniform resin layer. .
[0015]
[Means for Solving the Problems]
The above object is achieved by a developer carrier according to the present invention and a developing device using the developer carrier. That is, the present invention relates to a developer carrier used in a developing device that develops a latent image formed on a latent image carrier with a developer carried and conveyed by the developer carrier, and that is used to develop a visible image. The developer carrier has at least a substrate and a resin layer formed on the surface of the substrate, and the resin layer is formed of a resin composition containing at least an aminosilane coupling agent, and is used for the resin layer. The resin binder relates to a developer carrier, which is a copolymer of a vinyl polymerizable monomer and a nitrogen-containing vinyl monomer.
[0016]
Further, the present invention provides a developer container in which a developer contained in a developing container is supported on a developer carrier, and the developer carrier is pressed against or abuts on the developer carrier via the developer. While forming a thin layer of the developer on the carrier, the developer is conveyed to a development area facing the latent image carrier, and the latent image on the latent image carrier is developed with the developer to develop a visible image. The present invention relates to a developing device using the developer carrier described above.
[0017]
Here, it is preferable that the vinyl polymerizable monomer has a methyl methacrylate monomer. Preferably, the resin layer is a conductive resin layer containing a conductive fine powder and / or a solid lubricant.^-2Ω · cm to 1 × 10⁵It is preferably Ω · cm.
[0018]
BEST MODE FOR CARRYING OUT THE INVENTION
In the developer carrier of the present invention, the resin coating layer formed on the substrate surface is formed of a resin composition containing an aminosilane coupling agent, and the binder resin contained in the resin coating layer has high mechanical strength. Since it has a copolymer of a vinyl polymerizable monomer and a nitrogen-containing vinyl monomer having a high negative triboelectrification property with respect to the developer, the developer carrier has an abrasion resistance, It has high toner adhesion and fusing properties, and has good triboelectric charging properties until after many sheets have been used.
[0019]
Further, since the copolymer has a nitrogen-containing vinyl monomer, the dispersibility of the conductive fine powder such as carbon black and graphite in the resin coating layer is improved. Therefore, the electric resistance of the resin coating layer is favorably reduced, the uniformity of the triboelectric charging characteristics on the surface of the resin coating layer is improved, the triboelectric charging characteristics with respect to the developer are higher, and the charge amount of the developer is increased. Since the distribution becomes sharp and the film strength of the resin coating layer itself is also improved, the durability of a large number of sheets is excellent. It is not clear why the copolymer has this nitrogen-containing vinyl monomer to improve the dispersibility of the conductive fine powder such as carbon black and graphite in the resin coating layer. Since the nitrogen-vinyl monomer contains a polar group based on a nitrogen atom, the solubility in a solvent, particularly a polar solvent, is improved, so that the wettability of the solution in which the resin is dissolved to the conductive fine particles is improved. However, it is considered that the dispersibility of the conductive fine particles in the resin coating layer is improved when the conductive fine particles in the solution are applied to form the resin coating layer. In particular, in the case where the conductive fine particles are substances having a polar group such as carbon black on the surface, the affinity is further increased by the polar group based on the nitrogen atom, which is more effective.
[0020]
Furthermore, the aminosilane coupling agent enhances the anti-adhesion effect despite the fact that the developer can be quickly charged and stably maintained at a relatively high level by the effect of the N-vinyl monomer contained in the resin coating layer. Therefore, contamination due to durability does not occur, and the effect of imparting charge to the resin layer is not impaired throughout the durability. Further, compared to the case where a toner-based toner is added by adding a pigment-based charge control agent or fine powder such as silica or Teflon (registered trademark), a polymer made of an N-vinyl monomer-containing resin is used. Since the coating layer is uniformly dispersed therein, the mechanical strength and abrasion resistance of the coating layer itself are improved, so that it is possible to withstand long-term durability and provide a stable and good image for a long period of time. In addition, the aminosilane coupling agent also has a good charge-providing effect on the toner. In addition, the effect of the N-vinyl monomer and the synergistic effect of the aminosilane coupling agent further improve the dispersion and binding properties of the conductive agent and the lubricant, so that the mechanical strength of the resin layer can be improved. In Japanese Patent Application Laid-Open No. H11-125966, a polymerization ratio of each monomer to be used and a molecular weight of a copolymer are limited to specific ranges in order to achieve the above object. By adding a coupling agent, the same or better effects can be achieved without significantly limiting the types of monomers constituting the usable binder resin and the physical properties of the binder resin.
[0021]
That is, due to the above effects, the developer carrying member of the present invention is applied to a developing method in which a resin coating layer is easily worn due to the use of a developer layer thickness regulating member that presses or abuts on the surface of the developer carrying member via a developer layer. In this case, a high and uniform amount of triboelectric charge can be stably applied to the developer from the initial stage to the end of multi-sheet durability under each environment. It is also possible to prevent the accumulation, adhesion and fusion of fine powder toner due to charge-up on the developer carrier, stabilize the image density, and obtain a sufficient line image and dark solid image.
[0022]
Next, the present invention will be described in more detail by way of preferred embodiments.
[0023]
As the substrate used for the developer carrying member, a columnar member, a cylindrical member, a belt member, or the like made of metal, resin, rubber, or a composite material thereof can be used. In particular, a cylindrical tube is preferably used. As such a cylindrical tube, a non-magnetic metal or alloy such as aluminum, stainless steel, or brass, which is formed into a cylindrical shape, polished, ground, or the like is preferably used. These metal cylindrical tubes are molded or processed with high precision in order to improve the uniformity of images. For example, the straightness in the longitudinal direction is preferably 30 μm or less or 20 μm or less, and the fluctuation of the gap between the sleeve and the photosensitive drum, for example, abutting against a vertical surface via a uniform spacer, and the vertical surface when the sleeve is rotated. Is preferably 30 μm or less, or 20 μm or less.
[0024]
In the present invention, the copolymerization molar ratio of the copolymer having the vinyl polymerizable monomer (M) and the nitrogen-containing vinyl monomer (N) preferably satisfies M: N = 4 to 999: 1. When M exceeds 999, there is almost no effect of adding the nitrogen-containing vinyl monomer, that is, the effect of improving the triboelectric charging property is extremely small, and the effect of copolymerization is hardly observed. When M is less than 4, or when a specific N-containing vinyl monomer is used, the resin layer is not stabilized due to, for example, a decrease in Tg. Properties may be impaired, or the toner may be easily fixed. Even if the ratio of the N-containing vinyl monomer is further increased, the charging effect is saturated, so that it is not particularly required.
[0025]
In the present invention, examples of the vinyl polymerizable monomer that can be a main component of the copolymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and iso- Butyl methacrylate, cyclohexyl (meth) acrylate, dimethyl (amino) ethyl methacrylate, diethyl (amino) methacrylate, hydroxyethyl (meth) acrylate, styrene, α-methyl styrene, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate , Dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile , A monocarboxylic acid having a double bond such as acrylamide or an ester compound thereof; for example, a dicarboxylic acid having a double bond such as maleic acid, butyl maleate, methyl maleate or dimethyl maleate, and an ester compound thereof; These can be used alone or in combination of two or more. In particular, when an acid monomer or acid ester monomer having a vinyl group is contained, the charge stability of the developer on the developer carrier is effective. In this case, the effect of stabilizing the triboelectric charge is slightly better when an acid monomer is used than when an acid ester monomer is used.
[0026]
In the present invention, it is preferable to use methyl methacrylate as the vinyl polymerizable monomer. Methyl methacrylate, when used as a polymer, has excellent mechanical strength. Also, when used as a binder resin for the sleeve surface layer, the triboelectric charging property to the developer is good. However, when used as a homopolymer, triboelectricity is often insufficient, and the dispersibility of pigments such as carbon black and graphite is not so good. By using as a copolymer containing a nitrogen-containing vinyl monomer as in the present invention, the triboelectric charging property can be improved. Further, in the present invention, since the methyl methacrylate component is preferably contained at a ratio of 80% or more, the mechanical strength, for example, abrasion resistance is not impaired even in comparison with a methyl methacrylate homopolymer. Further, since a nitrogen-containing vinyl monomer component is contained, when a pigment component such as a conductive fine powder is dispersed in the resin layer, the dispersibility is improved, and this point is also preferable for abrasion resistance and the like. .
[0027]
Further, in the present invention, the copolymer may contain other vinyl monomer units, but the vinyl polymerizable monomer (M) is preferably based on all monomers constituting the copolymer. Is preferably contained in an amount of from 70 to less than 99.9 mol%, and the nitrogen-containing monomer (N) is preferably contained in an amount of from 0.1 to less than 20 mol%, based on all monomers constituting the copolymer. This is advantageous in terms of the abrasion resistance of the resin coating layer and the property of imparting triboelectricity to the developer.
[0028]
When the amount of the vinyl polymerizable monomer (M) is less than 70 mol%, the mechanical strength of the resin coating layer tends to decrease, and the abrasion resistance may be impaired. When the amount is 99.9 mol% or more, Sufficient triboelectric charging characteristics to the developer cannot be obtained. When the content of the nitrogen-containing monomer (N) is less than 0.1 mol%, no triboelectric charging property to the developer can be obtained, and when the content is 20 mol% or more, the resin layer becomes stable due to, for example, a decrease in Tg. In addition, the increase in the temperature of the main body of the electrophotographic apparatus may impair the charge application and abrasion resistance of the resin layer, or may make the toner more likely to adhere. Even if the ratio of the N-containing vinyl monomer is further increased, the charging effect is saturated, so that it is not particularly required.
[0029]
The molecular weight of the resin binder used in the present invention is preferably in the range of 3,000 to 50,000 in terms of weight average molecular weight Mw. When the molecular weight Mw is 3,000 or less, the amount of the low molecular weight component is too large, so that the toner easily adheres or adheres to the sleeve and the charge imparting property of the resin decreases. When the molecular weight exceeds 50,000, the molecular weight is too high, and the viscosity of the resin in the solvent is high, so that poor coating or the addition of pigments causes poor dispersion, and the composition of the resin layer becomes uneven. This may cause unstable toner charging, unstable surface roughness, and reduced abrasion resistance.
[0030]
Further, Mw / Mn representing the ratio of the weight average molecular weight to the number average molecular weight of the resin binder used in the present invention is preferably 3.5 or less. When Mw / Mn exceeds 3.5, the low molecular weight component increases, so that the adhesion and fusion of the toner increase, and the triboelectric charging property to the toner tends to decrease.
[0031]
In the present invention, the molecular weight distribution of the chromatogram of the resin binder by GPC is measured as follows. That is, the column is stabilized in a heat chamber at 40 ° C., THF as a solvent is flown into the column at this temperature at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution is injected for measurement. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration and the count number prepared from several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, Tosoh Corporation or Showa Denko²-10⁷It is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector. As the column, a combination of a plurality of commercially available polystyrene gel columns may be used. Combinations of TSKgel G1000H (HXL), G2000H (HXL), G3000H (HXL), G4000H (HXL), G5000H (HXL), G6000H (HXL), G7000H (HXL), and TSKguardcolumn.
[0032]
Representative examples of the nitrogen-containing vinyl monomer include, for example, p-dimethylaminostyrene, dimethylaminomethyl acrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminomethyl acrylate, diethylaminoethyl acrylate, dimethylaminomethyl methacrylate, dimethylaminomethyl methacrylate Dimethylaminopropyl methacrylate, diethylaminomethyl methacrylate, diethylaminoethyl methacrylate, and the like. Further, N-vinylimidazole, N-vinylbenzimidazole, N-vinylcarbazole, N-vinylpyrrole, N-vinylpiperidine, N-vinylmorpholine , N-vinylindole and the like. In particular, it is preferable to use a nitrogen-containing vinyl monomer represented by the following general formula such as dimethylaminoethyl methacrylate or diethylaminoethyl methacrylate, or a quaternary ammonium group-containing vinyl monomer.
[0033]
[Outside 3]

[However, R₁, R₂, R₃, R₄Represents a hydrogen atom or a saturated hydrocarbon group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4. ]
[0034]
The structure of the quaternary ammonium group-containing vinyl monomer used in the present invention is not particularly limited as long as it can be copolymerized with methyl methacrylate. There is a quaternary ammonium group-containing vinyl monomer represented by the following general formula (2).
[Outside 4]

[Wherein, R₅Represents a hydrogen atom or a methyl group;₆Represents an alkylene group having 1 to 4 carbon atoms;₇~ R₉Represents a methyl group, an ethyl group or a propyl group, and X₁Represents -COO- or -CONH-;⁻Is Cl⁻, (1/2) SO₄ ^2-And an anion such as ]
[0035]
As the aminosilane coupling agent to be added to the resin binder of the present invention, generally known aminosilane coupling agents can be used. Examples include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, monobutylaminopropyltrimethoxysilane Silane, dioctylaminopropyltrimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltrimethoxysilane, trimethoxysilyl-γ-propylphenylamine, trimethoxysilyl-γ-propylbenzylamine, Methoxysilyl-γ-propylpihelidine, trimethoxysilyl-γ-propylmorpholine, trimethoxysilyl-γ- And propylimidazole. These treatment agents may be used alone or in combination of two or more, or in combination or in multiple treatments. The amount of the aminosilane coupling agent to be added to the resin binder is preferably 1 to 100 parts, more preferably 1 to 50 parts, per 100 parts of the resin. If the amount is less than 1 part, little improvement in charge imparting property, surface releasability, and lubricity due to the addition of the aminosilane coupling agent is hardly observed, and if it exceeds 100 parts, the coating strength is liable to decrease.
[0036]
As a material added to the resin layer of the present invention to impart conductivity to the resin layer, generally known conductive fine powder can be used. For example, powders of metals or alloys such as copper, nickel, silver, and aluminum; metal oxides such as antimony oxide, indium oxide, tin oxide, and titanium oxide; and carbon-based conductive agents such as carbon fiber, carbon black, and graphite. No. The amount of the conductive fine powder varies depending on the developing system.^-2Ω · cm to 1 × 10⁵It is preferable to add so as to be in the range of Ω · cm. Carbon black, especially conductive amorphous carbon, is particularly excellent in electric conductivity, and can be given conductivity by adding a small amount compared to others, and a certain degree of resistance can be obtained by controlling the added amount. Therefore, it is preferably used. It is also preferable to include a lubricating powder in the resin layer of the present invention. Examples of such lubricating powders include fluorinated molybdenum disulfide, boron nitride, mica, graphite, graphite fluoride, silver-niobium selenide, calcium chloride-graphite, talc, Teflon (registered trademark), PVDF and the like. Examples thereof include polymers, fatty acid metal salts such as zinc stearate, magnesium stearate, aluminum stearate, and zinc palmitate. Among them, graphite is preferably used because it has conductivity as well as lubricity. As a method for obtaining the resin layer of the present invention, for example, the resin layer can be obtained by dispersing and mixing each component in a solvent to form a coating, and applying the coating on the substrate. For dispersing and mixing the components, a known dispersing apparatus using beads such as a sand mill, a paint shaker, a dyno mill, and a pearl mill can be suitably used. In addition, as a coating method, a known method such as a dipping method, a spray method, and a roll coating method can be applied. The surface roughness of this coating layer is preferably in the range of 0.3 to 3.5 μm in JIS center line average roughness (Ra). When Ra is less than 0.3 μm, the toner on the toner carrier forms an immobile layer on the surface of the developer carrier due to the mirroring force, and the charge application to the toner becomes insufficient in developing property, and unevenness, scattering, and low density occur. And other image defects. If Ra exceeds 3.5 μm, the regulation of the toner coat layer on the toner carrier becomes insufficient, resulting in insufficient uniformity of the image and a low image density due to insufficient charging. The more preferable range varies depending on the method of regulating the thickness of the developer layer, but it is preferable that the range be in the above range according to any form.
[0037]
In addition, as a constitution of the resin coating layer of the developer carrying member, in addition to the above-mentioned additive substances, spherical particles having a particle size of 0.3 to 30 μm are dispersed in the coating resin layer to stabilize the surface roughness. As a result, it is possible to optimize the amount of toner coating on the developer carrying member. The spherical particles not only maintain uniform surface roughness on the surface of the coating layer of the developer carrying member, but also have a small change in the surface roughness of the coating layer even when the surface of the coating layer is worn out, as well as toner contamination and toner melting. This has the effect of making it less likely to wear.
[0038]
The spherical particles used in the present invention have a number average diameter of 0.3 to 30 μm, preferably 2 to 20 μm. When the number average particle diameter of the spherical particles is less than 0.3 μm, the effect of imparting uniform roughness to the surface and the effect of enhancing the charging performance are small, and the rapid and uniform charging of the developer becomes insufficient, and the coating layer This is not preferable because toner charge-up, toner contamination and toner fusion occur due to abrasion of the toner, which tends to cause ghost deterioration and image density reduction. When the number average particle size exceeds 30 μm, the surface roughness of the coating layer becomes too large, and it becomes difficult to sufficiently charge the toner, and the mechanical strength of the coating layer is reduced, which is preferable. Absent.
[0039]
More preferably, the true density of the spherical particles is 3 g / cm³Or less, preferably 2.7 g / cm³Or less, more preferably 0.9 to 2.3 g / cm³Good to be. That is, the true density of the spherical particles is 3 g / cm.³When the ratio is more than 1, the dispersibility of the spherical particles in the coating layer becomes insufficient, so that it is difficult to impart uniform roughness to the surface of the coating layer. In addition, since the storage stability of the paint is not good, it is difficult to obtain a triboelectric charging member surface having uniform surface irregularities. True density of spherical particles is 0.9 g / cm³Even when the particle size is smaller, the dispersibility and storage stability of the spherical particles in the coating layer become insufficient.
[0040]
In the present invention, the term “spherical” in a spherical particle means a particle having a ratio of major axis / minor axis of about 1.0 to 1.5, and in the present invention, preferably a ratio of major axis / minor axis is used. Is preferably 1.0 to 1.2. When the ratio of the major axis / minor axis of the spherical particles exceeds 1.5, unevenness of the surface roughness of the coating layer occurs, resulting in rapid and uniform charging of the toner and strength of the conductive coating layer. Not preferred.
[0041]
As the spherical particles used in the present invention, known spherical particles can be used. For example, there are spherical resin particles, spherical metal oxide particles, and spherical carbonized particles. As the spherical particles, for example, spherical resin particles obtained by suspension polymerization, dispersion polymerization, or the like are used. Spherical resin particles can obtain a suitable surface roughness with a smaller addition amount, and can easily obtain a more uniform surface shape. Examples of such spherical particles include acrylic resin particles such as polyacrylate and polymethacrylate, polyamide resin particles such as nylon, polyolefin resin particles such as polyethylene and polypropylene, silicone resin particles, phenol resin particles, and polyurethane resin particles. Resin particles, styrene resin particles, benzoguanamine particles, and the like. The resin particles obtained by the pulverization method may be used after subjecting them to thermal or physical sphering treatment.
[0042]
Further, an inorganic substance may be attached to or fixed to the surface of the spherical particles. Examples of such inorganic fine powder include SiO₂, SrTiO₃, CeO₂, CrO, Al₂O₃Oxides, such as ZnO, ZnO, MgO, Si₃N₄Such as nitride, carbide such as SiC, CaSO₄, BaSO₄, CaCO₃And the like, such as sulfates and carbonates. Such an inorganic fine powder may be used after being treated with a coupling agent.
[0043]
In particular, it can be preferably used for the purpose of improving the adhesion to the binder resin or for imparting hydrophobicity to the particles. Examples of such a coupling agent include a silane coupling agent, a titanium coupling agent, a zircoaluminate coupling agent, and the like. More specifically, for example, as a silane coupling agent, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethyl Diethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltet Lamethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane having from 2 to 12 siloxane units per molecule and having hydroxyl groups bonded to silicon atoms, each of which is located at one of the terminal units. Siloxane and the like. By treating the surface of the spherical resin particles with the inorganic fine powder as described above, dispersibility in the coating layer, uniformity of the coating layer surface, stain resistance of the coating layer, charge imparting property to the toner, coating layer Can be improved in abrasion resistance and the like.
[0044]
Further, the spherical particles used in the present invention are more preferably conductive. That is, by imparting conductivity to the spherical particles, charge is less likely to be accumulated on the surface of the particles due to the conductivity, and it is possible to reduce adhesion of toner and to improve toner charging ability. In the present invention, the volume resistivity of the spherical particles is 10⁶Ω · cm or less, more preferably 10^-3-10⁶The particles are preferably Ω · cm. In the present invention, the volume resistance of the spherical particles is 10⁶If it exceeds Ω · cm, spherical particles are exposed on the surface of the coating layer due to abrasion and become partially insulative, and this becomes a nucleus, so that toner contamination and fusing easily occur, and quick and uniform charging is achieved. This is not preferable because it is difficult to perform the operation.
[0045]
As a method for obtaining the conductive spherical particles used in the present invention, the following methods are preferable, but are not necessarily limited thereto. As a particularly preferable method for obtaining conductive spherical particles used in the present invention, for example, carbonized and / or graphitized by firing spherical resin particles or mesocarbon microbeads to obtain low-concentration and good-conductive spherical particles. A method for obtaining carbon particles may be mentioned. Examples of the resin used for the spherical resin particles include a phenol resin, a naphthalene resin, a furan resin, a xylene resin, a divinylbenzene polymer, a styrene-divinylbenzene copolymer, and polyacrylonitrile. In addition, mesocarbon microbeads can be usually produced by washing spherical crystals generated in the process of heating and firing a medium pitch with a large amount of a solvent such as tar, medium oil, and quinoline.
[0046]
As a method of obtaining more preferable conductive spherical particles, a phenol resin, a naphthalene resin, a furan resin, a xylene resin, a divinylbenzene polymer, a styrene-divinylbenzene copolymer, a polyacrylonitrile and the like spherical particle surface, by a mechanochemical method. There is a method in which a bulk mesophase pitch is coated, and the coated particles are heat-treated in an oxidizing atmosphere and then fired to be carbonized and / or graphitized to obtain conductive spherical carbon particles.
[0047]
The conductive spherical carbon particles obtained by the above method can control the conductivity of the spherical carbon particles obtained by changing the firing conditions to some extent in any method, and are preferably used in the present invention. Is done. In some cases, the spherical carbon particles obtained by the above method may have a true density of the conductive spherical particles of 3 g / cm 3 in order to further increase the conductivity.³The plating of a conductive metal and / or metal oxide may be performed within a range not exceeding.
[0048]
Another method of obtaining the conductive spherical particles used in the present invention is to mechanically mix conductive fine particles smaller than the particle size of the core particles with a suitable mixing ratio with respect to the core particles composed of spherical resin particles. After the conductive fine particles are uniformly attached around the core particles by the action of van der Waals force and electrostatic force, for example, the surface of the core particles is caused by a local temperature rise caused by applying a mechanical impact force. Is softened, and conductive fine particles are formed on the surface of the core particles to obtain conductive resin-treated spherical resin particles.
[0049]
For the core particles, it is preferable to use spherical resin particles having a small true density made of an organic compound, and examples of the resin include PMMA, acrylic resin, polybutadiene resin, polystyrene resin, polyethylene, polypropylene, polybutadiene, or These copolymers, benzoguanamine resin, phenol resin, polyamide resin, nylon, fluorine resin, silicone resin, epoxy resin, and polyester resin are exemplified. As conductive fine particles (small particles) used when forming a film on the surface of the core particles (base particles), in order to uniformly provide a conductive fine particle coating, the particle size of the small particles is smaller than that of the base particles. It is preferable to use one that is 1/8 or less.
[0050]
As another method of obtaining the conductive spherical particles used in the present invention, a method of uniformly dispersing conductive fine particles in spherical resin particles to obtain conductive spherical particles in which the conductive fine particles are dispersed may be mentioned. . As a method of uniformly dispersing the conductive fine particles in the spherical resin particles, for example, kneading a binder resin and the conductive fine particles to disperse the conductive fine particles, then solidify by cooling, and pulverized to a predetermined particle size Then, a method of obtaining conductive spherical particles by spheroidizing by mechanical treatment and thermal treatment, or adding a polymerization initiator, conductive fine particles and other additives in the polymerizable monomer, and uniformly by a dispersing machine The dispersed monomer composition is suspended in an aqueous phase containing a dispersion stabilizer so as to have a predetermined particle size by a stirrer and polymerized to obtain spherical particles in which conductive fine particles are dispersed. Method.
[0051]
Also in the conductive spherical particles in which the conductive fine particles obtained by these methods are dispersed, van der Waals are mechanically mixed with conductive fine particles having a particle diameter smaller than the above-mentioned core particles at an appropriate mixing ratio. After the conductive fine particles are uniformly attached around the conductive spherical particles by the action of force and electrostatic force, for example, the surface of the conductive spherical particles is softened by a local temperature rise caused by applying a mechanical impact force. Then, conductive fine particles may be formed on the surface to further increase the conductivity before use.
[0052]
The surface roughness in the present invention is measured using a surface roughness meter SE-3300H manufactured by Kosaka Laboratories. The measurement conditions are a cutoff of 0.8 mm, a specified distance of 8.0 mm, and a feed rate of 0.5 mm / sec. The average of the measured values at 12 points was calculated.
[0053]
Next, the toner will be described. The toner is a fine powder in which a resin, a release agent, a charge control agent, a coloring agent, and the like are melt-kneaded, solidified, pulverized, and then classified to have a uniform particle size distribution. As the binder resin used for the toner, generally known resins can be used.
[0054]
For example, homopolymers of styrene such as styrene, α-methylstyrene, p-chlorostyrene and the like, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-ethyl acrylate copolymer, styrene -Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer Polymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid Copolymer, styrene-maleic acid Styrene copolymers such as tercopolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene polyvinyl butyral, polyacrylic resin, rosin, modified rosin, tempel resin, phenolic resin, aliphatic or fatty A cyclic hydrocarbon resin, an aromatic petroleum resin, paraffin wax, carnauba wax and the like can be used alone or in combination.
[0055]
Further, a pigment can be contained in the toner. For example, carbon black, nigrosine dye, lamp black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgazine Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Permanent Bordeaux FRR, Pigment Orange R, Risor Red 2G, Lake Red C, Rhodamine FB, Rhodamine B Lake, Methyl Bio Red B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green B, Phthalocyanine Green, Oil Yellow GG, Pomelo First Yellow CGG, Kaya Set Y963, Kaya Set YG, Pomelo First Orange RR, Oil Scarlet, Orazol Bra Down B, pomelo First Scarlet CG, Oil Pink OP, etc. can be applied.
[0056]
In order to use the toner as a magnetic toner, a magnetic powder may be included in the toner. As such magnetic powder, a substance which is magnetized in a magnetic field is used, and examples thereof include powder of a ferromagnetic metal such as iron, cobalt, and nickel, and alloys and compounds such as magnetite, hematite, and ferrite. The content of the magnetic powder is preferably from 15 to 70% by weight based on the weight of the toner.
[0057]
A wax can be contained in the toner for the purpose of improving the releasability at the time of fixing and improving the fixing property. Examples of such waxes include paraffin wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, carnauba wax and its derivatives. , A block copolymer with a vinyl monomer, and a graft-modified product. In addition, alcohols, fatty acids, acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, mineral waxes, petrolactam, and the like can also be used.
[0058]
If necessary, the toner may contain a charge control agent. The charge control agent includes a negative charge control agent and a positive charge control agent. For example, the following substances control the toner to be negatively charged. For example, organic metal complexes and chelate compounds are effective, and examples thereof include monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid-based metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. The following substances are used for positively charging the toner. Modified products such as nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and oniums such as phosphonium salts which are analogs thereof Salts and lake pigments thereof, metal salts of higher fatty acids (such as phosphotungstic acid, phosphomolybdic acid, phosphotungstate molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.) Diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate, dicyclohexyltin borate; Emissions compounds, imidazole compounds.
[0059]
The toner is used by externally adding a powder such as an inorganic fine powder, if necessary, for the purpose of improving fluidity. Examples of such fine powders include silica fine powder, metal oxides such as alumina, titania, germanium oxide, and zirconium oxide; carbides such as silicon carbide and titanium carbide; and inorganic fine powders such as nitrides such as silicon nitride and germanium nitride. The body is used. These fine powders can be used after being organically treated with an organosilicon compound, a titanium coupling agent or the like. For example, organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyl Dimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, Diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, Examples include 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane having 2 to 12 siloxane units per molecule and having hydroxyl groups bonded to Si, each of which is located at one of the terminal units. Further, an untreated fine powder treated with a nitrogen-containing silane coupling agent may be used. Particularly, a positive toner is preferable. Examples of such treating agents include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, Monobutylaminopropyltrimethoxysilane, dioctylaminopropyltrimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltrimethoxysilane, trimethoxysilyl-γ-propylphenylamine, trimethoxysilyl-γ -Propylbenzylamine, trimethoxysilyl-γ-propylpiperidine, trimethoxysilyl-γ-propylmorpholine, Tokishishiriru -γ- propyl imidazole, and the like.
[0060]
Examples of the method of treating the inorganic fine powder with the silane coupling agent include 1) a spray method, 2) an organic solvent method, and 3) an aqueous solution method. In general, the treatment by the spray method is a method in which a pigment is stirred, an aqueous solution or a solvent solution of a coupling agent is sprayed thereon, and then the water or the solvent is removed at about 120 to 130 ° C. and dried. In addition, the treatment by the organic solvent method means that a coupling agent is dissolved in an organic solvent (alcohol, benzene, halogenated hydrocarbon, etc.) containing a hydrolysis catalyst together with a small amount of water, and the pigment is immersed in the solution, followed by filtration. Alternatively, solid-liquid separation is performed by pressing and drying is performed at about 120 to 130 ° C. In the aqueous solution method, about 0.5% of a coupling agent is hydrolyzed in water or a water-solvent having a constant pH, and the pigment is immersed therein, followed by solid-liquid separation and drying.
[0061]
As another organic treatment, fine powder treated with silicone oil can be used. Preferred silicone oils have a viscosity at 25 ° C. of about 0.5 to 10000 mm.²/ S, preferably 1 to 1000 mm²/ S, for example, methyl hydrogen silicone oil, dimethyl silicone oil, phenyl methyl silicone oil, chlorophenyl methyl silicone oil, alkyl-modified silicone oil, fatty acid-modified silicone oil, polyoxyalkylene-modified silicone oil, fluorine-modified silicone Oil and the like. Further, a silicone oil having a nitrogen atom in a side chain may be used. Particularly, a positive toner is preferable. The treatment with silicone oil can be performed, for example, as follows. The pigment is violently stirred while heating as necessary, and the silicone oil or a solution thereof is sprayed or vaporized and sprayed on the pigment, or the pigment is slurried, and the silicone oil or the slurry is stirred while stirring. It can be easily treated by dropping the solution. These silicone oils are used singly or as a mixture of two or more, or used in combination or in multiple treatments. Moreover, you may use together with the process by a silane coupling agent. It is preferable to use such a toner which has been subjected to a sphering treatment and a surface smoothing treatment by various methods, because the transferability is good. Such a method includes, for example, a device having a stirring blade or a blade, and a liner or a casing, for example, when the toner is passed through a minute gap between the blade and the liner, the surface is smoothed by mechanical force. Or a method of making the toner spherical, a method of suspending the toner in warm water to make the toner spherical, and a method of exposing the toner to a hot air flow to make the toner spherical. As a method for producing a spherical toner, there is a method in which a mixture containing a monomer as a main component as a toner binder resin is suspended in water and polymerized to form a toner. As a general method, a polymerizable monomer, a colorant, a polymerization initiator, and, if necessary, a crosslinking agent, a charge control agent, a release agent, and other additives are uniformly dissolved or dispersed to form a single monomer. After the body composition, the monomer composition is dispersed in a continuous layer containing a dispersion stabilizer to an appropriate particle size using a suitable stirrer in an aqueous phase, for example, and further subjected to a polymerization reaction. This is a method for obtaining a developer having a desired particle size.
[0062]
Next, a developing device and a device unit using the developer carrier of the present invention will be described and exemplified.
[0063]
FIG. 1 schematically shows an example of the configuration of a developing device used when a non-magnetic one-component developer is used. In FIG. 1, an image carrier that carries an electrostatic latent image formed by a known process, for example, an electrophotographic photosensitive drum 1 is rotated in the direction of arrow B. The developing sleeve 8 as a developer carrying member includes a metal cylindrical tube (base) 6 and a resin coating layer 7 formed on the surface thereof. Since a non-magnetic one-component developer is used, no magnet is provided inside the metal cylindrical tube 6. A cylindrical member can be used instead of the metal cylindrical tube. A stirring blade 10 for stirring the non-magnetic one-component developer 4 is provided in the hopper 3 as a developing device. The developer supply / peeling member 12 for supplying the developer 4 to the developing sleeve 8 and for peeling off the developer 4 existing on the surface of the developed sleeve 8 after the development is in contact with the developing sleeve 8. When the supply / peeling roller 12 serving as the developer supply / peeling member rotates in the same direction as the developing sleeve 8, the surface of the supply / peeling roller 12 moves in the counter direction with the surface of the developing sleeve 8. The one-component non-magnetic developer having the non-magnetic toner supplied from the hopper 3 is supplied to the developer sleeve 8, and the developing sleeve 8 carries the one-component developer 4 and rotates in the direction of arrow A. As a result, the non-magnetic one-component developer 4 is transported to the developing section D where the developing sleeve 8 and the photosensitive drum 1 face each other. The developer layer thickness of the one-component developer carried on the developing sleeve 8 is regulated by the developer layer thickness regulating member 11 which is pressed against the surface of the developing sleeve 8 via the developer layer. The non-magnetic one-component developer 4 obtains a triboelectric charge capable of developing the electrostatic latent image on the photosensitive drum 1 by friction with the developing sleeve 8. The thickness of the thin layer of the nonmagnetic one-component developer 4 formed on the developing sleeve 8 is preferably smaller than the minimum gap D between the developing sleeve 8 and the photosensitive drum 1 in the developing section. The present invention is particularly effective for a non-contact type developing device that develops an electrostatic latent image using such a developer layer. However, the present invention can also be applied to a contact type developing device in which the thickness of the developer layer in the developing section is equal to or greater than the minimum gap D between the developing sleeve 8 and the photosensitive drum 1. For the sake of simplicity, the following description will be made by taking a non-contact developing device as an example.
[0064]
A power supply 9 applies a developing bias voltage to the developing sleeve 8 to fly the one-component non-magnetic developer 4 having the non-magnetic toner carried thereon. When a DC voltage is used as the developing bias voltage, a voltage having a value between the potential of the image portion of the electrostatic latent image (the region where the non-magnetic developer 4 is adhered and visualized) and the potential of the background portion is used. Is preferably applied to the developing sleeve 8. In order to increase the density of the developed image or improve the gradation, an alternating bias voltage may be applied to the developing sleeve 8 to form an oscillating electric field in which the direction is alternately reversed in the developing unit. In this case, it is preferable to apply to the developing sleeve 8 an alternating bias voltage on which a DC voltage component having a value between the potential of the image portion and the potential of the background portion is superimposed. In so-called normal development in which a developer is applied to a high potential portion of an electrostatic latent image having a high potential portion and a low potential portion to visualize the developer, a developer charged to a polarity opposite to the polarity of the electrostatic latent image is used. In so-called reversal development in which toner is attached to a low potential portion of an electrostatic latent image to make it visible, a developer that is charged to the same polarity as the polarity of the electrostatic latent image is used. The high potential and the low potential are expressed by absolute values. In any case, the nonmagnetic one-component developer 4 charges a polarity for developing the electrostatic latent image by friction with the developing sleeve 8. As the developer supply / peeling member, an elastic roller member such as resin, rubber, and sponge is preferable. As the stripping member, a belt member or a brush member can be used instead of the elastic roller. The developer that has not been transferred to the photoreceptor 1 for development is once peeled off from the sleeve surface by the developer supply / peeling member 12, thereby preventing generation of immobile developer on the sleeve and uniform charge of the developer. It has the function of transforming. When the supply / peeling roller 12 composed of an elastic roller is used as the developer supply / peeling member, the peripheral speed of the supply / peeling roller 12 is equal to the peripheral speed of the developing sleeve 8 when the surface rotates in the counter direction. It is preferably 20 to 120%, more preferably 30 to 100% with respect to 100%. If the peripheral speed of the supply / peeling roller 12 is less than 20%, the supply of the developer is insufficient, the followability of a solid image is reduced, and a ghost image is caused. The supply amount of the agent is increased, which causes fog due to poor regularity of the developer layer thickness or insufficient charge amount, and further easily causes damage to the toner, fog due to toner deterioration and toner fusion. When the rotation direction of the supply / peeling roller is the same (forward) direction as the surface of the developing sleeve, the peripheral speed of the supply roller is preferably 100 to 300%, more preferably 101 to 300% of the peripheral speed of the sleeve. A value of 200% is good in terms of the toner supply amount. The rotation direction of the supply / peeling roller is more preferably rotated in the counter direction with respect to the surface of the developing sleeve from the viewpoint of the peeling property and the supply property. It is preferable that the penetration amount of the developer supply / peeling member 12 into the developing sleeve 8 is 0.5 to 2.5 mm in view of the developer supply / peelability. When the intrusion amount of the developer supply / peeling member 12 is less than 0.5 mm, ghost is likely to occur due to insufficient peeling, and when the penetration amount exceeds 2.5 mm, toner damage is large. It is easy to cause fusion and fog due to toner deterioration.
[0065]
In the developing device shown in FIG. 1, as a member for regulating the layer thickness of the non-magnetic one-component developer 4 on the developing sleeve 8, a material having rubber elasticity such as urethane rubber or silicone rubber, or a metal such as phosphor bronze or stainless steel is used. An elastic regulating blade 11 made of a material having elasticity is used. In the developing device of FIG. 1, the elastic regulating blade 11 is pressed against the developing sleeve 8 in a direction opposite to the rotation direction, and a thinner developer layer is formed on the developing sleeve 8. Can be formed. As the elastic regulating blade 11, a polyamide elastomer (PAE) is adhered to the surface of a phosphor bronze plate from which a stable pressing force can be obtained, particularly for stable regulating force and stable (negative) charging property to the toner. It is preferable to use one having a different structure. Examples of the polyamide elastomer (PAE) include a copolymer of polyamide and polyether. When the contact pressure of the developer layer thickness regulating member 11 with respect to the developing sleeve 8 is a linear pressure of 5 to 50 g / cm, regulation of the developer can be stabilized and the developer layer thickness can be made suitable. Is preferred. When the contact pressure of the developer layer thickness regulating member 11 is less than a linear pressure of 5 g / cm, the regulation of the developer becomes weak, which causes fogging and toner leakage. When the linear pressure exceeds 50 g / cm, In addition, the damage to the toner is increased, which is likely to cause deterioration of the toner and fusion to the sleeve and the blade.
[0066]
The developer carrier of the present invention is particularly effective when applied to an apparatus in which the developer supply / peeling member 12 and the developer layer thickness regulating member 11 press against such a developing sleeve 8. That is, when the developer supply / peeling member 12 and the developer layer thickness regulating member 11 are pressed against the developing sleeve 8, the surface of the developing sleeve 8 is worn or the developer is Since the use environment is more likely to cause fusing, the effect of the developer carrier having a resin coating layer with excellent durability of a large number of sheets of the present invention is effectively exhibited.
[0067]
FIG. 2 schematically shows an example of the configuration of a developing device used when a magnetic one-component developer is used. In FIG. 2, an image carrier for carrying an electrostatic latent image formed by a known process, for example, an electrophotographic photosensitive drum 1 is rotated in the direction of arrow B. The developing sleeve 18 as a developer carrier is composed of a metal cylindrical tube (base) 16 and a resin coating layer 17 formed on the surface thereof. A stirring blade 20 for stirring the magnetic one-component developer 14 is provided in the hopper 13 as a developing container. By carrying the magnetic toner 14 as a one-component magnetic developer supplied from the hopper 13 and rotating in the direction of arrow A, the magnetic one-component developer 14 is placed on the developing portion where the developing sleeve 18 and the photosensitive drum 1 are opposed to each other. Is transported. A magnet 15 is arranged in the developing sleeve 18 in order to magnetically attract and hold the magnetic one-component developer 14 on the developing sleeve 18. The magnetic one-component developer 14 obtains a triboelectric charge capable of developing the electrostatic latent image on the photosensitive drum 1 by friction with the developing sleeve 18.
[0068]
In the developing device shown in FIG. 2, as a member for regulating the layer thickness of the magnetic one-component developer 14 on the developing sleeve 18, a material having rubber elasticity such as urethane rubber or silicone rubber, or a metal elastic material such as phosphor bronze or stainless steel copper is used. An elastic regulating blade 21 made of a material having the following formula is used. In the developing device shown in FIG. 2, the elastic regulating blade 21 is pressed against the developing sleeve 18 in a posture opposite to the rotation direction to form a thinner developer layer on the developing sleeve 18. can do.
[0069]
3 is characterized in that the elastic regulating blade 21 is pressed against the developing sleeve 18 in the same direction as the rotation direction. The thickness of the thin layer of the magnetic one-component developer 14 formed on the developing sleeve 18 is preferably smaller than the minimum gap D between the developing sleeve 18 and the photosensitive drum 1 in the developing section. The present invention is particularly effective for a non-contact type developing device that develops an electrostatic latent image using such a developer layer. However, the present invention can also be applied to a contact-type developing device in which the thickness of the developer layer in the developing section is equal to or more than the minimum gap D between the developing sleeve 18 and the photosensitive drum 1.
[0070]
For the sake of simplicity, the following description will be made by taking a non-contact developing device as an example.
[0071]
A power supply 19 applies a developing bias voltage to the developing sleeve 18 in order to fly the one-component magnetic developer 14 having the magnetic toner carried on the developing sleeve 18. When a DC voltage is used as the developing bias voltage, a voltage having a value between the potential of the image portion of the electrostatic latent image (the region where the magnetic one-component developer 14 is adhered and visualized) and the potential of the background portion is used. Is preferably applied to the developing sleeve 18. In order to increase the density of the developed image or improve the gradation, an alternating bias voltage may be applied to the developing sleeve 18 to form an oscillating electric field in which the direction is alternately reversed in the developing unit. In this case, it is preferable to apply to the developing sleeve 18 an alternating bias voltage on which a DC voltage component having a value between the potential of the image portion and the potential of the background portion is superimposed. In so-called regular development in which a developer is attached to a high potential portion of an electrostatic latent image having a high potential portion and a low potential portion to visualize the toner, a toner charged to a polarity opposite to the polarity of the electrostatic latent image is used. In so-called reversal development in which a developer is attached to a low-potential portion of an electrostatic latent image for visualization, a developer charged to the same polarity as the polarity of the electrostatic latent image is used. The high potential and the low potential are expressed by absolute values. In any case, the magnetic one-component developer 14 charges a polarity for developing an electrostatic latent image by friction with the developing sleeve 18. The above-described developing device can be used as an apparatus unit that is detachably attached to the image forming apparatus main body.
[0072]
An example of an image forming apparatus using the developing device having the developer carrier of the present invention illustrated in FIG. 1 will be described with reference to FIG. First, the surface of the photosensitive drum 1 as an electrostatic latent image carrier is negatively charged by contact (roller) charging means 29 as primary charging means, and a digital latent image is formed by image scanning by exposure 25 with laser light. 1 is formed. Next, the digital latent image is transferred to the hopper 3 as a developing container by a developing device having an elastic regulating blade 11 as a developer layer thickness regulating member and a developing sleeve 8 as a developer carrier. The reversal development is performed by the negatively chargeable one-component developer 4 having the non-magnetic toner therein. As shown in FIG. 3, the conductive substrate of the photosensitive drum 1 is grounded in the developing area D, and an alternating bias, a pulse bias and / or a DC bias is applied to the developing sleeve 8 by a bias applying unit 9. Next, when the recording material P is conveyed and arrives at the transfer section, the contact (roller) transfer means 23 as a transfer means is charged from the back surface (the surface opposite to the photosensitive drum side) of the recording material P by the voltage application means 24. As a result, the developed image formed on the surface of the photosensitive drum 1 is transferred onto the recording material P by the contact transfer unit 23. Next, the recording material P separated from the photosensitive drum 1 is conveyed to a heat and pressure roller fixing device 27 as a fixing unit, and the fixing device 27 performs a fixing process of a developed image on the recording material P. . The one-component developer 4 remaining on the photosensitive drum 1 after the transfer process is removed by a cleaning unit 28 having a cleaning blade 28a. When the remaining one-component developer 4 is small, the cleaning step can be omitted. After the cleaning, the photosensitive drum 1 is de-charged by the erase exposure 26 if necessary, and the above-described steps starting from the charging step by the contact (roller) charging means 29 as the primary charging means are repeated again. In the above series of steps, the photosensitive drum (that is, the electrostatic latent image carrier) 1 has a photosensitive layer and a conductive substrate, and moves in the direction of the arrow. The non-magnetic cylindrical developing sleeve 8 serving as a developer carrier rotates so as to advance in the same direction as the surface of the photosensitive drum 1 in the developing region D. The supply roller 12 is in contact with the front portion of the developing sleeve 8 and rotates so that the surface moves in a direction opposite to the moving direction of the surface of the developing sleeve 8. Due to the rotation of the supply roller 12, the one-component developer 4 in the hopper 3 is applied and carried on the developing sleeve 8, and is caused by friction with the surface of the developing sleeve 8 and / or friction between the non-magnetic toners. For example, a negative triboelectric charge is provided. Further, an elastic regulating blade 11 is provided so as to elastically press the developing sleeve 8 via the developer layer, and the thickness of the developer layer is regulated thinly (30 μm to 300 μm) and uniformly, so that the developing region D A developer layer thinner than the gap between the photosensitive drum 1 and the developing sleeve 8 is formed. By adjusting the rotation speed of the developing sleeve 8, the surface speed of the developing sleeve 8 is substantially equal to or close to the speed of the surface of the photosensitive drum 1. In the developing region D, an AC bias or a pulse bias may be applied to the developing sleeve 8 as a developing bias voltage by the bias applying unit 9. The AC bias may be such that f is 200 to 4,000 Hz and Vpp is 500 to 3,000 V.
[0073]
When the developer is transferred in the developing area D, the developer is transferred to the electrostatic latent image side by the electrostatic force on the surface of the photosensitive drum 1 and the action of a developing bias voltage such as an AC bias or a pulse bias.
[0074]
The primary charging means has been described using the charging roller 29 as the contact charging means as described above, but may be a contact charging means such as a charging blade or a charging brush, or a non-contact corona charging means. However, the contact charging means is preferable in that the generation of ozone due to charging is small.
[0075]
Although the transfer unit has been described using the contact transfer unit such as the transfer roller 23 as described above, a non-contact corona transfer unit may be used. However, in this case, the contact transfer unit is more preferable because ozone is less generated by the transfer.
[0076]
In the present invention, the apparatus unit detachably mounts the developing device shown in FIGS. 1 to 3 to an image forming apparatus main body (for example, a copying machine, a laser beam printer, a facsimile machine). As the device unit, in addition to the developing device shown in FIGS. 1 to 3, a drum-shaped electrostatic latent image carrier (photosensitive drum) 1, a cleaning unit 28 having a cleaning blade 28a, and a contact (roller) as a primary charging unit One or more components selected from the group consisting of the charging means 29 may be integrally provided.
[0077]
When the image forming method of the present invention is applied to a facsimile printer, the light image exposure L is an exposure for printing received data. FIG. 5 is a block diagram showing an example of this case. The controller 31 controls the image reading unit 40 and the printer 39. The whole controller 31 is controlled by the CPU 37. The read data from the image reading unit is transmitted to the partner station through the transmission circuit 33. Data received from the partner station is sent to the printer 39 through the receiving circuit 32. Predetermined image data is stored in the image memory. The printer controller 38 controls a printer 39. 34 is a telephone. The image received from the circuit 35 (image information from a remote terminal connected via a line) is demodulated by the receiving circuit 32, and then the CPU 37 performs a composite process of the image information and sequentially stores it in the image memory 36. . When the image of at least one page is stored in the memory 36, the image of the page is recorded. The CPU 37 reads one page of image information from the memory 36 and sends out the combined one page image information to the printer controller 38. When receiving the image information of one page from the CPU 37, the printer controller 38 controls the printer 39 to record the image information of the page. Note that the CPU 37 is receiving the next page during recording by the printer 39. As described above, image reception and recording are performed.
[0078]
(Example)
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. Table 1 summarizes the configurations of the triboelectric charging members obtained in the examples and comparative examples.
[0079]

The structure of the aminosilane coupling agent (1) is shown below.
[Outside 5]

[0080]
Methyl methacrylate-dimethylaminoethyl methacrylate copolymer A was previously dissolved in a part of MEK. Carbon black, crystalline graphite, and an aminosilane coupling agent were added and dispersed by a sand mill using glass beads. Further, MEK was added to adjust the solid concentration to 30%. After the dispersion, the mixture was separated from the glass beads and the viscosity was measured at room temperature. The result was 72 mPa · s. The coating of the sleeve was performed using this paint. An aluminum cylindrical round bar with an outer diameter of 16 mmφ, both ends of which are flanged, is set up on a turntable and rotated. The spray gun is lowered at a constant speed while masking both ends, and the film is applied to the surface of the round bar. A coating sleeve having a uniform thickness was obtained. This was dried and cured at 160 ° C. for 30 minutes in a drying furnace to obtain a sleeve 1. 9000 mg / m of paint after drying²Met. When the surface roughness was measured, the center line average roughness Ra was 0.62 μm.
[0081]
An OHP sheet and an aluminum sheet are wound around another round bar and coated in the same manner, and these sheets are used as samples for volume resistivity measurement (measure the resistance with the OHP sheet and measure the coating thickness with the aluminum sheet). ). When the volume resistivity was measured, it was 40.2 Ω · cm. The volume specific resistance value was measured by attaching a four-terminal probe to a Low Lester AP manufactured by Mitsubishi Yuka Co., Ltd. (However, for a sample having a higher volume resistance, the company's High Lester was used).
[0082]
Next, using this sleeve 1, an image was formed using a modified LBP-2260 manufactured by Canon Inc. as an image forming apparatus shown in FIG. This sleeve was processed and attached to an EP-82 cartridge so that it could be mounted. Using a cyan toner, a durability test was performed on up to 3,000 single-color sheets. FIG. 1 is a schematic view showing the vicinity of the sleeve of the EP-82 cartridge. The production example of the toner used in this evaluation is shown below.
[0083]
0.1 mol / L-Na is added to 10000 parts of ion-exchanged water in a reaction vessel.₃PO₄85 parts by weight of an aqueous solution and 85 parts by weight of a 1 mol / L-HCl aqueous solution₂The temperature was kept at 65 ° C. for 60 minutes while purging. 1.0 mol / L-CaCl while stirring at 12000 rpm using a high-speed stirrer TK-homomixer.₂60 parts by weight of the aqueous solution was added all at once to prepare an aqueous medium containing a calcium phosphate salt having a pH of 6.5.
[0084]

The above material was kept at 65 ° C. in a separate container, and was uniformly dissolved and dispersed at 12,000 rpm using a TK homomixer. Into this, 4 parts by weight of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.
[0085]
The polymerizable monomer composition was charged into the aqueous medium in a reaction vessel,₂Under a purge, the mixture was stirred at 10,000 rpm for 10 minutes using a TK homomixer to granulate a polymerizable monomer composition. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C for 6 hours, further raised to 85 ° C, and reacted for 9 hours, followed by distillation at 85 ° C.
[0086]
After the completion of the polymerization reaction, the reaction vessel is cooled, hydrochloric acid is added, and Ca is added.₃(PO₄)₂Was dissolved, filtered, washed with water and dried to obtain yellow toner particles. Hydrophobic silica fine powder (BET: 250 m) treated with hexamethyldisilazane as a flow improver with respect to 100 parts by mass of the yellow toner particles.²/ G) 1.5 parts by mass were dry-mixed with a Henschel mixer to obtain the toner of the present invention.
[0087]
The image evaluation was performed in two environments: a low humidity environment of 23 ° C./5% RH and a high humidity environment of 30 ° C./80% RH. Table 2 shows the image evaluation results at this time.
[0088]
〔Evaluation method〕
The following items were evaluated.
[0089]
(1) Image density (5 density, solid density)
Reflection densities were measured at 10 points in the page when 5 mm square black and solid black printing were performed by a reflection densitometer RD918 (manufactured by Macbeth), and the average of the 10 points was taken as the image density.
[0090]
(2) Toner charge amount (Q / M)
The toner carried on the developing sleeve is absorbed and collected by a metal cylindrical tube and a cylindrical filter. At this time, the amount of charge Q stored in the condenser through the metal cylindrical tube and the collected toner weight M are calculated based on the weight per unit weight. The charge amount Q / M (mC / kg) is calculated.
[0091]
(3) Fog (paper fog)
Measure the reflectance of the solid white image, and further measure the reflectance of the unused transfer paper (the worst value of the reflectance of the solid white image)-(the highest value of the reflectance of the unused transfer paper) as the fog density. (However, the reflectance was measured ten times at random). The reflectance was measured using TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.). As evaluation criteria, 1.5 or less; almost unknown. 1.5-2.5; cannot be understood without careful observation. 2.5 to 3.5; fog becomes gradually recognizable. 4.0; fog can be confirmed at a glance at the practical level lower limit. 5.0 or more; quite bad.
[0092]
(4) Fog on drum (drum fog)
At the time of a solid white image, the toner transferred to the drum before the transfer was pasted and collected with a Mylar tape, and the reflection density was measured by pasting it on white paper, and the difference from the reflection density of the Mylar tape pasted on the white paper was defined as the fog density. . The same TC-6DS as above was used for the measurement.
[0093]
(5) Solid white stripe, white belt (white belt)
In a solid image, a phenomenon in which white streaks or a white band-like low density portion occurs in the image advancing direction, where the toner is insufficiently charged and development is not performed uniformly, or toner sticking or fusion occurs. Occurs when: Evaluation was made based on the following evaluation criteria.
[0094]
(Evaluation criteria)
A: Not seen at all.
B: The density is low when seen through.
C: The solid image is slightly recognized visually, but there is almost no difference in image density.
D: This is confirmed by visual observation of a normal solid image, but is difficult to recognize in a photographic image.
E: It is clearly recognized by visual observation of a normal solid image. Also recognized in halftones such as photographs.
F: An image having a considerable density difference.
[0095]
(6) Toner scattering (scattering)
The scattering state of the toner from the sleeve is evaluated and compared based on the following evaluation criteria.
[0096]
A: There is almost no scattering near the sleeve of the cartridge.
B: A degree at which some toner adhesion is seen on the stage portion under the sleeve of the cartridge.
C: Although the above-mentioned contamination is slightly observed, the contamination does not reach the main body.
D: The above contamination is observed, and some contamination is observed in the main body.
E: Scattering is observed up to the main body, but toner does not drop from the sleeve.
F: A portion where the toner is not coated occurs on the sleeve, and the toner is dripping from the sleeve in the portion (the dropped toner accumulates on the stage below the sleeve and spills out of the toner).
G: Dropping occurs from a considerable portion on the sleeve.
[0097]
(7) Abrasion amount of coating layer (film abrasion)
Measure the outer diameter of the sleeve (aluminum round bar) before coating and the outer diameter including the resin layer after coating with a laser measuring device (average of 10 locations) and include the resin layer after durability. The measured outer diameter is measured by a laser length measuring instrument, and expressed as (μm unit) as (amount of outer diameter including resin layer before image formation) − (outer diameter including resin layer after durability).
[0098]
<Example 2>
[Outside 6]

[0099]
A sleeve 2 was produced in the same manner as in Example 1 except that the aminosilane coupling agent (2) was used instead of the aminosilane coupling agent (1) used in Example 1, and the same as in Example 1 was used. An evaluation was performed.
[0100]
<Example 3>
[Outside 7]

[0101]
A sleeve 3 was produced in the same manner as in Example 1 except that the aminosilane coupling agent (3) was used instead of the aminosilane coupling agent (1) used in Example 1, and the same as in Example 1 was used. An evaluation was performed.
[0102]
<Examples 4 to 7>
In place of the copolymer A used in Example 1, the sleeves 4 to 4 were prepared in the same manner as in Example 1 except that copolymers B to E in which the molar ratio between methyl methacrylate and dimethylaminoethyl methacrylate was changed were used. 7 was produced, and the same evaluation as in Example 1 was performed.
[0103]
Copolymer used for sleeve 4
Methyl methacrylate-dimethylaminoethyl methacrylate copolymer B (40% MEK solution)
(Molar ratio 997: 3, Mw = 19000, Mn = 5000, Mw / Mn = 1.9)
Copolymer used for sleeve 5
Methyl methacrylate-dimethylaminoethyl methacrylate copolymer C (40% MEK solution)
(Molar ratio 9999: 1, Mw = 22000, Mn = 9000, Mw / Mn = 2.4)
Copolymer used for sleeve 6
Methyl methacrylate-dimethylaminoethyl methacrylate copolymer D (40% MEK solution)
(Molar ratio 82:18, Mw = 9900, Mn = 4400, Mw / Mn = 2.3)
Copolymer used for sleeve 7
Methyl methacrylate-dimethylaminoethyl methacrylate copolymer E (40% MEK solution)
(Molar ratio 70:30, Mw = 8500, Mn = 2900, Mw / Mn = 2.9)
[0104]
<Examples 8 to 13>
In place of copolymer A used in Example 1, sleeves 8 to 13 were produced in the same manner as in Example 1 except that copolymers F to K in which the molecular weight of the copolymer was changed were used. The same evaluation as in Example 1 was performed.
[0105]
Copolymer used for sleeve 8
Methyl methacrylate-dimethylaminoethyl methacrylate copolymer F (40% MEK solution)
(Molar ratio 90:10, Mw = 3700, Mn = 2300, Mw / Mn = 1.6)
Copolymer used for sleeve 9
Methyl methacrylate-dimethylaminoethyl methacrylate copolymer G (40% MEK solution)
(Molar ratio 90:10, Mw = 2500, Mn = 1300, Mw / Mn = 1.9)
Copolymer used for sleeve 10
Methyl methacrylate-dimethylaminoethyl methacrylate copolymer H (40% MEK solution)
(Molar ratio 90:10, Mw = 40000, Mn = 19000, Mw / Mn = 2.1)
Copolymer used for sleeve 11
Methyl methacrylate-dimethylaminoethyl methacrylate copolymer I (40% MEK solution)
(Molar ratio 90:10, Mw = 52500, Mn = 22200, Mw / Mn = 2.4)
Copolymer used for sleeve 12
Methyl methacrylate-dimethylaminoethyl methacrylate copolymer J (40% MEK solution)
(Molar ratio 90:10, Mw = 12900, Mn = 3900, Mw / Mn = 3.3)
Copolymer used for sleeve 13
Methyl methacrylate-dimethylaminoethyl methacrylate copolymer K (40% MEK solution)
(Molar ratio 90:10, Mw = 12900, Mn = 3200, Mw / Mn = 4.0)
[0106]
<Example 14>
A sleeve 14 was produced in the same manner as in Example 1 except that the amount of the aminosilane coupling agent (1) used in Example 1 was changed to 15 parts, and the same evaluation as in Example 1 was performed.
[0107]
<Example 15>
A sleeve 15 was produced in the same manner as in Example 1 except that the amount of the aminosilane coupling agent (1) used in Example 1 was changed to 30 parts, and the same evaluation as in Example 1 was performed.
[0108]
<Example 16>
A sleeve 16 was prepared in the same manner as in Example 1 except that the addition amount of the copolymer A used in Example 1 was 20 parts and the addition amount of the aminosilane coupling agent (1) was 5 parts. The same evaluation as in Example 1 was performed.
[0109]
<Example 17>
A sleeve 17 was produced in the same manner as in Example 1 except that the addition amount of the copolymer A used in Example 1 was changed to 50 parts and the addition amount of the aminosilane coupling agent (1) was changed to 12.5 parts. The same evaluation as in Example 1 was performed.
[0110]
<Example 18>
A sleeve 18 was produced in the same manner as in Example 1 except that the addition amount of the copolymer A used in Example 1 was changed to 80 parts and the addition amount of the aminosilane coupling agent (1) was changed to 20 parts. The same evaluation as in Example 1 was performed.
[0111]
<Examples 19 to 21>
A copolymer prepared by copolymerizing with a methyl methacrylate monomer using a diethylaminoethyl methacrylate monomer, a dibutylaminoethyl methacrylate monomer, and a dimethylaminostyrene monomer instead of the dimethylaminoethyl methacrylate monomer of the copolymer A used in Example 1 Except for using L to N, sleeves 19 to 21 were produced in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.
[0112]
<Examples 22 to 25>
Acrylic acid, methacrylic acid, butyl maleate, and styrene are used in place of the methyl methacrylate monomer of copolymer A used in Example 1, and copolymers O to R copolymerized with dimethylaminoethyl methacrylate monomer are used. Except for this, sleeves 22 to 25 were produced in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.
[0113]
<Examples 26 to 28>
Instead of the copolymer A used in Example 1, the following copolymers S to U, which are terpolymers, were used to produce sleeves 26 to 28 in the same manner as in Example 1. The same evaluation was performed.
[0114]
Copolymer used for sleeve 26
Methyl methacrylate-dimethylaminoethyl methacrylate-acrylic acid copolymer S (40% MEK solution) (molar ratio 90: 5: 5, Mw = 1500, Mn = 4800, Mw / Mn = 2.4)
Copolymer used for sleeve 27
Methyl methacrylate-dimethylaminoethyl methacrylate-methacrylic acid copolymer T (40% MEK solution) (molar ratio 90: 5: 5, Mw = 12,500, Mn = 5700, Mw / Mn = 2.2)
Copolymer used for sleeve 28
Methyl methacrylate-dimethylaminoethyl methacrylate-butyl maleate copolymer U (40% MEK solution) (molar ratio 90: 5: 5, Mw = 1900, Mn = 4900, Mw / Mn = 2.4)
[0115]
<Example 29>
Instead of the dimethylaminoethyl methacrylate monomer of the copolymer A used in Example 1, the following quaternary ammonium group-containing vinyl monomer (1) was used, and a copolymer V copolymerized with a methyl methacrylate monomer was used. A sleeve 29 was produced in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.
[Outside 8]

[0116]
<Example 30>
A sleeve 30 was prepared in the same manner as in Example 29 except that the copolymer W used in Example 29 was replaced with a copolymer W in which the quaternary ammonium group-containing vinyl monomer was replaced with the following (2), and a similar sleeve 30 was manufactured. An evaluation was performed.
[Outside 9]

[0117]
<Example 31>
A sleeve 31 was produced in the same manner as in Example 29 except that the copolymer X in which the quaternary ammonium group-containing vinyl monomer was replaced with the following (3) was used instead of the copolymer V used in Example 29, and the same as in Example 29. An evaluation was performed.
[Outside 10]

[0118]
<Example 32>
A sleeve 32 was produced in the same manner as in Example 31, except that the copolymer Y using a styrene monomer was used instead of the methyl methacrylate monomer used in Example 31, and the same evaluation was performed.
[0119]
(Comparative Example 1)
In Example 31, a sleeve A was prepared and evaluated in the same manner as in Example 31 except that a homopolymer of methyl methacrylate was used.
[0120]
(Comparative Example 2)
A sleeve B was prepared and evaluated in the same manner as in Comparative Example 1, except that the aminosilane coupling agent (1) was added to the homopolymer of methyl methacrylate used in Comparative Example 1.
[0121]
(Comparative Example 3)
A sleeve C was prepared in the same manner as in Example 1 except that a phenolic paint having the following composition was used instead of the paint using the copolymer used in Example 1. The drying and curing time of the paint was 150 ° C. for 30 minutes.
[0122]
・ 100 parts by weight of phenolic resin intermediate
・ 25 parts by weight of crystalline graphite having an average particle size of 3 μm
・ 250 parts by weight of methanol
The same evaluation as in Example 1 was performed using the obtained sleeve C.
[0123]
(Comparative Example 4)
The surface of the aluminum cylindrical tube used in Example 1 was subjected to sandblasting using glass beads (FGB # 300). The same evaluation as in Example 1 was performed using this sleeve D.
[0124]
(Comparative Example 5)
In Example 1, a sleeve E was prepared and evaluated in the same manner as in Example 1 except that the aminosilane coupling agent (1) was not added.
[0125]
(Comparative Example 6)
In Example 25, a sleeve F was prepared and evaluated in the same manner as in Example 1, except that the aminosilane coupling agent (1) was not added.
[0126]
[Table 1]

[0127]
[Table 2]

[0128]
[Table 3]

[0129]
【The invention's effect】
According to the present invention, the developer on the developer carrying member has a stable and appropriate charge even in repeated image formation, is uniform, has no unevenness, and has no image density reduction or ghost. A high-quality image can be obtained. In particular, for the purpose of high image quality and energy saving, even in a toner having a small particle size and a low-temperature fixing material, by reducing the toner adhesion to the resin coating layer, and further improving the chargeability or developability, High definition and high quality images can be obtained. Further, by ensuring the abrasion resistance of the resin coating layer and forming a uniform resin layer, a long and stable image can be obtained.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing an example of a non-magnetic one-component developing device having a developer carrying member of the present invention.
FIG. 2 is a schematic diagram showing another example of a magnetic one-component developing type developing device having a developer carrying member of the present invention.
FIG. 3 is a schematic diagram showing another example of a magnetic one-component developing type developing device having a developer carrier of the present invention.
FIG. 4 is a block diagram when the image forming apparatus of the present invention is applied to a printer of a facsimile machine.
[Explanation of symbols]
1. Electrophotographic photosensitive drum (latent image carrier)
3 Hopper
4 Non-magnetic toner (developer)
6. Metallic cylindrical tube (substrate)
7 Resin coating layer
8 Developing sleeve (developer carrier)
9 Power supply
10 Toner stirring blade
11 Elasticity regulating blade (developer layer thickness regulating member)
12 Developer supply / peel-off roller (developer supply / peel-off member)
13 Hopper
14 Magnetic toner (developer)
15 magnet
16 Metallic cylindrical tube (substrate)
17 Resin coating layer
18 Developing sleeve (developer carrier)
19 Power supply
20 Toner stirring blade
21 Elasticity regulating blade (developer layer thickness regulating member)

Claims (11)

In a developer carrier used in a developing device that develops a latent image formed on the latent image carrier with a developer carried and conveyed by the developer carrier, the developer carrier is used in a developing device that visualizes the latent image. At least a substrate and a resin layer formed on the surface of the substrate, the resin layer is formed of a resin composition containing at least an aminosilane coupling agent, and a binder resin used for the resin layer is a vinyl polymerizable resin. A developer carrier having a copolymer containing a monomer and a nitrogen-containing vinyl monomer. The developer carrier according to claim 1, wherein the vinyl polymerizable monomer includes a methyl methacrylate monomer. 3. The developer carrier according to claim 1, wherein the resin layer is a conductive resin layer containing a conductive fine powder and / or a solid lubricant. 4. The developer carrier according to claim 3, wherein the volume resistivity of the conductive resin layer is 1 × 10 ⁻² Ω · cm to 1 × 10 ⁵ Ω · cm. The developer carrier according to any one of claims 1 to 4, wherein the binder resin has a weight average molecular weight (Mw) of 3,000 to 50,000. 6. The binder resin according to claim 1, wherein the binder resin has a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of 3.5 or less. Developer carrier. 7. The nitrogen-containing vinyl monomer comprises at least one monomer selected from the group consisting of a (meth) acrylic monomer and a nitrogen-containing heterocyclic N-vinyl compound. A developer carrier according to any one of the above. The nitrogen-containing vinyl monomer has the following general formula (1)
[Outside 1]

[Wherein, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a saturated hydrocarbon group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4. The developer carrier according to any one of claims 1 to 7, wherein: 9. The developer carrier according to claim 1, wherein the nitrogen-containing vinyl monomer has a quaternary ammonium group-containing vinyl monomer. The quaternary ammonium group-containing vinyl monomer has the following general formula (2)
[Outside 2]

[Wherein, R ₅ represents a hydrogen atom or a methyl group, R ₆ represents an alkylene group having 1 to 4 carbon atoms, R _{7 to} R ₉ represent a methyl group, an ethyl group or a propyl group, and X ₁ shows a -COO- or -CONH-, a ^{- is} Cl -, indicating the (1/2) _SO ^{4 2-.} The developer-carrying member according to claim 9, wherein: The developer accommodated in the developing container is carried on the developer carrier, and faces the latent image carrier while forming a thin layer of the developer on the developer carrier by the developer layer thickness regulating member. A developing device for transporting the latent image on the latent image carrier with a developer to visualize the latent image on the latent image carrier, wherein the developer carrier is described in any one of claims 1 to 10. A developing device comprising a developer carrier.

Images