JP2004126238A - Developer carrier, developing device and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developer carrier which secures developer carrying ability over a long term and yields a high-quality image. <P>SOLUTION: The developer carrier used for the developing device where a latent image formed on an electrostatic latent image carrier is developed to be a visible image with developer carried and fed by the developer carrier has at least base substance and a resin covering layer formed on the surface of the base substance. The resin covering layer incorporates at least resin and boric acid aluminum granular substance dispersed in the resin. <P>COPYRIGHT: (C)2004,JPO

Description

【００４６】
上記一般式で表されるチタン系カップリング剤のうち更に具体的化合物としては下記のようなものがある。
【００４７】
【化２】

【００４８】
【化３】

【００４９】
ホウ酸アルミニウム粒子に対するチタン系カップリング剤の処理量は、ホウ酸アルミニウム粒子の粒度，表面構造等によっても異なるが、ホウ酸アルミニウム粒子１００質量部に対して０．０００１〜０．５質量部用いることが好ましい。上記アルミニウムカップリング剤の処理量が０．０００１質量部未満ではホウ酸アルミニウム粒子の分散性に対して効果がなく、また、０．５質量部を超えるとホウ酸アルミニウム粒子と結合しない遊離のカップリング剤が多く発生することになり好ましくない。
【００５０】
アルミニウムカップリング剤としては、アセトアルコキシアルミニウムジイソプロピレート等が挙げられる。ホウ酸アルミニウム粒子に対する処理量は、ホウ酸アルミニウム粒子１００質量部に対して０．０００１〜０．５質量部用いることが好ましい。上記アルミニウムカップリング剤の処理量が０．０００１質量部未満ではホウ酸アルミニウム粒子の分散性に対して効果がなく、また、０．５質量部を超えるとホウ酸アルミニウム粒子と結合しない遊離のカップリング剤が多く発生することになり好ましくない。
【００５１】
上述の各カップリング剤は必要に応じて２種以上の組合せとして用いてもよい。
【００５２】
上記カップリング剤によりホウ酸アルミニウム粒状物を処理する方法としては、例えば、有機溶媒法及び水溶液法等がある。一般に、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、これにホウ酸アルミニウム粒状物を浸漬した後、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。また、水溶液法とは、０．５％程度のカップリング剤を、一定ｐＨの水、或いは水−有機溶媒の混合溶媒中で加水分解させ、ここにホウ酸アルミニウム粒状物を浸漬した後、同様に固液分離を行い、乾燥させるものである。
【００５３】
他の有機処理であるシリコーンオイルとしては、一般に次式により示されるものである。
【００５４】
【化４】

【００５５】
Ｒ　：　Ｃ_１〜Ｃ_３のアルキル基
Ｒ’：アルキル，ハロゲン変性アルキル，フェニル，変性フェニル等のシリコーンオイル変性基
Ｒ”：Ｃ_１〜Ｃ_３のアルキル基又はアルコキシ基
【００５６】
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０．５〜１，０００ｍｍ^２／ｓ、好ましくは１〜１，０００ｍｍ^２／ｓのものが用いられる。分子量が低すぎるシリコーンオイルは加熱処理等により、希発分が発生することがあり、また、分子量が高すぎると粘度が高くなりすぎ処理操作がしにくくなる。シリコーンオイルの種類としては、例えば、メチルハイドロジェ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好ましい。
【００５７】
上記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ホウ酸アルミニウム粒状物を激しく撹乱させておき、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若しくは気化して吹き付けるか、又は、ホウ酸アルミニウム粒状物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種或いは２種以上の混合物或いは併用や多重処理して用いられる。また、カップリング剤による処理と併用しても構わない。
【００５８】
図１〜４は、粒子状のホウ酸アルミニウム４が結着樹脂３中に分散され表面樹脂被覆層２を形成している様子を示す断面の模式図である。１は基体を示す。図１においては、ホウ酸アルミニウム粒子が結着樹脂中に分散され且つ樹脂被覆層表面の凹凸形成に寄与している。５は樹脂被覆層に導電性を与えるために添加された導電性微粉末であり、ここでは実質的な凹凸形成には寄与していない。しかしながら、導電性微粉末に限らず、添加される別の固体粒子により微小な凹凸が形成される様態も含まれる。図２において、６は樹脂被覆層表面に比較的大きな凹凸を与えるために添加された別の固体粒子を示し、ホウ酸アルミニウム粒子４は樹脂被覆層表面に微小な凹凸を形成している。このような構成は、現像剤規制部材が現像剤担持体に対して（トナーを介して）弾性的に圧接されるタイプの現像装置に用いる場合に有利である。すなわち、別の固体粒子により弾性規制部材の圧接力を規制し且つホウ酸アルミニウム粒子４は微小な凹凸を形成してトナーと樹脂間の接触帯電機会を調整する役割も果たす。図３は、ホウ酸アルミニウム粒子４と別の固体粒子７の双方が樹脂被覆層表面の凹凸形成に寄与している。このような形態は、例えば、別の固体粒子７に凹凸付与以外に導電性や摩擦帯電付与性等の別の機能を持たせようとした場合に実施される場合がある。図４は、スリーブヘのトナー付着防止等の目的でグラファイト等の固体潤滑剤８を併用した場合のモデル図である。
【００５９】
次に本発明に用いられる現像剤担持体の構成について説明を加える。現像剤担持体は基体と、それを取り巻いて被覆する樹脂層とからなるが、基体としては、円筒状部材、円柱状部材、ベルト状部材等があるが、ドラムに非接触の現像方法においては金属のような剛体の円筒管もしくは中実棒が好ましく用いられる。このような基体はアルミニウム、ステンレス鋼、真鍮等の非磁性の金属または合金を円筒状あるいは円柱状に成型し、研磨、研削等を施したものが好適に用いられる。これらの基体は画像の均一性を良くするために、高精度に成型あるいは加工されて用いられる。例えば長手方向の真直度は３０μｍ以下もしくは２０μｍ以下、さらに好ましくは１０μｍ以下が好ましく、スリーブと感光ドラムとの間隙の振れ、例えば、垂直面に対し均一なスペーサーを介して突き当て、スリーブを回転させた場合の垂直面との間隙の振れも３０μｍ以下もしくは２０μｍ以下、さらに好ましくは１０μｍ以下であることが好ましい。材料コストや加工のしやすさからアルミニウムが好ましく用いられる。このような形態のものは、磁性、非磁性の一成分非接触現像や、二成分現像の現像剤担持体基体として好ましく用いられる。
【００６０】
また、弾性層を有する基体としては、芯材と、ウレタン、ＥＰＤＭ、シリコン等のゴムやエラストマーを含む層構成を有する円筒部材が、特にドラムに現像剤担持体を直接接触させる現像方法の場合好ましく用いられる。
【００６１】
本発明の現像剤担持体を構成する導電性被覆層の結着樹脂材料としては、一般に公知の樹脂が使用可能である。例えば、スチレン系樹脂、ビニル系樹脂、ポリエーテルスルホン樹脂、ポリカーボネート樹脂、ポリフェニレンオキサイド樹脂、ポリアミド樹脂、フッ素樹脂、繊維素系樹脂、アクリル系樹脂等の熱可塑性樹脂、エポキシ樹脂、ポリエステル樹脂、アルキッド樹脂、フェノール樹脂、メラミン樹脂、ポリウレタン樹脂、尿素樹脂、シリコーン樹脂、ポリイミド樹脂等の熱あるいは光硬化性樹脂等を使用することができる。なかでもシリコーン樹脂、フッ素樹脂のような離型性のあるもの、或いはポリエーテルスルホン、ポリカーボネート、ポリフェニレンオキサイド、ポリアミド、フェノール、ポリエステル、ポリウレタン、スチレン系樹脂、アクリル系樹脂のような機械的性質に優れたものがより好ましい。
【００６２】
本発明において、上記した形成材料によって現像剤担持体上に形成される被覆層は、チャージアップによる現像剤の現像剤担持体上への固着や、現像剤のチャージアップに伴って生じる現像剤担持体の表面から現像剤への帯電付与不良を防ぐためには、導電性であることが望ましい。また、被覆層の体積抵抗値としては、好ましくは１０^４Ω・ｃｍ以下、より好ましくは１０^３Ω・ｃｍ以下である。
【００６３】
現像剤担持体表面の導電性被覆層の体積抵抗値が１０^４Ω・ｃｍを超えると現像剤への帯電付与不良が発生し易く、その結果、ブロッチ（斑点画像や波模様画像）が発生し易い。
【００６４】
本発明において、被膜層の低抗値を、上記の値に調整するためには、下記に挙げる導電性物質を被覆層中に含有させることが好ましい。この際に使用される導電性物質としては、例えば、アルミニウム、銅、ニッケル、銀等の金属粉体の微粉末、酸化アンチモン、酸化インジウム、酸化スズ、酸化チタン、酸化亜鉛、酸化モリブデン、チタン酸カリウム等の金属酸化物、各種カーボンファイバー、ファーネスブラック、ランプブラック、サーマルブラック、アセチレンブラック、チャネルブラック等のカーボンブラック、グラファイト等の炭素物、更には金属繊維等が挙げられる。
【００６５】
本発明においては、これらのうち、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、高分子材料に充填して導電性を付与したり、その添加量をコントロールするだけで、ある程度任意の導電度を得ることができるため好適に用いられる。塗料にした場合の分散安定性も良好となりうる。また、本発明において好適なこれらの導電性物質の添加量は、結着樹脂１００質量部に対して１〜１００質量部の範囲とすることが好ましい。１質量部未満では被覆層の抵抗値を所望のレベルに下げることは、通常困難であり、また、現像剤担持体被覆層に用いられる結着樹脂に対するトナー付着が発生する可能性が高い。１００質量部超であると、特にサブミクロンオーダーの粒度を有する微粉体を用いた場合、被覆層の強度（摩耗性）が低下しうる。
【００６６】
更に、本発明においては、現像剤担持体表面への現像剤の付着をより軽減化するため、被覆層中に固体潤滑材を混合させることもできる。この際に使用し得る固体潤滑材としては、例えば、二硫化モリブデン、窒化硼素、グラファイト、フッ化グラファイト、銀−セレンニオブ、塩化カルシウム−グラファイト、滑石等が挙げられる。また、本発明で使用することのできるこれらの固体潤滑材の添加量は、結着樹脂１００質量部に対して１〜１００質量部の範囲とすることが好ましい。１質量部未満では被覆層の結着樹脂表面に対する現像剤の付着性の改善効果は少なく、１００質量部超となると、特にサブミクロンオーダーの粒度を有する微粉体が多く含まれる材料を用いた場合、被覆層の強度（摩耗性）が低下しうる。これらの潤滑性粒子は、個数平均粒径が好ましくは０．２〜２０μｍ程度、より好ましくは１〜１５μｍのものを使用するのが良い。潤滑性粒子の個数平均粒径が０．２μｍ未満の場合には、潤滑性が十分に得られ難く好ましくなく、個数平均粒径が２０μｍを超える場合には、導電性被覆層表面の形状への影響が大きく表面性が不均一となり、トナーの均一な帯電化、及び被覆層の強度の点で好ましくない。
【００６７】
本発明の樹脂被覆層中には、被覆層表面に凹凸を形成するための別の固体粒子を含有させることができる。このような固体粒子としては、例えば、ポリメチルメタクリレート、ポリエチルアクリレート、ポリブタジエン、ポリエチレン、ポリプロピレン、ポリスチレン等のビニル系重合体や共重合体、ベンゾグアナミン樹脂、フェノール樹脂、ポリアミド、フッ素系樹脂、シリコーン樹脂、エポキシ樹脂、ポリエステル樹脂等の樹脂粒子、アルミナ、酸化亜鉛、シリコーン、酸化チタン、酸化錫等の酸化物粒子、炭素化粒子、導電処理を施した樹脂粒子等の導電性粒子、その他、例えばイミダゾール化合物のような有機化合物を粒子状にして用いることも可能である。この場合にイミダゾール化合物は、トナーに摩擦帯電電荷を付与する役割も果たす。図３はそのような形態を示している。
【００６８】
特に図２のような形態で用いる場合、これらの粒子の中では特に導電性の粒子を用いることが好ましい。即ち、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、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。このような粒子の体積抵抗が１０^６Ω・ｃｍを超えると、摩耗によって被覆層表面に露出した球状粒子を核としてトナーの汚染や融着を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。さらには粒子の真密度としては３０００ｋｇ／ｍ^３程度以下であることがより好ましい。導電性であっても、粒子の真密度が高すぎる場合、同じ粗さを形成するための添加量は増加してくることと、樹脂または樹脂組成物と真密度差が、大きくなるため、製造時の粒子の分散状態が非均一となりやすく、したがって形成された被覆層においても分散状態が不均一となり好ましくない。また粒子が球状であると、圧接される現像剤規制部材等との接触面積が低減されるので、摩擦力によるスリーブ回転トルクの増加や、トナーの付着などを軽減することができるのでより好ましい。特に下記に示すような導電性の球状粒子を用いた場合には、より良い効果が得られる。
【００６９】
すなわち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、樹脂系球状粒子やメソカーボンマイクロビーズを焼成して炭素化及び／又は黒鉛化して得た低密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、樹脂系球状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。また、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、キノリンの如き溶剤で洗浄することによって製造することができる。
【００７０】
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の如き球状樹脂粒子表面に、メカノケミカル法によってバルクメソフェースピッチを被覆し、被覆された粒子を酸化性雰囲気化で熱処理した後に不活性雰囲気下または真空下で焼成して炭素化及び／又は黒鉛化し、導電性球状炭素粒子を得る方法が挙げられる。この方法で得る球状炭素粒子は、黒鉛化すると得られる球状炭素粒子の被覆部の結晶化が進んだものとなるので導電性が向上し、より好ましい。
【００７１】
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。また、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ために導電性球状粒子の真密度が大きくなりすぎない範囲で、導電性の金属及び／又は金属酸化物のメッキを施していても良い。
【００７２】
本発明で好適に使用される上記のような構成を有する現像剤担持体表面の被覆層の表面粗さは、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。更に好ましくは、０．４〜２．５μｍである。即ち、Ｒａが０．３μｍ未満では、現像剤担持体上におけるトナーの帯電量が高くなり過ぎ現像性が不充分となるし、また、現像領域への現像剤の搬送性に劣り、充分な画像濃度が得られにくくなる。一方、Ｒａが３．５μｍを超えると、現像剤担持体上に形成されるトナーコート層厚にムラが生じ、画像上での濃度ムラの原因となる。
【００７３】
上記のような表面粗さを得るためにはホウ酸アルミニウム粒子の個数平均粒径は０．３〜３０μｍであることが好ましい。個数平均が０．３μｍ未満では、上記のような表面粗さの付与はなしがたく、多量に添加した場合には相対的に樹脂分が減少するために結着性が低下し樹脂層が脆くなる可能性があり、また樹脂によるトナーへの帯電付与がされ難くなる。３０μｍを超える場合には、表面粗さが大きくなりすぎ、また表面凹凸が不均一になるため、トナーの搬送性が不均一であったり、トナーの層厚規制力は弱まりトナーのコート状態が不均一になったり不安定になる。
【００７４】
同様な理由から、更に添加される別の固体粒子においても、個数平均粒径は０．３〜３０μｍであることが好ましい。
【００７５】
図５は、本発明の現像剤担持体を有する一実施形態の現像装置の模式図を示す。
【００７６】
図５において、公知のプロセスにより形成された静電潜像を保持する静電潜像保持体潜像保持体、例えば、電子写真感光ドラム５０１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５０８は、現像剤容器としてのホッパー５０３によって供給された磁性トナーを有する一成分系現像剤４を担持して、矢印Ａ方向に回転することによって、現像スリーブ５０８と感光ドラム５０１とが対向している現像領域Ｄに現像剤５０４を搬送する。図５に示すように、現像スリーブ５０８内には，現像剤５０４を現像スリーブ５０８上に磁気的に吸引且つ保持する為に、磁石が内接されているマグネットローラー５０５が配置されている。
【００７７】
本発明の現像装置で用いられる現像スリーブ５０８は、基体としての金属円筒管５０６上に被覆された導電性被覆層５０７を有する。ホッパー５０３中には、現像剤５０４を撹拌するための撹拌翼５１０が設けられている。５１３は、現像スリーブ５０８とマゲネットローラー５０５とが非接触状態にあることを示す間隙である。
【００７８】
現像剤５０４は、磁性トナー相互間及び現像スリーブ５０８上の導電性被覆層５０７との摩擦により、感光ドラム５０１上の静電潜像を現像することが可能な摩擦帯電電荷を得る。図５の例では、現像領域Ｄに搬送される現像剤５０４の層厚を規制するために、現像剤層厚規制部材としての強磁性金属製の磁性規制ブレード５０２が、現像スリーブ５０８の表面から約５０〜５００μｍのギャップ幅を持って現像スリーブ５０８に臨む様に、ホッパー５０３から垂下されている。マグネットローラー５０５の磁極Ｎ１からの磁力線が磁性規制ブレード５０２に集中することにより、現像スリーブ５０８上に現像剤５０４の薄層が形成される。本発明においては、この磁性規制ブレード５０２にかえて非磁性ブレードを使用することもできる。
【００７９】
この様にして、現像スリーブ５０８上に形成される現像剤５０４の薄層の厚みは，現像領域Ｄにおける現像スリーブ５０８と感光ドラム５０１との間の最小間隙よりも更に薄いものであることが好ましい。
【００８０】
本発明の現像剤担持体は、以上の様な現像剤の薄層により静電潜像を現像する方式の現像装置、即ち、非接触型現像装置に組み込むのが特に有効であるが、現像領域Ｄにおいて、現像剤層の厚みが現像スリーブ５０８と感光ドラム５０１との間の最小間隙以上の厚みである現像装置、即ち接触型現像装置にも本発明の現像剤担持体を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、上記したような非接触型現像装置を例にとって行う。
【００８１】
上記現像スリーブ５０８に担持された磁性トナーを有する一成分系現像剤５０４を飛翔させるため、上記現像スリーブ５０８にはバイアス手段としての現像バイアス電源５０９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に、静電潜像の画像部（現像剤５０４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を現像スリーブ５０８に印加するのが好ましい。
【００８２】
現像された画像の濃度を高め、或は階調性を向上するためには、現像スリーブ５０８に交番バイアス電圧を印加し、現像領域Ｄに向きが交互に反転する振動電界を形成してもよい。この場合には、上記した現像画像部の電位と背景部の電位の中間の値を有する直流電圧成分を重畳した交番バイアス電圧を現像スリーブ５０８に印加するのが好ましい。
【００８３】
高電位部と低電位部を有する静電潜像の高電位部にトナーを付着させて可視化する、所謂、正規現像の場合には、静電潜像の極性と逆極性に帯電するトナーを使用する。
【００８４】
高電位部と低電位部を有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、反転現像の場合には、静電潜像の極性と同極性に帯電するトナーを使用する。
【００８５】
高電位、低電位というのは、絶対値による表現である。これらいずれの場合にも、現像剤５０４は少なくとも現像スリーブ５０８との摩擦により帯電する。
【００８６】
図６は、本発明の現像装置の他の実施形態を示す構成模式図、図７は、本発明の現像装置の更に他の実施形態を示す構成模式図である。図６及び図７に示した現像装置では、現像スリーブ５０８上の現像剤５０４の層厚を規制する現像剤層厚規制部材として、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、ステンレス鋼の如き金属弾性を有する材料の弾性板からなる弾性規制ブレード５１１を使用し、この弾性規制ブレード５１１を図６の現像装置では現像スリーブ５０８の回転方向と逆方向の向きで圧接させており、図７の現像装置では、この弾性規制ブレード５１１を現像スリーブ５０８の回転方向と順方向の向きで圧接させているのが特徴である。これらの現像装置では、現像スリーブ５０８に対して、現像剤層を介して現像剤層厚規制部材を弾性的に圧接することによって、現像スリーブ上に現像剤の薄層を形成することから、現像スリーブ５０８上に、上記した図５の引用例の場合よりも更に薄い現像剤層を形成することができる。
【００８７】
図６及び図７の現像装置の他の基本的構成は図１１に示した現像装置と同じであり、同符号のものは、基本的には同一の部材であることを示す。
【００８８】
図８及び図９は、磁性トナーを用いる現像装置において、弾性規制部材が備わった構成を示す模式図である。
【００８９】
図５〜９はあくまでも本発明の現像装置を模式的に例示したものであり、現像剤容器（ホッパー５０３）の形状、撹拌翼５１０の有無、磁極の配置に様々な形態があることは言うまでもない。
【００９０】
勿論、これらの装置では、トナーとキャリアを含む二成分系現像剤を用いる現像に使用することもできる。
【００９１】
次に本発明の現像剤担持体が組み込まれる二成分現像装置について説明例示する。
【００９２】
図１０において、現像容器２２５の現像室２４５内に、矢印ａ方向に回転される静電潜像保持体２２４に対向して現像剤担持体としての非磁性現像スリーブ（現像剤担持体）２２１を備えており本発明においてはここには図示しきれない樹脂被覆層が設けられている。この現像スリーブ２２１内に磁界発生手段としての磁性ローラー２２２が不動に放置されており、磁性ローラー２２２は略頂部の位置から矢印ｂの回転方向に順にＳ１、Ｎ１、Ｓ２、Ｎ２、Ｎ３に着磁されている。現像室２４５内には、トナー２４０と磁性キャリア２４３とを混合した二成分現像剤２４１が収容されている。
【００９３】
この現像剤２４１は、現像室２４５の一端で上端開放の隔壁２４８の図示しない一方の開口を通って現像容器２２５の撹拌室２４２内に送られると、トナー室２４７から撹拌室２４２内に供給されたトナー２４０が補給され、撹拌室２４２内の第１現像剤撹拌・搬送手段２５０によって混合しながら、撹拌室２４２の他端に搬送される。撹拌室２４２の他端に搬送された現像剤２４１は、隔壁２４８の図示しない他方の開口を通って現像室２４５内に戻され、そこで現像室２４５内の第２現像剤撹拌・搬送手段２５１と、現像室２４５内上部で搬送手段２５１による搬送方向と逆方向に現像剤を搬送する第３現像剤撹拌・搬送手段により、撹拌・搬送されながら現像スリーブ２２１に搬送される。現像スリーブ２２１に供給された現像剤２４１は、上記の磁石ローラ２２２の磁力の作用により磁気的に拘束され、現像スリーブ２２１上に担持され、現像スリーブ２２１の略頂部上に設けた現像剤規制部材ブレード２２３での規制によって現像スリーブ２２１上で現像剤２４１の薄層に形成されながら、現像スリーブ２２１の矢印ｂ方向への回転に伴い潜像保持体２２４と対向した現像部Ｃへと搬送され、そこで潜像保持体２２４上の静電潜像の現像に供される。現像に消費されなかった残余の現像剤２４１は、現像スリーブ２２１の回転により現像容器２２５内に回収される。現像容器２２５内では同趣のＮ２、Ｎ３間での反発磁界により現像スリーブ２２１上に磁気的に拘束されている現像残りの残余の現像剤２４１を剥ぎ取るようになっている。上記の磁極Ｎ２により現像剤２４１が磁力線に沿って穂立ちしたときのトナー飛散を防止するために、現像容器２の下部には弾性シール部材２３１がその一端を現像剤２４１を接触するようにして固定、設置されている。図１０はあくまでも模式的な例であり、容器の形状、撹拌部材の有無、磁極の配置等に様々な形態があることは言うまでもない。
【００９４】
図６は、トナー５０４として非磁性一成分現像剤を用いる場合の現像装置を表わす模式図である。ここにおいて、トナーは非磁性であるため、現像スリーブ内の磁石は存在せず、スリーブとしては、中実の金属棒５１４が用いられている。非磁性トナーは層厚規制ブレード５１１、あるいはスリーブコート層５１７との摩擦により摩擦帯電され、現像スリーブ５０８の表面上に担持され搬送される。
【００９５】
図７においては、剥ぎ取り部材５１２が設置されている。剥ぎ取り部材としては樹脂、ゴム、スポンジなどのローラー部材やさらに、ベルト部材、ブラシ部材などが用いられる、図においてローラー状部材５１２は現像スリーブ５０８とは反対方向に回転されている。感光体５０１に現像移行されなかった現像剤を剥ぎ取り部材により一旦スリーブ表面から剥ぎ取ることにより、スリーブ上の不動トナーの発生を防いだり、現像剤の帯電を均一化する働きを有する。また現像スリーブ５０６には、金属の円筒管が用いられている。
【００９６】
上述の感光ドラムの如き静電潜像保持体や現像装置、クリーニング手段などの構成要素のうち、複数のものを装置ユニットとして一体に結合してプロセスカートリッジを構成し、このプロセスカートリッジを装置本体に対して着脱可能に構成しても良い。例えば、帯電手段及び現像装置を感光ドラムとともに一体に支持してプロセスカートリッジを形成し、装置本体に着脱自在の単一ユニットとし、装置本体のレールなどの案内手段を用いて着脱自在の構成にしても良い。このとき、上記のプロセスカートリッジのほうにクリーニング手段を伴って構成しても良い。
【００９７】
図１１と１２は、本発明に関わるプロセスカートリッジの一実施例を示している。図１１では、現像装置８１、ドラム状の静電潜像保持体（感光ドラム）８３、クリーナー９４、一次帯電器９１を一体としたプロセスカートリッジ９９が例示される。
【００９８】
プロセスカートリッジにおいては、現像装置８１のトナー９３がなくなった時に新たなカートリッジと交換される。
【００９９】
図１１において、一次帯電手段としては、接触帯電手段として帯電ローラー９１を用いているが、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。転写手段としては、転写ローラー８４を用いている。転写手段としては、転写ブレード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、こちらも転写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。
【０１００】
次に、本発明の現像装置で用いられる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。
【０１０１】
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。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、テルペン樹脂、フェノール樹脂、脂肪族又は脂環族炭化水素樹脂、芳香族系石油樹脂、パラフィンワックス、カルナバワックスなどが単独或は混合して使用できる。
【０１０２】
また、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・バイオレット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。
【０１０３】
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質量に対して１５〜７０質量％が良い。
【０１０４】
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、硬化ヒマシ油およびその誘導体、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。
【０１０５】
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、ブセチルアセトン金属錯体、芳香族ハイドロキジカルボン酸、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およびその金属塩、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。
【０１０６】
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、および１分子当り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。
【０１０７】
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積した後、濾過或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の水あるいは水一溶媒中で加水分解させ、ここにピグメントを浸積し後、同様に固液分離を行い乾燥するものである。
【０１０８】
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ェ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。
【０１０９】
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ない得る。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。
【０１１０】
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、およ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、例えば水相中に適当な撹拌機を用いて適度な粒径に分散し、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。
【０１１１】
トナーはキャリアと混合して二成分現像剤として用いることもできる。
【０１１２】
キャリア材料としては、例えば、鉄、ニッケル、コバルトといった磁性体金属、及びそれらの合金、或いは希土類を含有する合金類、ヘマタイト、マグネタイト、マンガン−亜鉛系フェライト、ニッケル−亜鉛系フェライト、マンガン−マグネシウム系フェライト及びリチウム系フェライト等のソフトフェライト、銅−亜鉛系フェライトといった鉄系酸化物、およびそれらの混合物、さらには、ガラス、炭化ケイ素などのセラミックス粒子、樹脂粉体、磁性体を含有する樹脂粉体などをあげることができ、通常は平均粒径が２０〜３００μｍ程度の粒状物として用いる。
【０１１３】
このようなキャリアは上記に挙げた粒状物を直接キャリア粒子として用いるても良いが、トナーの摩擦帯電電荷を調整したりキャリアヘのトナースペントを防止したりするために、シリコーン樹脂、フッ素樹脂、アクリル樹脂、フェノール樹脂等のコート剤により適宜粒子表面に樹脂コートを施して用いることもできる。
【０１１４】
【実施例】
次に具体的な実施例をもって本発明をさらに詳しく説明する。
【０１１５】
＜実施例１＞
以下のような樹脂組成物を調製した。
・フェノール樹脂中間体　　　　　　　　　　　　　　　　　　　２５０質量部
・導電性カーボンブラック　　　　　　　　　　　　　　　　　　　１５質量部
・結晶性グラファイト（平均粒径４．３μｍ）　　　　　　　　　　８５質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　３５０質量部
【０１１６】
これらの材料を、ガラスビーズを用いた横形連続式サンドミルにより分散し、塗料原液Ａを得た。この原液Ａの粒度分布を測定したところ平均粒径は３．９μｍであった。
【０１１７】
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・ホウ酸アルミニウム粒状物（平均粒径３．５μｍ）　　　　　　１００質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　３２５質量部
塗料原液Ａに、ホウ酸アルミニウム粒状物およびメタノールを上記組成にてさらに加え、サンドミルにてホウ酸アルミニウム粒状物を分散した。この分散液をさらにメタノールにて希釈し、２５０メッシュおよび５００メッシュの篩いを通過させた（塗料１）。この時の塗料１の粘度は、９０ｍＰａ・ｓであった。アルミニウム円筒管を研削加工し、外径３２ｍｍφ、表面粗さＲａ＝０．２μｍ、振れ５〜１０μｍ程度とし、これに片側に現像スリーブ用フランジを取り付けたワークを用意した。回転台にワークを立て、スリーブ端部をマスキングしながら回転させ、上記塗料１をスプレーガンにて、一定速度で下降させながらワークにスプレー塗布し、塗布スリーブを得た。これを通風式乾燥機にて１５０℃、３０分間、乾燥硬化させ樹脂表面層を形成させた。この時の表面樹脂被覆層の厚みは１３．４μｍ、表面粗さは平均でＲａ＝０．７２μｍであった。また被覆層の体積低抗値は、１．１３Ω・ｃｍであった。
【０１１８】
この現像スリーブにマグネットを装着してステンレス製フランジを嵌合し、キヤノン社製複写機ＮＰ−６０８５改造機の現像装置に装着可能とした。本実験に用いたＮＰ−６０８５改造機は、８５枚機を９５枚機に改造したものであり、プロセススピードは、５１３ｍｍ／ｓｅｃのものを５７３ｍｍ／ｓｅｃにアップさせ、且つドラム周速に対し、スリーブ周速を１．８倍とした。磁性トナー（下記）を補給しながら、１００万枚までの連続耐久を行い、評価を行った。評価としては、総合的な画像評価および被覆層の耐久性を判断基準とした。環境は、２４℃／１０％の常温低湿（Ｎ／Ｌ）環境と、３０℃／８０％の高温高湿（Ｈ／Ｈ）環境にて行った。結果を表１および２に示す。画像および耐久性共に良好な結果が得られた。トナーとしては、下記のものを用いた。
【０１１９】
・スチレン−ブチルアクリレート系樹脂　　　　　　　　　　　　１００質量部
・マグネタイト　　　　　　　　　　　　　　　　　　　　　　　　９５質量部
・低分子量ポリプロピレンワックス　　　　　　　　　　　　　　　　４質量部
・ジターシャリーブチルサリチル酸のＡｌ錯体（負電荷制御剤）　　　３質量部
上記材料をヘンシェルミキサーで分散混合後、１３０℃に加熱された二軸エクストルーダーで溶融混練し、冷却した混合物をハンマーミルで粗粉砕した。粗粉砕物をジェットミルで微粉砕し、得られた微粉砕物を風力分級機で分級し、トナーの粒度分布が、質量平均粒径７．２μｍ、４μｍ以下の粒子の個数割合が１７．５％、１２．７μｍ以上の粒子の質量割合が０．９％の磁性トナーを得た。このトナー１００質量部に、シランカップリング剤で疎水化処理したコロイダルシリカ０．９質量部、およびチタン酸ストロンチウム微粒子３質量部をヘンシェルミキサーにて外添して用いた。
【０１２０】
＜物性及び画像の測定方法及び評価方法＞
トナーおよび現像スリーブの物性測定、及び、得られた画像の評価については、下記に示す方法にて行った。
【０１２１】
［測定方法］
（１）中心線平均粗さ（Ｒａ）の測定ＪＩＳＢ０６０１の表面粗さに基づき、小坂研究所製サーフコーダーＳＥ−３３００にて、軸方向３点Ｘ周方向２点＝６点について各々測定し、その平均値をとった。
【０１２２】
（２）被覆層の体積抵抗の測定
１００μｍの厚さのＰＥＴシート上に７〜２０μｍの厚さの被覆層を形成し、ＡＳＴＭ規格（Ｄ−９９１−８２）及び、日本ゴム協会標準規格ＳＲＩＳ（２３０１−１９６９）に準拠した、導電性ゴム及びプラスチックの体積低抗測定用の４端子構造の電極を設けた電圧降下式デジタルオーム計（川口電機製作所製）を使用して測定した。尚、測定環境は２０〜２５℃、５０〜６０ＲＨ％とする。
【０１２３】
（３）グラファイト・炭素粒子の粒径測定
レーザー回折型粒度分布計のコールターＬＳ−１３０型粒度分布計（コールター社製）を用いて測定する。測定方法としては、水系モジュールを用い、測定溶媒としては純水を使用する。純水にて粒度分布計の測定系内を約５分間洗浄し、消泡剤として測定系内に亜硫酸ナトリウムを１０〜２５ｍｇ加えて、バックグラウンドファンクションを実行する。
【０１２４】
次に純水１０ｍｌ中に界面活性剤３〜４滴を加え、更に測定試料を５〜２５ｍｇ加える。試料を懸濁した水溶液は超音波分散機で約１〜３分間分散処理を行ない試料液を得て、前記測定装置の測定系内に試料液を徐々に加えて、装置の画面上のＰＩＤＳが４５〜５５％になるように測定系内の試料濃度を調整して測定を行い、個数分布から算術した個数平均粒径および体積平均粒径を求める。有機溶媒中に分散された塗料を測定する際には、有機溶剤用の循環モジュールを用いて同様に測定を行う。
【０１２５】
（４）ホウ酸アルミニウム粒子の粒径測定
電子顕微鏡を用いて、ホウ酸アルミニウム粒子の粒径を測定する。撮影倍率は１千〜１万倍とする。写真上で１次粒子の粒径を測る。この際、長軸と短軸を測り、平均した値を粒径とする。これを、１００サンプルについて測定し、５０％値をもって平均粒径とする。
【０１２６】
（５）トナーおよび樹脂粒子粒径の測定
コールターカウンターのマルチサイザーＩＩ（コールター社製）を用いて測定し、体積分布から出した質量基準の質量平均径を求めた。
【０１２７】
（６）樹脂被覆層の膜厚（削れ量）の測定
ＫＥＹＥＮＣＥ社製レーザー寸法測定器を用いた。コントローラＬＳ−５５００およびセンサーヘッドＬＳ−５０４０Ｔを用い、スリーブ固定治具およびスリーブ送り機構を取り付けた装置にセンサー部を別途固定し、スリーブの外径寸法の平均値から測定を行った。測定はスリーブ長手方向に対し３０分割して３０箇所測定し、さらにスリーブを周方向に９０°回転させた後さらに３０箇所、計６０箇所の測定を行い、その平均値をとった。表面被覆層塗布前のスリーブの外径を予め測定しておき、表面被覆層形成後の外径、さらに耐久使用後の外径を測定し、その差分をコート膜厚および削れ量とした。
【０１２８】
［評価方法］
（１）画像濃度
複写機においては、画像比率５．５％のテストチャート上の５ｍｍφ黒丸のコピー画像濃度を、反射濃度計ＲＤ９１８（マクベス製）により反射濃度測定を行い、５点の平均値をとって画像濃度とした。また、ＬＢＰにおいては、キャラクタージェネレーターを用いて信号を送りプリンターで出力した、５ｍｍ■のプリント画像濃度を同様に測定し画像濃度とした。
【０１２９】
（２）カブリ
現像適性条件における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）をカブリ濃度とした。反射率はＴＣ−６ＤＳ（東京電色製）で測定した。ここで、測定値を目視で判断した場合、１．５以下は目視ではほとんど確認できないレベル、２．０〜３．０程度はよく見ると確認できるレベル、４．０を超えると一見してカブリが確認できるレベルである。
【０１３０】
（３）トナー帯電量（Ｑ／Ｍ）及びトナー搬送量（Ｍ／Ｓ）
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引捕集し、その際金属円筒管を通じてコンデンサーに蓄えられた電荷量Ｑ、捕集されたトナー質量Ｍと、トナーを吸引した面積Ｓから、単位質量当たりの電荷量Ｑ／Ｍ（ｍＣ／ｋｇ）と単位面積当たりのトナー質量Ｍ／Ｓ（ｄｇ／ｍ^２）を計算し、それぞれトナー帯電量（Ｑ／Ｍ）、トナー搬送量（Ｍ／Ｓ）とした。
【０１３１】
（４）ブロッチ（画像不良）
ベタ黒、ハーフトーン、ライン画像等の各種画像及び、その際、現像スリーブ上の波状ムラ、及びブロッチ（斑点状ムラ）等、スリーブ上でのトナーコート不良の目視による観察を参考にして、評価結果を下記の指標で示した。
◎　：画像にもスリーブ上にも全く確認できない。
○　：スリーブ上でわずかに確認できるが、画像ではほとんど確認できない。
○△：数枚〜数十枚に１枚程度画像を透かしてみると確認できる。
△○：ハーフトーン画像又はベタ黒画像の１枚目で、スリーブ周期の１周目に確認できる。
△　：ハーフトーン画像又はベタ黒画像で確認できる。実用レベル下限。
△×：ベタ黒画像全体で画像不良が確認できる。実用不可レベル。
×　：ベタ白画像上にも確認できる。
【０１３２】
（５）ハーフトーン均一性（白スジ、白帯）
特にハーフトーンに発生する、画像進行方向に走る、線状、帯状のスジについて、下記指標にて評価した。
◎　：画像にもスリーブ上にも全く確認できない。
Ｏ　：良く見るとわずかに確認できるが、一見ではほとんど確認できない。
○△：ハーフトーンではわずかに確認されるが、ベタ黒では問題ないレベル。
△○：ハーフトンでは、スジが確認できるが、ベタ黒ではほんのわずか確認できるレベル。
△　：ベタ黒画像でも濃淡差が確認できるが、実用レベル下限程度。
△×：ベタ黒画像全体で濃淡差が目立つ。実用不可レベル。
×　：濃度が低く、スジの多い画像。
【０１３３】
（６）スリーブゴースト
画像耐久中にベタ白を流した後、画像チャートのスリーブ一周分の白上にベタ黒の太文字や象形画像を置き、残り部分をハーフトーンとした画像チャートを用い、ハーフトーン上に太文字や象形画像のゴーストがどの程度発生するかで評価した。
◎　：ゴーストなし。
○　：ごくわずかに濃淡差がみられるが良好
○△：やや濃淡差が確認できるが問題とならないレベル
△○：○△と△の中問レベル
△　：ややゴーストが目立つ。実用レベル内。
Ｎ１：実用には問題となるネガゴースト（ゴースト部が薄い）がスリーブ１周分出る
Ｐ１：実用には問題となるポジコースト（ゴースト部が濃い）がスリーブ１周分出る
Ｎ２：実用には問題となるネガゴーストがスリーブ２周分以上出る
Ｐ２：実用には問題となるポジコーストがスリーブ２周分以上出る
【０１３４】
＜実施例２＞
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・ホウ酸アルミニウム粒状物（平均粒径５．２μｍ）　　　　　　　８０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２９５質量部
とした以外は実施例１と同様に塗料を調製した（塗料２）。この塗料の粘度は８５ｍＰａ・ｓであった。実施例１と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．２μｍ、表面粗さＲａ＝０．９４μｍであった。また被覆層の体積抵抗値は、１．１０Ω・ｃｍであった。この現像スリーブを用いて実施例１と同様の評価を行った。結果を表１および２に示す。
【０１３５】
＜比較例１＞
原液Ａをメタノールで希釈した後、篩い操作を行い塗料とした（塗料５１）。この塗料の粘度は６５ｍＰａ・ｓであった。実施例１と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．０μｍ、表面粗さＲａ＝０．４４μｍであった。また被覆層の体積抵抗値は、０．９４Ω・ｃｍであった。この現像スリーブを用いて実施例１と同様の評価を行った。耐久により樹脂表面被覆層が削れていたため表面粗さが低下し画像欠陥が発生した。結果を表１および２に示す。
【０１３６】
＜比較例２＞
原液Ａ（比較例１の塗料５１）において、結晶性グラファイトの平均粒径を４．３μｍからｌ０．２μｍに替え、原液Ｂを作製した。分散後のこの原液Ｂの粒度分布を測定したところ平均粒径は９．５μｍであった。原液Ｂをメタノールで希釈した後、前い操作を行い塗料とした（塗料５２）。この塗料の粘度は６７．５ｍＰａ・ｓであった。実施例１と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１４．０μｍ、表面粗さＲａ＝０．８９μｍであった。また被覆層の体積抵抗値は、１．０２Ω・ｃｍであった。この現像スリーブを用いて実施例１と同様の評価を行った。グラファイトが樹脂表面被覆層の粗さ形成の主要粒子であったため、耐久による削れが大きく耐久により画像欠陥が発生した。結果を表１および２に示す。
【０１３７】
＜比較例３＞
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・架橋タイプＰＭＭＡ球状粒子（平均粒径４．８μｍ）　　　　　　８０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２９５質量部
とした以外は実施例１と同様に塗料を調整した（塗料５３）。この塗料の粘度は８２．５ｍＰａ・ｓであった。実施例１と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．５μｍ、表面粗さＲａ＝１．００μｍであった。また被覆層の体積抵抗値は、１．２５Ω・ｃｍであった。この現像スリーブを用いて実施例１と同様の評価を行った。耐久により表面粗さが低下し画像欠陥が発生した。結果を表１および２に示す。
【０１３８】
＜比較例４＞
実施例１と同様のアルミニウム円筒管をサンドブラスト処理により表面粗さＲａ＝１．５０μｍに粗した。このワークを用い、比較例１の塗料５１を用いて実施例１と同様の方法にてブラスト表面に樹脂被覆層を形成した。この時の表面樹脂被覆層の厚みは１１．７μｍ、表面粗さＲａ＝０．９９μｍであった。また被覆層の体積低抗値は比較例１と同等であった。この現像スリーブを用いて実施例１と同様の評価を行った。下地にブラストを施しても樹脂自体の削れは比較例１と変わらず、凸部から削れが進んでいくために耐久により平滑化し画像欠陥が発生した。また、ブラストによりアルミニウム円筒管が変形したことが原因で、スリーブピッチでの濃度ムラが発生した。結果を表１および２に示す。
【０１３９】
＜実施例３＞
以下のような樹脂組成物を調製した。
・ポリウレタン樹脂　　　　　　　　　　　　　　　　　　　　　２５０質量部
・導電性カーボンブラック　　　　　　　　　　　　　　　　　　　２０質量部
・結晶性グラファイト（平均粒径４．３μｍ）　　　　　　　　　　８０質量部
・トルエン・ＭＩＢＫ・ＩＰＡの混合溶媒　　　　　　　　　　　５２５質量部
【０１４０】
これらの材料を、ガラスビーズを用いた横形連続式サンドミルにより分散し、塗料原液Ｃを得た。この原液Ｃの粒度分布を測定したところ平均粒径は４．０μｍであった。
【０１４１】
・塗料原液Ｃ　　　　　　　　　　　　　　　　　　　　　　　　８７５質量部
・ホウ酸アルミニウム粒状物（平均粒径３．５μｍ）　　　　　　　５０質量部
・下記式（１）のイミダゾール化合物（平均粒径４．１μｍ）　　　５０質量部
・トルエン・ＭＩＢＫ・ＩＰＡの混合溶媒　　　　　　　　　　　３１０質量部
塗料原液Ｃに、ホウ酸アルミニウム粒状物、イミダゾール化合物、および上記混合溶媒を上記組成にてさらに加え、サンドミルにてホウ酸アルミニウム粒状物およびイミダゾール化合物を分散した。この分散液をさらに混合溶媒にて希釈し、２５０メッシュおよび５００メッシュの篩いを通過させた（塗料３）。この時の塗料３の粘度は、５０ｍＰａ・ｓであった。この塗料を用いて実施例１と同様の方法で表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１２．９μｍ、表面粗さＲａ＝０．８１μｍであった。また被覆層の体積抵抗値は、１．１６Ω・ｃｍであった。この現像スリーブを用いて実施例１と同様の評価を行った。結果を表１および２に示す。
【０１４２】
＜実施例４＞
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・ホウ酸アルミニウム粒状物（平均粒径３．５μｍ）　　　　　　　９０質量部
・下記式（１）のイミダゾール化合物（平均粒径４．１μｍ）　　　１０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　３２５質量部
塗料原液Ａに、ホウ酸アルミニウム粒状物およびメタノールを上記組成にてさらに加え、サンドミルにてホウ酸アルミニウム粒状物を分散した。この分散液をさらにメタノールにて希釈し、２５０メッシュおよび５００メッシュの篩いを通過させた（塗料４）。この時の塗料４の粘度は、９２．５ｍＰａ・ｓであった。この塗料を用いて実施例１と同様の方法で表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．８μｍ、表面粗さＲａ＝０．７９μｍであった。また被覆層の体積抵抗値は、１．０３Ω・ｃｍであった。この現像スリーブを用いて実施例１と同様の評価を行った。トナーは下記のものを用いた。
【０１４３】
・ポリエステル系樹脂　　　　　　　　　　　　　　　　　　　　１００質量部
・マグネタイト　　　　　　　　　　　　　　　　　　　　　　　　９５質量部
・アルコール系ワックス　　　　　　　　　　　　　　　　　　　　　４質量部
・ジターシャリーブチルサリチル酸のＡｌ錯体（負電荷制御剤）　　　４質量部
上記材料をヘンシェルミキサーで分散混合後、１３０℃に加熱された二軸エクストルーダーで溶融混練し、冷却した混合物をハンマーミルで粗粉砕した。粗粉砕物をジェットミルで微粉砕し、得られた微粉砕物を風力分級機で分級し、トナーの粒度分布が、質量平均粒径７．０μｍ、４μｍ以下の粒子の個数割合が１８．５％、１２．７μｍ以上の粒子の質量割合が０．８％の磁性トナーを得た。このトナー１００質量部に、シランカップリング剤で疎水化処理したコロイダルシリカ１．０質量部、およびチタン酸ストロンチウム微粒子４質量部をヘンシェルミキサーにて外添して用いた。結果を表１および２に示す。
【０１４４】
＜比較例５＞
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・架橋タイプＰＭＭＡ粒子（平均粒径４．６μｍ）　　　　　　　　７０質量部
・下記式（１）のイミダゾール化合物（平均粒径４．１μｍ）　　　１０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２９５質量部
【０１４５】
実施例４において、ホウ酸アルミニウム粒状物に替えてＰＭＭＡ粒子を用いて実施例１と同様な方法で塗料を調製した（塗料５５）。この時の塗料５５の粘度は、８７．５ｍＰａ・ｓであった。この塗料を用いて実施例１と同様の方法で表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１４．１μｍ、表面粗さＲａ＝０．９１μｍであった。また被覆層の体積低抗値は、１．１３Ω・ｃｍであった。この現像スリーブを用いて実施例４と同様の評価を行った。結果を表１および２に示す。
【０１４６】
【化５】

【０１４７】
＜実施例５＞
以下のような樹脂組成物を調製した。
・フェノール樹脂中間体　　　　　　　　　　　　　　　　　　　１００質量部
・導電性カーボンブラック　　　　　　　　　　　　　　　　　　　２０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　１２０質量部
【０１４８】
これらの材料を、ガラスビーズを用いた横形連続式サンドミルにより分散し、塗料原液Ｄを得た。
・塗料原液Ｄ　　　　　　　　　　　　　　　　　　　　　　　　２４０質量部
・ホウ酸アルミニウム粒状物（平均粒径２．８μｍ）　　　　　　１００質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２１０質量部
【０１４９】
塗料原液Ｄに、ホウ酸アルミニウム粒状物およびメタノールを上記組成にてさらに加え、サンドミルにてホウ酸アルミニウム粒状物を分散した。この分散液をさらにメタノールにて希釈し、３５０メッシュの篩いを通過させた（塗料５）。この時の塗料５の粘度は、５５ｍＰａ・ｓであった。アルミニウム円筒管を研削加工し、外径３２ｍｍφ、表面粗さＲａ＝０．２μｍ、振れ５〜１０μｍ程度とし、これに片側に現像スリーブ用フランジを取り付けたワークを用意した。回転台にワークを立て、スリーブ端部をマスキングしながら回転させ、上記塗料５をスプレーガンにて、一定速度で下降させながらワークにスプレー塗布し、塗布スリーブを得た。これを通風式乾燥機にて１５０℃、３０分間、乾燥硬化させ樹脂表面層を形成させた。この時の表面樹脂被覆層の厚みは１８．５μｍ、表面粗さは平均でＲａ＝０．６０μｍであった。また被覆層の体積抵抗値は、１２．３Ω・ｃｍであった。
【０１５０】
この現像スリーブにマグネットを装着してステンレス製フランジを嵌合し、キヤノン社製複写機ＣＬＣ−１０００の現像装置に装着可能とした。シアントナーを用い、５万枚までの画出し評価を行い、その後現像スリーブの耐久性を確認するため、２０万枚相当までの空回転テストを行い被膜の削れおよび表面粗さを確認し、また新現像剤に交換した時の特性評価を行った。環境は２４℃／６０％の常温常湿（Ｎ／Ｎ）環境にて行った。現像剤としては次のようなものを用いた。
【０１５１】
・ポリエステル系樹脂　　　　　　　　　　　　　　　　　　　　１００質量部
・フタロシアニン顔料（シアン）　　　　　　　　　　　　　　　　　５質量部
・ジターシャリーブチルサリチル酸のＡｌ錯体　　　　　　　　　　　６質量部
ポリエステル樹脂の５質量部とフタロシアニン顔料５質量部は、予め３本ロールを用いて十分に混練を行いマスターバッチを作製しておく。粉砕されたマスターバッチ、残りのポリエステル樹脂、ジターシャリーブチルサリチル酸のＡｌ錯体をヘンシェルミキサーを用いて十分に混合した後、１１０℃に加熱された二軸エクストルーダーで溶融混練し、冷却した混合物をハンマーミルで粗粉砕した。粗粉砕物をジェットミルで微粉砕し、得られた微粉砕物を風力分級機で分級し、トナーの粒度分布が、質量平均粒径８．１μｍ、４μｍ以下の粒子の個数割合が９．５％、１２．７μｍ以上の粒子の質量割合が１．８％のシアントナーを得た。このトナー１００質量部に、疎水性の酸化チタン微粒子１．８質量部をヘンシェルミキサーにて外添トナーとした。平均粒径が３５〜５０μｍの間に分級されたフェライト粒子にシリコーン系樹脂を１．０％添加して混合し加熱硬化させた後解砕し、篩い処理を行い、現像用キャリアとした。上記トナーＴとキャリアＣをＴ／Ｃ比率が７％となるように混合しスタート剤とした。
【０１５２】
結果を表３に示す。
【０１５３】
＜実施例６＞
・塗料原液Ｄ　　　　　　　　　　　　　　　　　　　　　　　　２４０質量部
・ホウ酸アルミニウム粒状物（平均粒径２．８μｍ）　　　　　　　６０質量部
・ホウ酸アルミニウム粒状物（平均粒径７．８μｍ）　　　　　　　３０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　１９０質量部
とした以外は実施例５と同様にして塗料を調製した。この塗料の粘度は５２．５ｍＰａ・ｓであった。実施例５と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１９．５μｍ、表面粗さＲａ＝０．９１μｍであった。また被覆層の体積抵抗値は、１１．０Ω・ｃｍであった。この現像スリーブを用いて実施例５と同様の評価を行った。結果を表３に示す。
【０１５４】
＜比較例６＞
原液Ｄをメタノールで希釈した後、篩い操作を行い塗料とした（塗料５６）。この塗料の粘度は３０ｍＰａ・ｓであった。実施例１と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１７．０μｍ、表面粗さＲａ＝０．２５μｍであった。また被覆層の体積抵抗値は、９．６Ω・ｃｍであった。この現像スリーブを用いて実施例５と同様の評価を行った。十分な表面粗さが得られないため画像欠陥が発生した。また樹脂表面被覆層が削れていたため基体表面が露出しはじめていた。結果を表３に示す。
【０１５５】
＜比較例７＞
アルミニウム円筒管を＃１５０のガラスビーズを用いてサンドブラスト処理を行い、表面粗さＲａ＝０．８５μｍの粗し表面を得た。この現像スリーブを用いて実施例５と同様の評価を行った。結果を表３に示す。耐久による表面粗さの低下が著しかった。またトナーによるスリーブ汚染も発生していた。
【０１５６】
＜比較例８＞
アルミニウム円筒管に替えてステンレス製円筒管を用いた。ステンレス自体硬いためガラスビーズが割れて所定の粗さを得ることがきびしいためブラストはアランダム＃１５０にて行った。表面粗さＲａ＝０．８６μｍの粗し表面を得た。この現像スリーブを用いて実施例５と同様の評価を行った。アルミニウム円筒管のような表面粗さの低下は見られなかったが、トナーによるスリーブ汚染が発生していた。結果を表３に示す。
【０１５７】
＜実施例７＞
・ポリウレタン樹脂　　　　　　　　　　　　　　　　　　　　　１００質量部
・導電性カーボンブラック　　　　　　　　　　　　　　　　　　　１０質量部
・結晶性グラファイト（平均粒径４．３μｍ）　　　　　　　　　　１０質量部
・トルエン・ＭＩＢＫ・ＩＰＡの混合溶媒　　　　　　　　　　　１２０質量部
【０１５８】
これらの材料を、ガラスビーズを用いた横形連続式サンドミルにより分散し、塗料原液Ｅを得た。
【０１５９】
・塗料原液Ｅ　　　　　　　　　　　　　　　　　　　　　　　　２４０質量部
・ホウ酸アルミニウム粒状物（平均粒径２．８μｍ）　　　　　　　６０質量部
・ホウ酸アルミニウム粒状物（平均粒径７．８μｍ）　　　　　　　３０質量部
・トルエン・ＭＩＢＫ・ＩＰＡの混合溶媒　　　　　　　　　　　２１０質量部
塗料原液Ｅに、ホウ酸アルミニウム粒状物およびトルエン・ＭＩＢＫ・ＩＰＡの混合溶媒を上記組成にてさらに加え、サンドミルにてホウ酸アルミニウム粒状物を分散した。この分散液をさらにトルエン・ＭＩＢＫ・ＩＰＡの混合溶媒にて希釈し、３５０メッシュの箭いを通過させた（塗料７）。この時の塗料７の粘度は、４７．５ｍＰａ・ｓであった。実施例１と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１８．８μｍ、表面粗さＲａ：０．８９μｍであった。また被覆層の体積低抗値は、１５．４Ω・ｃｍであった。この現像スリーブを用いて実施例５と同様の評価を行った。結果を表３に示す。
【０１６０】
スリーブ汚染評価は次のような基準で判定した。基本的にはスリーブの一部をエアーでトナーを吹き飛ばした後、ウエスでかるく拭き、さらにエタノールを浸したウエスでこすり、その汚れ具合で判定した。
◎　：汚染なし。
○　：溶剤を浸したウエスにわずかに青みがつく程度。
△　：溶剤なしでもウエスは青く汚れる
△×：簡単なエアー吹きでは汚染が飛んで行かないのがわかる。ウエスはかなり汚れる。
×　：かなり強固な付着状態である。
【０１６１】
＜実施例８＞
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・ホウ酸アルミニウム粒状物（平均粒径９．８μｍ）　　　　　　　４０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２３５質量部
【０１６２】
塗料原液Ａに、ホウ酸アルミニウム粒状物およびメタノールを上記組成にてさらに加え、サンドミルにてホウ酸アルミニウム粒状物を分散した。この分散液をさらにメタノールにて希釈し、２５０メッシュおよび５００メッシュの篩いを通過させた（塗料８）。この時の塗料８の粘度は、７０ｍＰａ・ｓであった。片側にアルミニウムフランジのついたアルミニウム円筒管を一体に研削加工し、外径２０ｍｍφ、表面粗さＲａ＝０．２μｍ、振れ５μｍ程度とした。回転台にワークを立て、スリーブ端部をマスキングしながら回転させ、上記塗料８をスプレーガンにて、一定速度で下降させながらワークにスプレー塗布し、塗布スリーブを得た。これを通風式乾燥機にて１５０℃、３０分間、乾燥硬化させ樹脂表面層を形成させた。この時の表面樹脂被覆層の厚みは１２．８μｍ、表面粗さは平均でＲａ＝１．５８μｍであった。また被覆層の体積低抗値は、０．９７Ω・ｃｍであった。
【０１６３】
この現像スリーブにマグネットを装着して残りの片側にアルミニウム製フランジを嵌合し、キヤノン社製レーザービームプリンターＬＢＰ−９３０改造機のカートリッジの現像装置に装着可能とした。本実験に用いたＬＢＰ−９３０改造機は、ＬＢＰ−９３０をべースにＡ４横送り２４枚機を５０枚相当に改造したものであり、プロセススピードを１０６ｍｍ／ｓｅｃから２３６ｍｍ／ｓｅｃにアップさせ、且つドラム周速に対し、スリーブ周速を１．３倍とした。さらにトナー容器のキャパシティーを上げている。さらに高速化による現像剤規制ブレードでの規制不均一を防ぐため規制部材に金属板で補強を施しブレード圧接力を強めている。また本体およびカートリッジにはそれぞれメカ的強度補強を加えている。外部のキャラクタージェネレーター（ＣＧ）から画像信号を送り、画像を出力させ画出しを行った。カートリッジのトナー残検が表示されるごとに磁性トナーを補給しながら６万枚までの連続耐久テストを行い、評価を行った。環境は２４℃／１０％ＲＨの常温低湿（Ｎ／Ｌ）環境と、３０℃／８０％ＲＨの高温高湿（Ｈ／Ｈ）環境にて行った。結果を表４および５に示す。
【０１６４】
トナーとしては、下記のものを用いた。
・スチレン−ブチルアクリレート系樹脂　　　　　　　　　　　　１００質量部
・マグネタイト　　　　　　　　　　　　　　　　　　　　　　　１００質量部
・低分子量ポリエチレンワックス　　　　　　　　　　　　　　　　　３質量部
・長鎖アルコール系ワックス　　　　　　　　　　　　　　　　　　　３質量部
・アゾ系Ｆｅ錯体化合物（負電荷制御剤）　　　　　　　　　　　　　３質量部
上記材料をヘンシェルミキサーで分散混合後、１３０℃に加熱された二軸エクストルーダーで溶融混練し、冷却した混合物をハンマーミルで粗粉砕した。粗粉砕物をジェットミルで微粉砕し、得られた微粉砕物を風力分級機で分級し、トナーの粒度分布が、質量平均粒径６．３μｍ、４μｍ以下の粒子の個数割合が１９．５％、１２．７μｍ以上の粒子の質量割合が０．４％の磁性トナーを得た。このトナー１００質量部に、シランカップリング剤およびシリコーンオイルで処理したコロイダルシリカ１．２質量部、およびチタン酸ストロンチウム微粒子０．５質量部をヘンシェルミキサーにて外添して用いた。
【０１６５】
＜実施例９＞
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・ホウ酸アルミニウム粒状物（平均粒径９．８μｍ）　　　　　　　３０質量部
・ホウ酸アルミニウム粒状物（平均粒径２．８μｍ）　　　　　　　３０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２６５質量部
とした以外は実施例８と同様に塗料を調製した（塗料９）。この塗料の粘度は５５ｍＰａ・ｓであった。実施例８と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．２μｍ、表面粗さＲａ＝１．５０μｍであった。また被覆層の体積低抗値は、１．０５Ω・ｃｍであった。この現像スリーブを用いて実施例８と同様の評価を行った。結果を表４および５に示す。
【０１６６】
＜実施例１０＞
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・ホウ酸アルミニウム粒状物（平均粒径９．８μｍ）　　　　　　　３０質量部
・式（１）のイミダゾール化合物（平均粒径４．１μｍ）　　　　　２０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２５０質量部
とし、ホウ酸アルミニウム粒状物を分散した後更にイミダゾール化合物を加えた以外は実施例８と同様に塗料を調製した（塗料１０）。この塗料の粘度は７５ｍＰａ・ｓであった。実施例８と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．２μｍ、表面粗さＲａ＝１．５８μｍであった。また被覆層の体積低抗値は、１．１１Ω・ｃｍであった。この現像スリーブを用いて実施例８と同様の評価を行った。結果を表４および５に示す。
【０１６７】
＜実施例１１＞
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・ホウ酸アルミニウム粒状物（平均粒径２．８μｍ）　　　　　　　３０質量部
・球状炭素粒子（平均粒径９．７μｍ）　　　　　　　　　　　　　３０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２６５質量部
とし、ホウ酸アルミニウム粒状物を分散した後更に球状炭素粒子を加えた以外は実施例８と同様に塗料を調製した（塗料１１）。この塗料の粘度は４７．５ｍＰａ・ｓであった。実施例８と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．２μｍ、表面粗さＲａ＝１．５５μｍであった。また被覆層の体積低抗値は、０．９５Ω・ｃｍであった。この現像スリーブを用いて実施例８と同様の評価を行った。結果を表４および５に示す。
【０１６８】
＜実施例１２＞
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・ホウ酸アルミニウム粒状物（平均粒径９．８μｍ）　　　　　　　２０質量部
・球状炭素粒子（平均粒径９．７μｍ）　　　　　　　　　　　　　２０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２３５質量部
とし、ホウ酸アルミニウム粒状物を分散した後更に球状炭素粒子を加えた以外は実施例８と同様に塗料を調製した（塗料１２）。この塗料の粘度は５２．５ｍＰａ・ｓであった。実施例８と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１４．０μｍ、表面粗さＲａ＝１．６５μｍであった。また被覆層の体積抵抗値は、０．９８Ω・ｃｍであった。この現像スリーブを用いて実施例８と同様の評価を行った。結果を表４および５に示す。
【０１６９】
＜実施例１３＞
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・ホウ酸アルミニウム粒状物（平均粒径１６．０μｍ）　　　　　　２０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２３５質量部
とした以外は実施例８と同様に塗料を調製した（塗料１３）。この塗料の粘度は５５ｍＰａ・ｓであった。実施例８と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．５μｍ、表面粗さＲａ＝１．６２μｍであった。また被覆層の体積低抗値は、０．９９Ω・ｃｍであった。この現像スリーブを用いて実施例８と同様の評価を行った。結果を表４および５に示す。
【０１７０】
＜実施例１４＞
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・ホウ酸アルミニウム粒状物（平均粒径２７．５μｍ）　　　　　　１５質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２３５質量部
とした以外は実施例８と同様に塗料を調製した（塗料１４）。この塗料の粘度は５５ｍＰａ・ｓであった。実施例８と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１４．６μｍ、表面粗さＲａ＝１．８２μｍであった。また被覆層の体積低抗値は、０．９８Ω・ｃｍであった。この現像スリーブを用いて実施例８と同様の評価を行った。結果を表４および５に示す。
【０１７１】
＜比較例９＞
原液Ａをメタノールで希釈した後、篩い操作を行い塗料とした（塗料５９）。この塗料の粘度は６０ｍＰａ・ｓであった。実施例８と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．１μｍ、表面粗さＲａ＝０．４０μｍであり、塗工条件を変えても表面粗さを大きくできなかった。また被覆層の体積低抗値は、０．９４Ω・ｃｍであった。この現像スリーブを用いて実施例８と同様の評価を行った。耐久により樹脂表面被覆層が削れていたため表面粗さが低下し画像欠陥が発生した。結果を表４および５に示す。
【０１７２】
＜比較例１０＞
原液Ａにおいて、結晶性グラファイトの平均粒径を４．３μｍから２５．０μｍに替え、原液Ｆを作製した。分散後のこの原液Ｂの粒度分布を測定したところ平均粒径は２３．５μｍであった。原液Ｆをメタノールで希釈した後、篩い操作を行い塗料とした（塗料６０）。この塗料の粘度は５７．５ｍＰａ・ｓであった。比較例９と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１４．８μｍ、表面粗さＲａ＝１．４８μｍであった。また被覆層の体積低抗値は、１．５４Ω・ｃｍであった。この現像スリーブを用いて実施例８と同様の評価を行った。グラファイトが樹脂表面被覆層の粗さ形成の主要粒子であったため耐久による削れが大きく耐久により画像欠陥が発生した。結果を表４および５に示す。
【０１７３】
＜比較例１１＞
塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
架橋タイプＰＭＭＡ球状粒子（平均粒径１０．３μｍ）　　　　　２０質量部
メタノール　　　　　　　　　　　　　　　　　　　　　　　　２３５質量部
とした以外は実施例８と同様に塗料を調製した（塗料６１）。この塗料の粘度は５２．５ｍＰａ・ｓであった。実施例８と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１４．５μｍ、表面粗さＲａ＝１．５２μｍであった。また被覆層の体積低抗値は、１．０８Ω・ｃｍであった。この現像スリーブを用いて実施例８と同様の評価を行った。表面粗さの低下が大きかった。結果を表４および５に示す。
【０１７４】
＜比較例１２＞
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・架橋タイプＰＭＭＡ球状粒子（平均粒径２６．３μｍ）　　　　　１５質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２３５質量部
とした以外は実施例８と同様に塗料を調製した（塗料６２）。この塗料の粘度は５０ｍＰａ・ｓであった。実施例８と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１４．６μｍ、表面粗さＲａ＝１．９０μｍであった。また被覆層の体積低抗値は、１．０５Ω・ｃｍであった。この現像スリーブを用いて実施例８と同様の評価を行った。表面粗さの低下が大きかった。結果を表４および５に示す。
【０１７５】
＜比較例１３＞
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・球状炭素粒子（平均粒径９．７μｍ）　　　　　　　　　　　　　３０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２２０質量部
とした以外は実施例８と同様に塗料を調製した（塗料６３）。この塗料の粘度は５０ｍＰａ・ｓであった。実施例８と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１４．６μｍ、表面粗さＲａ＝１．４９μｍであった。また被覆層の体積抵抗値は、１．００Ω・ｃｍであった。この現像スリーブを用いて実施例８と同様の評価を行った。球状炭素粒子自身は削れに対しかなりの強度を有しＰＭＭＡ粒子に比較すると表面粗さの変化は格段に小さいが、ホウ酸アルミニウム粒子に比較するとやや劣っていた。また、粒子自体の削れは小さく表面粗さを保持する効果は或程度持っているが、樹脂層の補強効果にはやや劣っていて膜厚の減少がやや大きかった。結果を表４および５に示す。
【０１７６】
＜比較例１４＞
実施例１と同様のアルミニウム円筒管を＃１００のアランダム砥粒にてサンドブラスト処理を行い、表面粗さＲａ＝２．１５μｍに粗した。このワークを用い、比較例９の塗料５９を用いて実施例８と同様の方法にてブラスト表面に樹脂被覆層を形成した。この時の表面樹脂被覆層の厚みは１１．５μｍ、表面粗さＲａ＝１．８９μｍであった。また被覆層の体積低抗値は比較例９と同等であった。この現像スリーブを用いて実施例８と同様の評価を行った。下地にブラストを施しても樹脂自体の削れは比較例９と変わらず、凸部から削れが進んでいくために表面が耐久により平滑化し画像欠陥が発生した。また、ブラストによりアルミニウム円筒管が変形したことが原因で、スリーブピッチでの濃度ムラが発生した。結果を表４および５に示す。
【０１７７】
【表１】

【０１７８】
【表２】

【０１７９】
【表３】

【０１８０】
【表４】

【０１８１】
【表５】

【０１８２】
以下、有機処理されたホウ酸アルミニウム粒状物を用いた実施例を示す。
【０１８３】
＜実施例１５＞
以下のような樹脂組成物を調製した。
・フェノール樹脂中間体　　　　　　　　　　　　　　　　　　　２５０質量部
・導電性カーボンブラック　　　　　　　　　　　　　　　　　　　１５質量部
・結晶性グラファイト（平均粒径４．３μｍ）　　　　　　　　　　８５質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　３５０質量部
【０１８４】
これらの材料を、ガラスビーズを用いた横形連続式サンドミルにより分散し、塗料原液Ａを得た。この原液Ａの粒度分布を測定したところ平均粒径は３．９μｍであった。
【０１８５】
次に、シランカップリング剤であるメタクリロキシシラン系カップリング剤０．０５質量部をメチルエチルケトン２０質量部に溶解した溶液に、ホウ酸アルミニウム粒状物（平均粒径３．５μｍ）１００質量部を加え、撹拌しながら７０℃に保ち、溶媒を蒸発した後に、１５０℃のオーブンに入れ、キュアリングを行った。
【０１８６】
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・メタクリロキシシラン系カップリング剤で処理したホウ酸アルミニウム粒状物
（平均粒径３．５μｍ）　　　　　　　　　　　　　　　　　　　１００質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　３２５質量部
塗料原液Ａに、メタクリロキシシラン系カップリング剤で処理したホウ酸アルミニウム粒状物およびメタノールを上記組成にてさらに加え、サンドミルにてホウ酸アルミニウム粒状物を分散した。この分散液をさらにメタノールにて希釈し、２５０メッシュおよび５００メッシュの篩いを通過させた（塗料１’）。この時の塗料１’の粘度は、９５ｍＰａ・ｓであった。アルミニウム円筒管を研削加工し、外径３２ｍｍφ、表面粗さＲａ＝０．２μｍ、振れ５〜１０μｍ程度とし、これに片側に現像スリーブ用フランジを取り付けたワークを用意した。回転台にワークを立て、スリーブ端部をマスキングしながら回転させ、上記塗料１’をスプレーガンにて、一定速度で下降させながらワークにスプレー塗布し、塗布スリーブを得た。これを通風式乾燥機にて１５０℃、３０分間、乾燥硬化させ樹脂表面層を形成させた。この時の表面樹脂被覆層の厚みは１３．４μｍ、表面粗さは平均でＲａ＝０．７２μｍであった。また被覆層の体積低抗値は、１．１３Ω・ｃｍであった。
【０１８７】
この現像スリーブにマグネットを装着してステンレス製フランジを嵌合し、キヤノン社製複写機ＮＰ−６０８５改造機の現像装置に装着可能とした。本実験に用いたＮＰ−６０８５改造機は、８５枚機を９５枚機に改造したものであり、プロセススピードは、５１３ｍｍ／ｓｅｃのものを５７３ｍｍ／ｓｅｃにアップさせ、且つドラム周速に対し、スリーブ周速を１．８倍とした。磁性トナー（下記）を補給しながら、１００万枚までの連続耐久を行い、評価を行った。評価としては、総合的な画像評価および被覆層の耐久性を判断基準とした。環境は、２４℃／１０％の常温低湿（Ｎ／Ｌ）環境と、３０℃／８０％の高温高湿（Ｈ／Ｈ）環境にて行った。結果を表６および７に示す。画像および耐久性共に良好な結果が得られた。トナーとしては、下記のものを用いた。
【０１８８】
・スチレン−ブチルアクリレート系樹脂　　　　　　　　　　　　１００質量部
・マグネタイト　　　　　　　　　　　　　　　　　　　　　　　　９５質量部
・低分子量ポリプロピレンワックス　　　　　　　　　　　　　　　　４質量部
・ジターシャリーブチルサリチル酸のＡｌ錯体（負電荷制御剤）　　　３質量部
上記材料をヘンシェルミキサーで分散混合後、１３０℃に加熱された二軸エクストルーダーで溶融混練し、冷却した混合物をハンマーミルで粗粉砕した。粗粉砕物をジェットミルで微粉砕し、得られた微粉砕物を風力分級機で分級し、トナーの粒度分布が、質量平均粒径７．２μｍ、４μｍ以下の粒子の個数割合が１７．５％、１２．７μｍ以上の粒子の質量割合が０．９％の磁性トナーを得た。このトナー１００質量部に、シランカップリング剤で疎水化処理したコロイダルシリカ０．９質量部、およびチタン酸ストロンチウム微粒子３質量部をヘンシェルミキサーにて外添して用いた。
【０１８９】
＜実施例１６＞
ホウ酸アルミニウム粒状物（平均粒径５．２μｍ）をアミノシラン系カップリング剤にて、実施例１５と同様にして処理を行った。
【０１９０】
・塗料原液Ａ　　　　　　　　　　　　　　　　　　　　　　　　７００質量部
・アミノシラン系カップリング剤で処理したホウ酸アルミニウム粒状物（平均粒
径５．２μｍ）　　　　　　　　　　　　　　　　　　　　　　　　８０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２９５質量部
とした以外は実施例１５と同様に塗料を調製した（塗料２’）。この塗料の粘度は９０ｍＰａ・ｓであった。実施例１５と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．２μｍ、表面粗さＲａ＝０．９４μｍであった。また被覆層の体積抵抗値は、１．１０Ω・ｃｍであった。この現像スリーブを用いて実施例１と同様の評価を行った。結果を表６および７に示す。
【０１９１】
＜実施例１７＞
以下のような樹脂組成物を調製した。
・ポリウレタン樹脂　　　　　　　　　　　　　　　　　　　　　２５０質量部
・導電性カーボンブラック　　　　　　　　　　　　　　　　　　　２０質量部
・結晶性グラファイト（平均粒径４．３μｍ）　　　　　　　　　　８０質量部
・トルエン・ＭＩＢＫ・ＩＰＡの混合溶媒　　　　　　　　　　　５２５質量部
【０１９２】
これらの材料を、ガラスビーズを用いた横形連続式サンドミルにより分散し、塗料原液Ｃを得た。この原液Ｃの粒度分布を測定したところ平均粒径は４．０μｍであった。
【０１９３】
次にホウ酸アルミニウム粒状物（平均粒径３．５μｍ）をヘキサメチルジシラザン（ＨＭＤＳ）を用いて実施例１５と同様の操作でカップリング処理を行った後、ジメチルシリコーンオイル０．１５質量部を溶剤で希釈したものに混合した後、溶剤を減圧下で揮発除去させた後、１９０℃で加熱処理を行ない、オイル処理ホウ酸アルミニウム粒状物を得た。
【０１９４】

塗料原液Ｃに、ホウ酸アルミニウム粒状物、イミダゾール化合物、および上記混合溶媒を上記組成にてさらに加え、サンドミルにてホウ酸アルミニウム粒状物およびイミダゾール化合物を分散した。この分散液をさらに混合溶媒にて希釈し、２５０メッシュおよび５００メッシュの篩いを通過させた（塗料３’）。この時の塗料３’の粘度は、５５ｍＰａ・ｓであった。この塗料を用いて実施例１５と同様の方法で表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１２．９μｍ、表面粗さＲａ＝０．８１μｍであった。また被覆層の体積抵抗値は、１．１６Ω・ｃｍであった。この現像スリーブを用いて実施例１５と同様の評価を行った。結果を表６および７に示す。
【０１９５】
＜実施例１８＞

塗料原液Ａに、ホウ酸アルミニウム粒状物およびメタノールを上記組成にてさらに加え、サンドミルにてホウ酸アルミニウム粒状物を分散した。この分散液をさらにメタノールにて希釈し、２５０メッシュおよび５００メッシュの篩いを通過させた（塗料４’）。この時の塗料４’の粘度は、９７．５ｍＰａ・ｓであった。この塗料を用いて実施例１５と同様の方法で表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．８μｍ、表面粗さＲａ＝０．７９μｍであった。また被覆層の体積抵抗値は、１．０３Ω・ｃｍであった。この現像スリーブを用いて実施例１５と同様の評価を行った。トナーは下記のものを用いた。
【０１９６】
・ポリエステル系樹脂　　　　　　　　　　　　　　　　　　　　１００質量部
・マグネタイト　　　　　　　　　　　　　　　　　　　　　　　　９５質量部
・アルコール系ワックス　　　　　　　　　　　　　　　　　　　　　４質量部
・ジターシャリーブチルサリチル酸のＡｌ錯体（負電荷制御剤）　　　４質量部
上記材料をヘンシェルミキサーで分散混合後、１３０℃に加熱された二軸エクストルーダーで溶融混練し、冷却した混合物をハンマーミルで粗粉砕した。粗粉砕物をジェットミルで微粉砕し、得られた微粉砕物を風力分級機で分級し、トナーの粒度分布が、質量平均粒径７．０μｍ、４μｍ以下の粒子の個数割合が１８．５％、１２．７μｍ以上の粒子の質量割合が０．８％の磁性トナーを得た。このトナー１００質量部に、シランカップリング剤で疎水化処理したコロイダルシリカ１．０質量部、およびチタン酸ストロンチウム微粒子４質量部をヘンシェルミキサーにて外添して用いた。結果を表６および７に示す。
【０１９７】
＜実施例１９＞
以下のような樹脂組成物を調製した。
・フェノール樹脂中間体　　　　　　　　　　　　　　　　　　　１００質量部
・導電性カーボンブラック　　　　　　　　　　　　　　　　　　　２０質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　１２０質量部
【０１９８】
これらの材料を、ガラスビーズを用いた横形連続式サンドミルにより分散し、塗料原液Ｄを得た。
【０１９９】
次にホウ酸アルミニウム粒状物（平均粒径２．８μｍ）を実施例１５と同様の操作でメタクリロキシシラン系カップリング剤で処理を行った。
【０２００】
・塗料原液Ｄ　　　　　　　　　　　　　　　　　　　　　　　　２４０質量部
・メタクリロキシシラン系カップリング剤で処理したホウ酸アルミニウム粒状物
（平均粒径２．８μｍ）　　　　　　　　　　　　　　　　　　１００質量部
・メタノール　　　　　　　　　　　　　　　　　　　　　　　　２１０質量部
【０２０１】
塗料原液Ｄに、ホウ酸アルミニウム粒状物およびメタノールを上記組成にてさらに加え、サンドミルにてホウ酸アルミニウム粒状物を分散した。この分散液をさらにメタノールにて希釈し、３５０メッシュの篩いを通過させた（塗料５’）。この時の塗料５’の粘度は、６０ｍＰａ・ｓであった。アルミニウム円筒管を研削加工し、外径３２ｍｍφ、表面粗さＲａ＝０．２μｍ、振れ５〜１０μｍ程度とし、これに片側に現像スリーブ用フランジを取り付けたワークを用意した。回転台にワークを立て、スリーブ端部をマスキングしながら回転させ、上記塗料５’をスプレーガンにて、一定速度で下降させながらワークにスプレー塗布し、塗布スリーブを得た。これを通風式乾燥機にて１５０℃、３０分間、乾燥硬化させ樹脂表面層を形成させた。この時の表面樹脂被覆層の厚みは１８．５’μｍ、表面粗さは平均でＲａ＝０．６０μｍであった。また被覆層の体積抵抗値は、１２．３Ω・ｃｍであった。
【０２０２】
この現像スリーブにマグネットを装着してステンレス製フランジを嵌合し、キヤノン社製複写機ＣＬＣ−１０００の現像装置に装着可能とした。シアントナーを用い、５万枚までの画出し評価を行い、その後現像スリーブの耐久性を確認するため、２０万枚相当までの空回転テストを行い被膜の削れおよび表面粗さを確認し、また新現像剤に交換した時の特性評価を行った。環境は２４℃／６０％の常温常湿（Ｎ／Ｎ）環境にて行った。現像剤としては次のようなものを用いた。
・ポリエステル系樹脂　　　　　　　　　　　　　　　　　　　　１００質量部
・フタロシアニン顔料（シアン）　　　　　　　　　　　　　　　　　５質量部
・ジターシャリーブチルサリチル酸のＡｌ錯体　　　　　　　　　　　６質量部
【０２０３】
ポリエステル樹脂の５質量部とフタロシアニン顔料５質量部は、予め３本ロールを用いて十分に混練を行いマスターバッチを作成しておく。粉砕されたマスターバッチ、残りのポリエステル樹脂、ジターシャリーブチルサリチル酸のＡｌ錯体をヘンシェルミキサーを用いて十分に混合した後、１１０℃に加熱された二軸エクストルーダーで溶融混練し、冷却した混合物をハンマーミルで粗粉砕した。粗粉砕物をジェットミルで微粉砕し、得られた微粉砕物を風力分級機で分級し、トナーの粒度分布が、質量平均粒径８．１μｍ、４μｍ以下の粒子の個数割合が９．５％、１２．７μｍ以上の粒子の質量割合が１．８％のシアントナーを得た。このトナー１００質量部に、疎水性の酸化チタン微粒子１．８質量部をヘンシェルミキサーにて外添トナーとした。平均粒径が３５〜５０μｍの間に分級されたフェライト粒子にシリコーン系樹脂を１．０％添加して混合し加熱硬化させた後解砕し、篩い処理を行い、現像用キャリアとした。上記トナーＴとキャリアＣをＴ／Ｃ比率が７％となるように混合しスタート剤とした。
【０２０４】
結果を表８に示す。
【０２０５】
＜実施例２０＞
ホウ酸アルミニウム粒状物の平均粒径２．８μｍ及び平均粒径７．８μｍをアミノシラン系カップリング剤にて、実施例１５と同様にして処理を行った。
【０２０６】

とした以外は実施例１９と同様にして塗料を調製した。この塗料の粘度は５７．５ｍＰａ・ｓであった。実施例１９と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１９．５μｍ、表面粗さＲａ＝０．９１μｍであった。また被覆層の体積抵抗値は、１１．０Ω・ｃｍであった。この現像スリーブを用いて実施例１９と同様の評価を行った。結果を表８に示す。
【０２０７】
＜実施例２１＞
・ポリウレタン樹脂　　　　　　　　　　　　　　　　　　　　　１００質量部
・導電性カーボンブラック　　　　　　　　　　　　　　　　　　　１０質量部
・結晶性グラファイト（平均粒径４．３μｍ）　　　　　　　　　　１０質量部
・トルエン・ＭＩＢＫ・ＩＰＡの混合溶媒　　　　　　　　　　　１２０質量部
【０２０８】
これらの材料を、ガラスビーズを用いた横形連続式サンドミルにより分散し、塗料原液Ｅを得た。
【０２０９】
次にホウ酸アルミニウム粒状物の平均粒径２．８μｍ及び平均粒径７．８μｍを実施例１７と同様の操作にてジメチルシリコーンオイル処理を行った。
【０２１０】

塗料原液Ｅに、ホウ酸アルミニウム粒状物およびトルエン・ＭＩＢＫ・ＩＰＡの混合溶媒を上記組成にてさらに加え、サンドミルにてホウ酸アルミニウム粒状物を分散した。この分散液をさらにトルエン・ＭＩＢＫ・ＩＰＡの混合溶媒にて希釈し、３５０メッシュの箭いを通過させた（塗料７’）。この時の塗料７’の粘度は、５２．５ｍＰａ・ｓであった。実施例１５と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１８．８μｍ、表面粗さＲａ：０．８９μｍであった。また被覆層の体積低抗値は、１５．４Ω・ｃｍであった。この現像スリーブを用いて実施例１５と同様の評価を行った。結果を表８に示す。
【０２１１】
＜実施例２２＞
ホウ酸アルミニウム粒状物（平均粒径９．８μｍ）を実施例１５と同様の操作にてメタクリロキシシラン系カップリング剤で処理を行った。
【０２１２】

【０２１３】
塗料原液Ａに、ホウ酸アルミニウム粒状物およびメタノールを上記組成にてさらに加え、サンドミルにてホウ酸アルミニウム粒状物を分散した。この分散液をさらにメタノールにて希釈し、２５０メッシュおよび５００メッシュの篩いを通過させた（塗料８’）。この時の塗料８’の粘度は、７５ｍＰａ・ｓであった。片側にアルミニウムフランジのついたアルミニウム円筒管を一体に研削加工し、外径２０ｍｍφ、表面粗さＲａ＝０．２μｍ、振れ５μｍ程度とした。回転台にワークを立て、スリーブ端部をマスキングしながら回転させ、上記塗料８をスプレーガンにて、一定速度で下降させながらワークにスプレー塗布し、塗布スリーブを得た。これを通風式乾燥機にて１５０℃、３０分間、乾燥硬化させ樹脂表面層を形成させた。この時の表面樹脂被覆層の厚みは１２．８μｍ、表面粗さは平均でＲａ＝１．５８μｍであった。また被覆層の体積低抗値は、０．９７Ω・ｃｍであった。
【０２１４】
この現像スリーブにマグネットを装着して残りの片側にアルミニウム製フランジを嵌合し、キヤノン社製レーザービームプリンターＬＢＰ−９３０改造機のカートリッジの現像装置に装着可能とした。本実験に用いたＬＢＰ−９３０改造機は、ＬＢＰ−９３０をべースにＡ４横送り２４枚機を５０枚相当に改造したものであり、プロセススピードを１０６ｍｍ／ｓｅｃから２３６ｍｍ／ｓｅｃにアップさせ、且つドラム周速に対し、スリーブ周速を１．３倍とした。さらにトナー容器のキャパシティーを上げている。さらに高速化による現像剤規制ブレードでの規制不均一を防ぐため規制部材に金属板で補強を施しブレード圧接力を強めている。また本体およびカートリッジにはそれぞれメカ的強度補強を加えている。外部のキャラクタージェネレーター（ＣＧ）から画像信号を送り、画像を出力させ画出しを行った。カートリッジのトナー残検が表示されるごとに磁性トナーを補給しながら６万枚までの連続耐久テストを行い、評価を行った。環境は２４℃／１０％ＲＨの常温低湿（Ｎ／Ｌ）環境と、３０℃／８０％ＲＨの高温高湿（Ｈ／Ｈ）環境にて行った。結果を表９および１０に示す。
【０２１５】
トナーとしては、下記のものを用いた。
・スチレン−ブチルアクリレート系樹脂　　　　　　　　　　　　１００質量部
・マグネタイト　　　　　　　　　　　　　　　　　　　　　　　１００質量部
・低分子量ポリエチレンワックス　　　　　　　　　　　　　　　　　３質量部
・長鎖アルコール系ワックス　　　　　　　　　　　　　　　　　　　３質量部
・アゾ系Ｆｅ錯体化合物（負電荷制御剤）　　　　　　　　　　　　　３質量部
上記材料をヘンシェルミキサーで分散混合後、１３０℃に加熱された二軸エクストルーダーで溶融混練し、冷却した混合物をハンマーミルで粗粉砕した。粗粉砕物をジェットミルで微粉砕し、得られた微粉砕物を風力分級機で分級し、トナーの粒度分布が、質量平均粒径６．３μｍ、４μｍ以下の粒子の個数割合が１９．５％、１２．７μｍ以上の粒子の質量割合が０．４％の磁性トナーを得た。このトナー１００質量部に、シランカップリング剤およびシリコーンオイルで処理したコロイダルシリカ１．２質量部、およびチタン酸ストロンチウム微粒子０．５質量部をヘンシェルミキサーにて外添して用いた。
【０２１６】
＜実施例２３＞
ホウ酸アルミニウム粒状物の平均粒径２．８μｍ及び平均粒径９．８μｍをアミノシラン系カップリング剤にて、実施例１５と同様の操作にて処理を行った。
【０２１７】

とした以外は実施例２２と同様に塗料を調製した（塗料９’）。この塗料の粘度は６０ｍＰａ・ｓであった。実施例２２と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．２μｍ、表面粗さＲａ＝１．５０μｍであった。また被覆層の体積低抗値は、１．０５Ω・ｃｍであった。この現像スリーブを用いて実施例２２と同様の評価を行った。結果を表９および１０に示す。
【０２１８】
＜実施例２４＞

とし、ホウ酸アルミニウム粒状物を分散した後更にイミダゾール化合物を加えた以外は実施例２２と同様に塗料を調製した（塗料１０’）。この塗料の粘度は８０ｍＰａ・ｓであった。実施例２２と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．２μｍ、表面粗さＲａ＝１．５８μｍであった。また被覆層の体積低抗値は、１．１１Ω・ｃｍであった。この現像スリーブを用いて実施例２２と同様の評価を行った。結果を表９および１０に示す。
【０２１９】
＜実施例２５＞

とし、ホウ酸アルミニウム粒状物を分散した後更に球状炭素粒子を加えた以外は実施例２２と同様に塗料を調製した（塗料１１’）。この塗料の粘度は５２．５ｍＰａ・ｓであった。実施例２２と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．２μｍ、表面粗さＲａ＝１．５５μｍであった。また被覆層の体積低抗値は、０．９５Ω・ｃｍであった。この現像スリーブを用いて実施例２２と同様の評価を行った。結果を表９および１０に示す。
【０２２０】
＜実施例２６＞
ホウ酸アルミニウム粒状物（平均粒径９．８μｍ）を実施例１７と同様の操作にてジメチルシリコーンオイル処理を行った。
【０２２１】

とし、ホウ酸アルミニウム粒状物を分散した後更に球状炭素粒子を加えた以外は実施例２２と同様に塗料を調製した（塗料１２’）。この塗料の粘度は５７．５ｍＰａ・ｓであった。実施例２２と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１４．０μｍ、表面粗さＲａ＝１．６５μｍであった。また被覆層の体積抵抗値は、０．９８Ω・ｃｍであった。この現像スリーブを用いて実施例２２と同様の評価を行った。結果を表９および１０に示す。
【０２２２】
＜実施例２７＞
ホウ酸アルミニウム粒状物（平均粒径１６．０μｍ）を実施例１７と同様の操作にてジメチルシリコーンオイル処理を行った。
【０２２３】

とした以外は実施例２２と同様に塗料を調製した（塗料１３’）。この塗料の粘度は６０ｍＰａ・ｓであった。実施例２２と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１３．５μｍ、表面粗さＲａ＝１．６２μｍであった。また被覆層の体積低抗値は、０．９９Ω・ｃｍであった。この現像スリーブを用いて実施例２２と同様の評価を行った。結果を表９および１０に示す。
【０２２４】
＜実施例２８＞
ホウ酸アルミニウム粒状物（平均粒径２７．５μｍ）を実施例１７と同様の操作にてジメチルシリコーンオイル処理を行った。
【０２２５】

とした以外は実施例２２と同様に塗料を調製した（塗料１４’）。この塗料の粘度は６０ｍＰａ・ｓであった。実施例２２と同様に表面樹脂層を形成した。この時の表面樹脂被覆層の厚みは１４．６μｍ、表面粗さＲａ＝１．８２μｍであった。また被覆層の体積低抗値は、０．９８Ω・ｃｍであった。この現像スリーブを用いて実施例２２と同様の評価を行った。結果を表９および１０に示す。
【０２２６】
【表６】

【０２２７】
【表７】

【０２２８】
【表８】

【０２２９】
【表９】

【０２３０】
【表１０】

【０２３１】
【発明の効果】
以上説明したように、本発明の現像剤担持体、現像装置、及びプロセスカートリッジにおいては、現像剤担持体の表面樹脂被覆層にホウ酸アルミニウム粒状物が含有されるため、均一な表面凹凸形状を有するため均一なトナー搬送性が得られ、またトナーに対する帯電付与性が良好であるため、現像性が良好であり、高精細、高画質の電子写真画像を提供できる。更に、耐摩耗性、耐汚染性に優れているため、一成分現像、二成分現像にかかわらず、長期の繰り返し使用に対しても、良好な画像を提供しつづけることのできるものである。
【図面の簡単な説明】
【図１】本発明の現像剤担持体の表面層の構成の一例を示す模式図である。
【図２】本発明の現像剤担持体の表面層の構成の他の一例を示す模式図である。
【図３】本発明の現像剤担持体の表面層の構成のまた他の一例を示す模式図である。
【図４】本発明の現像剤担持体の表面層の構成のまた他の一例を示す模式図である。
【図５】本発明の一成分現像機構成の一例を示す模式図である。
【図６】本発明の一成分現像機構成の他の一例を示す模式図である。
【図７】本発明の一成分現像機構成のまた他の一例を示す模式図である。
【図８】本発明の一成分現像機構成のまた他の一例を示す模式図である。
【図９】本発明の一成分現像機構成のまた他の一例を示す模式図である。
【図１０】本発明の二成分現像機構成の一例を示す模式図である。
【図１１】本発明のプロセスカートリッジ構成の一例を示す模式図である。
【図１２】本発明のプロセスカートリッジ構成の他の一例を示す模式図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a developer carrier having an improved resin coating layer on a substrate, a developing device using the same, and a process cartridge.
[0002]
[Prior art]
Conventionally, a number of methods are known as electrophotography. In general, a photoconductive substance is used to form an electric latent image on an electrostatic latent image carrier (photoreceptor) by various means. Then, the latent image is developed with a developer (toner) to form a visible image, and if necessary, the toner image is transferred to a transfer material such as paper, and then the toner image is formed on the transfer material by heat, pressure, or the like. This is to fix and obtain a visible image. The dry developing system in the electrophotographic method is mainly classified into a one-component developing system and a two-component developing system.
[0003]
In the two-component developing method, each toner is frictionally charged by stirring the toner and the carrier, and the electrostatic latent image is visualized using the charged toner. Depending on the type of carrier that transports the toner, those belonging to this method are referred to as a magnetic brush method using a magnetic material such as iron powder, a car skate method using a bead carrier, a fur brush method using fur, and the like. I have. Among them, a magnetic brush method is generally used.
[0004]
In addition, those belonging to the one-component developing method include a powder cloud method in which toner particles are used in a spray state, and contact of toner particles on a flexible or elastic developer carrier directly with an electrostatic latent image surface. Contact development method, in which the toner particles fly directly toward the latent image surface by the action of an electric field between the electrostatic latent image and the developer carrier without directly contacting the toner particles with the electrostatic latent image surface There is a magnedry method in which a magnetic conductive toner is brought into contact with an electrostatic latent image surface for development, and a contact development method and a jumping development method are generally used.
[0005]
As a toner applied to these developing methods, a fine powder obtained by dispersing a colorant in a natural or synthetic resin has been conventionally used. For example, a dispersion of colored particles such as various pigments, dyes, carbon black, and iron oxide in a binder resin such as a styrene-acrylic resin or a polyester resin is made into fine particles having an average particle size of about 4 to 15 μm. Is used as a toner.
[0006]
The toner must have a certain positive or negative charge, depending on the polarity of the electrostatic latent image to be developed and the development process. As a method for imparting electric charge to the toner, a method utilizing the triboelectricity of the binder resin of the toner and a method of imparting triboelectricity to various particles added to the toner are generally used. In general, a specific substance to be added is added to the toner. These toners generally generate triboelectric charges when they come into contact with various members used in a developing device. The main member is a carrier in a two-component developer, and may be affected by a developing sleeve or the like. Further, in the one-component developer, triboelectric charges are generated mainly by the action of the developing sleeve and the developer regulating blade. In addition, a developer supply member, a stirring member, a transport member, a developer container, and the like can also be involved in triboelectric charging.
[0007]
In general, in the development process, when an appropriate charge is to be imparted to a toner, first of all, the toner is made of a material capable of being triboelectrically charged, that is, a binder resin, an additive, and a charge control. Whether the appropriate material has been selected for the agent. However, since the binder resin, which accounts for the majority of the toner components, plays an important role not only in the development but also in the fixing step, it is not possible to select a material that emphasizes only triboelectric charging. In recent years, from the viewpoint of energy saving, a technology for fixing at lower temperature or lower power consumption has been required. In a toner, a binder resin that attaches importance to fixability is often inferior in chargeability. For example, as a material selection for fixing the toner with low energy, there is a method of increasing the low molecular weight component in the Tg (glass transition point) of the binder resin and the molecular weight distribution of the binder resin. Is often inferior in chargeability. In addition, so-called waxes are often added to the toner for the purpose of improving the anti-offset property in the fixing step, and for improving the plasticity of the resin to improve the fixing property. As for the property, it is easy to give a property in a bad direction. Also, a charge control agent is added to the toner to improve the triboelectric charging property. However, since most of the charge control agent is a dye or a pigment, if a large amount is added to the toner, the toner particles may be reduced in the toner manufacturing process. Due to the charge control agent released from the toner or present on the toner surface, members such as the photosensitive drum, the charging member, the developing sleeve, and the regulating blade are easily contaminated.
[0008]
As a second means for imparting triboelectric charge to the toner, an appropriate material is selected and used for the triboelectric imparting member. Many methods have been proposed for balancing the triboelectric charge of the toner by an appropriate combination of the toner material and the triboelectric charging member material.
[0009]
Iron powder was once used as a carrier for a magnetic brush, which is a frictional charging member as a two-component developer, but in recent years, in order to adjust the frictional charge amount of toner, iron powder as a magnetic material has been used. In many cases, a coating agent mainly composed of an acrylic resin, a silicone resin, a fluororesin, a phenol resin, or the like is applied to the surface of a carrier core material using powder, ferrite, or the like.
[0010]
In the case of a one-component developer, in the developing device, the toner passes between the developing sleeve and the regulating blade and comes into contact with the developing sleeve and the regulating blade when the toner is thinned. Affects charging. In the case of the one-component magnetic toner, the toner moves on the sleeve by the action of the magnetic force and has a chance to come into contact with the developing sleeve during this time.
[0011]
As the regulating blade, there are a type in which a narrow gap is provided between the regulating blade and the developing sleeve to regulate the amount of toner transport, a type in which the regulating blade elastically contacts the developing sleeve to regulate, and the like. Materials such as metal, rubber, and the like are used. When elastically contacting the developing sleeve, a rubber such as urethane rubber or silicone rubber, or a plate made of phosphor bronze or stainless steel is used. In consideration of the triboelectric chargeability with the toner, for example, when giving the toner a negative chargeability, a positively chargeable nylon-based elastomer is used for the surface layer that comes in contact with the toner so that the toner is easily charged. Is taken. These triboelectric charging materials are used by being directly processed into a blade shape, pasted to a plate material as a chip, or coated with a resin.
[0012]
Next, the developing sleeve (developer carrier) will be described.
[0013]
In a so-called contact phenomenon method in which a developer carrier is brought into direct contact with a latent image carrier to perform development, generally, an elastic body such as urethane rubber, EPDM rubber, or silicone rubber is cylindrically mounted on a metal main shaft such as stainless steel. It may be formed into a shape, or may be formed by forming an elastomer layer on the surface of a cylindrical member made of aluminum or stainless steel. In these cases, the so-called rubber contains impurities such as a plasticizer, a vulcanizing agent, a release agent, and a low molecular weight component, and when this comes into contact with the latent image carrier or the developer layer forming member, Since the bleeding adversely affects these members and images, a layer such as a barrier layer or a protective layer is provided on the surface of the rubber layer to prevent the above-mentioned adverse effects. Further, it is also known that a surface layer is formed on the outermost surface with a material having good releasability or a resin which easily gives a triboelectric charge to the toner.
[0014]
Conventionally, a developing sleeve used for non-contact type development has, for example, been formed of a metal, an alloy thereof, or a compound thereof in a cylindrical or cylindrical shape, and the surface thereof is subjected to electrolytic, plating, blasting, sanding, etc. to a predetermined surface roughness. What was processed so that it might be used is used. When a one-component magnetic developer is used, a magnet having a predetermined magnetic force and a magnetic pole configuration is arranged in a cylinder. A similar developing sleeve is used in a two-component magnetic brush developing device.
[0015]
However, when the developing sleeve having the surface as described above is used, the developer existing near 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 charge. As a result, the toner is intensely attracted to the surface of the carrier, which makes it impossible to have a chance of friction between the toner and the carrier that comes later, so that a suitable charge is not given to the developer, which causes a so-called charge-up phenomenon. . In such a situation, sufficient development and transfer are not performed, resulting in an image with no image density, image unevenness, and many character scattering. In order to prevent the generation of such an excessively charged developer and the strong adhesion of the developer, a film in which a conductive substance such as carbon black and graphite or a solid lubricant is dispersed in a triboelectrically chargeable resin. Is formed on the developer-carrying member substrate as disclosed in, for example, Japanese Patent Application Laid-Open No. H11-163,036.
[0016]
In addition to the function of imparting an appropriate charge to the toner, the developing sleeve also plays a role of stably and uniformly transporting the toner or developer layer-formed on the developing sleeve to the developing area. The amount of toner transported on the developing sleeve is, of course, affected by the strength of the regulation in the developer layer forming area, the Coulomb force due to charging between the toner and the sleeve, the magnetic composition of the magnet, etc. Is known to be quite large. Therefore, if the shape of the surface of the developing sleeve changes due to repeated use, the transport amount of the developer changes, which causes various problems in developing property and the like. As described above, a resin-coated sleeve to which carbon black or graphite has been added can provide sufficient performance with a low-capacity cartridge that does not require much durability, but when a high-durability number is required, the surface due to scraping can be obtained. The change in roughness is problematic.
[0017]
Patent Document 2 proposes adding spherical fine particles as a material for forming irregularities on the surface of a developing sleeve. The method of adding spherical particles is a good means for forming a uniform surface shape. However, in the case of long-term use or a developing method in which a strong stress is applied to the sleeve surface, when resin particles as disclosed in the above technology are used, defects such as reduction in surface roughness and toner adhesion due to wear due to durability occur. It's easy to do. As a method of increasing the strength of the resin layer on the developing sleeve, Patent Literature 3 and Patent Literature 4 disclose a technique of adding a fibrous substance such as potassium titanate whisker to a polymer substance. Although the method of adding these fibrous substances is a good method for increasing the strength of the resin layer, the fibrous substances have a considerably indeterminate shape, are difficult to control the particle size, and are difficult to disperse. When the surface is formed by the method, there is a disadvantage that it is difficult to form a uniform surface shape. Patent Literature 5 discloses a technology for forming a resin layer to which conductive spherical particles having a true density of 3 or less are added as a technology for adding spherical particles to improve durability. According to the above-mentioned method, the durability of the surface resin layer is considerably improved. However, even in the case of one-component magnetic development, a high-speed copier developing device or a carrier using a large specific gravity carrier such as iron or ferrite is used. When applied to a developing device for component development, the required durability may not be satisfied. Patent Literature 6 discloses a technique in which a spherical particle and a fibrous substance are shared, and a good portion of both is obtained. However, as described above, the fibrous substance has some difficulties in handling. Patent Document 7 discloses a high-hardness silica-based material as an unevenness imparting substance, and Patent Document 8 discloses a technique of adding silica having two kinds of particle sizes as an inorganic substance. Silica-based materials have poor compatibility with resins, and when formed with a resin layer, are apt to become brittle and are easily exposed to the surface. In addition, since the toner has a high chargeability with the toner, a charge-up phenomenon easily occurs when the toner is exposed on the surface. Patent Document 9 discloses a method in which iron oxide is contained as a conductive metal oxide. However, many of the general metal oxides have a high true density, are likely to precipitate in a resin, and have a tendency to precipitate in a resin layer. Dispersion tends to be worse.
[0018]
Further, a developing sleeve for a two-component developing device using a carrier has a large abrasion when an inexpensive aluminum cylindrical tube is used. Therefore, a stainless steel cylindrical tube has been used in most cases conventionally. However, even when stainless steel is used, unevenness due to blasting of the surface is worn and smoothed by repeated use, and the transportability of the developer is reduced.
[0019]
[Patent Document 1]
JP-A-01-277265
[Patent Document 2]
JP-A-03-200986
[Patent Document 3]
JP-A-60-230175
[Patent Document 4]
JP-A-63-314576
[Patent Document 5]
JP-A-08-240981
[Patent Document 6]
JP-A-10-186839
[Patent Document 7]
JP 04-078881 A
[Patent Document 8]
JP 07-306586 A
[Patent Document 9]
JP-A-01-142563
[0020]
[Problems to be solved by the invention]
As described above, the developing sleeve not only has a material configuration that has good triboelectric charging property with respect to the developer, but also is less likely to be contaminated by toner and the like even when used repeatedly, and the surface shape changes over a long period of time. The toner is required to have a uniform surface roughness and to have stable triboelectric charging characteristics for the toner.
[0021]
Similarly, a configuration is required in which developer transportability is ensured for a long period of time.
[0022]
Furthermore, a technology that can realize this durability at low cost is required. For example, more specifically, in a two-component developing apparatus, even if a carrier that exerts a strong force on a sleeve made of iron or ferrite carrier is used, the wear of the sleeve surface layer is small, the change in surface roughness is small, and the sleeve It is required that the surface of the developer is not contaminated and that the transportability of the developer is stable. By achieving this, it is possible to prevent a decrease in the density due to a decrease in the transport amount of the developer and a decrease in image quality such as fog. In addition, by using an inexpensive aluminum cylindrical tube as the base, it is possible to reduce the cost of a generally expensive two-component developing device.
[0023]
In a high-speed machine using a one-component magnetic developer, the developing sleeve has a stable triboelectric charging property to the toner, and the surface of the sleeve has a small wear, the surface roughness changes little, and the sleeve surface is contaminated. Output hundreds of thousands or millions of high-quality images without changing the developing device, developer, or developing sleeve without impairing the basic image quality such as ghost, unevenness, blotch, fog, etc. It is required to achieve.
[0024]
Also, in a developing device in which the developer regulating blade and the developer stripping / supplying member are strongly pressed against the developing sleeve, wear of the developing sleeve surface due to the pressure contact can be prevented, and toner contamination and fusion can be prevented to prevent the developing sleeve surface. There is a demand for a developing sleeve and a developing device that can stabilize the shape and material composition of the surface and can continue to provide high-definition images without ghosts, unevenness, blotches, fog, and the like.
[0025]
That is, an object of the present invention is to provide a developing sleeve, a developing device using the same, and a process cartridge that can achieve the above-mentioned requirements.
[0026]
[Means for Solving the Problems]
The present invention for achieving the above object is used in a developing device that develops a latent image formed on an electrostatic latent image carrier with a developer carried and conveyed by a developer carrier and visualizes the latent image. In the developer carrier obtained, the developer carrier has at least a substrate and a resin coating layer formed on the surface of the substrate, and the resin coating layer comprises at least a resin and aluminum borate dispersed in the resin. A developer-carrying member characterized by containing particulate matter.
[0027]
The resin coating layer has conductivity, and the conductivity is preferably a developer carrier provided by including a conductive agent in the resin coating layer. It is more preferable that the developer carrier further contains a lubricating fine powder in the resin coating layer. The outer surface of the resin coating layer preferably has surface irregularities with a center line average roughness Ra of about 0.3 to 3.5 μm.
[0028]
As a preferred embodiment having irregularities on the outer surface of the resin coating layer, one embodiment in which the irregularities are formed mainly by the addition of the aluminum borate granules is mentioned, and in this case, the aluminum borate granules are number averaged. When the particle size is 0.3 to 30 μm, the surface tends to have a preferable surface roughness. It is also a preferable embodiment that the aluminum borate particulates are organically treated.
[0029]
Further, another solid particle on which surface irregularities can be formed is added to the resin, and the irregularities on the outer surface of the resin coating layer are mainly formed by the further added solid particles, and the aluminum borate granular material is formed. Contribution to the unevenness is less or harder than other solid particles, or another solid particle or large irregularities are formed, and aluminum borate granular material has a mode of forming finer irregularities. No. In this case, the number average particle diameter of the solid particles further added is preferably 0.3 to 30 μm, so that the solid particles can easily have preferable surface roughness.
[0030]
It is also preferable that the irregularities on the outer surface of the resin coating layer are formed mainly by both the aluminum borate granules and further added solid particles.
[0031]
Further, the present invention for achieving the above-mentioned object further comprises a container accommodating at least a developer and a developer carrier for carrying and transporting the developer stored in the container. A developing device that forms a developer layer on a developer carrier, conveys the developer to a development area opposed to the latent image carrier, and develops the latent image on the latent image carrier with a developer to form a visible image. , A developing device characterized by using the developer carrier described above,
A developing device in which the developer is a non-magnetic one-component developer, and the layer thickness regulating member is in contact with or in pressure contact with the developer carrier via the toner,
The developer carrier is a developing device in which a magnet is built in the base. The developer is a magnetic one-component developer. In this case, the layer thickness regulating member is a non-magnetic member. A developing device in contact with or in pressure contact with the developer carrier, a layer thickness regulating member that is a non-magnetic or magnetic member, and a configuration in which the developer carrier is disposed with a small gap, The carrier is provided as a developing device in which a magnet is built in the base and the developer is a two-component developer having a toner and a carrier.
[0032]
The present invention for achieving the above object further includes: i) an electrostatic latent image holding member for holding an electrostatic latent image, and (ii) the electrostatic latent image is developed by a developer in a development area with a developer. A process cartridge detachable from an image forming apparatus main body having at least an integrated developing means, wherein the developing device is the developing device described above, and the electrostatic latent image holding member is Preferably, the photosensitive member is an electrophotographic photosensitive member. In addition to the electrophotographic photosensitive member as the electrostatic latent image holding member and the developing unit, at least one of the cleaning unit and the primary charging unit is integrally formed as a cartridge. Is also preferred.
[0033]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, the resin coating layer on the surface of the developer carrier comprises at least a binder resin and particulate aluminum borate dispersed in the binder resin.
[0034]
Generally aluminum borate is nAl₂O₃・ MB₂O₃9Al₂O₃・ 2B₂O₃, 2Al₂O₃・ B₂O₃, Al₂O₃・ B₂O₃Etc. have been confirmed. Originally, borate has a structure in which all the oxygen contained is covalently bonded to boron,₃ ^3-(Orthoborate ion), (BO^2-) Constituting ionic groups or ionic networks, such as continuous chains (metaborate ions), and neutralizing Na⁺, Ca²⁺Ordinarily takes a structure in which a cation such as is coordinated to the oxygen of borate ion. On the other hand, 9Al₂O₃・ 2B₂O₃Is completely incorporated in the network formed by aluminum and oxygen, and a composite oxide of aluminum and boron is more appropriate than a borate.
[0035]
Aluminum borate is available in granular and whisker-like forms. As a result of studies by the present inventors, the strength of the resin coating layer formed on the substrate (e.g., ) Was found to improve, but when examining the unevenness of the surface, the granular material could form more uniform unevenness than the whisker, and the amount of developer transported by the developer carrier was uniform, and the It was also found that the triboelectric charge of the agent was stable. That is, even if whiskers are used, surface irregularities are formed and can be used in a process in which only irregularities are required, but for example, as in a developing method using a thinner layer of a developer on a developer carrier, In a more precise process for supplying a higher-definition image, the particulate material is preferable in that uniformity can be maintained over the surface of the coating layer of the developer carrier and the entire coating layer.
[0036]
The aluminum borate particles can be obtained by mixing an aluminum oxide component and a boron oxide component, and heating and reacting at a temperature of about 800 to 1300 ° C. Further, purification is performed using water, an acidic aqueous solution or an alkaline aqueous solution. Further, a surface treatment such as a reheating treatment, a treatment with a silane coupling agent or the like may be performed.
[0037]
Aluminum borate is characterized by high hardness (7 in the former notation of Mohs hardness = literature value) and relatively low true density (2.9-3.0 g / cm).³= Literature value). The hardness of the particles added to the resin layer on the developer carrier and the abrasion resistance of the resin coating layer when repeatedly used as the developer carrier are not necessarily correlated. As a result, when aluminum borate particles were added, as shown in the specific examples described later, they exhibited excellent wear resistance as compared with those without addition of aluminum borate and those containing resin-based particles. . Furthermore, because of its high hardness, magnetic particles as a carrier on the developer carrier, magnetic substances contained in the toner, external additives such as abrasives, and a developer regulating blade and a developing Even if it receives the force from the agent supply member etc., the shaving is small, so the shape of the particle itself is unlikely to change, and even if the resin component is shaved, or even if the particle itself falls off due to the effect, the resin layer will remain in the resin layer. In some cases, the particles may re-extrude or become exposed, and the change in the surface shape can be kept small. Further, since the true density is relatively small as a hard metal oxide, the dispersion state in the resin layer is relatively stable, and the dispersion state of the aluminum borate particles in the resin layer after the formation of the resin coating layer is made uniform. Cheap. That is, the inventors of the present application also disclose in the specification of Patent Document 5 filed earlier that when the conductive spherical particles are added to the resin layer, the true density of the particles is 3 g / cm.³The following is proposed to be preferable in order to obtain a uniform dispersion state, but the aluminum borate particles of the present invention are near the upper limit and fall within this range. In the results of the study by the present inventors, although it is close to the upper limit of the preferable true density, it is within a specified range, and if it is within this range, it is a range that can be dealt with with some improvement of the manufacturing method, and is uniform. It is possible to achieve both dispersibility and abrasion resistance.
[0038]
Furthermore, when aluminum borate particles are triboelectrically charged, for example, with an iron powder carrier, they exhibit a weak positive chargeability, but the triboelectric chargeability is not so large. It is difficult to cause so-called charge-up, which is preferable from that point.
[0039]
In the present invention, one of the features is to use organically treated aluminum borate granules, but such an organic treatment method includes a silane coupling agent that reacts or physically adsorbs with the aluminum borate granules, A method of treating with an organometallic compound such as a titanium coupling agent, a method of treating with an organosilicon compound such as silicone oil, or a method of treating with a coupling agent or an organosilicon compound such as silicone oil at the same time as treating with a coupling agent Method.
[0040]
Coupling agents suitably used as a treating agent for aluminum borate particles in the present invention include, for example, a silane coupling agent, a titanate coupling agent and an aluminum coupling agent.
[0041]
As the silane coupling agent, known ones (for example, those conventionally used for surface modification of silica and glass) can be used without particular limitation.
General formula
(1) RmSiYm
R: alkoxy group
m: an integer from 1 to 3
Y: alkyl group
n: an integer from 1 to 3
And, for example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane , Γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, stearyltrimethoxysilane, diphenyldiethoxysilane and the like can be used.
[0042]
In the present invention, the silane coupling agent as described above is preferably used in an amount of 0.0001 to 0.5 part (more preferably 0.001 to 0.2 mass) per 100 parts of (untreated) aluminum borate particles. Part) used.
[0043]
When the amount of the coupling agent is less than 0.0001 part by mass, the effect of using the coupling agent is not recognized. On the other hand, when the amount of the coupling agent exceeds 0.5 part by mass, the reaction with the aluminum borate particles occurs. It is not preferable because a coupling agent not involved in the reaction is likely to be generated.
[0044]
Next, the general formula of a typical titanium-based coupling agent is shown below.
[0045]
Embedded image

[0046]
More specific compounds among the titanium-based coupling agents represented by the above general formula include the following.
[0047]
Embedded image

[0048]
Embedded image

[0049]
The treatment amount of the titanium-based coupling agent with respect to the aluminum borate particles depends on the particle size, surface structure, etc. of the aluminum borate particles, but is used in an amount of 0.0001 to 0.5 parts by mass with respect to 100 parts by mass of the aluminum borate particles. Is preferred. If the processing amount of the aluminum coupling agent is less than 0.0001 part by mass, there is no effect on the dispersibility of the aluminum borate particles. A large amount of ring agent is generated, which is not preferable.
[0050]
Examples of the aluminum coupling agent include acetoalkoxy aluminum diisopropylate and the like. The treatment amount for the aluminum borate particles is preferably 0.0001 to 0.5 parts by mass based on 100 parts by mass of the aluminum borate particles. If the processing amount of the aluminum coupling agent is less than 0.0001 part by mass, there is no effect on the dispersibility of the aluminum borate particles. A large amount of ring agent is generated, which is not preferable.
[0051]
Each of the above-mentioned coupling agents may be used as a combination of two or more as necessary.
[0052]
Examples of a method of treating the aluminum borate particulates with the coupling agent include an organic solvent method and an aqueous solution method. In general, 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 aluminum borate granules are immersed in the solution. After that, solid-liquid separation is performed by filtration or pressing, and drying is performed at about 120 to 130 ° C. Further, the aqueous solution method is to hydrolyze a coupling agent of about 0.5% in water of a constant pH or a mixed solvent of water and an organic solvent, and then immerse the aluminum borate particulates in the same manner. Is subjected to solid-liquid separation and dried.
[0053]
Silicone oil which is another organic treatment is generally represented by the following formula.
[0054]
Embedded image

[0055]
R: C₁~ C₃Alkyl group
R ': silicone oil-modified groups such as alkyl, halogen-modified alkyl, phenyl, and modified phenyl
R ": C₁~ C₃Alkyl or alkoxy group of
[0056]
Preferred silicone oils have a viscosity of about 0.5 to 1,000 mm at 25 ° C.²/ S, preferably 1 to 1,000 mm²/ S. A silicone oil having a molecular weight that is too low may generate a rare substance due to heat treatment or the like. If the molecular weight is too high, the viscosity becomes too high, and the processing operation becomes difficult. Examples of the type of silicone oil include 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, and fluorine-modified silicone. Oil and the like are preferred.
[0057]
The treatment with the silicone oil can be performed, for example, as follows. The aluminum borate granules are vigorously agitated while heating, if necessary, and sprayed or vaporized with the silicone oil or a solution thereof, or the aluminum borate granules are slurried. It can be easily treated by dropping silicone oil or its solution while stirring. These silicone oils may be used alone or in combination of two or more, or in combination or in multiple treatments. Moreover, you may use together with the process by a coupling agent.
[0058]
1 to 4 are schematic cross-sectional views showing a state in which particulate aluminum borate 4 is dispersed in binder resin 3 to form surface resin coating layer 2. 1 indicates a substrate. In FIG. 1, the aluminum borate particles are dispersed in the binder resin and contribute to the formation of irregularities on the surface of the resin coating layer. Reference numeral 5 denotes a conductive fine powder added to impart conductivity to the resin coating layer, and does not substantially contribute to the formation of irregularities. However, the present invention is not limited to the conductive fine powder, but also includes a mode in which minute irregularities are formed by another solid particle to be added. In FIG. 2, reference numeral 6 denotes another solid particle added to give relatively large irregularities to the surface of the resin coating layer, and the aluminum borate particles 4 form minute irregularities on the surface of the resin coating layer. Such a configuration is advantageous when used in a developing device in which the developer regulating member is elastically pressed (via toner) against the developer carrier. That is, the pressure contact force of the elasticity regulating member is regulated by another solid particle, and the aluminum borate particles 4 also form minute irregularities to play a role of adjusting a contact charging opportunity between the toner and the resin. FIG. 3 shows that both the aluminum borate particles 4 and the other solid particles 7 contribute to the formation of irregularities on the surface of the resin coating layer. Such a form may be implemented, for example, when another solid particle 7 is to be given another function such as conductivity or triboelectricity in addition to the provision of unevenness. FIG. 4 is a model diagram when a solid lubricant 8 such as graphite is used in combination for the purpose of preventing toner adhesion to the sleeve.
[0059]
Next, the configuration of the developer carrying member used in the present invention will be described. The developer carrier comprises a substrate and a resin layer surrounding and covering the substrate. Examples of the substrate include a cylindrical member, a columnar member, and a belt-like member. A rigid cylindrical tube or solid rod such as metal is preferably used. As such a substrate, a nonmagnetic metal or alloy such as aluminum, stainless steel, or brass, which is formed into a cylindrical or columnar shape, and polished, ground, or the like is suitably used. These substrates are molded or processed with high precision in order to improve the uniformity of the image. For example, the straightness in the longitudinal direction is preferably 30 μm or less, or 20 μm or less, and more preferably 10 μm or less. Deflection of the gap between the sleeve and the photosensitive drum, for example, abutting against a vertical surface via a uniform spacer, and rotating the sleeve In this case, the deviation of the gap from the vertical plane is preferably 30 μm or less, or 20 μm or less, and more preferably 10 μm or less. Aluminum is preferably used from the viewpoint of material cost and ease of processing. Such a form is preferably used as a developer carrying base for magnetic or non-magnetic one-component non-contact development or two-component development.
[0060]
Further, as the substrate having an elastic layer, a core member and a cylindrical member having a layer configuration containing rubber or an elastomer such as urethane, EPDM, or silicon are preferable, particularly in the case of a developing method in which a developer carrier is brought into direct contact with a drum. Used.
[0061]
As the binder resin material of the conductive coating layer constituting the developer carrier of the present invention, generally known resins can be used. For example, thermoplastic resins such as styrene resin, vinyl resin, polyether sulfone resin, polycarbonate resin, polyphenylene oxide resin, polyamide resin, fluorine resin, cellulose resin, acrylic resin, epoxy resin, polyester resin, and alkyd resin For example, a heat or light curable resin such as a phenol resin, a melamine resin, a polyurethane resin, a urea resin, a silicone resin, and a polyimide resin can be used. Among them, those with releasability such as silicone resin and fluorine resin, or excellent in mechanical properties such as polyether sulfone, polycarbonate, polyphenylene oxide, polyamide, phenol, polyester, polyurethane, styrene resin and acrylic resin Are more preferred.
[0062]
In the present invention, the coating layer formed on the developer carrying member by the above-mentioned forming material is used to fix the developer onto the developer carrying member due to charge-up and to carry the developer carrying-out caused by the charge-up of the developer. In order to prevent poor charging of the developer from the surface of the body, it is desirable that the developer be conductive. The volume resistance of the coating layer is preferably 10⁴Ω · cm or less, more preferably 10³Ω · cm or less.
[0063]
The conductive coating layer on the surface of the developer carrier has a volume resistance of 10⁴If it exceeds Ω · cm, charging failure to the developer is likely to occur, and as a result, blotches (spot images and wave pattern images) tend to occur.
[0064]
In the present invention, in order to adjust the low resistance value of the coating layer to the above value, it is preferable to include the following conductive substance in the coating layer. Examples of the conductive substance used at this time include fine powders of metal powders such as aluminum, copper, nickel, and silver, antimony oxide, indium oxide, tin oxide, titanium oxide, zinc oxide, molybdenum oxide, and titanic acid. Examples thereof include metal oxides such as potassium, various carbon fibers, furnace black, lamp black, thermal black, acetylene black, carbon black such as channel black, graphite such as graphite, and metal fibers.
[0065]
In the present invention, among these, carbon black, particularly conductive amorphous carbon, is particularly excellent in electrical conductivity, and is filled with a polymer material to impart conductivity, or only by controlling the addition amount, It is suitably used because any degree of conductivity can be obtained. Dispersion stability when made into a paint can also be good. In the present invention, the amount of the conductive material is preferably in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the binder resin. If the amount is less than 1 part by mass, it is usually difficult to reduce the resistance value of the coating layer to a desired level, and there is a high possibility that toner adheres to the binder resin used for the developer carrier coating layer. If it exceeds 100 parts by mass, the strength (abrasion) of the coating layer may be reduced, especially when a fine powder having a submicron order particle size is used.
[0066]
Further, in the present invention, a solid lubricant can be mixed in the coating layer in order to further reduce the adhesion of the developer to the surface of the developer carrier. Examples of the solid lubricant that can be used at this time include molybdenum disulfide, boron nitride, graphite, graphite fluoride, silver-selenium niobium, calcium chloride-graphite, talc, and the like. The amount of the solid lubricant that can be used in the present invention is preferably in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the binder resin. When the amount is less than 1 part by mass, the effect of improving the adhesion of the developer to the binder resin surface of the coating layer is small, and when the amount exceeds 100 parts by mass, particularly when a material containing a large amount of fine powder having a submicron order particle size is used. In addition, the strength (wearability) of the coating layer may decrease. These lubricating particles preferably have a number average particle size of about 0.2 to 20 μm, more preferably 1 to 15 μm. When the number average particle diameter of the lubricating particles is less than 0.2 μm, it is not preferable because lubricity is not sufficiently obtained, and when the number average particle diameter exceeds 20 μm, the shape of the surface of the conductive coating layer is reduced. The effect is large and the surface properties become uneven, which is not preferable in terms of uniform charging of the toner and strength of the coating layer.
[0067]
The resin coating layer of the present invention may contain other solid particles for forming irregularities on the surface of the coating layer. Examples of such solid particles include, for example, vinyl polymers and copolymers such as polymethyl methacrylate, polyethyl acrylate, polybutadiene, polyethylene, polypropylene, and polystyrene, benzoguanamine resins, phenol resins, polyamides, fluorine resins, and silicone resins. , Resin particles such as epoxy resin, polyester resin, etc., oxide particles such as alumina, zinc oxide, silicone, titanium oxide, tin oxide, carbonized particles, conductive particles such as resin particles subjected to conductive treatment, etc., for example, imidazole It is also possible to use an organic compound such as a compound in the form of particles. In this case, the imidazole compound also serves to impart triboelectric charge to the toner. FIG. 3 shows such a configuration.
[0068]
In particular, when used in the form as shown in FIG. 2, it is preferable to use conductive particles among these particles. That is, by imparting conductivity to the particles, charge is less likely to accumulate on the surface of the particles due to the conductivity, so that it is possible to reduce the adhesion of the toner and to improve the charging property of the toner. In the present invention, as the conductivity of the particles, a volume resistance value of 10⁶Ω · cm or less, more preferably 10^-3-10⁶The particles are preferably Ω · cm. The volume resistance of such particles is 10⁶If it exceeds Ω · cm, the toner tends to be contaminated or fused by spherical particles exposed on the surface of the coating layer due to abrasion, and it is difficult to perform quick and uniform charging. Furthermore, the true density of the particles is 3000 kg / m³It is more preferable that it is not more than the degree. Even if it is conductive, if the true density of the particles is too high, the amount added to form the same roughness will increase, and the true density difference between the resin or the resin composition and the resin will increase. In this case, the dispersion state of the particles tends to be non-uniform, and therefore the dispersion state of the formed coating layer is not uniform, which is not preferable. Further, when the particles are spherical, the contact area with the developer regulating member or the like to be pressed is reduced, so that an increase in sleeve rotation torque due to frictional force and the adhesion of toner can be reduced, which is more preferable. In particular, when the conductive spherical particles shown below are used, a better effect can be obtained.
[0069]
That is, a particularly preferable method for obtaining conductive spherical particles is, for example, obtaining resin-based spherical particles or mesocarbon microbeads to obtain low-density and good-conductive spherical carbon particles obtained by carbonization and / or graphitization. Method. Examples of the resin used for the resin-based spherical 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.
[0070]
As a more preferable method for obtaining conductive spherical particles, a phenol resin, a naphthalene resin, a furan resin, a xylene resin, a divinylbenzene polymer, a styrene-divinylbenzene copolymer, a surface of a spherical resin particle such as polyacrylonitrile, a mechanochemical method. A method for obtaining conductive spherical carbon particles by coating a bulk mesoface pitch with an oxidizing atmosphere and then heat-treating the coated particles in an oxidizing atmosphere followed by firing in an inert atmosphere or under vacuum to carbonize and / or graphitize the particles. No. Spherical carbon particles obtained by this method are more preferable because, when they are graphitized, the coating of the obtained spherical carbon particles has advanced crystallization, so that the conductivity is improved.
[0071]
The conductive spherical carbon particles obtained by the above-described method can control the conductivity of the spherical carbon particles obtained by changing the firing conditions in any method, and are preferably used in the present invention. . Further, in some cases, the spherical carbon particles obtained by the above method may contain a conductive metal and / or metal oxide as long as the true density of the conductive spherical particles does not become too large in order to further increase the conductivity. It may be plated.
[0072]
The surface roughness of the coating layer on the surface of the developer carrying member preferably used in the present invention having the above-described configuration is in the range of 0.3 to 3.5 μm in JIS center line average roughness (Ra). Is preferred. More preferably, it is 0.4 to 2.5 μm. That is, when Ra is less than 0.3 μm, the charge amount of the toner on the developer carrying member becomes too high and the developing property becomes insufficient, and the transportability of the developer to the developing area is inferior. It is difficult to obtain a concentration. On the other hand, when Ra exceeds 3.5 μm, unevenness occurs in the thickness of the toner coat layer formed on the developer carrying member, which causes density unevenness on an image.
[0073]
In order to obtain the above surface roughness, the number average particle diameter of the aluminum borate particles is preferably 0.3 to 30 μm. When the number average is less than 0.3 μm, it is difficult to impart the above-mentioned surface roughness, and when added in a large amount, the resin content is relatively reduced, so that the binding property is reduced and the resin layer becomes brittle. There is a possibility that the toner is not easily charged by the resin. If the thickness exceeds 30 μm, the surface roughness becomes too large and the surface unevenness becomes uneven, so that the toner transportability is uneven, the toner layer thickness regulating force is weakened, and the toner coating state is poor. Become uniform or unstable.
[0074]
For the same reason, it is preferable that the number average particle diameter of the further added solid particles is 0.3 to 30 μm.
[0075]
FIG. 5 is a schematic view of a developing device according to an embodiment having the developer carrier of the present invention.
[0076]
In FIG. 5, a latent image holding member for holding an electrostatic latent image formed by a known process, for example, an electrophotographic photosensitive drum 501 is rotated in the direction of arrow B. The developing sleeve 508 as a developer carrying member carries the one-component developer 4 having the magnetic toner supplied by the hopper 503 as the developer container, and rotates in the direction of arrow A to form the developing sleeve 508 with the developing sleeve. The developer 504 is transported to the developing area D where the photosensitive drum 501 faces. As shown in FIG. 5, in the developing sleeve 508, a magnet roller 505 in which a magnet is inscribed is arranged in order to magnetically attract and hold the developer 504 on the developing sleeve 508.
[0077]
The developing sleeve 508 used in the developing device of the present invention has a conductive coating layer 507 coated on a metal cylindrical tube 506 as a base. A stirring blade 510 for stirring the developer 504 is provided in the hopper 503. A gap 513 indicates that the developing sleeve 508 and the magenet roller 505 are in a non-contact state.
[0078]
The developer 504 obtains a triboelectric charge capable of developing an electrostatic latent image on the photosensitive drum 501 by friction between the magnetic toner and the conductive coating layer 507 on the developing sleeve 508. In the example of FIG. 5, in order to regulate the layer thickness of the developer 504 conveyed to the development area D, a magnetic regulation blade 502 made of a ferromagnetic metal as a developer layer thickness regulation member is moved from the surface of the development sleeve 508 to the bottom. It is suspended from the hopper 503 so as to face the developing sleeve 508 with a gap width of about 50 to 500 μm. When the lines of magnetic force from the magnetic pole N1 of the magnet roller 505 concentrate on the magnetic regulating blade 502, a thin layer of the developer 504 is formed on the developing sleeve 508. In the present invention, a non-magnetic blade can be used instead of the magnetic regulating blade 502.
[0079]
In this manner, the thickness of the thin layer of the developer 504 formed on the developing sleeve 508 is preferably smaller than the minimum gap between the developing sleeve 508 and the photosensitive drum 501 in the developing area D. .
[0080]
The developer carrying member of the present invention is particularly effective to be incorporated in a developing device of a system for developing an electrostatic latent image with a thin layer of the developer as described above, that is, a non-contact type developing device. In D, the developer carrier of the present invention can also be applied to a developing device in which the thickness of the developer layer is equal to or greater than the minimum gap between the developing sleeve 508 and the photosensitive drum 501, that is, a contact-type developing device. . In order to avoid the complexity of the description, the following description will be made by taking the above-described non-contact type developing device as an example.
[0081]
A developing bias voltage is applied to the developing sleeve 508 by a developing bias power source 509 as a bias unit in order to fly the one-component developer 504 having the magnetic toner carried on the developing sleeve 508. 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 area where the developer 504 is adhered and visualized) and the potential of the background portion is used as the developing sleeve. 508 is preferably applied.
[0082]
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 508 to form an oscillating electric field in which the direction is alternately reversed in the developing region D. . In this case, it is preferable to apply, to the developing sleeve 508, an alternating bias voltage in which a DC voltage component having a value intermediate between the potential of the developed image portion and the potential of the background portion is superimposed.
[0083]
In the case of so-called regular development, toner is attached to the high potential portion of an electrostatic latent image having a high potential portion and a low potential portion to visualize the toner. I do.
[0084]
In the case of so-called reversal development, a toner charged to the same polarity as the polarity of the electrostatic latent image is used for visualizing the toner by attaching toner to the low potential portion of the electrostatic latent image having a high potential portion and a low potential portion. I do.
[0085]
High potential and low potential are expressed by absolute values. In any of these cases, the developer 504 is charged by at least friction with the developing sleeve 508.
[0086]
FIG. 6 is a schematic configuration diagram illustrating another embodiment of the developing device of the present invention, and FIG. 7 is a schematic configuration diagram illustrating still another embodiment of the developing device of the present invention. In the developing device shown in FIGS. 6 and 7, as a developer layer thickness regulating member for regulating the layer thickness of the developer 504 on the developing sleeve 508, a material having rubber elasticity such as urethane rubber or silicone rubber, or phosphor bronze is used. An elastic regulating blade 511 made of an elastic plate made of a material having a metal elasticity such as stainless steel is used, and the elastic regulating blade 511 is pressed against the rotating direction of the developing sleeve 508 in the developing device of FIG. 7 is characterized in that the elastic regulating blade 511 is pressed against the rotating direction of the developing sleeve 508 in the forward direction. In these developing devices, a thin layer of the developer is formed on the developing sleeve by elastically pressing the developer layer thickness regulating member against the developing sleeve 508 via the developer layer. On the sleeve 508, a thinner developer layer can be formed than in the case of the above-mentioned reference example of FIG.
[0087]
Other basic configurations of the developing devices in FIGS. 6 and 7 are the same as those of the developing device shown in FIG. 11, and those having the same reference numerals indicate basically the same members.
[0088]
FIG. 8 and FIG. 9 are schematic views showing a configuration in which the elasticity regulating member is provided in the developing device using the magnetic toner.
[0089]
5 to 9 schematically illustrate the developing device of the present invention, and it goes without saying that there are various forms in the shape of the developer container (hopper 503), the presence or absence of the stirring blade 510, and the arrangement of the magnetic poles. .
[0090]
Of course, these devices can also be used for development using a two-component developer containing a toner and a carrier.
[0091]
Next, a two-component developing apparatus in which the developer carrier of the present invention is incorporated will be described and exemplified.
[0092]
In FIG. 10, a non-magnetic developing sleeve (developer carrier) 221 as a developer carrier is opposed to an electrostatic latent image carrier 224 rotated in the direction of arrow a in a developing chamber 245 of a developing container 225. In the present invention, a resin coating layer, which cannot be shown, is provided. A magnetic roller 222 as a magnetic field generating means is immovably left in the developing sleeve 221. The magnetic roller 222 is magnetized in the order of S1, N1, S2, N2, and N3 in the rotation direction of the arrow b from a position substantially at the top. Have been. In the developing chamber 245, a two-component developer 241 in which the toner 240 and the magnetic carrier 243 are mixed is accommodated.
[0093]
When the developer 241 is sent into the stirring chamber 242 of the developing container 225 at one end of the developing chamber 245 through one opening (not shown) of the partition 248 that is open at the upper end, the developer 241 is supplied from the toner chamber 247 into the stirring chamber 242. The toner 240 is supplied and conveyed to the other end of the stirring chamber 242 while being mixed by the first developer stirring and conveying means 250 in the stirring chamber 242. The developer 241 conveyed to the other end of the stirring chamber 242 returns to the inside of the developing chamber 245 through the other opening (not shown) of the partition 248, where the second developer agitating / conveying means 251 in the developing chamber 245 The developer is transported to the developing sleeve 221 while being agitated and transported by a third developer agitating / transporting unit that transports the developer in a direction opposite to the transport direction of the transport unit 251 in the upper part of the developing chamber 245. The developer 241 supplied to the developing sleeve 221 is magnetically constrained by the action of the magnetic force of the magnet roller 222, carried on the developing sleeve 221, and provided on a substantially top portion of the developing sleeve 221. While being formed in a thin layer of the developer 241 on the developing sleeve 221 by the regulation by the blade 223, the developer is conveyed to the developing section C facing the latent image holding member 224 with the rotation of the developing sleeve 221 in the direction of the arrow b, Then, the electrostatic latent image on the latent image holding member 224 is developed. The remaining developer 241 not consumed in the development is collected in the developing container 225 by the rotation of the developing sleeve 221. In the developing container 225, the remaining developer 241 which is magnetically constrained on the developing sleeve 221 by the repulsive magnetic field between N2 and N3 of the same nature is peeled off. In order to prevent toner scattering when the developer 241 spikes along the line of magnetic force due to the magnetic pole N2, an elastic seal member 231 is provided at the lower part of the developing container 2 so that one end thereof contacts the developer 241. Fixed and installed. FIG. 10 is only a schematic example, and it goes without saying that there are various forms in the shape of the container, the presence or absence of the stirring member, the arrangement of the magnetic poles, and the like.
[0094]
FIG. 6 is a schematic diagram illustrating a developing device when a non-magnetic one-component developer is used as the toner 504. Here, since the toner is non-magnetic, there is no magnet in the developing sleeve, and a solid metal rod 514 is used as the sleeve. The non-magnetic toner is frictionally charged by friction with the layer thickness regulating blade 511 or the sleeve coat layer 517, and is carried and conveyed on the surface of the developing sleeve 508.
[0095]
In FIG. 7, a stripping member 512 is provided. As the peeling member, a roller member such as resin, rubber, sponge, or a belt member, a brush member, or the like is used. In the drawing, the roller member 512 is rotated in a direction opposite to the developing sleeve 508. The developer that has not been transferred to the photoconductor 501 for development is once peeled off from the sleeve surface by a peeling member, thereby preventing the generation of immobile toner on the sleeve and making the charge of the developer uniform. Further, a metal cylindrical tube is used for the developing sleeve 506.
[0096]
Of the components such as the electrostatic latent image holding member such as the photosensitive drum, the developing device, and the cleaning unit, a plurality of components are integrally combined as a device unit to constitute a process cartridge, and this process cartridge is attached to the device body. Alternatively, it may be configured to be detachable. For example, a process cartridge is formed by integrally supporting the charging unit and the developing device together with the photosensitive drum, and is formed as a single unit detachable from the apparatus main body, and is configured to be detachable using guide means such as rails of the apparatus main body. Is also good. At this time, the above-described process cartridge may be provided with a cleaning unit.
[0097]
11 and 12 show an embodiment of the process cartridge according to the present invention. FIG. 11 illustrates a process cartridge 99 in which a developing device 81, a drum-shaped electrostatic latent image holder (photosensitive drum) 83, a cleaner 94, and a primary charger 91 are integrated.
[0098]
In the process cartridge, when the toner 93 of the developing device 81 runs out, the cartridge is replaced with a new cartridge.
[0099]
In FIG. 11, as the primary charging means, the charging roller 91 is used as the contact charging means, but it 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. A transfer roller 84 is used as a transfer unit. The transfer means may be a contact charging means such as a transfer blade or a non-contact corona charging means. However, the contact charging means is also preferable in that the generation of ozone due to transfer is small.
[0100]
Next, the toner used in the developing device of the present invention 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.
[0101]
As the binder resin used for the toner, generally known resins can be used. 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-based copolymers such as tercopolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or Alicyclic hydrocarbon resins, aromatic petroleum resins, paraffin wax, carnauba wax and the like can be used alone or in combination.
[0102]
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 Violet 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.
[0103]
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 mass based on the mass of the toner.
[0104]
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. 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, and the like. Including block copolymers with vinyl monomers and graft-modified products. 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.
[0105]
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, an organic metal complex and a chelate compound are effective, and examples thereof include a monoazo metal complex, a busethylacetone metal complex, an aromatic hydroxydicarboxylic acid, and an aromatic dicarboxylic acid-based metal complex. 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 their lake pigments (as the lacking agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids Diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate, dicyclohexyltin borate; Emissions compounds, imidazole compounds.
[0106]
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 from 2 to 12 siloxane units per molecule and containing 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, trimethoxysilylγ-propylmorpholine, trime There are Kishishiriru -γ- propyl imidazole.
[0107]
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. Further, 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 a pigment is immersed in the solution. The solid-liquid separation is carried out by filtration or pressing, followed by drying at about 120 to 130 ° C. In the aqueous solution method, about 0.5% of a coupling agent is hydrolyzed in water of a constant pH or water-one solvent, and after the pigment is immersed therein, solid-liquid separation and drying are similarly performed. .
[0108]
As another organic treatment, fine powder treated with silicone oil can be used. Preferred silicone oils have a viscosity of about 0.5 to 10000 mm at 25 ° C.²/ S, preferably 1 to 1000 mm²/ S, such as 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, and 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.
[0109]
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.
[0110]
It is preferable that such a toner is subjected to a sphering treatment and a surface smoothing treatment by various methods, because the transferability becomes 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. And a method of suspending the toner in warm water to form a sphere, and a method of exposing the toner to a hot air flow to form a sphere. 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.
[0111]
The toner can be mixed with a carrier and used as a two-component developer.
[0112]
Examples of the carrier material include magnetic metals such as iron, nickel, and cobalt, and alloys thereof, or alloys containing rare earth elements, hematite, magnetite, manganese-zinc ferrite, nickel-zinc ferrite, and manganese-magnesium ferrite. Soft ferrites such as ferrites and lithium-based ferrites, iron-based oxides such as copper-zinc-based ferrites, and mixtures thereof, as well as ceramic particles such as glass and silicon carbide, resin powders, and resin powders containing magnetic substances And the like, and are usually used as granules having an average particle size of about 20 to 300 μm.
[0113]
As such a carrier, the above-mentioned particulate matter may be directly used as carrier particles.However, in order to adjust the triboelectric charge of the toner or prevent toner spent on the carrier, a silicone resin, a fluororesin, an acrylic resin, or the like is used. The surface of the particles can be appropriately coated with a resin using a coating agent such as a resin or a phenol resin.
[0114]
【Example】
Next, the present invention will be described in more detail with reference to specific examples.
[0115]
<Example 1>
The following resin composition was prepared.
・ Phenol resin intermediate 250 parts by mass
・ Conductive carbon black 15 parts by mass
・ Crystalline graphite (average particle size 4.3 μm) 85 parts by mass
・ Methanol: 350 parts by mass
[0116]
These materials were dispersed by a horizontal continuous sand mill using glass beads to obtain a coating solution A. When the particle size distribution of this stock solution A was measured, the average particle size was 3.9 μm.
[0117]
・ Coating stock solution A 700 parts by mass
・ Aluminum borate granules (average particle size 3.5 μm) 100 parts by mass
・ Methanol 325 parts by mass
Aluminum borate granules and methanol were further added to the stock coating solution A with the above composition, and the aluminum borate granules were dispersed by a sand mill. This dispersion was further diluted with methanol and passed through a 250-mesh and a 500-mesh sieve (Paint 1). At this time, the viscosity of the coating material 1 was 90 mPa · s. A work was prepared by grinding an aluminum cylindrical tube to have an outer diameter of 32 mmφ, a surface roughness Ra of 0.2 μm, a runout of about 5 to 10 μm, and a flange for a developing sleeve attached to one side thereof. The work was placed on a turntable and rotated while masking the end of the sleeve. The coating material 1 was spray-coated on the work while being lowered at a constant speed by a spray gun to obtain a coated sleeve. This was dried and cured at 150 ° C. for 30 minutes using a ventilation dryer to form a resin surface layer. At this time, the thickness of the surface resin coating layer was 13.4 μm, and the surface roughness was Ra = 0.72 μm on average. The volume resistivity of the coating layer was 1.13 Ω · cm.
[0118]
A magnet was attached to the developing sleeve, and a stainless steel flange was fitted to the developing sleeve so that the developing sleeve could be mounted on a developing device of a modified copier NP-6085 manufactured by Canon Inc. The NP-6085 remodeling machine used in this experiment was a 85 machine remodeled into a 95 machine, and the process speed was increased from 513 mm / sec to 573 mm / sec. The sleeve peripheral speed was set to 1.8 times. While replenishing the magnetic toner (described below), continuous durability up to one million sheets was performed and evaluated. For evaluation, comprehensive image evaluation and durability of the coating layer were used as criteria. The environment was a normal temperature and low humidity (N / L) environment of 24 ° C./10% and a high temperature and high humidity (H / H) environment of 30 ° C./80%. The results are shown in Tables 1 and 2. Good images and durability were obtained. The following toner was used.
[0119]
・ Styrene-butyl acrylate resin 100 parts by mass
・ Magnetite 95 parts by mass
・ Low molecular weight polypropylene wax: 4 parts by mass
・ Al complex of di-tert-butylsalicylic acid (negative charge control agent) 3 parts by mass
The above materials were dispersed and mixed by a Henschel mixer, melt-kneaded by a biaxial extruder heated to 130 ° C., and the cooled mixture was roughly pulverized by a hammer mill. The coarsely pulverized material is finely pulverized by a jet mill, and the obtained finely pulverized material is classified by an air classifier. The particle size distribution of the toner is 7.2 μm, the number ratio of particles having a mass average particle diameter of 4 μm or less is 17.5. %, A magnetic toner having a mass ratio of particles of 12.7 μm or more of 0.9% was obtained. To 100 parts by mass of this toner, 0.9 parts by mass of colloidal silica hydrophobized with a silane coupling agent and 3 parts by mass of strontium titanate fine particles were externally added using a Henschel mixer.
[0120]
<Methods for measuring and evaluating physical properties and images>
The measurement of the physical properties of the toner and the developing sleeve and the evaluation of the obtained image were performed by the following methods.
[0121]
[Measuring method]
(1) Measurement of Center Line Average Roughness (Ra) Based on the surface roughness of JIS B0601, a surf coder SE-3300 manufactured by Kosaka Laboratories was used to measure three points in the axial direction and two points in the circumferential direction = 6 points, respectively. The average was taken.
[0122]
(2) Measurement of volume resistance of coating layer
A coating layer having a thickness of 7 to 20 μm is formed on a PET sheet having a thickness of 100 μm, and the conductive layer conforms to the ASTM standard (D-991-82) and the Japanese Rubber Association standard SRIS (2301-1969). The measurement was performed using a voltage drop type digital ohmmeter (manufactured by Kawaguchi Electric Works) provided with a four-terminal electrode for measuring the volume resistance of rubber and plastic. The measurement environment is 20 to 25 ° C and 50 to 60 RH%.
[0123]
(3) Measurement of particle size of graphite / carbon particles
It is measured using a Coulter LS-130 type particle size distribution analyzer (manufactured by Coulter Inc.) of a laser diffraction type particle size distribution meter. As a measurement method, an aqueous module is used, and pure water is used as a measurement solvent. The inside of the measuring system of the particle size distribution meter is washed with pure water for about 5 minutes, 10 to 25 mg of sodium sulfite is added to the measuring system as an antifoaming agent, and the background function is executed.
[0124]
Next, 3 to 4 drops of a surfactant are added to 10 ml of pure water, and 5 to 25 mg of a measurement sample is further added. The aqueous solution in which the sample is suspended is subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser to obtain a sample liquid, and the sample liquid is gradually added to the measurement system of the measurement apparatus. The measurement is performed by adjusting the sample concentration in the measurement system so as to be 45 to 55%, and the number average particle diameter and the volume average particle diameter calculated from the number distribution are obtained. When measuring the paint dispersed in the organic solvent, the measurement is performed in the same manner using a circulation module for the organic solvent.
[0125]
(4) Particle size measurement of aluminum borate particles
The particle size of the aluminum borate particles is measured using an electron microscope. The photographing magnification is 1,000 to 10,000 times. Measure the particle size of the primary particles on the photograph. At this time, the major axis and the minor axis are measured, and the average value is defined as the particle diameter. This is measured for 100 samples, and the 50% value is defined as the average particle size.
[0126]
(5) Measurement of toner and resin particle size
The measurement was performed using a Coulter Counter Multisizer II (manufactured by Coulter Corp.), and the mass-average diameter based on mass derived from the volume distribution was determined.
[0127]
(6) Measurement of film thickness (abrasion amount) of resin coating layer
A laser size measuring device manufactured by KEYENCE was used. Using the controller LS-5500 and the sensor head LS-5040T, the sensor section was separately fixed to a device to which a sleeve fixing jig and a sleeve feeding mechanism were attached, and measurement was performed from the average value of the outer diameter of the sleeve. The measurement was carried out at 30 points in 30 divisions in the longitudinal direction of the sleeve, and after the sleeve was rotated 90 ° in the circumferential direction, 30 points were further measured at a total of 60 points, and the average value was obtained. The outer diameter of the sleeve before the application of the surface coating layer was measured in advance, the outer diameter after the formation of the surface coating layer, and the outer diameter after the durable use were measured, and the difference was defined as the coating film thickness and the shaved amount.
[0128]
[Evaluation method]
(1) Image density
In a copying machine, the copy image density of a 5 mmφ black circle on a test chart with an image ratio of 5.5% is measured for reflection density by a reflection densitometer RD918 (manufactured by Macbeth), and the average value of the five points is taken as the image density. did. In the case of LBP, the image density was measured by similarly measuring the print image density of 5 mm ■, which was sent using a character generator and output by a printer.
[0129]
(2) Fog
The reflectance of a solid white image under the development suitability condition is measured, and the reflectance of an unused transfer paper is further measured, and (the worst value of the reflectance of a solid white image−the maximum value of the reflectance of an unused transfer paper) is calculated. The fog density was used. The reflectance was measured with TC-6DS (manufactured by Tokyo Denshoku). Here, when the measured value is visually judged, 1.5 or less is a level that can hardly be confirmed visually, 2.0 to 3.0 is a level that can be confirmed by observing well, and if it exceeds 4.0, fog appears at first glance. Is a level that can be confirmed.
[0130]
(3) Toner charge amount (Q / M) and toner transport amount (M / S)
The toner carried on the developing sleeve was collected by suction using a metal cylindrical tube and a cylindrical filter. At that time, the charge amount Q stored in the condenser, the collected toner mass M, and the toner were suctioned through the metal cylindrical tube. From the area S, the charge amount per unit mass Q / M (mC / kg) and the toner mass per unit area M / S (dg / m²) Was calculated, and the toner charge amount (Q / M) and the toner transport amount (M / S) were obtained.
[0131]
(4) Blotch (image defect)
Evaluation by referring to various images such as solid black, halftone and line images, and visual observation of toner coat defects on the sleeve such as wavy unevenness and blotch (spotted unevenness) on the developing sleeve. The results were shown by the following indices.
: No image or sleeve can be confirmed at all.
: Slight confirmation on the sleeve, but almost no confirmation on the image.
△: This can be confirmed by seeing through about one image out of several to several tens of images.
Δ ○: The first halftone image or solid black image, which can be confirmed in the first cycle of the sleeve cycle.
Δ: It can be confirmed as a halftone image or a solid black image. Practical level lower limit.
Δ ×: Image defects can be confirmed on the entire solid black image. Impossible level.
×: Can also be confirmed on a solid white image.
[0132]
(5) Uniformity of halftone (white stripe, white band)
In particular, linear or band-shaped streaks that occur in halftone and run in the image traveling direction were evaluated using the following indices.
: No image or sleeve can be confirmed at all.
O: Although it can be confirmed slightly when viewed closely, it can hardly be confirmed at first glance.
○ △: Level slightly confirmed by halftone, but no problem with solid black.
Δ ○: A level at which streaks can be confirmed at halfton, but can be slightly confirmed at solid black.
Δ: Although the difference in shading can be confirmed even with a solid black image, it is about the lower limit of the practical level.
Δ ×: The density difference is conspicuous throughout the solid black image. Impossible level.
×: Image with low density and many streaks.
[0133]
(6) Sleeve ghost
After flushing solid white during image durability, place a solid black bold character or hieroglyphic image on the white of one round of the sleeve of the image chart, and use the image chart with the remaining part in halftone, and bold on halftone The degree of occurrence of ghosts in the image and the hieroglyphic image was evaluated.
: No ghost.
○: Very slight difference in shading, but good
○ △: A level at which slight differences in shading can be confirmed but do not cause any problems
△ ○: Intermediate level between ○ △ and △
Δ: Ghosts are somewhat conspicuous. Within practical level.
N1: Negative ghost (thin ghost part), which is a problem in practical use, appears for one round of the sleeve
P1: Positive coast (dark ghost), which is a problem in practical use, appears for one turn of the sleeve
N2: Negative ghost, which poses a problem in practical use, appears for two or more turns of the sleeve
P2: Positive coast, which is a problem in practical use, appears for 2 or more turns of the sleeve
[0134]
<Example 2>
・ Coating stock solution A 700 parts by mass
・ Aluminum borate granules (average particle size 5.2 μm) 80 parts by mass
・ Methanol 295 parts by mass
A coating material was prepared in the same manner as in Example 1 except that the above conditions were used (paint 2). The viscosity of this paint was 85 mPa · s. A surface resin layer was formed in the same manner as in Example 1. At this time, the thickness of the surface resin coating layer was 13.2 μm, and the surface roughness Ra was 0.94 μm. The volume resistance value of the coating layer was 1.10 Ω · cm. The same evaluation as in Example 1 was performed using this developing sleeve. The results are shown in Tables 1 and 2.
[0135]
<Comparative Example 1>
After the stock solution A was diluted with methanol, a sieving operation was performed to obtain a paint (paint 51). The viscosity of this paint was 65 mPa · s. A surface resin layer was formed in the same manner as in Example 1. At this time, the thickness of the surface resin coating layer was 13.0 μm, and the surface roughness Ra was 0.44 μm. The volume resistance of the coating layer was 0.94 Ω · cm. The same evaluation as in Example 1 was performed using this developing sleeve. Since the resin surface coating layer was shaved due to durability, the surface roughness was reduced and image defects occurred. The results are shown in Tables 1 and 2.
[0136]
<Comparative Example 2>
In stock solution A (paint 51 of Comparative Example 1), stock solution B was prepared by changing the average particle size of crystalline graphite from 4.3 μm to 10.2 μm. When the particle size distribution of the stock solution B after dispersion was measured, the average particle size was 9.5 μm. After diluting stock solution B with methanol, the previous operation was performed to obtain a paint (paint 52). The viscosity of this paint was 67.5 mPa · s. A surface resin layer was formed in the same manner as in Example 1. At this time, the thickness of the surface resin coating layer was 14.0 μm, and the surface roughness Ra was 0.89 μm. The volume resistance of the coating layer was 1.02 Ω · cm. The same evaluation as in Example 1 was performed using this developing sleeve. Since graphite was the main particle for forming the roughness of the resin surface coating layer, it was greatly scraped by the durability and image defects occurred due to the durability. The results are shown in Tables 1 and 2.
[0137]
<Comparative Example 3>
・ Coating stock solution A 700 parts by mass
・ Cross-linked PMMA spherical particles (average particle size: 4.8 μm) 80 parts by mass
・ Methanol 295 parts by mass
A paint was prepared in the same manner as in Example 1 except that the paint was used (paint 53). The viscosity of this paint was 82.5 mPa · s. A surface resin layer was formed in the same manner as in Example 1. At this time, the thickness of the surface resin coating layer was 13.5 μm, and the surface roughness Ra was 1.00 μm. The volume resistance of the coating layer was 1.25 Ω · cm. The same evaluation as in Example 1 was performed using this developing sleeve. The surface roughness decreased due to the durability, and image defects occurred. The results are shown in Tables 1 and 2.
[0138]
<Comparative Example 4>
The same aluminum cylindrical tube as in Example 1 was roughened to a surface roughness Ra = 1.50 μm by sandblasting. Using this work, a resin coating layer was formed on the blast surface in the same manner as in Example 1 using the paint 51 of Comparative Example 1. At this time, the thickness of the surface resin coating layer was 11.7 μm, and the surface roughness Ra was 0.99 μm. The volume resistivity of the coating layer was equivalent to that of Comparative Example 1. The same evaluation as in Example 1 was performed using this developing sleeve. Even when blasting was applied to the base, the abrasion of the resin itself was the same as in Comparative Example 1, and as the abrasion proceeded from the convex portions, the resin was smoothened by durability and image defects occurred. In addition, density irregularity at the sleeve pitch occurred due to deformation of the aluminum cylindrical tube due to blasting. The results are shown in Tables 1 and 2.
[0139]
<Example 3>
The following resin composition was prepared.
・ Polyurethane resin 250 parts by mass
・ Conductive carbon black 20 parts by mass
・ Crystalline graphite (average particle size: 4.3 μm) 80 parts by mass
・ Toluene / MIBK / IPA mixed solventＡ525 parts by mass
[0140]
These materials were dispersed by a horizontal continuous sand mill using glass beads to obtain a coating solution C. When the particle size distribution of this stock solution C was measured, the average particle size was 4.0 μm.
[0141]
・ Coating solution C 875 parts by mass
・ Aluminum borate granules (average particle size 3.5 μm) 50 parts
・ Imidazole compound of the following formula (1) (average particle size 4.1 μm) 50 parts by mass
・ Toluene / MIBK / IPA mixed solventＡ310 parts by mass
The aluminum borate granules, the imidazole compound, and the above-mentioned mixed solvent were further added to the coating solution C with the above composition, and the aluminum borate granules and the imidazole compound were dispersed by a sand mill. This dispersion was further diluted with a mixed solvent, and passed through sieves of 250 mesh and 500 mesh (paint 3). The viscosity of the paint 3 at this time was 50 mPa · s. Using this paint, a surface resin layer was formed in the same manner as in Example 1. At this time, the thickness of the surface resin coating layer was 12.9 μm, and the surface roughness Ra was 0.81 μm. The volume resistance of the coating layer was 1.16 Ω · cm. The same evaluation as in Example 1 was performed using this developing sleeve. The results are shown in Tables 1 and 2.
[0142]
<Example 4>
・ Coating stock solution A 700 parts by mass
・ Aluminum borate granules (average particle size 3.5 μm) 90 parts
・ Imidazole compound of the following formula (1) (average particle size 4.1 μm) 10 parts by mass
・ Methanol 325 parts by mass
Aluminum borate granules and methanol were further added to the stock coating solution A with the above composition, and the aluminum borate granules were dispersed by a sand mill. This dispersion was further diluted with methanol and passed through a 250-mesh and a 500-mesh sieve (paint 4). At this time, the viscosity of the coating material 4 was 92.5 mPa · s. Using this paint, a surface resin layer was formed in the same manner as in Example 1. At this time, the thickness of the surface resin coating layer was 13.8 μm, and the surface roughness Ra was 0.79 μm. The volume resistance value of the coating layer was 1.03 Ω · cm. The same evaluation as in Example 1 was performed using this developing sleeve. The following toner was used.
[0143]
・ 100% by mass of polyester resin
・ Magnetite 95 parts by mass
・ Alcohol wax 4 parts by mass
・ Al complex of di-tert-butylsalicylic acid (negative charge control agent) 4 parts by mass
The above materials were dispersed and mixed by a Henschel mixer, melt-kneaded by a biaxial extruder heated to 130 ° C., and the cooled mixture was roughly pulverized by a hammer mill. The coarsely pulverized product is finely pulverized by a jet mill, and the obtained finely pulverized product is classified by an air classifier. The particle size distribution of the toner is such that the mass average particle diameter is 7.0 μm, and the number ratio of particles having a weight average particle diameter of 4 μm or less is 18.5. %, A magnetic toner having a mass ratio of particles of 12.7 μm or more of 0.8% was obtained. To 100 parts by mass of the toner, 1.0 part by mass of colloidal silica hydrophobized with a silane coupling agent and 4 parts by mass of strontium titanate fine particles were externally added using a Henschel mixer. The results are shown in Tables 1 and 2.
[0144]
<Comparative Example 5>
・ Coating stock solution A 700 parts by mass
・ Cross-linked PMMA particles (average particle size 4.6 μm) 70 parts by mass
・ Imidazole compound of the following formula (1) (average particle size 4.1 μm) 10 parts by mass
・ Methanol 295 parts by mass
[0145]
In Example 4, a coating material was prepared in the same manner as in Example 1 except that PMMA particles were used instead of the aluminum borate particles (paint 55). At this time, the viscosity of the paint 55 was 87.5 mPa · s. Using this paint, a surface resin layer was formed in the same manner as in Example 1. At this time, the thickness of the surface resin coating layer was 14.1 μm, and the surface roughness Ra was 0.91 μm. The volume resistivity of the coating layer was 1.13 Ω · cm. The same evaluation as in Example 4 was performed using this developing sleeve. The results are shown in Tables 1 and 2.
[0146]
Embedded image

[0147]
<Example 5>
The following resin composition was prepared.
・ Phenol resin intermediate 100 parts by mass
・ Conductive carbon black 20 parts by mass
・ Methanol 120 parts by mass
[0148]
These materials were dispersed by a horizontal continuous sand mill using glass beads to obtain a stock coating solution D.
・ Paint stock solution D 原 240 mass parts
・ Aluminum borate granules (average particle size 2.8 μm) 100 parts by mass
・ Methanol 210 parts by mass
[0149]
Aluminum borate granules and methanol were further added to the stock coating solution D with the above composition, and the aluminum borate granules were dispersed by a sand mill. This dispersion was further diluted with methanol and passed through a 350 mesh sieve (paint 5). At this time, the viscosity of the coating material 5 was 55 mPa · s. A work was prepared by grinding an aluminum cylindrical tube to have an outer diameter of 32 mmφ, a surface roughness Ra of 0.2 μm, a runout of about 5 to 10 μm, and a flange for a developing sleeve attached to one side thereof. The work was placed on a turntable and rotated while masking the end of the sleeve, and the paint 5 was spray-coated on the work while being lowered at a constant speed by a spray gun to obtain a coated sleeve. This was dried and cured at 150 ° C. for 30 minutes using a ventilation dryer to form a resin surface layer. At this time, the thickness of the surface resin coating layer was 18.5 μm, and the surface roughness was Ra = 0.60 μm on average. The volume resistance of the coating layer was 12.3 Ω · cm.
[0150]
A magnet was attached to the developing sleeve, and a stainless steel flange was fitted. Using cyan toner, evaluate image output up to 50,000 sheets, and then, to confirm the durability of the developing sleeve, perform an idle rotation test up to 200,000 sheets equivalent to confirm the abrasion and surface roughness of the coating, Further, the characteristics were evaluated when the developer was replaced with a new developer. The environment was set in a normal temperature and normal humidity (N / N) environment of 24 ° C./60%. The following were used as the developer.
[0151]
・ 100% by mass of polyester resin
・ Phthalocyanine pigment (cyan) 5 parts by mass
・ Al complex of di-tert-butylsalicylic acid 酸 6 parts by mass
5 parts by mass of the polyester resin and 5 parts by mass of the phthalocyanine pigment are sufficiently kneaded in advance using three rolls to prepare a master batch. After the pulverized master batch, the remaining polyester resin, and the Al complex of ditertiary butyl salicylic acid were sufficiently mixed using a Henschel mixer, the mixture was melt-kneaded with a twin-screw extruder heated to 110 ° C., and the cooled mixture was hammered. Coarsely pulverized with a mill. The coarsely pulverized product is finely pulverized by a jet mill, and the obtained finely pulverized product is classified by an air classifier. %, And a cyan toner having a mass ratio of particles of 12.7 μm or more of 1.8% was obtained. 1.8 parts by mass of hydrophobic titanium oxide fine particles were used as an externally added toner with a Henschel mixer to 100 parts by mass of this toner. 1.0% of a silicone resin was added to ferrite particles classified with an average particle size of 35 to 50 μm, mixed, heated and cured, then crushed, sieved, and used as a carrier for development. The toner T and the carrier C were mixed so that the T / C ratio became 7%, and used as a start agent.
[0152]
Table 3 shows the results.
[0153]
<Example 6>
・ Paint stock solution D 原 240 mass parts
・ Aluminum borate granules (average particle size 2.8 μm) 60 parts by mass
・ Aluminum borate granules (average particle size: 7.8 μm) 30 parts by mass
・ Methanol 190 parts by mass
A coating material was prepared in the same manner as in Example 5, except that The viscosity of this paint was 52.5 mPa · s. A surface resin layer was formed in the same manner as in Example 5. At this time, the thickness of the surface resin coating layer was 19.5 μm, and the surface roughness Ra was 0.91 μm. The volume resistance of the coating layer was 11.0 Ω · cm. The same evaluation as in Example 5 was performed using this developing sleeve. Table 3 shows the results.
[0154]
<Comparative Example 6>
After the stock solution D was diluted with methanol, a sieving operation was performed to obtain a paint (paint 56). The viscosity of this paint was 30 mPa · s. A surface resin layer was formed in the same manner as in Example 1. At this time, the thickness of the surface resin coating layer was 17.0 μm, and the surface roughness Ra was 0.25 μm. The volume resistance of the coating layer was 9.6 Ω · cm. The same evaluation as in Example 5 was performed using this developing sleeve. Since sufficient surface roughness was not obtained, image defects occurred. In addition, since the resin surface coating layer was shaved, the surface of the base was beginning to be exposed. Table 3 shows the results.
[0155]
<Comparative Example 7>
The aluminum cylindrical tube was subjected to sandblasting using # 150 glass beads to obtain a roughened surface having a surface roughness Ra of 0.85 μm. The same evaluation as in Example 5 was performed using this developing sleeve. Table 3 shows the results. The surface roughness was significantly reduced due to durability. In addition, sleeve contamination by toner occurred.
[0156]
<Comparative Example 8>
A stainless steel cylindrical tube was used in place of the aluminum cylindrical tube. Since the stainless steel itself is hard, it is difficult to break the glass beads to obtain a predetermined roughness, so that the blast was performed by Alundum # 150. A rough surface having a surface roughness Ra = 0.86 μm was obtained. The same evaluation as in Example 5 was performed using this developing sleeve. Although the surface roughness was not reduced as in the case of the aluminum cylindrical tube, sleeve contamination by toner occurred. Table 3 shows the results.
[0157]
<Example 7>
・ Polyurethane resin 100 parts by mass
・ Conductive carbon black 10 parts by mass
・ Crystalline graphite (average particle size: 4.3 μm) 10 parts by mass
・ Toluene / MIBK / IPA mixed solventＡ120 parts by mass
[0158]
These materials were dispersed by a horizontal continuous sand mill using glass beads to obtain a coating solution E.
[0159]
・ Paint stock solution E 液 240 mass parts
・ Aluminum borate granules (average particle size 2.8 μm) 60 parts by mass
・ Aluminum borate granules (average particle size: 7.8 μm) 30 parts by mass
・ Toluene / MIBK / IPA mixed solventＡ210 parts by mass
Aluminum borate granules and a mixed solvent of toluene, MIBK, and IPA were further added to the stock coating solution E with the above composition, and the aluminum borate granules were dispersed by a sand mill. This dispersion was further diluted with a mixed solvent of toluene, MIBK, and IPA, and passed through a 350 mesh jaw (Paint 7). At this time, the viscosity of the paint 7 was 47.5 mPa · s. A surface resin layer was formed in the same manner as in Example 1. At this time, the thickness of the surface resin coating layer was 18.8 μm, and the surface roughness Ra was 0.89 μm. The volume resistivity of the coating layer was 15.4 Ω · cm. The same evaluation as in Example 5 was performed using this developing sleeve. Table 3 shows the results.
[0160]
The sleeve contamination evaluation was determined based on the following criteria. Basically, a portion of the sleeve was blown off with toner with air, wiped lightly with a rag, rubbed with a rag soaked with ethanol, and evaluated for the degree of dirt.
: No contamination.
○: Slightly bluish in the waste soaked in the solvent.
△: The waste stains blue without solvent
Δ ×: It can be seen that contamination does not fly by simple air blowing. The waste is quite dirty.
×: fairly strong adhesion state.
[0161]
<Example 8>
・ Coating stock solution A 700 parts by mass
・ Aluminum borate granules (average particle size 9.8 μm) 40 parts by mass
・ Methanol 235 parts by mass
[0162]
Aluminum borate granules and methanol were further added to the stock coating solution A with the above composition, and the aluminum borate granules were dispersed by a sand mill. This dispersion was further diluted with methanol, and passed through sieves of 250 mesh and 500 mesh (paint 8). At this time, the viscosity of the coating material 8 was 70 mPa · s. An aluminum cylindrical tube having an aluminum flange on one side was integrally ground to have an outer diameter of 20 mm, a surface roughness Ra of 0.2 μm, and a runout of about 5 μm. The work was placed on a turntable and rotated while masking the end of the sleeve, and the paint 8 was spray-coated on the work while being lowered at a constant speed by a spray gun to obtain a coated sleeve. This was dried and cured at 150 ° C. for 30 minutes using a ventilation dryer to form a resin surface layer. At this time, the thickness of the surface resin coating layer was 12.8 μm, and the average surface roughness was Ra = 1.58 μm. The volume resistivity of the coating layer was 0.97 Ω · cm.
[0163]
A magnet was attached to this developing sleeve, and an aluminum flange was fitted on the other side, so that it could be attached to a cartridge developing device of a modified laser beam printer LBP-930 manufactured by Canon Inc. The LBP-930 remodeling machine used in this experiment was a LBP-930 base modified from a 24-sheet A4 sheet feeding machine equivalent to 50 sheets, and the process speed was increased from 106 mm / sec to 236 mm / sec. In addition, the peripheral speed of the sleeve was set to 1.3 times the peripheral speed of the drum. Furthermore, the capacity of the toner container has been increased. Further, in order to prevent non-uniform regulation by the developer regulating blade due to high speed, the regulating member is reinforced with a metal plate to increase the blade pressing force. The main body and the cartridge are each provided with mechanical strength reinforcement. An image signal was sent from an external character generator (CG), and an image was output to produce an image. Each time the residual toner check of the cartridge was displayed, a continuous durability test was performed on up to 60,000 sheets while replenishing the magnetic toner, and evaluation was performed. The environment was a normal temperature and low humidity (N / L) environment of 24 ° C./10% RH and a high temperature and high humidity (H / H) environment of 30 ° C./80% RH. The results are shown in Tables 4 and 5.
[0164]
The following toner was used.
・ Styrene-butyl acrylate resin 100 parts by mass
・ Magnetite 100 parts by mass
・ Low molecular weight polyethylene wax: 3 parts by mass
・ Long chain alcohol wax 3 parts by mass
・ Azo-based Fe complex compound (negative charge control agent) 3 parts by mass
The above materials were dispersed and mixed by a Henschel mixer, melt-kneaded by a biaxial extruder heated to 130 ° C., and the cooled mixture was roughly pulverized by a hammer mill. The coarsely pulverized product is finely pulverized by a jet mill, and the obtained finely pulverized product is classified by an air classifier. The particle size distribution of the toner is as follows. %, A magnetic toner having a mass ratio of particles of 12.7 μm or more of 0.4% was obtained. To 100 parts by mass of this toner, 1.2 parts by mass of colloidal silica treated with a silane coupling agent and silicone oil and 0.5 part by mass of strontium titanate fine particles were externally added using a Henschel mixer.
[0165]
<Example 9>
・ Coating stock solution A 700 parts by mass
・ Aluminum borate granules (average particle size 9.8 μm) 30 parts by mass
・ Aluminum borate granules (average particle size 2.8 μm) 30 parts by mass
・ Methanol 265 parts by mass
A coating material was prepared in the same manner as in Example 8 except that the above conditions were used (Paint 9). The viscosity of this paint was 55 mPa · s. A surface resin layer was formed in the same manner as in Example 8. At this time, the thickness of the surface resin coating layer was 13.2 μm, and the surface roughness Ra was 1.50 μm. The volume resistivity of the coating layer was 1.05 Ω · cm. The same evaluation as in Example 8 was performed using this developing sleeve. The results are shown in Tables 4 and 5.
[0166]
<Example 10>
・ Coating stock solution A 700 parts by mass
・ Aluminum borate granules (average particle size 9.8 μm) 30 parts by mass
・ Imidazole compound of formula (1) (average particle size 4.1 μm) 20 parts by mass
・ Methanol 250 parts by mass
A coating material was prepared in the same manner as in Example 8 except that the imidazole compound was further added after dispersing the aluminum borate particles (paint 10). The viscosity of this paint was 75 mPa · s. A surface resin layer was formed in the same manner as in Example 8. At this time, the thickness of the surface resin coating layer was 13.2 μm, and the surface roughness Ra was 1.58 μm. The volume resistivity of the coating layer was 1.11 Ω · cm. The same evaluation as in Example 8 was performed using this developing sleeve. The results are shown in Tables 4 and 5.
[0167]
<Example 11>
・ Coating stock solution A 700 parts by mass
・ Aluminum borate granules (average particle size 2.8 μm) 30 parts by mass
・ Spherical carbon particles (average particle size: 9.7 μm) 30 parts by mass
・ Methanol 265 parts by mass
A coating material was prepared in the same manner as in Example 8 except that spherical carbon particles were further added after dispersing the aluminum borate particles (paint 11). The viscosity of this paint was 47.5 mPa · s. A surface resin layer was formed in the same manner as in Example 8. At this time, the thickness of the surface resin coating layer was 13.2 μm, and the surface roughness Ra was 1.55 μm. The volume resistivity of the coating layer was 0.95 Ω · cm. The same evaluation as in Example 8 was performed using this developing sleeve. The results are shown in Tables 4 and 5.
[0168]
<Example 12>
・ Coating stock solution A 700 parts by mass
・ Aluminum borate granules (average particle size: 9.8 μm) 20 parts by mass
・ Spherical carbon particles (average particle size: 9.7 μm) 20 parts by mass
・ Methanol 235 parts by mass
A coating material was prepared in the same manner as in Example 8 except that the aluminum borate particles were dispersed and spherical carbon particles were further added (paint 12). The viscosity of this paint was 52.5 mPa · s. A surface resin layer was formed in the same manner as in Example 8. At this time, the thickness of the surface resin coating layer was 14.0 μm, and the surface roughness Ra was 1.65 μm. The volume resistance of the coating layer was 0.98 Ω · cm. The same evaluation as in Example 8 was performed using this developing sleeve. The results are shown in Tables 4 and 5.
[0169]
<Example 13>
・ Coating stock solution A 700 parts by mass
・ Aluminum borate granules (average particle size 16.0 μm) 20 parts by mass
・ Methanol 235 parts by mass
A coating material was prepared in the same manner as in Example 8 except that the above conditions were used (Paint 13). The viscosity of this paint was 55 mPa · s. A surface resin layer was formed in the same manner as in Example 8. At this time, the thickness of the surface resin coating layer was 13.5 μm, and the surface roughness Ra was 1.62 μm. The volume resistivity of the coating layer was 0.99 Ω · cm. The same evaluation as in Example 8 was performed using this developing sleeve. The results are shown in Tables 4 and 5.
[0170]
<Example 14>
・ Coating stock solution A 700 parts by mass
・ Aluminum borate granules (average particle size 27.5 μm) 15 parts by mass
・ Methanol 235 parts by mass
A coating material was prepared in the same manner as in Example 8 except that the above conditions were used (Paint 14). The viscosity of this paint was 55 mPa · s. A surface resin layer was formed in the same manner as in Example 8. At this time, the thickness of the surface resin coating layer was 14.6 μm, and the surface roughness Ra was 1.82 μm. The volume resistivity of the coating layer was 0.98 Ω · cm. The same evaluation as in Example 8 was performed using this developing sleeve. The results are shown in Tables 4 and 5.
[0171]
<Comparative Example 9>
After the stock solution A was diluted with methanol, a sieving operation was performed to obtain a paint (paint 59). The viscosity of this paint was 60 mPa · s. A surface resin layer was formed in the same manner as in Example 8. At this time, the thickness of the surface resin coating layer was 13.1 μm, and the surface roughness Ra was 0.40 μm, and the surface roughness could not be increased even if the coating conditions were changed. The volume resistivity of the coating layer was 0.94 Ω · cm. The same evaluation as in Example 8 was performed using this developing sleeve. Since the resin surface coating layer was shaved due to durability, the surface roughness was reduced and image defects occurred. The results are shown in Tables 4 and 5.
[0172]
<Comparative Example 10>
In Stock Solution A, Stock Solution F was prepared by changing the average particle size of crystalline graphite from 4.3 μm to 25.0 μm. When the particle size distribution of the stock solution B after dispersion was measured, the average particle size was 23.5 μm. After the stock solution F was diluted with methanol, a sieving operation was performed to obtain a paint (paint 60). The viscosity of this paint was 57.5 mPa · s. A surface resin layer was formed in the same manner as in Comparative Example 9. At this time, the thickness of the surface resin coating layer was 14.8 μm, and the surface roughness Ra was 1.48 μm. The volume resistivity of the coating layer was 1.54 Ω · cm. The same evaluation as in Example 8 was performed using this developing sleeve. Since graphite was the main particle for forming the roughness of the resin surface coating layer, it was largely scraped by durability and image defects occurred due to durability. The results are shown in Tables 4 and 5.
[0173]
<Comparative Example 11>
Stock solution of paint A 700 parts by mass
Crosslinked PMMA spherical particles (average particle diameter 10.3 μm) 20 parts by mass
Methanol @ 235 parts by mass
A coating material was prepared in the same manner as in Example 8 except that the above conditions were used (Paint 61). The viscosity of this paint was 52.5 mPa · s. A surface resin layer was formed in the same manner as in Example 8. At this time, the thickness of the surface resin coating layer was 14.5 μm, and the surface roughness Ra was 1.52 μm. The volume resistivity of the coating layer was 1.08 Ω · cm. The same evaluation as in Example 8 was performed using this developing sleeve. The surface roughness was greatly reduced. The results are shown in Tables 4 and 5.
[0174]
<Comparative Example 12>
・ Coating stock solution A 700 parts by mass
・ Crosslinked PMMA spherical particles (average particle size 26.3 μm) 15 parts by mass
・ Methanol 235 parts by mass
A coating material was prepared in the same manner as in Example 8 except that the above conditions were used (Paint 62). The viscosity of this paint was 50 mPa · s. A surface resin layer was formed in the same manner as in Example 8. At this time, the thickness of the surface resin coating layer was 14.6 μm, and the surface roughness Ra was 1.90 μm. The volume resistivity of the coating layer was 1.05 Ω · cm. The same evaluation as in Example 8 was performed using this developing sleeve. The surface roughness was greatly reduced. The results are shown in Tables 4 and 5.
[0175]
<Comparative Example 13>
・ Coating stock solution A 700 parts by mass
・ Spherical carbon particles (average particle size: 9.7 μm) 30 parts by mass
・ Methanol 220 parts by mass
A coating material was prepared in the same manner as in Example 8 except that the above conditions were used (paint 63). The viscosity of this paint was 50 mPa · s. A surface resin layer was formed in the same manner as in Example 8. At this time, the thickness of the surface resin coating layer was 14.6 μm, and the surface roughness Ra was 1.49 μm. The volume resistance value of the coating layer was 1.00 Ω · cm. The same evaluation as in Example 8 was performed using this developing sleeve. The spherical carbon particles themselves have considerable strength against abrasion, and the change in surface roughness is much smaller than that of PMMA particles, but slightly inferior to that of aluminum borate particles. In addition, although the particles themselves were small and had an effect of maintaining the surface roughness to some extent, the effect of reinforcing the resin layer was slightly inferior and the decrease in the film thickness was somewhat large. The results are shown in Tables 4 and 5.
[0176]
<Comparative Example 14>
The same aluminum cylindrical tube as in Example 1 was subjected to sandblasting using # 100 alundum abrasive grains to roughen to a surface roughness Ra of 2.15 μm. Using this work, a resin coating layer was formed on the blast surface in the same manner as in Example 8 using the paint 59 of Comparative Example 9. At this time, the thickness of the surface resin coating layer was 11.5 μm, and the surface roughness Ra was 1.89 μm. The volume resistivity of the coating layer was equivalent to that of Comparative Example 9. The same evaluation as in Example 8 was performed using this developing sleeve. Even when blasting was applied to the base, the abrasion of the resin itself was the same as in Comparative Example 9, and as the abrasion progressed from the convex portions, the surface became smoother due to durability and image defects occurred. In addition, density irregularity at the sleeve pitch occurred due to deformation of the aluminum cylindrical tube due to blasting. The results are shown in Tables 4 and 5.
[0177]
[Table 1]

[0178]
[Table 2]

[0179]
[Table 3]

[0180]
[Table 4]

[0181]
[Table 5]

[0182]
Hereinafter, examples using organically treated aluminum borate granules will be described.
[0183]
<Example 15>
The following resin composition was prepared.
・ Phenol resin intermediate 250 parts by mass
・ Conductive carbon black 15 parts by mass
・ Crystalline graphite (average particle size 4.3 μm) 85 parts by mass
・ Methanol: 350 parts by mass
[0184]
These materials were dispersed by a horizontal continuous sand mill using glass beads to obtain a coating solution A. When the particle size distribution of this stock solution A was measured, the average particle size was 3.9 μm.
[0185]
Next, 100 parts by mass of aluminum borate granules (average particle size: 3.5 μm) were added to a solution of 0.05 parts by mass of a methacryloxysilane-based coupling agent as a silane coupling agent dissolved in 20 parts by mass of methyl ethyl ketone. After maintaining the temperature at 70 ° C. while stirring and evaporating the solvent, the solution was placed in an oven at 150 ° C. and cured.
[0186]
・ Coating stock solution A 700 parts by mass
・ Aluminum borate granules treated with methacryloxysilane coupling agent
(Average particle size 3.5 μm) 100 parts by mass
・ Methanol 325 parts by mass
Aluminum borate granules treated with a methacryloxysilane-based coupling agent and methanol were further added to the stock coating solution A with the above composition, and the aluminum borate granules were dispersed by a sand mill. This dispersion was further diluted with methanol and passed through a 250-mesh and a 500-mesh sieve (paint 1 '). At this time, the viscosity of the coating material 1 'was 95 mPa · s. A work was prepared by grinding an aluminum cylindrical tube to have an outer diameter of 32 mmφ, a surface roughness Ra of 0.2 μm, a runout of about 5 to 10 μm, and a flange for a developing sleeve attached to one side thereof. A work was placed on a turntable and rotated while masking the end of the sleeve. The paint 1 'was spray-coated on the work while being lowered at a constant speed by a spray gun to obtain a coated sleeve. This was dried and cured at 150 ° C. for 30 minutes using a ventilation dryer to form a resin surface layer. At this time, the thickness of the surface resin coating layer was 13.4 μm, and the surface roughness was Ra = 0.72 μm on average. The volume resistivity of the coating layer was 1.13 Ω · cm.
[0187]
A magnet was attached to the developing sleeve, and a stainless steel flange was fitted to the developing sleeve so that the developing sleeve could be mounted on a developing device of a modified copier NP-6085 manufactured by Canon Inc. The NP-6085 remodeling machine used in this experiment was a 85 machine remodeled into a 95 machine, and the process speed was increased from 513 mm / sec to 573 mm / sec. The sleeve peripheral speed was set to 1.8 times. While replenishing the magnetic toner (described below), continuous durability up to one million sheets was performed and evaluated. For evaluation, comprehensive image evaluation and durability of the coating layer were used as criteria. The environment was a normal temperature and low humidity (N / L) environment of 24 ° C./10% and a high temperature and high humidity (H / H) environment of 30 ° C./80%. The results are shown in Tables 6 and 7. Good images and durability were obtained. The following toner was used.
[0188]
・ Styrene-butyl acrylate resin 100 parts by mass
・ Magnetite 95 parts by mass
・ Low molecular weight polypropylene wax: 4 parts by mass
・ Al complex of di-tert-butylsalicylic acid (negative charge control agent) 3 parts by mass
The above materials were dispersed and mixed by a Henschel mixer, melt-kneaded by a biaxial extruder heated to 130 ° C., and the cooled mixture was roughly pulverized by a hammer mill. The coarsely pulverized material is finely pulverized by a jet mill, and the obtained finely pulverized material is classified by an air classifier. The particle size distribution of the toner is 7.2 μm, the number ratio of particles having a mass average particle diameter of 4 μm or less is 17.5. %, A magnetic toner having a mass ratio of particles of 12.7 μm or more of 0.9% was obtained. To 100 parts by mass of this toner, 0.9 parts by mass of colloidal silica hydrophobized with a silane coupling agent and 3 parts by mass of strontium titanate fine particles were externally added using a Henschel mixer.
[0189]
<Example 16>
Aluminum borate granules (average particle size 5.2 μm) were treated with an aminosilane coupling agent in the same manner as in Example 15.
[0190]
・ Coating stock solution A 700 parts by mass
-Aluminum borate granules treated with aminosilane-based coupling agents (average granules
Diameter 5.2μm) 80 mass parts
・ Methanol 295 parts by mass
A coating material was prepared in the same manner as in Example 15 except that the above conditions were used (Paint 2 '). The viscosity of this paint was 90 mPa · s. A surface resin layer was formed in the same manner as in Example 15. At this time, the thickness of the surface resin coating layer was 13.2 μm, and the surface roughness Ra was 0.94 μm. The volume resistance value of the coating layer was 1.10 Ω · cm. The same evaluation as in Example 1 was performed using this developing sleeve. The results are shown in Tables 6 and 7.
[0191]
<Example 17>
The following resin composition was prepared.
・ Polyurethane resin 250 parts by mass
・ Conductive carbon black 20 parts by mass
・ Crystalline graphite (average particle size: 4.3 μm) 80 parts by mass
・ Toluene / MIBK / IPA mixed solventＡ525 parts by mass
[0192]
These materials were dispersed by a horizontal continuous sand mill using glass beads to obtain a coating solution C. When the particle size distribution of this stock solution C was measured, the average particle size was 4.0 μm.
[0193]
Next, aluminum borate granules (average particle size: 3.5 μm) were subjected to coupling treatment using hexamethyldisilazane (HMDS) in the same manner as in Example 15, and then 0.15 parts by mass of dimethyl silicone oil was obtained. Was mixed with a solution diluted with a solvent, the solvent was evaporated and removed under reduced pressure, and then heat treatment was performed at 190 ° C. to obtain oil-treated aluminum borate granules.
[0194]

The aluminum borate granules, the imidazole compound, and the above-mentioned mixed solvent were further added to the coating solution C with the above composition, and the aluminum borate granules and the imidazole compound were dispersed by a sand mill. This dispersion was further diluted with a mixed solvent and passed through a 250-mesh and a 500-mesh sieve (paint 3 '). At this time, the viscosity of the coating material 3 ′ was 55 mPa · s. Using this paint, a surface resin layer was formed in the same manner as in Example 15. At this time, the thickness of the surface resin coating layer was 12.9 μm, and the surface roughness Ra was 0.81 μm. The volume resistance of the coating layer was 1.16 Ω · cm. The same evaluation as in Example 15 was performed using this developing sleeve. The results are shown in Tables 6 and 7.
[0195]
<Example 18>

Aluminum borate granules and methanol were further added to the stock coating solution A with the above composition, and the aluminum borate granules were dispersed by a sand mill. This dispersion was further diluted with methanol and passed through a 250-mesh and a 500-mesh sieve (paint 4 '). At this time, the viscosity of the paint 4 'was 97.5 mPa · s. Using this paint, a surface resin layer was formed in the same manner as in Example 15. At this time, the thickness of the surface resin coating layer was 13.8 μm, and the surface roughness Ra was 0.79 μm. The volume resistance value of the coating layer was 1.03 Ω · cm. The same evaluation as in Example 15 was performed using this developing sleeve. The following toner was used.
[0196]
・ 100% by mass of polyester resin
・ Magnetite 95 parts by mass
・ Alcohol wax 4 parts by mass
・ Al complex of di-tert-butylsalicylic acid (negative charge control agent) 4 parts by mass
The above materials were dispersed and mixed by a Henschel mixer, melt-kneaded by a biaxial extruder heated to 130 ° C., and the cooled mixture was roughly pulverized by a hammer mill. The coarsely pulverized product is finely pulverized by a jet mill, and the obtained finely pulverized product is classified by an air classifier. The particle size distribution of the toner is such that the mass average particle diameter is 7.0 μm, and the number ratio of particles having a weight average particle diameter of 4 μm or less is 18.5. %, A magnetic toner having a mass ratio of particles of 12.7 μm or more of 0.8% was obtained. To 100 parts by mass of the toner, 1.0 part by mass of colloidal silica hydrophobized with a silane coupling agent and 4 parts by mass of strontium titanate fine particles were externally added using a Henschel mixer. The results are shown in Tables 6 and 7.
[0197]
<Example 19>
The following resin composition was prepared.
・ Phenol resin intermediate 100 parts by mass
・ Conductive carbon black 20 parts by mass
・ Methanol 120 parts by mass
[0198]
These materials were dispersed by a horizontal continuous sand mill using glass beads to obtain a stock coating solution D.
[0199]
Next, aluminum borate granules (average particle size: 2.8 μm) were treated with a methacryloxysilane coupling agent in the same manner as in Example 15.
[0200]
・ Paint stock solution D 原 240 mass parts
・ Aluminum borate granules treated with methacryloxysilane coupling agent
(Average particle size 2.8 μm) 100 parts by mass
・ Methanol 210 parts by mass
[0201]
Aluminum borate granules and methanol were further added to the stock coating solution D with the above composition, and the aluminum borate granules were dispersed by a sand mill. This dispersion was further diluted with methanol and passed through a 350 mesh sieve (paint 5 '). At this time, the viscosity of the paint 5 'was 60 mPa · s. A work was prepared by grinding an aluminum cylindrical tube to have an outer diameter of 32 mmφ, a surface roughness Ra of 0.2 μm, a runout of about 5 to 10 μm, and a flange for a developing sleeve attached to one side thereof. The work was placed on a turntable and rotated while masking the end of the sleeve, and the paint 5 'was spray-coated on the work while being lowered at a constant speed by a spray gun to obtain a coated sleeve. This was dried and cured at 150 ° C. for 30 minutes using a ventilation dryer to form a resin surface layer. At this time, the thickness of the surface resin coating layer was 18.5 ′ μm, and the surface roughness was Ra = 0.60 μm on average. The volume resistance of the coating layer was 12.3 Ω · cm.
[0202]
A magnet was attached to the developing sleeve, and a stainless steel flange was fitted. Using cyan toner, evaluate image output up to 50,000 sheets, and then, to confirm the durability of the developing sleeve, perform an idle rotation test up to 200,000 sheets equivalent to confirm the abrasion and surface roughness of the coating, Further, the characteristics were evaluated when the developer was replaced with a new developer. The environment was set in a normal temperature and normal humidity (N / N) environment of 24 ° C./60%. The following were used as the developer.
・ 100% by mass of polyester resin
・ Phthalocyanine pigment (cyan) 5 parts by mass
・ Al complex of di-tert-butylsalicylic acid 酸 6 parts by mass
[0203]
5 parts by mass of the polyester resin and 5 parts by mass of the phthalocyanine pigment are sufficiently kneaded using three rolls in advance to prepare a master batch. After the pulverized master batch, the remaining polyester resin, and the Al complex of ditertiary butyl salicylic acid were sufficiently mixed using a Henschel mixer, the mixture was melt-kneaded with a twin-screw extruder heated to 110 ° C., and the cooled mixture was hammered. Coarsely pulverized with a mill. The coarsely pulverized product is finely pulverized by a jet mill, and the obtained finely pulverized product is classified by an air classifier. %, And a cyan toner having a mass ratio of particles of 12.7 μm or more of 1.8% was obtained. 1.8 parts by mass of hydrophobic titanium oxide fine particles were used as an externally added toner with a Henschel mixer to 100 parts by mass of this toner. 1.0% of a silicone resin was added to ferrite particles classified with an average particle size of 35 to 50 μm, mixed, heated and cured, then crushed, sieved, and used as a carrier for development. The toner T and the carrier C were mixed so that the T / C ratio became 7%, and used as a start agent.
[0204]
Table 8 shows the results.
[0205]
<Example 20>
The average particle size of 2.8 μm and the average particle size of 7.8 μm of the aluminum borate particles were treated with an aminosilane-based coupling agent in the same manner as in Example 15.
[0206]

A coating material was prepared in the same manner as in Example 19, except that The viscosity of this paint was 57.5 mPa · s. A surface resin layer was formed in the same manner as in Example 19. At this time, the thickness of the surface resin coating layer was 19.5 μm, and the surface roughness Ra was 0.91 μm. The volume resistance of the coating layer was 11.0 Ω · cm. The same evaluation as in Example 19 was performed using this developing sleeve. Table 8 shows the results.
[0207]
<Example 21>
・ Polyurethane resin 100 parts by mass
・ Conductive carbon black 10 parts by mass
・ Crystalline graphite (average particle size: 4.3 μm) 10 parts by mass
・ Toluene / MIBK / IPA mixed solventＡ120 parts by mass
[0208]
These materials were dispersed by a horizontal continuous sand mill using glass beads to obtain a coating solution E.
[0209]
Next, the average particle size of 2.8 μm and 7.8 μm of the aluminum borate particles was treated with dimethyl silicone oil in the same manner as in Example 17.
[0210]

Aluminum borate granules and a mixed solvent of toluene, MIBK, and IPA were further added to the stock coating solution E with the above composition, and the aluminum borate granules were dispersed by a sand mill. This dispersion was further diluted with a mixed solvent of toluene, MIBK, and IPA, and passed through a 350 mesh jaw (Paint 7 '). At this time, the viscosity of the paint 7 'was 52.5 mPa · s. A surface resin layer was formed in the same manner as in Example 15. At this time, the thickness of the surface resin coating layer was 18.8 μm, and the surface roughness Ra was 0.89 μm. The volume resistivity of the coating layer was 15.4 Ω · cm. The same evaluation as in Example 15 was performed using this developing sleeve. Table 8 shows the results.
[0211]
<Example 22>
Aluminum borate granules (average particle size: 9.8 μm) were treated with a methacryloxysilane coupling agent in the same manner as in Example 15.
[0212]

[0213]
Aluminum borate granules and methanol were further added to the stock coating solution A with the above composition, and the aluminum borate granules were dispersed by a sand mill. This dispersion was further diluted with methanol and passed through a 250-mesh and a 500-mesh sieve (paint 8 '). At this time, the viscosity of the coating material 8 'was 75 mPa · s. An aluminum cylindrical tube having an aluminum flange on one side was integrally ground to have an outer diameter of 20 mm, a surface roughness Ra of 0.2 μm, and a runout of about 5 μm. The work was placed on a turntable and rotated while masking the end of the sleeve, and the paint 8 was spray-coated on the work while being lowered at a constant speed by a spray gun to obtain a coated sleeve. This was dried and cured at 150 ° C. for 30 minutes using a ventilation dryer to form a resin surface layer. At this time, the thickness of the surface resin coating layer was 12.8 μm, and the average surface roughness was Ra = 1.58 μm. The volume resistivity of the coating layer was 0.97 Ω · cm.
[0214]
A magnet was attached to this developing sleeve, and an aluminum flange was fitted on the other side, so that it could be attached to a cartridge developing device of a modified laser beam printer LBP-930 manufactured by Canon Inc. The LBP-930 remodeling machine used in this experiment was a LBP-930 base modified from a 24-sheet A4 sheet feeding machine equivalent to 50 sheets, and the process speed was increased from 106 mm / sec to 236 mm / sec. In addition, the peripheral speed of the sleeve was set to 1.3 times the peripheral speed of the drum. Furthermore, the capacity of the toner container has been increased. Further, in order to prevent non-uniform regulation by the developer regulating blade due to high speed, the regulating member is reinforced with a metal plate to increase the blade pressing force. The main body and the cartridge are each provided with mechanical strength reinforcement. An image signal was sent from an external character generator (CG), and an image was output to produce an image. Each time the residual toner check of the cartridge was displayed, a continuous durability test was performed on up to 60,000 sheets while replenishing the magnetic toner, and evaluation was performed. The environment was a normal temperature and low humidity (N / L) environment of 24 ° C./10% RH and a high temperature and high humidity (H / H) environment of 30 ° C./80% RH. The results are shown in Tables 9 and 10.
[0215]
The following toner was used.
・ Styrene-butyl acrylate resin 100 parts by mass
・ Magnetite 100 parts by mass
・ Low molecular weight polyethylene wax: 3 parts by mass
・ Long chain alcohol wax 3 parts by mass
・ Azo-based Fe complex compound (negative charge control agent) 3 parts by mass
The above materials were dispersed and mixed by a Henschel mixer, melt-kneaded by a biaxial extruder heated to 130 ° C., and the cooled mixture was roughly pulverized by a hammer mill. The coarsely pulverized product is finely pulverized by a jet mill, and the obtained finely pulverized product is classified by an air classifier. The particle size distribution of the toner is as follows. %, A magnetic toner having a mass ratio of particles of 12.7 μm or more of 0.4% was obtained. To 100 parts by mass of this toner, 1.2 parts by mass of colloidal silica treated with a silane coupling agent and silicone oil and 0.5 part by mass of strontium titanate fine particles were externally added using a Henschel mixer.
[0216]
<Example 23>
The average particle size of 2.8 μm and the average particle size of 9.8 μm of the aluminum borate particles were treated with an aminosilane coupling agent in the same manner as in Example 15.
[0219]

A coating material was prepared in the same manner as in Example 22 except that the above conditions were used (paint 9 '). The viscosity of this paint was 60 mPa · s. A surface resin layer was formed in the same manner as in Example 22. At this time, the thickness of the surface resin coating layer was 13.2 μm, and the surface roughness Ra was 1.50 μm. The volume resistivity of the coating layer was 1.05 Ω · cm. The same evaluation as in Example 22 was performed using this developing sleeve. The results are shown in Tables 9 and 10.
[0218]
<Example 24>

A coating material was prepared in the same manner as in Example 22 except that the imidazole compound was further added after dispersing the aluminum borate granules (paint 10 '). The viscosity of this paint was 80 mPa · s. A surface resin layer was formed in the same manner as in Example 22. At this time, the thickness of the surface resin coating layer was 13.2 μm, and the surface roughness Ra was 1.58 μm. The volume resistivity of the coating layer was 1.11 Ω · cm. The same evaluation as in Example 22 was performed using this developing sleeve. The results are shown in Tables 9 and 10.
[0219]
<Example 25>

A coating material was prepared in the same manner as in Example 22 except that the aluminum borate particles were dispersed and spherical carbon particles were further added (paint 11 '). The viscosity of this paint was 52.5 mPa · s. A surface resin layer was formed in the same manner as in Example 22. At this time, the thickness of the surface resin coating layer was 13.2 μm, and the surface roughness Ra was 1.55 μm. The volume resistivity of the coating layer was 0.95 Ω · cm. The same evaluation as in Example 22 was performed using this developing sleeve. The results are shown in Tables 9 and 10.
[0220]
<Example 26>
The aluminum borate granules (average particle size: 9.8 μm) were treated with dimethyl silicone oil in the same manner as in Example 17.
[0221]

A coating material was prepared in the same manner as in Example 22 except that the aluminum borate particles were dispersed and spherical carbon particles were further added (paint 12 '). The viscosity of this paint was 57.5 mPa · s. A surface resin layer was formed in the same manner as in Example 22. At this time, the thickness of the surface resin coating layer was 14.0 μm, and the surface roughness Ra was 1.65 μm. The volume resistance of the coating layer was 0.98 Ω · cm. The same evaluation as in Example 22 was performed using this developing sleeve. The results are shown in Tables 9 and 10.
[0222]
<Example 27>
The aluminum borate granules (average particle size: 16.0 μm) were treated with dimethyl silicone oil in the same manner as in Example 17.
[0223]

A coating material was prepared in the same manner as in Example 22 except that the above conditions were used (Paint 13 '). The viscosity of this paint was 60 mPa · s. A surface resin layer was formed in the same manner as in Example 22. At this time, the thickness of the surface resin coating layer was 13.5 μm, and the surface roughness Ra was 1.62 μm. The volume resistivity of the coating layer was 0.99 Ω · cm. The same evaluation as in Example 22 was performed using this developing sleeve. The results are shown in Tables 9 and 10.
[0224]
<Example 28>
The aluminum borate granules (average particle size: 27.5 μm) were treated with dimethyl silicone oil in the same manner as in Example 17.
[0225]

A coating material was prepared in the same manner as in Example 22 except that the above-mentioned was used (paint 14 '). The viscosity of this paint was 60 mPa · s. A surface resin layer was formed in the same manner as in Example 22. At this time, the thickness of the surface resin coating layer was 14.6 μm, and the surface roughness Ra was 1.82 μm. The volume resistivity of the coating layer was 0.98 Ω · cm. The same evaluation as in Example 22 was performed using this developing sleeve. The results are shown in Tables 9 and 10.
[0226]
[Table 6]

[0227]
[Table 7]

[0228]
[Table 8]

[0229]
[Table 9]

[0230]
[Table 10]

[0231]
【The invention's effect】
As described above, in the developer carrying member, the developing device, and the process cartridge of the present invention, since the surface resin coating layer of the developer carrying member contains aluminum borate particulates, a uniform surface unevenness is obtained. As a result, uniform toner transportability can be obtained, and chargeability to toner is good, so that developability is good and high definition and high quality electrophotographic images can be provided. Further, since it is excellent in abrasion resistance and stain resistance, it can continue to provide a good image even for long-term repeated use regardless of one-component development or two-component development.
[Brief description of the drawings]
FIG. 1 is a schematic diagram illustrating an example of a configuration of a surface layer of a developer carrying member of the present invention.
FIG. 2 is a schematic view showing another example of the configuration of the surface layer of the developer carrying member of the present invention.
FIG. 3 is a schematic diagram showing another example of the configuration of the surface layer of the developer carrying member of the present invention.
FIG. 4 is a schematic view showing another example of the configuration of the surface layer of the developer carrying member of the present invention.
FIG. 5 is a schematic view showing an example of the configuration of a one-component developing machine of the present invention.
FIG. 6 is a schematic view showing another example of the configuration of the one-component developing machine of the present invention.
FIG. 7 is a schematic diagram showing another example of the configuration of the one-component developing machine of the present invention.
FIG. 8 is a schematic view showing another example of the configuration of the one-component developing machine of the present invention.
FIG. 9 is a schematic view showing another example of the configuration of the one-component developing machine of the present invention.
FIG. 10 is a schematic view showing an example of the configuration of a two-component developing machine of the present invention.
FIG. 11 is a schematic view illustrating an example of a process cartridge according to the present invention.
FIG. 12 is a schematic view showing another example of the configuration of the process cartridge of the present invention.

Claims (20)

A developer carrier used in a developing device that develops a latent image formed on the electrostatic latent image carrier with a developer carried and transported by the developer carrier and visualizes the image, wherein the developer carrier Has at least a substrate and a resin coating layer formed on the surface of the substrate, and the resin coating layer contains at least a resin and aluminum borate particulates dispersed in the resin. Carrier. The developer carrier according to claim 1, wherein the resin coating layer has conductivity, and the conductivity is provided by including a conductive agent in the resin coating layer. 3. The developer carrier according to claim 1, wherein the resin coating layer further contains a lubricating fine powder. The developer carrier according to claim 1, wherein the resin coating layer has irregularities on an outer surface, and the irregularities are mainly formed by adding the aluminum borate granules. . The developer carrier according to any one of claims 1 to 4, wherein the aluminum borate particles have a number average particle size of 0.3 to 30 m. 7. The developing method according to claim 1, wherein the resin coating layer has irregularities on an outer surface, and the irregularities are mainly formed by another solid particle further added. Agent carrier. The developer carrier according to claim 6, wherein the number average particle diameter of the solid particles is 0.3 to 30 m. The resin coating layer has irregularities on its outer surface, and the irregularities are mainly formed by both the aluminum borate granules and further added solid particles. 8. The developer carrying member according to 3, 5, or 7. 4. The developer carrier according to claim 1, wherein the outer surface of the resin coating layer has a center line average roughness Ra of 0.3 to 3.5 [mu] m. The developer carrier according to any one of claims 1 to 9, wherein the aluminum borate particles are organically treated. A developer container that contains at least a developer and a developer carrier that carries and transports the developer stored in the container; The developer according to any one of claims 1 to 10, wherein the developer is transported to a development area facing the image carrier, and the latent image on the latent image carrier is developed by the developer to visualize the latent image. A developing device comprising a carrier. The developing device according to claim 11, wherein the developer is a non-magnetic one-component developer, and the layer thickness regulating member is in contact with or in pressure contact with the developer carrier via the toner. The developing device according to claim 11, wherein the developer carrier has a magnet built in the base. 14. The developing device according to claim 11, wherein the developer is a magnetic one-component developer. 13. The developing device according to claim 12, wherein the layer thickness regulating member is a non-magnetic member, and is in contact with or in pressure contact with the developer carrying member via the toner. The developing device according to claim 14, wherein the layer thickness regulating member is a non-magnetic or magnetic member, and is arranged with a minute gap in the developer carrier. 14. The developing device according to claim 11, wherein the developer is a two-component developer having a toner and a carrier. (I) Image formation having at least integrally an electrostatic latent image holding member for holding an electrostatic latent image and (ii) developing means for converting the electrostatic latent image into a developed image with a developer in a development area 18. A process cartridge detachable from the apparatus main body, wherein the developing device is the developing device according to claim 11. 19. The process cartridge according to claim 18, wherein the electrostatic latent image holding member is a photoconductor for electrophotography. 20. The cartridge according to claim 18, wherein at least one of the cleaning unit and the primary charging unit is integrally formed as a cartridge in addition to the electrophotographic photosensitive member as the electrostatic latent image holding member and the developing unit. Process cartridge.

Images