JP2004287151A - Image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method for stably obtaining good image quality over a prolonged period of time, by which contamination of a latent image carrier and scuffing of a photoreceptor can be prevented. <P>SOLUTION: In the image forming method which forms an image using an image forming apparatus comprising a charging means to charge a latent image carrier, a latent image forming means to form an electrostatic latent image on the charged latent image carrier by exposure, a developing means to develop the electrostatic latent image with a toner, a transferring and separating means to transfer the formed toner image to a recording material and to separate the image from the latent image carrier as a toner image support, and a fixing means to bring the transferred toner image into contact heat fixation on the recording material, the toner contains at least inorganic particles having a Mohs hardness of 2-4.5 and a surface layer of the latent image carrier has a charge transporting property and comprises a siloxane resin having a crosslinked structure. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００８６】
一般式（ＩＩ）中、Ａｒ_１〜Ａｒ_４は、それぞれ独立に置換又は未置換のアリール基を表し、Ａｒ_５は、置換若しくは未置換のアリール基又はアリーレン基を表す。但し、Ａｒ_１〜Ａｒ_５のうち１〜４個は、前記−Ｄ−Ｇで表される結合基と結合可能な結合手を有する。ｋは０または１を表す。
【００８７】
【化２】

【００８８】
上記中、Ａｒは下記構造群２に挙げられるものが好ましい。
【００８９】
【化３】

【００９０】
また、前記Ｚ’は下記構造群３に挙げられるものが好ましい。
【００９１】
【化４】

【００９２】
ここで、Ｒ_６ は、水素、炭素数１〜４のアルキル基、炭素数１〜４のアルキル基もしくは炭素数１〜４のアルコキシ基で置換されたフェニル基、または未置換のフェニル基、炭素数７〜１０のアラルキル基を表す。Ｒ_７〜Ｒ_１３は、水素、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、もしくは炭素数１〜４のアルコキシ基で置換されたフェニル基、または未置換のフェニル基、炭素数７〜１０のアラルキル基、ハロゲンを表す。ｍ及びｓはそれぞれ独立に０または１を表し、ｑ及びｒはそれぞれ独立に１〜１０の整数、ｔ、ｔ’はそれぞれ独立に１〜３の整数を表す。ここで、Ｘは化合物（Ｉ）の定義で既に示した−Ｄ−Ａと同様である。
【００９３】
また、前記Ｗは下記に構造群４に挙げられるものが好ましい。
【００９４】
【化５】

【００９５】
ここで、ｓ’は０〜３の整数を表す。
【００９６】
一般式（ＩＩ）におけるＡｒ_５の具体的構造としては、ｋ＝０の時は、上記Ａｒ_１〜Ａｒ_４のｍ＝１の構造が、ｋ＝１の時は、上記Ａｒ_１〜Ａｒ_４のｍ＝０の構造が挙げられる。化合物（ＩＩ）の具体例を表１〜５５に示すが、これらに限定されるものではない。
【００９７】
【表１】

【００９８】
【表２】

【００９９】
【表３】

【０１００】
【表４】

【０１０１】
【表５】

【０１０２】
【表６】

【０１０３】
【表７】

【０１０４】
【表８】

【０１０５】
【表９】

【０１０６】
【表１０】

【０１０７】
【表１１】

【０１０８】
【表１２】

【０１０９】
【表１３】

【０１１０】
【表１４】

【０１１１】
【表１５】

【０１１２】
【表１６】

【０１１３】
【表１７】

【０１１４】
【表１８】

【０１１５】
【表１９】

【０１１６】
【表２０】

【０１１７】
【表２１】

【０１１８】
【表２２】

【０１１９】
【表２３】

【０１２０】
【表２４】

【０１２１】
【表２５】

【０１２２】
【表２６】

【０１２３】
【表２７】

【０１２４】
【表２８】

【０１２５】
【表２９】

【０１２６】
【表３０】

【０１２７】
【表３１】

【０１２８】
【表３２】

【０１２９】
【表３３】

【０１３０】
【表３４】

【０１３１】
【表３５】

【０１３２】
【表３６】

【０１３３】
【表３７】

【０１３４】
【表３８】

【０１３５】
【表３９】

【０１３６】
【表４０】

【０１３７】
【表４１】

【０１３８】
【表４２】

【０１３９】
【表４３】

【０１４０】
【表４４】

【０１４１】
【表４５】

【０１４２】
【表４６】

【０１４３】
【表４７】

【０１４４】
【表４８】

【０１４５】
【表４９】

【０１４６】
【表５０】

【０１４７】
【表５１】

【０１４８】
【表５２】

【０１４９】
【表５３】

【０１５０】
【表５４】

【０１５１】
【表５５】

【０１５２】
化合物（Ｉ）は、１種単独で使用してもよいし、２種以上併用してもよい。表面層形成に際しては、硬化膜の機械的強度をさらに向上させる目的で、化合物（Ｉ）と結合可能な基を有する化合物の少なくとも１種を添加することが好ましい。
【０１５３】
化合物（Ｉ）と結合可能な基とは、化合物（Ｉ）を加水分解した際に生じるシラノール基と結合可能な基を意味し、具体的には、−Ｓｉ（Ｒ_１）_{（３−ａ）}Ｑ_ａで示される基、エポキシ基、イソシアネート基、カルボキシル基、ヒドロキシ基、ハロゲンなどを意味する。これらのうち、−Ｓｉ（Ｒ_１）_{（３−ａ）}Ｑ_ａで示される加水分解性基、エポキシ基、イソシアネート基を有する化合物が、より強い機械的強度を有するため好ましい。さらに、化合物（Ｉ）と結合可能な基を有する化合物としては、これらの基を分子内に２つ以上持つものが、硬化膜の架橋構造を３次元的にし、膜により強い機械的強度を与えるため好ましい。これらのうち、最も好ましい化合物例として一般式（ＩＩＩ）で示される化合物が挙げられる。
【０１５４】
【化６】

【０１５５】
一般式（ＩＩＩ）中、Ａ’は−Ｓｉ（Ｒ_１）_{（３−ａ）}Ｑ_ａで表される加水分解性基を有する置換けい素基、Ｂは枝分かれを含んでも良いｎ価の炭化水素基、ｎ価のフェニル基、−ＮＨ−、−Ｏ−Ｓｉ−から選ばれる基の少なくとも１つ、あるいはこれらの組み合わせから構成される。ａは１〜３の整数、ｎは２以上の整数を表す。
【０１５６】
一般式（ＩＩＩ）で示される化合物は、−Ｓｉ（Ｒ_１）_{（３−ａ）}Ｑ_ａで表される加水分解性基を有する置換けい素基Ａ’を２個以上有している化合物である。Ａ’に含まれるＳｉ基の部分が、化合物（Ｉ）あるいは化合物（ＩＩＩ）自身と反応し、Ｓｉ−Ｏ−Ｓｉ結合となって３次元的な架橋硬化膜を形成していく。化合物（Ｉ）も同様のＳｉ基を有しているので、それのみで硬化膜を形成することも可能であるが、化合物（ＩＩＩ）は２個以上のＡ’を有しているので硬化膜の架橋構造が３次元的になり、より強い機械的強度を有するようになると考えられる。また、化合物（Ｉ）におけるＤ部分と同様、架橋硬化膜に適度な可とう性を与える役割もある。化合物（ＩＩＩ）としては、下記構造群５に示されるものがより好ましい。
【０１５７】
【化７】

【０１５８】
上記式中、Ｔ_１、Ｔ_２はそれぞれ独立に枝分かれしていてもよい２価あるいは３価の炭化水素基、Ａ’は前記した置換基を表わす。ｈ、ｉ、ｊは１〜３の整数であり、かつ、分子内のＡ’の数が２以上となるように選ばれる。
【０１５９】
これらの式で表わされる一般式（ＩＩＩ）の化合物の具体例を以下に示すが、これらに限定されるわけではない。
【０１６０】
【化８】

【０１６１】
化合物（Ｉ）は単独で使用してもよいし、膜の成膜性、可とう性を調整するなどの目的から、一般式（ＩＩＩ）で示される化合物や、他のカップリング剤、フッ素化合物などを混合して用いてもよい。このような化合物として、各種シランカップリング剤、および市販のシリコーン系ハードコート剤を用いることができる。
【０１６２】
前記シランカップリング剤としては、ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルメチルジメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリエトキシシラン、テトラメトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、等を用いることができる。市販のシリコーン系ハードコート剤としては、ＫＰ−８５、Ｘ−４０−９７４０、Ｘ−４０−２２３９ （以上、信越シリコーン社製）、およびＡＹ４２−４４０、ＡＹ４２−４４１、ＡＹ４９−２０８ （以上、東レダウコーニング社製）、などを用いることができる。また、撥水性などの付与のために、（トリデカフルオロ−１，１，２，２−テトラヒドロオクチル）トリエトキシシラン、（３，３，３−トリフルオロプロピル）トリメトキシシラン、３−（ヘプタフルオロイソプロポキシ）プロピルトリエトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロアルキルトリエトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロデシルトリエトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロオクチルトリエトシキシラン、などの含フッ素化合物を加えてもよい。
【０１６３】
シランカップリング剤は任意の量で使用できるが、含フッ素化合物の量は、フッ素を含まない化合物に対して２５ｗｔ％以下とすることが望ましい。これを越えると、架橋膜の成膜性に問題が生じる場合がある。
【０１６４】
また、表面保護層として架橋膜を形成する場合は、有機金属化合物、あるいは硬化型マトリックスを添加することが好ましい。
【０１６５】
有機金属化合物としては、ジルコニウムキレート化合物、ジルコニウムアルコキシド化合物、ジルコニウムカップリング剤などの有機ジルコニウム化合物；チタンキレート化合物、チタンアルコキシド化合物、チタネートカップリング剤などの有機チタン化合物；アルミニウムキレート化合物、アルミニウムカップリング剤などの有機アルミニウム化合物；のほか、アンチモンアルコキシド化合物、ゲルマニウムアルコキシド化合物、インジウムアルコキシド化合物、インジウムキレート化合物、マンガンアルコキシド化合物、マンガンキレート化合物、スズアルコキシド化合物、スズキレート化合物、アルミニウムシリコンアルコキシド化合物、アルミニウムチタンアルコキシド化合物、アルミニウムジルコニウムアルコキシド化合物、などの有機金属化合物、特に有機ジルコニウム化合物、有機チタニル化合物、有機アルミニウム化合物が残留電位が低く良好な電子写真特性を示すため、好ましいものとして挙げられる。
【０１６６】
硬化型マトリックスとしては、ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス−２−メトキシエトキシシラン、ビニルトリアセトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−２−アミノエチルアミノプロピルトリメトキシシラン、γ−メルカプロプロピルトリメトキシシラン、γ−ウレイドプロピルトリエトキシシラン、β−３，４−エポキシシクロヘキシルトリメトキシシラン等のシランカップリング剤などを用いることができる。
【０１６７】
これらのコーティング液の調整は、無溶媒で行うか、必要に応じてメタノール、エタノール、プロパノール、ブタノール等のアルコール類；アセトン、メチルエチルケトン等のケトン類；テトラヒドロフラン、ジエチルエーテル、ジオキサン等のエーテル類等が使用できるが、好ましくは沸点が１００℃以下のものであり、任意に混合しての使用もできる。溶剤量は任意に設定できるが、少なすぎると化合物（Ｉ）が析出しやすくなるため、化合物（Ｉ）１質量部に対し０．５〜３０質量部、好ましくは１〜２０質量部で使用される。
【０１６８】
コーティング液調製においては、化合物（Ｉ）と、必要に応じてその他の化合物と、を固体触媒に接触させて反応させるが、反応温度および時間は原料の種類によっても異なり、通常は０〜１００℃で行われ、０〜７０℃で行うことがより好ましく、１０〜３５℃の温度で行うことが特に好ましい。反応時間に特に制限はないが、反応時間が長くなるとゲル化を生じ易くなるため、１０分から１００時間の範囲で行うことが好ましい。
【０１６９】
化合物（Ｉ）と結合可能な基を有するポリマーを添加する場合、固体触媒と上記ポリマーとが同時に存在すると著しくゲル化を促進し、コーティングが困難となる場合があるため、固体触媒を除去した後に添加することが好ましい。このような固体触媒は、触媒成分が化合物（Ｉ）溶液、その他の化合物、溶媒等のいずれにも不溶であるものであれば、特に限定されない。系に不溶な固体触媒としては、以下のような触媒を用い、あらかじめ加水分解することができる。
【０１７０】
・陽イオン交換樹脂：アンバーライト１５、アンバーライト２００Ｃ、アンバーリスト１５（以上、ローム・アンド・ハース社製）；ダウエックスＭＷＣ−１−Ｈ、ダウエックス８８、ダウエックスＨＣＲ−Ｗ２（以上、ダウ・ケミカル社製）；レバチットＳＰＣ−１０８、レバチットＳＰＣ−１１８（以上、バイエル社製）；ダイヤイオンＲＣＰ−１５０Ｈ（三菱化成社製）；スミカイオンＫＣ−４７０、デュオライトＣ２６−Ｃ、デュオライトＣ−４３３、デュオライト−４６４（以上、住友化学工業社製）；ナフィオン−Ｈ（デュポン社製）など。
・陰イオン交換樹脂：アンバーライトＩＲＡ−４００、アンバーライトＩＲＡ−４５（以上、ローム・アンド・ハース社製）など。
プロトン酸基を含有する基が表面に結合されている無機固体：Ｚｒ（Ｏ_３ ＰＣＨ_２ ＣＨ_２ ＳＯ_３ Ｈ）_２、、Ｔｈ（Ｏ_３ ＰＣＨ_２ ＣＨ_２ ＣＯＯＨ）_２ など。
・プロトン酸基を含有するポリオルガノシロキサン：スルホン酸基を有するポリオルガノシロキサンなど。
・ヘテロポリ酸：コバルトタングステン酸、リンモリブデン酸など。
・イソポリ酸：ニオブ酸、タンタル酸、モリブデン酸など。
・単元系金属酸化物：シリカゲル、アルミナ、クロミア、ジルコニア、ＣａＯ、ＭｇＯなど。
・複合系金属酸化物：シリカ−アルミナ、シリカ−マグネシア、シリカ−ジルコニア、ゼオライト類など。
・粘土鉱物：酸性白土、活性白土、モンモリロナイト、カオリナイトなど。
・金属硫酸塩：ＬｉＳＯ_４ ，ＭｇＳＯ_４ など。
・金属リン酸塩：リン酸ジルコニア、リン酸ランタンなど。
・金属硝酸塩：ＬｉＮＯ_３ ，Ｍｎ（ＮＯ_３ ）_２ など。
・アミノ基を含有する基が表面に結合されている無機固体：シリカゲル上にアミノプロピルトリエトキシシランを反応させて得られた固体など。
・アミノ基を含有するポリオルガノシロキサン：アミノ変性シリコーン樹脂など。
【０１７１】
これらの触媒のうち、少なくとも１種を用いて加水分解縮合反応を行わせる。これらの触媒は、固定床中に設置し反応を流通式で行うこともできるし、バッチ式で行うこともできる。触媒の使用量は、特に限定されないが、加水分解性けい素置換基を含有する材料の合計量に対して０．１〜２０ｗｔ％が好ましい。
【０１７２】
加水分解縮合させる際の水の添加量は、特に限定されないが、生成物の保存安定性やさらに重合に供する際のゲル化抑制に影響するため、好ましくは、化合物（Ｉ）の加水分解性基をすべて加水分解するに必要な理論量に対して３０〜５００％、さらに５０〜３００％の範囲の割合で使用することが好ましい。水の量が５００％よりも多い場合、生成物の保存安定性が悪くなったり、析出しやすくなる。一方、水の量が３０％より少ない場合、未反応物が増大してコーティング液塗布時、硬化時に相分離を起こしたり、塗膜の強度低下を起こしやすい。
【０１７３】
さらに、硬化触媒としては、塩酸、酢酸、リン酸、硫酸などのプロトン酸；アンモニア、トリエチルアミン等の塩基；ジブチル錫ジアセテート、ジブチル錫ジオクトエート、オクエ酸第一錫等の有機錫化合物；テトラ−ｎ−ブチルチタネート、テトライソプロピルチタネート等の有機チタン化合物；アルミニウムトリブトキシド、アルミニウムトリアセチルアセトナート等の有機アルミニウム化合物；有機カルボン酸の鉄塩、マンガン塩、コバルト塩、亜鉛塩、ジルコニウム塩等が挙げられるが、保存安定性の点で金属化合物が好ましく、さらに、金属のアセチルアセトナート、あるいは、アセチルアセテートが好ましい。
硬化触媒の使用量は任意に設定できるが、保存安定性、特性、強度などの点で加水分解性けい素置換基を含有する材料の合計量に対して０．１〜２０ｗｔ％が好ましく、０．３〜１０ｗｔ％がより好ましい。
【０１７４】
硬化温度は、任意に設定できるが、所望の強度を得るためには６０℃以上、より好ましくは８０℃以上に設定される。硬化時間は、必要に応じて任意に設定できるが、１０分〜５時間が好ましい。また、硬化反応を行ったのち、高湿度状態に保ち、特性の安定化を図ることも有効である。さらに、用途によっては、ヘキサメチルジシラザンや、トリメチルクロロシランなどを用いて表面処理を行い、疎水化することもできる。
【０１７５】
感光体の表面架橋硬化膜には、帯電器で発生するオゾン等の酸化性ガスによる劣化を防止する目的で、酸化防止剤を添加することが好ましい。感光体表面の機械的強度を高め、感光体を長寿命化すると、感光体が酸化性ガスに長時間接触することになるため、従来より強い酸化耐性が要求される。
【０１７６】
酸化防止剤としては、ヒンダードフェノール系あるいはヒンダードアミン系が望ましく、有機イオウ系酸化防止剤、フォスファイト系酸化防止剤、ジチオカルバミン酸塩系酸化防止剤、チオウレア系酸化防止剤、ベンズイミダゾール系酸化防止剤、などの公知の酸化防止剤を用いてもよい。酸化防止剤の添加量としては、硬化膜全体に対して１５ｗｔ％以下が望ましく、１０ｗｔ％以下がさらに望ましい。
【０１７７】
ヒンダードフェノール系酸化防止剤としては、２，６−ジ−ｔ−ブチル‐４‐メチルフェノール、２，５−ジ−ｔ−ブチルヒドロキノン、Ｎ，Ｎ’−ヘキサメチレンビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシヒドロシンナマイド）、３，５−ジ−ｔ−ブチル−４−ヒドロキシ−ベンジルフォスフォネート−ジエチルエステル、２，４−ビス［（オクチルチオ）メチル］−ｏ−クレゾール、２，６−ジ−ｔ−ブチル−４−エチルフェノール、２，２′−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、２，２′−メチレンビス（４−エチル−６−ｔ−ブチルフェノール）、４，４′−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、２，５−ジ−ｔ−アミルヒドロキノン、２−ｔ−ブチル−６−（３−ブチル−２−ヒドロキシ−５−メチルベンジル）−４−メチルフェニルアクリレート、４，４′−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、などが挙げられる。
【０１７８】
電荷輸送性を有し、架橋構造を有するシロキサン系樹脂は、優れた機械強度を有する上に光電特性も十分であるため、これをそのまま積層型感光体の電荷輸送層として用いることもできる。
【０１７９】
塗布方法としては、ブレードコーティング法、マイヤーバーコーティング法、スプレーコーティング法、浸漬コーティング法、ビードコーティング法、エアーナイフコーティング法、カーテンコーティング法等の通常の方法を用いることができる。ただし、１回の塗布により必要な膜厚が得られない場合、複数回重ね塗布することにより必要な膜厚を得ることができる。複数回の重ね塗布を行なう場合、加熱処理は塗布の度に行なっても良いし、複数回重ね塗布した後でも良い。
【０１８０】
表面層の架橋の度合いは、表面層の硬さにより知ることができるが、この硬さは、感光体の硬度として求めることができる。感光体の硬度は、ダイナミック硬さで、１５〜３５ｍＮ／μｍ^２の範囲が好ましい。なお、ダイナミック硬さは、島津ダイナミック硬度計ＤＵＨ−２０１により測定することができる。
【０１８１】
単層型感光層の場合は、前記の電荷発生物質と結着樹脂を含有して形成される。結着樹脂としては、電荷発生層および電荷輸送層に用いられる結着樹脂と同様のものを用いることができる。単層型感光層中の電荷発生物質の含有量は、１０から８５ｗｔ％程度、好ましくは２０から５０ｗｔ％とする。単層型感光層には、光電特性を改善する等の目的で電荷輸送物質や高分子電荷輸送物質を添加してもよい。その添加量は５〜５０ｗｔ％とすることが好ましい。また、化合物（Ｉ）を加えてもよい。塗布に用いる溶剤や塗布方法は、上記と同様のものを用いることができる。膜厚は５〜５０μｍ程度が好ましく、１０〜４０μｍとするのがさらに好ましい。
【０１８２】
電荷発生層
次に電荷発生層について説明する。
【０１８３】
電荷発生材料は、ビスアゾ、トリスアゾなどのアゾ顔料、ジブロモアントアントロンなどの縮環芳香族顔料、ペリレン顔料、ピロロピロール顔料、フラトシアニン顔料等既知のもの全て使用することができるが、とくに金属及び無金属フタロシアニン顔料が好ましい。その中でも、特定の結晶を有するヒドロキシガリウムフタロシアニン、クロロガリウムフタロシアニン、ジクロロスズフタロシアニン、チタニルフタロシアニンが特に好ましい。本発明に用いるクロロガリウムフタロシアニンは、特開平５−９８１８１号公報に公開したように、公知の方法で製造されるクロロガリウムフタロシアニン結晶を、自動乳鉢、遊星ミル、振動ミル、ＣＦミル、ローラーミル、サンドミル、ニーダー等で機械的に乾式粉砕するか、乾式粉砕後溶剤と共にボールミル、乳鉢、サンドミル、ニーダー等を用いて湿式粉砕処理を行うことによって製造することができる。上記の処理において使用される溶剤は、芳香族類（トルエン、クロロベンゼン等）、アミド類（ジメチルホルムアミド、Ｎ−メチルピロリドン等）、脂肪族アルコール類（メタノール、エタノール、ブタノール等）、脂肪族多価アルコール類（エチレングリコール、グリセリン、ポリエチレングリコール等）、芳香族アルコール類（ベンジルアルコール、フェネチルアルコール等）、エステル類（酢酸エステル、酢酸ブチル等）、ケトン類（アセトン、メチルエチルケトン等）、ジメチルスルホキサイド、エーテル類（ジエチルエーテル、テトラヒドロフラン等）、さらには数種の混合系、水とこれら有機溶剤の混合系などである。使用される溶剤は、クロロガリウムフタロシアニンに対して、１〜２００部、好ましくは１０〜１００部の範囲で用いる。処理温度は、０℃〜溶剤の沸点以下、好ましくは１０〜６０℃の範囲で行う。また、粉砕の際に食塩、ぼう硝等の磨砕助剤を用いることもできる。磨砕助剤は顔料に対し０．５〜２０倍、好ましくは１〜１０倍用いる。
【０１８４】
ジクロロスズフタロシアニンは、特開平５−１４０４７２公報及び、特開平５−１４０４７３公報に公開したように、公知の方法で製造されるジクロロスズフタロシアニン結晶を、前記のクロロガリウムフタロシアニンと同様に粉砕、溶剤処理することにより得ることができる。
【０１８５】
ヒドロキシガリウムフタロシアニンは、特開平５−２６３００７公報及び、特開平５−２７９５９１公報に記載されているように、公知の方法で製造されるクロロガリウムフタロシアニン結晶を、酸またはアルカリ性溶液中での加水分解またはアシッドペースティングを行って、ヒドロキシガリウムフタロシアニン結晶を合成し、直接溶剤処理を行うか、或るいは、合成によって得られたヒドロキシガリウムフタロシアニン結晶を溶剤と共にボールミル、乳鉢、サンドミル、ニーダー等を用いて湿式粉砕処理を行うか、溶剤を用いずに乾式粉砕処理を行った後に溶剤処理することによって製造することができる。上記の処理において使用される溶剤は、芳香族類（トルエン、クロロベンゼン等）、アミド類（ジメチルホルムアミド、Ｎ−メチルピロリドン等）、脂肪族アルコール類（メタノール、エタノール、ブタノール等）、脂肪族多価アルコール類（エチレングリコール、グリセリン、ポリエチレングリコール等）、芳香族アルコール類（ベンジルアルコール、フェネチルアルコール等）、エステル類（酢酸エステル、酢酸ブチル等）、ケトン類（アセトン、メチルエチルケトン等）、ジメチルスルホキサイド、エーテル類（ジエチルエーテル、テトラヒドロフラン等）、さらには数種の混合系、水とこれら有機溶剤の混合系などである。使用される溶剤は、ヒドロキシガリウムフタロシアニンに対して、１〜２００部、好ましくは１０〜１００部の範囲で用いる。処理温度は、０〜１５０℃、好ましくは室温〜１００℃の範囲で行う。また、粉砕の際に食塩、ぼう硝等の磨砕助剤を用いることもできる。磨砕助剤は顔料に対し０．５〜２０倍、好ましくは１〜１０倍用いる。
【０１８６】
オキシチタニルフタロシアニンは、特開平４−１８９８７３号公報及び、特開平５−４３８１３号公報に記載されているように、公知の方法で製造されるオキシチタニルフタロシアニン結晶を、アシッドペースティングするか、あるいは、ボールミル、乳鉢、サンドミル、ニーダー等を用いて無機塩とともにソルトミリングを行って、Ｘ線回折スペクトルにおいて２７．２にピークを持つ、比較的結晶性の低いオキシチタニルフタロシアニン結晶としたのち、直接溶剤処理を行うか、或るいは、溶剤と共にボールミル、乳鉢、サンドミル、ニーダー等を用いて湿式粉砕処理を行うことによって製造することができる。アシッドペースティングに用いる酸としては、硫酸が好ましく、濃度７０〜１００％、好ましくは９５〜１００％のものが使用され、溶解は、−２０〜１００℃好ましくは０〜６０℃の範囲に設定される。濃硫酸の量は、オキシチタニルフタロシアニン結晶の重量に対して、１〜１００倍、好ましくは３〜５０倍の範囲に設定される。析出させる溶剤としては、水あるいは、水と有機溶剤の混合溶剤が任意の量で用いられ、水とメタノール、エタノール等のアルコール系溶剤、あるいは、水とベンゼン、トルエン等の芳香族系溶剤の混合溶剤が特に好ましい。析出させる温度については特に制限はないが、発熱を防ぐために、氷等で冷却することが好ましい。また、オキシチタニルフタロシアニン結晶と無機塩との比率は、重量比で１／０．１〜１／２０で、１／０．５〜１／５の範囲が好ましい。上記の溶剤処理において使用される溶剤は、芳香族類（トルエン、クロロベンゼン等）、脂肪族アルコール類（メタノール、エタノール、ブタノール等）、ハロゲン系炭化水素類（ジクロロメタン、クロロホルム、トリクロロエタン等）、さらには数種の混合系、水とこれら有機溶剤の混合系などである。使用される溶剤は、オキシチタニルフタロシアニンに対して、１〜１００部、好ましくは５〜５０部の範囲で用いる。処理温度は、室温〜１００℃、好ましくは５０〜１００℃の範囲で行う。磨砕助剤は顔料に対し０．５〜２０倍、好ましくは１〜１０倍用いる。
【０１８７】
結着樹脂としては、広範な絶縁性樹脂から選択することができる、また、ポリ−Ｎ−ビニルカルバゾール、ポリビニルアントラセン、ポリビニルピレン、ポリシランなどの有機光導電性ポリマーから選択することもできる。好ましい結着樹脂としては、ポリビニルブチラール樹脂、ポリアリレート樹脂（ビスフェノールＡとフタル酸の重縮合体等）、ポリカーボネート樹脂、ポリエステル樹脂、フェノキシ樹脂、塩化ビニル−酢酸ビニル共重合体、ポリアミド樹脂、アクリル樹脂、ポリアクリルアミド樹脂、ポリビニルピリジン樹脂、セルロース樹脂、ウレタン樹脂、エポキシ樹脂、カゼイン、ポリビニルアルコール樹脂、ポリビニルピロリドン樹脂等の絶縁性樹脂をあげることができるが、これらに限定されるものではない。これらの結着樹脂は単独あるいは２種以上混合して用いることができる。
【０１８８】
電荷発生材料と結着樹脂の配合比は（重量比）は１０：１〜１：１０の範囲が好ましい。またこれらを分散させる方法としてはボールミル分散法、アトライター分散法、サンドミル分散法等の通常の方法を用いることができるが、この際、分散によって該の結晶型が変化しない条件が必要とされる。ちなみに実施した前記の分散法のいずれについても分散前と結晶型が変化していないことが確認されている。さらにこの分散の際、粒子を０．５μｍ以下、好ましくは０．３μｍ以下、さらに好ましくは０．１５μｍ以下の粒子サイズにすることが有効である。またこれらの分散に用いる溶剤としては、メタノール、エタノール、ｎ−プロパノール、ｎ−ブタノール、ベンジルアルコール、メチルセルソルブ、エチルセルソルブ、アセトン、メチルエチルケトン、シクロヘキサノン、酢酸メチル、酢酸ｎ−ブチル、ジオキサン、テトラヒドロフラン、メチレンクロライド、クロロホルム、クロルベンゼン、トルエン等の通常の有機溶剤を単独あるいは２種以上混合して用いることができる。
【０１８９】
また、本発明で用いる電荷発生層の厚みは一般的には、０．１〜５μｍ、好ましくは０．２〜２．０μｍが適当である。また、電荷発生層を設けるときに用いる塗布方法としては、ブレードコーティング法、マイヤーバーコーティング法、スプレーコーティング法、浸漬コーティング法、ビードコーティング法、エアーナイフコーティング法、カーテンコーティング法等の通常の方法を用いることができる。さらに、顔料の分散安定性や、光感度を増す目的、あるいは、電気特性を安定化させる目的で化合物（Ｉ）を用いて顔料を処理したものを用いても良いし、顔料の分散溶液に加えてもよい。
【０１９０】
電荷輸送層
本発明の感光体における電荷輸送層としては、公知の技術によって形成されたものを使用できる。それらの電荷輸送層は、電荷輸送材料と結着樹脂を含有して形成されるか、あるいは高分子電荷輸送材を含有して形成される。
【０１９１】
電荷輸送材料としては、ｐ−ベンゾキノン、クロラニル、ブロマニル、アントラキノン等のキノン系化合物、テトラシアノキノジメタン系化合物、２，４，７−トリニトロフルオレノン等のフルオレノン化合物、キサントン系化合物、ベンゾフェノン系化合物、シアノビニル系化合物、エチレン系化合物等の電子輸送性化合物、トリアリールアミン系化合物、ベンジジン系化合物、アリールアルカン系化合物、アリール置換エチレン系化合物、スチルベン系化合物、アントラセン系化合物、ヒドラゾン系化合物などの正孔輸送性化合物があげられる。これらの電荷輸送材料は単独または２種以上混合して用いることができるが、これらに限定されるものではない。また、これらの電荷輸送材料は単独あるいは２種以上混合して用いることができる。電荷輸送材料特に、構造式（ＩＶ）で表わされるトリフェニルアミン系化合物、および構造式（Ｖ）で表わされるベンジジン系化合物は、高い電荷（正孔）輸送能と優れた安定性を有しているため、特に好ましく用いることができる。
【０１９２】
【化９】

【０１９３】
（式中、Ｒ_１４は、水素原子またはメチル基を示す。また、ｎは１又は２を意味する。Ａｒ_６及びＡｒ_７は置換又は未置換のアリール基を示し、置換基としてはハロゲン原子、炭素数が１〜５の範囲のアルキル基、炭素数が１〜５の範囲のアルコキシ基、又は炭素数が１〜３の範囲のアルキル基で置換された置換アミノ基を示す。）
【０１９４】
【化１０】

【０１９５】
（式中、Ｒ_１５及びＲ_１５は、同一でも異なってもよく、水素原子、ハロゲン原子、炭素数１〜５のアルキル基又は炭素数１〜５のアルコキシ基、を表わす。Ｒ_１６、Ｒ_１６’、Ｒ_１７及びＲ_１７’は同一でも異なってもよく、水素原子、ハロゲン原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基又は炭素数１〜２のアルキル基で置換されたアミノ基を表わし、ｍおよびｎは０〜２の整数である。）
【０１９６】
それぞれの化合物例を表５６〜６１に示す。
【０１９７】
【表５６】

【０１９８】
【表５７】

【０１９９】
【表５８】

【０２００】
【表５９】

【０２０１】
【表６０】

【０２０２】
【表６１】

【０２０３】
これらは、単独または２種以上混合して用いることができる。また、高分子電荷輸送材を用いることもできる。高分子電荷輸送材としては、ポリ−Ｎ−ビニルカルバゾール、ポリシランなどの電荷輸送性を有する公知のものを用いることができる。特に、特開平８−１７６２９３号公報や特開平８−２０８８２０号公報に示されているポリエステル系高分子電荷輸送材は、高い電荷輸送性を有しており、とくに好ましいものである。高分子電荷輸送材はそれだけでも成膜可能であるが、上記結着樹脂と混合して成膜してもよい。
【０２０４】
さらに電荷輸送層に用いる結着樹脂は、ポリカーボネート樹脂、ポリエステル樹脂、メタクリル樹脂、アクリル樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、ポリスチレン樹脂、ポリビニルアセテート樹脂、スチレン−ブタジエン共重合体、塩化ビニリデン−アクリロニトリル共重合体、塩化ビニル−酢酸ビニル共重合体、塩化ビニル−酢酸ビニル−無水マレイン酸共重合体、シリコン樹脂、シリコン−アルキッド樹脂、フェノール−ホルムアルデヒド樹脂、スチレン−アルキッド樹脂や、ポリ−Ｎ−ビニルカルバゾール、ポリシラン、特開平８−１７６２９３号公報や特開平８−２０８８２０号公報に示されているポリエステル系高分子電荷輸送材など高分子電荷輸送材を用いることもできる。さらに、ジルコニウムキレート化合物、ジルコニウムアルコキシド化合物、ジルコニウムカップリング剤などの有機ジルコニウム化合物、チタンキレート化合物、チタンアルコキシド化合物、チタネートカップリング剤などの有機チタン化合物、アルミニウムキレート化合物、アルミニウムカップリング剤などの有機アルミニウム化合物のほか、アンチモンアルコキシド化合物、ゲルマニウムアルコキシド化合物、インジウムアルコキシド化合物、インジウムキレート化合物、マンガンアルコキシド化合物、マンガンキレート化合物、スズアルコキシド化合物、スズキレート化合物、アルミニウムシリコンアルコキシド化合物、アルミニウムチタンアルコキシド化合物、アルミニウムジルコニウムアルコキシド化合物、などの有機金属化合物、とくに有機ジルコニウム化合物、有機チタニル化合物、有機アルミニウム化合物は残留電位が低く良好な電子写真特性を示すため、好ましく使用される。また、ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス−２−メトキシエトキシシラン、ビニルトリアセトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−２−アミノエチルアミノプロピルトリメトキシシラン、γ−メルカプロプロピルトリメトキシシラン、γ−ウレイドプロピルトリエトキシシラン、β−３，４−エポキシシクロヘキシルトリメトキシシラン等のシランカップリング剤など、あるいは光硬化性樹脂などの硬化型マトリックスを用いてもよく、さらにこれらと硬化可能な例えば化合物（Ｉ）の電荷輸送剤を用いてもよい。これらの結着樹脂は単独あるいは２種以上混合して用いることができる。電荷輸送材料と結着樹脂との配合比（重量比）は１０：１〜１：５が好ましい。
【０２０５】
本発明で用いる電荷輸送層の厚みは一般的には、５〜５０μｍ、好ましくは１０〜３０μｍが適当である。塗布方法としては、ブレードコーティング法、マイヤーバーコーティング法、スプレーコーティング法、浸漬コーティング法、ビードコーティング法、エアーナイフコーティング法、カーテンコーティング法等の通常の方法を用いることができる。
【０２０６】
さらに電荷輸送層を設けるときに用いる溶剤としては、ベンゼン、トルエン、キシレン、クロルベンゼン等の芳香族炭化水素類、アセトン、２−ブタノン等のケトン類、塩化メチレン、クロロホルム、塩化エチレン等のハロゲン化脂肪族炭化水素類、テトラヒドロフラン、エチルエーテル等の環状もしくは直鎖状のエーテル類等の通常の有機溶剤を単独あるいは２種以上混合して用いることができる。
【０２０７】
また、画像形成装置中で発生するオゾンや酸化性ガス、あるいは光、熱による感光体の劣化を防止する目的で、感光層中に酸化防止剤、光安定剤、熱安定剤等の添加剤を添加することができる。例えば、酸化防止剤としては、ヒンダードフェノール、ヒンダードアミン、パラフェニレンジアミン、アリールアルカン、ハイドロキノン、スピロクロマン、スピロインダノンおよびそれらの誘導体、有機硫黄化合物、有機燐化合物等があげられる。光安定剤の例としては、ベンゾフェノン、ベンゾトリアゾール、ジチオカルバメート、テトラメチルピペリジン等の誘導体が挙げられる。
【０２０８】
また、感度の向上、残留電位の低減、繰り返し使用時の疲労低減等を目的として、少なくとも１種の電子受容性物質を含有させることができる。本発明の感光体に使用可能な電子受容物質としては、例えば、無水コハク酸、無水マレイン酸、ジブロム無水マレイン酸、無水フタル酸、テトラブロム無水フタル酸、テトラシアノエチレン、テトラシアノキノジメタン、ｏ−ジニトロベンゼン、ｍ−ジニトロベンゼン、クロラニル、ジニトロアントラキノン、トリニトロフルオレノン、ピクリン酸、ｏ−ニトロ安息香酸、ｐ−ニトロ安息香酸、フタル酸等や、化合物（Ｉ）をあげることができる。これらのうち、フルオレノン系、キノン系やＣｌ，ＣＮ，ＮＯ_２等の電子吸引性置換基を有するベンゼン誘導体が特に好ましい。
【０２０９】
【実施例】
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらに限定されるものではない。なお、トナー組成物、キャリアの説明において、特に断りのない限り、「部」は全て「重量部」を意味する。
【０２１０】
なお、トナー組成物、キャリア、及び静電潜像現像剤の製造において、各測定は以下の方法で行った。
【０２１１】
＜カルシウム化合物粒子の体積平均粒子径測定＞
粒子を硬化性樹脂で包埋し、ダイアモンドカッターで薄くスライスしてＴＥＭにて観察する。その画像をプリントして１次粒子をサンプルとして任意に５０サンプル抽出し、その画像面積に相当する円形粒子の直径を体積平均粒子径とした。
【０２１２】
＜電気抵抗測定＞
図６に示されるように、測定試料３３を厚みＨとして下部電極３４と上部電極３２とで挟持し、上方より加圧しながらダイヤルゲージで厚みを測定し測定試料３３の電気抵抗を高電圧抵抗計で計測した。具体的には、特定酸化チタンの試料に成形機にて５００ｋｇ／ｃｍ^２ の圧力を加えて測定ディスクを作成した。次いで、ディスクの表面をハケで清掃し、セル内の上部電極３２と下部電極３４との間に挟み込み、ダイヤルゲージで厚みを測定した。次に電圧を印加し、エレクトロメーター３６の電流値を読み取ることにより、体積固有抵抗を求めた。
【０２１３】
また、キャリアの試料を１００φの下部電極４に充填し、上部電極２をセットし、その上から３．４３ｋｇの荷重を加え、ダイヤルゲージで厚みを測定した。次に電圧を印加し、エレクトロメーター５の電流値を読み取ることにより、体積固有抵抗を求めた。
【０２１４】
＜トナー平均形状指数ＳＦ１＞
本発明において、トナーの平均形状指数ＳＦ１とは、下記式で計算された値を意味し、真球の場合ＳＦ１＝１００となる。
【数２】
ＳＦ１＝（ＭＬ^２／Ａ）×（π／４）×１００
ここで、ＭＬ：粒子の絶対最大長、Ａ：粒子の投影面積であり、これらは、主に顕微鏡画像または走査電子顕微鏡画像を画像解析装置によって解析することによって数値化される。
【０２１５】
平均形状指数を求めるための具体的な手法として、トナー画像を光学顕微鏡から画像解析装置（ＬＵＺＥＸ ＩＩＩ、（株）ニレコ製）に取り込み、円相当径を測定して、最大長および面積から、個々の粒子について上記式のＭＬ^２／Ａの値を求める。
【０２１６】
＜帯電量測定＞
実機評価試験における帯電量は、現像器中のマグスリーブ上の現像剤を採取し、２５℃、５５％ＲＨの条件下で東芝社製ＴＢ２００にて測定した。
【０２１７】
［無機粒子の調整］
（Ａ）炭酸カルシウム粒子の調整
粒子作製：２Ｌのステンレスビーカー中で、１５重量％濃度の石灰乳１０００ｇに、化合開始温度２５℃で３０％濃度の炭酸ガスを２．０Ｌ／ｍｉｎの速度で吹き込み、懸濁液の電導度が二次降下して安定になるまで反応させた。反応液をヌッチェで吸引濾過し、母液を分離後、乾燥粉砕して、炭酸カルシウム粒子を得た。
【０２１８】
表面処理：次に炭酸カルシウム粒子をトルエン溶液中に分散し、シリコーンオイルを投入して超音波をかけエバポレーターでトルエンを留去し、更に１５０℃で１時間の加熱を加えた後粉砕して、平均粒径１５０ｎｍの表面処理炭酸カルシウム粒子Ａを得た。
【０２１９】
（Ｂ）炭酸カルシウム粒子の調整
炭酸カルシウム粒子の調整において、「粒子作製」は上記炭酸カルシウム粒子Ａと同様にして「表面処理」を以下のように行った。
【０２２０】
表面処理：固形分１０重量％の炭酸カルシウム粒子のスラリーを６５℃に調整した。該スラリーを分散機により攪拌させながら、オレイン酸ナトリウム含有量が６０重量％、ステアリン酸ナトリウム含有量が２０重量％及びパルミチン酸ナトリウム含有量が２０重量％である脂肪酸混合物を添加し、攪拌した後プレス脱水した。得られた濾過ケーキを箱型乾燥機で乾燥させた後、解砕することにより、平均粒径１５０ｎｍ、脂肪酸混合物で処理された表面処理炭酸カルシウム粒子Ｂを得た。
【０２２１】
（Ｃ）炭酸カルシウム粒子の調整
粒子作製：２Ｌのステンレスビーカー中で、１０重量％濃度の石灰乳１０００ｇに、化合開始温度２０℃で３０％濃度の炭酸ガスを２．０Ｌ／ｍｉｎの速度で吹き込み、懸濁液の電導度が二次降下して安定になるまで反応させた。反応液をヌッチェで吸引濾過し、母液を分離後、乾燥粉砕して、炭酸カルシウム粒子を得た。表面処理は、炭酸カルシウム粒子Ａの調整と同様に行って平均粒径７０ｎｍの表面処理炭酸カルシウム粒子Ｃを得た。
【０２２２】
（Ｄ）炭酸カルシウム粒子の調整
粒子作製：２Ｌのステンレスビーカー中で、２０重量％濃度の石灰乳１０００ｇに、化合開始温度２５℃で３０％濃度の炭酸ガスを２．０Ｌ／ｍｉｎの速度で吹き込み、懸濁液の電導度が二次降下して安定になるまで反応させた。反応液をヌッチェで吸引濾過し、母液を分離後、乾燥粉砕して、炭酸カルシウム粒子を得た。表面処理は、炭酸カルシウム粒子Ａ調整と同様に行って平均粒径２００ｎｍの表面処理炭酸カルシウム粒子Ｄを得た。
【０２２３】
（Ｅ）含水珪酸アルミニウム粒子の調整
原料としてケイ酸ナトリウムと硫酸アルミニウムを用い、モル比でＳｉ／Ａｌ＝１となるように攪拌しながら原料を連続的に混合した。同時に反応ｐＨが１０〜１２となるように水酸化ナトリウムを添加し中和することによりシリカ・アルミナゲルを調整した。つぎに硝酸アンモニウム水溶液をゲル中のナトリウムに対して２倍当量用い、室温にてナトリウムをアンモニウムにイオン交換した。ついで、交換したアンモニウムを６００℃、２ｈｒの焼成により除去した。さらに乾式粉砕し、原料粉体とした。上記原料粉体をスラリー濃度１０ｗｔ％になるようにオートクレーブに仕込み、２００℃、１日間さらに２５０℃、３日間水熱反応を行った。冷却後、反応液をヌッチェで吸引濾過し、母液を分離後、乾燥粉砕して、平均粒径２００ｎｍの含水珪酸アルミニウム粒子Ｅを得た。
【０２２４】
（Ｆ）未表面処理炭酸カルシウム粒子の調整
炭酸カルシウム粒子の調整において、「粒子作製」は上記炭酸カルシウム粒子Ａと同様にして平均粒径１４０ｎｍの未表面処理炭酸カルシウム粒子Ｆを得た。
【０２２５】
（Ｇ）炭酸カルシウム粒子の調整
粒子作製：２Ｌのステンレスビーカー中で、２２重量％濃度の石灰乳１０００ｇに、化合開始温度２８℃で３０％濃度の炭酸ガスを２．０Ｌ／ｍｉｎの速度で吹き込み、懸濁液の電導度が二次降下して安定になるまで反応させた。反応液をヌッチェで吸引濾過し、母液を分離後、乾燥粉砕して、炭酸カルシウム粒子を得た。表面処理は、炭酸カルシウム粒子Ａの調整と同様に行って平均粒径２６０ｎｍの表面処理炭酸カルシウム粒子Ｇを得た。
【０２２６】
［着色粒子の製造方法］
（ｉ）着色粒子Ａ製造方法
スチレン−ｎ−ブチルアクリレート樹脂 １００部
（Ｔｇ＝６１℃、Ｍｎ＝６０００、Ｍｗ＝３５０００）
カーボンブラック ３部
（モーガルＬ：キャボット製）
【０２２７】
上記混合物をエクストルーダーで混練し、ジェットミルで粉砕した後、風力式分級機で分散してＤ５０＝５．０μｍ、ＳＦ１＝１４８．８の黒トナーＡを得た。
【０２２８】
（ｉｉ）着色粒子Ｂ製造方法
＜樹脂分散液（１）の調整＞
スチレン ３７０質量部
ｎ−ブチルアクリレート ３０質量部
アクリル酸 ８質量部
ドデカンチオール ２４質量部
四臭化炭素 ４質量部
【０２２９】
以上の成分を混合して溶解したものを、非イオン性界面活性剤（ノニポール４００：三洋化成（株）製）６質量部及びアニオン性界面活性剤（ネオゲンＳＣ：第一工業製薬（株）製）１０質量部をイオン交換水５５０質量部に溶解したものにフラスコ中で乳化分散させ、１０分間ゆっくり混合しながら、これに過硫酸アンモニウム４質量部を溶解したイオン交換水５０質量部を投入した。窒素置換を行った後、前記フラスコ内を攪拌しながら内容物が７０℃になるまでオイルバスで加熱し、５時間そのまま乳化重合を継続した。その結果平均粒子径が１５５ｎｍであり、Ｔｇ＝５９℃、重量平均分子量Ｍｗ＝１２０００の樹脂粒子が分散された樹脂分散液（１）が得られた。
【０２３０】
＜樹脂分散液（２）の調整＞
スチレン ２８０質量部
ｎ−ブチルアクリレート １２０質量部
アクリル酸 ８質量部
【０２３１】
以上の成分を混合して溶解したものを、非イオン性界面活性剤（ノニポール４００：三洋化成（株）製）６質量部及びアニオン性界面活性剤（ネオゲンＳＣ：第一工業製薬（株）製）１２質量部をイオン交換水５５０質量部に溶解したものにフラスコ中で乳化分散させ、１０分間ゆっくり混合しながら、これに過硫酸アンモニウム３質量部を溶解したイオン交換水５０質量部を投入した。窒素置換を行った後、前記フラスコ内を攪拌しながら内容物が７０℃になるまでオイルバスで加熱し、５時間そのまま乳化重合を継続した。その結果平均粒子径が１０５ｎｍであり、Ｔｇ＝５３℃、重量平均分子量Ｍｗ＝５５００００の樹脂粒子が分散された樹脂分散液（２）が得られた。
【０２３２】
［着色剤分散液］
＜着色剤分散液（１）の調整＞
カーボンブラック ５０質量部
（モーガルＬ：キャボット製）
ノニオン性界面活性剤 ５質量部
（ノニポール４００：三洋化成（株）製）
イオン交換水 ２００質量部
【０２３３】
以上の成分を混合して、溶解、ホモジナイザー（ウルトラタラックスＴ５０：ＩＫＡ社製）を用いて１０分間分散し、平均粒子径が２５０ｎｍである着色剤（カーボンブラック）粒子が分散された着色剤分散液（１）を調整した。
【０２３４】
＜着色剤分散液（２）の調整＞
Ｃｙａｎ顔料Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ１５：３ ７０質量部
ノニオン性界面活性剤 ５質量部
（ノニポール４００：三洋化成（株）製）
イオン交換水 ２００質量部
【０２３５】
以上の成分を混合して、溶解、ホモジナイザー（ウルトラタラックスＴ５０：ＩＫＡ社製）を用いて１０分間分散し、平均粒子径が２５０ｎｍである着色剤（Ｃｙａｎ顔料）粒子が分散された着色剤分散液（２）を調整した。
【０２３６】
＜着色剤分散液（３）の調整＞
Ｍａｇｅｎｔａ顔料Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ１２２ ７０質量部
ノニオン性界面活性剤 ５質量部
（ノニポール４００：三洋化成（株）製）
イオン交換水 ２００質量部
【０２３７】
以上の成分を混合して、溶解、ホモジナイザー（ウルトラタラックスＴ５０：ＩＫＡ社製）を用いて１０分間分散し、平均粒子径が２５０ｎｍである着色剤（Ｍａｇｅｎｔａ顔料）粒子が分散された着色剤分散液（３）を調整した。
【０２３８】
＜着色剤分散液（４）の調整＞
Ｙｅｌｌｏｗ顔料Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ１８０ １００質量部
ノニオン性界面活性剤 ５質量部
（ノニポール４００：三洋化成（株）製）
イオン交換水 ２００質量部
【０２３９】
以上の成分を混合して、溶解、ホモジナイザー（ウルトラタラックスＴ５０：ＩＫＡ社製）を用いて１０分間分散し、平均粒子径が２５０ｎｍである着色剤（Ｙｅｌｌｏｗ顔料）粒子が分散された着色剤分散液（４）を調整した。
【０２４０】
［離型剤分散液（１）の調整］
パラフィンワックス ５０質量部
（ＨＮＰ０１９０：日本精蝋（株）製、融点８５℃）
カチオン性界面活性剤 ５質量部
（サニゾールＢ５０：花王（株）製）
【０２４１】
以上の成分を、丸型ステンレス鋼製フラスコ中でホモジナイザー（ウルトラタラックスＴ５０：ＩＫＡ社製）を用いて１０分間分散した後、圧力吐出型ホモジナイザーで分散処理し、平均粒径が５５０ｎｍである離型剤粒子が分散された離型剤分散液（１）を調整した。
【０２４２】
［凝集粒子の調整］
樹脂分散液（１） １２０質量部
樹脂分散液（２） ８０質量部
着色剤分散液（１） ２００質量部
離型分散液（１） ４０質量部
カチオン性界面活性剤 １．５質量部
（サニゾールＢ５０：花王（株）製）
【０２４３】
以上の成分を、丸型ステンレス鋼鉄フラスコ中でホモジナイザー（ウルトラタラックスＴ５０：ＩＫＡ社製）を用いて混合し、分散した後、加熱用オイルバス中でフラスコ内を攪拌しながら５０℃まで加熱した。４５℃で２０分間保持した後、光学顕微鏡で確認したところ、平均粒径が約５．０μｍである凝集粒子が形成されていることが確認された。更に上記分散液に、樹脂含有微粒子分散液として樹脂分散液（１）を緩やかに６０質量部追加した。そして加熱用オイルバスの温度を５０℃まで上げて３０分間保持した。光学顕微鏡にて観察したところ、平均粒径が約５．６μｍである付着粒子が形成されていることが確認された。
【０２４４】
［着色粒子Ｂの作成］
上記凝集粒子の分散液にアニオン性界面活性剤（ネオゲンＳＣ：第一工業製薬（株）製）３質量部を追加した後、前記ステンレス鋼鉄フラスコ中を密閉し、磁力シールを用いて攪拌しながら１０５℃まで加熱し、４時間保持した。そして、冷却後、反応生成物をろ過し、イオン交換水で充分に洗浄した後、乾燥させることにより、静電荷像現像用着色粒子Ｂを得た。
【０２４５】
＜着色粒子ＫｕｒｏＢの生成＞
着色剤分散液（１）を用いて上記凝集粒子の調整および着色粒子の作成の手法にてＳＦ１＝１２８．５、粒径Ｄ５０＝５．８μｍのＫｕｒｏトナーを得た。
【０２４６】
＜着色粒子ＣｙａｎＢの生成＞
上記凝集粒子の調整において着色剤分散液（１）の代わりに着色剤分散液（２）を用い、更に上記着色粒子の作成の手法にてＳＦ１＝１３０、粒径Ｄ５０＝５．６μｍのＣｙａｎトナーを得た。
【０２４７】
＜着色粒子ＭａｇｅｎｔａＢの生成＞
上記凝集粒子の調整において着色剤分散液（１）の代わりに着色剤分散液（３）を用い、更に上記着色粒子の作成の手法にてＳＦ１＝１３２．５、粒径Ｄ５０＝５．５μｍのＭａｇｅｎｔａトナーを得た。
【０２４８】
＜着色粒子ＹｅｌｌｏｗＢの生成＞
上記凝集粒子の調整において着色剤分散液（１）の代わりに着色剤分散液（４）を用い、更に上記着色粒子の作成の記手法にてＳＦ１＝１２７、粒径Ｄ５０＝５．９μｍのＹｅｌｌｏｗトナーを得た。
【０２４９】
［キャリアの生成］
フェライト粒子（平均粒径：５０μｍ） １００部
トルエン １４部
スチレン‐メチルメタクリレート共重合体 ２部
（成分比：９０／１０、Ｍｗ＝７５，０００）
カーボンブラック（Ｒ３３０：キャボット社製） ０．２部
【０２５０】
まず、フェライト粒子を除く上記成分を１０分間スターラーで撹拌させて、分散した被覆液を調整し、次に、この被覆液とフェライト粒子を真空脱気型ニーダーに入れて、６０℃において３０分撹拌した後、さらに加温しながら減圧して脱気し、乾燥させることによりキャリアを得た。このキャリアは、１０００Ｖ／ｃｍの印加電界時の体積固有抵抗値が１０^１１Ωｃｍであった。
【０２５１】
＜感光体１の製造＞
感光体表面層が電荷輸送性を有し、架橋構造を有するシロキサン系樹脂からなる感光体の作製例を以下に示す。
【０２５２】
ＪＩＳ Ａ３００３合金よりなる直径８４ｍｍの引き抜き管を用意し、センタレス研磨装置により研磨し、表面粗さをＲｚ＝０．５μｍとした。洗浄工程としてこのシリンダ−を脱脂処理、２ｗｔ％水酸化ナトリウム溶液で１分間エッチング処理、中和処理、更に純水洗浄を順に行った。次に、陽極酸化処理工程として１０ｗｔ％硫酸溶液によりシリンダ−表面に陽極酸化膜（電流密度１．０Ａ／ｄｍ^２ ）を形成した。水洗後、１ｗｔ％酢酸ニッケル溶液８０℃に２０分間浸漬して封孔処理を行った。更に純水洗浄、乾燥処理を行った。このようにして、アルミニウムシリンダ−表面に７μｍの陽極酸化膜を形成した。
【０２５３】
このアルミニウム基材上にＸ線回折スペクトルにおけるブラッグ角（２θ±０．２°）が、７．４°、１６．６°、２５．５°、２８．３°に強い回折ピークを持つクロロガリウムフタロシアニンの１部をポリビニルブチラール（エスレックＢＭ‐Ｓ、積水化学） １部、および酢酸ｎ‐ブチル１００部と混合し、ガラスビーズとともにペイントシェーカーで１時間処理して分散した後、得られた塗布液を前記下引き層上に浸漬コートし、１００℃で１０分間加熱乾燥して膜厚約０．１５μｍの電荷発生層を形成した。
【０２５４】
下記構造のベンジジン化合物２部、高分子化合物 （粘度平均分子量 ４０，０００）３部をクロロベンゼン２０部に溶解させた塗布液を前記電荷発生層上に浸漬コーティング法で塗布し、１１０℃、４０分の加熱を行なって膜厚２０μｍの電荷輸送層を形成した。これを感光体１とする。
【０２５５】
【化１１】

下記に示す構成材料を、イソプロピルアルコール５部、テトラヒドロフラン３部、蒸留水０．３部に溶解させ、イオン交換樹脂（アンバーリスト１５Ｅ）０．５部を加え、室温で攪拌することにより２４時間加水分解を行った。
【０２５６】
構成材料
例示化合物 ２６１ ２部
メチルトリメトキシシラン ２部
テトラメトキシシラン ０．５部
コロイダルシリカ ０．３部
【０２５７】
加水分解したものからイオン交換樹脂を濾過分離した液体２部に対し、アルミニウムトリスアセチルアセトナートを０．０４部、３，５‐ジ‐ｔ‐ブチル‐４‐ヒドロキシトルエン（ＢＨＴ）０．１部を加え、このコーティング液を前記電荷輸送層の上にリング型浸漬塗布法により塗布し、室温で３０分風乾した後、１７０℃で１時間加熱処理して硬化し、膜厚約３μｍの表面層を形成した。
【０２５８】
（実施例１）
上記着色粒子ＢのＫｕｒｏ、Ｃｙａｎ、Ｍａｇｅｎｔａ、Ｙｅｌｌｏｗトナーのそれぞれ１００部にデシルシランで表面処理した平均粒径１５ｎｍの疎水性チタニア０．８部、平均粒径４０ｎｍの疎水性シリカ（ＲＸ５０、日本アエロジル社製）１．２部、炭酸カルシウム粒子Ａ０．６部をヘンシェルミキサーを用い、周速３２ｍ／ｓで１０分間ブレンドをおこなった後、４５μｍ網目のシーブを用いて粗大粒子を除去し、トナーを得た。上述のキャリア１００部と上記トナー５部をＶ−ブレンダーを用い４０ｒｐｍで２０分間攪拌し、１７７μｍの網目を有するシーブで篩うことにより現像剤を得た。
【０２５９】
（実施例２）
上記着色粒子ＫｕｒｏＢ１００部にデシルシランで表面処理した平均粒径１５ｎｍの疎水性チタニア０．８部、平均粒径４０ｎｍの疎水性シリカ（ＲＸ５０、日本アエロジル社製）１．２部、炭酸カルシウム粒子Ｂ１．０部をヘンシェルミキサーを用い、周速３２ｍ／ｓで１０分間ブレンドをおこなった後、４５μｍ網目のシーブを用いて粗大粒子を除去し、トナーを得た。キャリア１００部と上記トナー５部をＶ−ブレンダーを用い４０ｒｐｍで２０分間攪拌し、１７７μｍの網目を有するシーブで篩うことにより現像剤を得た。
【０２６０】
（実施例３）
上記着色粒子ＫｕｒｏＢ１００部にデシルシランで表面処理した平均粒径１５ｎｍの疎水性チタニア０．８部、平均粒径４０ｎｍの疎水性シリカ（ＲＸ５０、日本アエロジル社製）１．２部、炭酸カルシウム粒子Ｃ０．６部をヘンシェルミキサーを用い、周速３２ｍ／ｓで１０分間ブレンドをおこなった後、４５μｍ網目のシーブを用いて粗大粒子を除去し、トナーを得た。キャリア１００部と上記トナー５部をＶ‐ブレンダーを用い４０ｒｐｍで２０分間攪拌し、１７７μｍの網目を有するシーブで篩うことにより現像剤を得た。
【０２６１】
（実施例４）
上記着色粒子ＫｕｒｏＢ１００部にデシルシランで表面処理した平均粒径１５ｎｍの疎水性チタニア０．８部、平均粒径４０ｎｍの疎水性シリカ（ＲＸ５０、日本アエロジル社製）１．２部、炭酸カルシウム粒子Ｄ１．３部をヘンシェルミキサーを用い、周速３２ｍ／ｓで１０分間ブレンドをおこなった後、４５μｍ網目のシーブを用いて粗大粒子を除去し、トナーを得た。キャリア１００部と上記トナー５部をＶ−ブレンダーを用い４０ｒｐｍで２０分間攪拌し、１７７μｍの網目を有するシーブで篩うことにより現像剤を得た。
【０２６２】
（実施例５）
上記着色粒子ＫｕｒｏＡ１００部にデシルシランで表面処理した平均粒径１５ｎｍの疎水性チタニア０．９部、平均粒径４０ｎｍの疎水性シリカ（ＲＸ５０、日本アエロジル社製）１．３部、炭酸カルシウム粒子Ａ１．３部をヘンシェルミキサーを用い、周速３２ｍ／ｓで１０分間ブレンドをおこなった後、４５μｍ網目のシーブを用いて粗大粒子を除去し、トナーを得た。キャリア１００部と上記トナー５部をＶ−ブレンダーを用い４０ｒｐｍで２０分間攪拌し、１７７μｍの網目を有するシーブで篩うことにより現像剤を得た。
【０２６３】
（実施例６）
上記着色粒子ＫｕｒｏＢ１００部にデシルシランで表面処理した平均粒径１５ｎｍの疎水性チタニア０．８部、シリコーンオイルで表面処理した平均粒径４０ｎｍの疎水性シリカ１．２部、炭酸カルシウム粒子Ｂ１．０部をヘンシェルミキサーを用い、周速３２ｍ／ｓで１０分間ブレンドをおこなった後、４５μｍ網目のシーブを用いて粗大粒子を除去し、トナーを得た。キャリア１００部と上記トナー５部をＶ−ブレンダーを用い４０ｒｐｍで２０分間攪拌し、１７７μｍの網目を有するシーブで篩うことにより現像剤を得た。
【０２６４】
（実施例７）
上記着色粒子ＫｕｒｏＢ１００部にデシルシランで表面処理した平均粒径１５ｎｍの疎水性チタニア０．８部、シリコーンオイルで表面処理した平均粒径４０ｎｍの疎水性シリカ１．２部、炭酸カルシウム粒子Ｆ０．６部をヘンシェルミキサーを用い、周速３２ｍ／ｓで１０分間ブレンドをおこなった後、４５μｍ網目のシーブを用いて粗大粒子を除去し、トナーを得た。キャリア１００部と上記トナー５部をＶ−ブレンダーを用い４０ｒｐｍで２０分間攪拌し、１７７μｍの網目を有するシーブで篩うことにより現像剤を得た。
【０２６５】
（実施例８）
実施例７において炭酸カルシウム粒子Ｆを含水珪酸アルミニウム粒子に変えた以外は同様に作製して現像剤を得た。
【０２６６】
（比較例１）
実施例２において炭酸カルシウム粒子Ｂを除いた他は同様に作製して現像剤を得た。（シリカのモース硬度は７、チタニアのモース硬度は６．５〜７）
【０２６７】
（比較例２）
上記着色粒子ＫｕｒｏＢ１００部にデシルシランで表面処理した平均粒径１５ｎｍの疎水性チタニア０．８部、シリコーンオイルで表面処理した平均粒径４０ｎｍの疎水性シリカ１．２部、平均粒径６５０ｎｍの酸化セリウム（モース硬度７）０．６部をヘンシェルミキサーを用い、周速３２ｍ／ｓで１０分間ブレンドをおこなった後、４５μｍ網目のシーブを用いて粗大粒子を除去し、トナーを得た。キャリア１００部と上記トナー５部をＶ−ブレンダーを用い４０ｒｐｍで２０分間攪拌し、１７７μｍの網目を有するシーブで篩うことにより現像剤を得た。
【０２６８】
（比較例３）
実施例４において炭酸カルシウム粒子Ｄを平均粒径２００ｎｍのアルミナ（モース硬度９）に変えた以外は同様に作製して現像剤を得た。
【０２６９】
［評価］
上記実施例及び比較例に記載の現像剤を用い、潜像担持体を帯電させる帯電手段と、帯電された潜像担持体上に露光して静電潜像を形成する潜像形成手段と、前記静電潜像をトナーを用いて現像する現像手段と、形成されたトナー像を記録材に転写し、トナー像保持体である潜像担持体より分離する転写分離手段と、転写されたトナー像を記録材上にロール熱定着する定着手段と、を有して画像形成方法をおこなうＦｕｊｉ Ｘｅｒｏｘ社製Ｄｏｃｕ Ｃｅｎｔｒｅ Ｃｏｌｏｒ ５００改造機を用いて２万枚複写の長期走行テストをし、転写性、感光体汚染、傷の評価を行った。そして、上記感光体は、Ｄｏｃｕ Ｃｅｎｔｒｅ Ｃｏｌｏｒ ５００オリジナル感光体（有機感光体）から表面層が架橋構造を有するシロキサン系樹脂からなる感光体１に取り替えて行った。
【０２７０】
トナー帯電量、転写効率はテスト初期の結果、感光体汚染、感光体傷は複写２万枚後の感光体の観察結果である。
【０２７１】
転写性の評価は、転写工程終了時にハードストップを行い、転写材のトナー重量をトナー除去前後の測定から転写トナー量ａを求め、同様に感光体上に残ったトナー量ｂを求め、次式により転写効率を求めた。
【数３】
転写効率η（％）＝ａ＊１００／（ａ＋ｂ）
そして、 次の様に判断を行った。
η≧９０％・・・○、η＜９０％・・・×
【０２７２】
感光体汚染および感光体傷は、汚染なしは○、汚染ありは×、傷なしは○、傷ありは×とした。
【０２７３】
その結果を表６２に示す。
【０２７４】
【表６２】

【０２７５】
本発明の、モース硬度が２〜４．５の無機粒子を用いたトナーの現像剤は、実施例１〜８の結果のように帯電維持性が良好であり、長期繰り返し使用においても転写性が良好であった。また各現像剤評価において２万枚複写後に感光体を抜き出し、表面観察を行ったところ、傷／偏磨耗、汚染は軽微であった。更に実施例２において、４万枚後でも感光体に問題はなかった。
【０２７６】
一方、モース硬度が２〜４．５の無機粒子を用いていないトナーの現像剤は、比較例１−３の結果のように、２万枚複写後に感光体を抜き出し表面観察を行ったところ、汚染がハッキリと確認できた。また、比較例２，３の結果のように、傷／偏磨耗がハッキリと確認できた。
【０２７７】
【発明の効果】
本発明の画像形成方法によれば、潜像担持体の汚染および潜像担持体への傷付きや偏磨耗を防止することができ、長期間安定して良好な画質を得ることができる。
【図面の簡単な説明】
【図１】本発明に用いられる感光体の一例を示す拡大断面図である。
【図２】本発明に用いられる感光体の他の一例を示す拡大断面図である。
【図３】本発明に用いられる感光体の他の一例を示す拡大断面図である。
【図４】本発明に用いられる感光体の他の一例を示す拡大断面図である。
【図５】本発明に用いられる感光体の他の一例を示す拡大断面図である。
【図６】本発明の実施例および比較例に用いたキャリアの体積固有抵抗を求めるための装置構成を示す模式図である。
【符号の説明】
１ 下引き層、２ 電荷発生層、３ 電荷輸送層、４ 導電性支持体、５ 表面保護層、６ 単層型感光層、３１ ガード電極、３２ 上部電極、３３ 測定試料、３４ 下部電極、３５ 試料保持リング、３６ エレクトロメーター。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a toner, a developer, a manufacturing method, and an image forming method used for developing an electrostatic latent image in electrophotography and electrostatic recording.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, when an image is formed by a copying machine, a laser beam printer, or the like, the Carlson method is generally used. In a conventional image forming method, an electrostatic latent image formed on a surface of a photoreceptor (electrostatic latent image carrier) by optical means or the like is developed in a developing process, and then is transferred to a recording medium such as a recording paper in a transfer process. Is transferred to the recording medium in a fixing step, generally by heat and pressure. Since the photoconductor is used repeatedly, a cleaning device is provided to remove residual toner remaining on the surface of the photoconductor after the transfer process.
[0003]
Development methods used for developing the electrostatic latent image include a one-component development method using only a toner and a two-component development method using a two-component developer composed of a toner and a carrier. Is that the toner is frictionally charged by stirring the toner and the carrier, so that the frictional charge amount of the toner can be controlled to a considerable extent by selecting the characteristics of the carrier and the stirring conditions, so that the reliability of the image quality is high. Has excellent properties.
[0004]
On the other hand, the toner used in the electrophotographic process generally includes a binder resin (for example, a polyester resin, a styrene-acryl resin, an epoxy resin, etc.), a colorant, a charge control agent, a release agent, and the like.
[0005]
Further, it is necessary to improve the storability (blocking resistance), transportability, developability, transfer characteristics, and cleaning characteristics of the toner, and various fine particles are added to the toner surface for the purpose of improving these characteristics. . For example, it has been proposed to externally add an additive such as silica or titanium oxide, or an additive whose surface is hydrophobized with an organic silane compound or coated with an inorganic oxide (Patent Documents 1 to 3). See Patent Document 4). Further, at the time of cleaning, it is necessary to have a cleaning property such that the residual toner is easily detached from the surface of the photoconductor and that the photoconductor is not damaged when used together with a cleaning member such as a blade or a web. In order to satisfy these requirements, various dry-developed toners have been proposed in which an inorganic fine powder such as silica, an organic fine powder such as a fatty acid, a metal salt thereof and a derivative thereof, and a fine powder of a fluorine resin are externally added. The durability or the cleaning property is improved.
[0006]
However, in the conventionally proposed additives, although inorganic compounds such as silica, titania and alumina significantly improve the fluidity, the photoreceptor surface layer is susceptible to dents and scratches due to hard inorganic compound fine powder, and damaged portions Therefore, there is a problem that the toner is easily fixed. In recent years, the use of recycled paper has been increasing for the purpose of resource saving. However, in general, recycled paper has a problem that a large amount of paper dust is generated. Induces poor cleaning such as Further, in order to solve these problems, in Patent Document 5, a fatty acid metal salt is externally added as an additive, and in Patent Documents 6 and 7, a wax is externally added. In any of the above-mentioned patent documents, the particle size of the additive is as large as 3 to 20 μm, and a considerable amount of addition is required for efficiently exhibiting the effect. In addition, although effective initially, there is a problem that film formation as a lubricant is not uniform due to filming of an additive (lubricant), and whitening or blurring of an image occurs in an image.
[0007]
Patent Document 8 discloses titanium oxide particles treated with a fatty acid metal salt, Patent Document 9 discloses titanium oxide fine particles surface-treated while hydrolyzing a fatty acid compound in an aqueous system, and Patent Document 10 discloses a fatty acid metal salt. Patent Document 11 proposes a fine particle titanium oxide surface-treated with a fatty acid aluminum and made hydrophobic. By using the fatty acid metal salt for the surface treatment, the above-mentioned problem caused by the particle size of the fatty acid metal salt itself is avoided to some extent. However, in each case, although some effects are obtained, the prevention of scratches on the photoreceptor surface is insufficient.
[0008]
On the other hand, in Patent Document 12, a hydrophobic hard fine powder is externally added to a toner, and a photoreceptor is shaved by a polishing effect of the hard fine powder to prevent toner filming. However, although this method is effective in suppressing filming, it has a drawback in that the surface of the photoreceptor is worn and the life of the photoreceptor is significantly reduced. At the same time, there is a disadvantage that the cleaning blade is worn by the hard fine powder, which significantly reduces the blade life.
[0009]
Further, in order to polish and remove the surface oxide layer of the photoreceptor, at least 3.5 Mohs hardness and a volume-based average particle diameter of 0.1 to 10 μm containing at least calcium carbonate with respect to 100 parts by weight of toner particles. There has been proposed an electrophotographic toner in which abrasive particles and a silica-based external additive are externally added in a total amount of 0.1 to 3 parts by weight (for example, see Patent Document 13). In recent years, an image forming method using a photoconductor having a high hardness surface has been proposed (for example, see Patent Document 14). However, if image formation is repeated using a photoconductor having such a high hardness surface, a problem of image deletion or other image defects occurs. These image defects are caused by accumulation of discharge products in charging of the photoreceptor or adhesion of contained substances such as toner and paper since the surface of the photoreceptor has high hardness, that is, hardly any film scraping occurs. .
[0010]
[Patent Document 1]
JP-A-4-204750
[Patent Document 2]
JP-A-6-208241
[Patent Document 3]
JP-A-7-295293
[Patent Document 4]
JP-A-8-160559
[Patent Document 5]
JP-A-60-198556
[Patent Document 6]
JP-A-61-231562
[Patent Document 7]
JP-A-61-231563
[Patent Document 8]
JP-A-4-452
[Patent Document 9]
JP-A-5-66607
[Patent Document 10]
JP-A-5-165250
[Patent Document 11]
JP-A-10-161342
[Patent Document 12]
JP-A-2-89064
[Patent Document 13]
JP-A-8-190221
[Patent Document 14]
JP-A-11-38656
[0011]
[Problems to be solved by the invention]
The present invention has been made in view of the above-described circumstances of the related art. SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method capable of simultaneously satisfying toner fluidity, chargeability, developability, transferability, cleaning properties, and fixability over a long period of time. Another object of the present invention is to provide an image forming method that can obtain high image quality for a long period of time even in an image forming method using a photoreceptor having a high hardness surface.
[0012]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and as a result, in an image forming method using a photoreceptor having a high hardness surface, by using specific inorganic compound particles for toner, the above object has been achieved. They have found that this can be achieved and have completed the present invention.
[0013]
Specifically, it is as follows.
[0014]
(1) charging means for charging the latent image carrier, latent image forming means for exposing the charged latent image carrier to form an electrostatic latent image, and developing the electrostatic latent image using toner Developing means for transferring the formed toner image to a recording material and separating the toner image from a latent image carrier serving as a toner image holding member; and fixing the transferred toner image to the recording material by contact heat fixing. Means for forming an image using an image forming apparatus having the above-mentioned means, wherein the toner contains at least inorganic particles having a Mohs hardness of 2 to 4.5, and the surface layer of the latent image carrier is charged. An image forming method comprising a siloxane-based resin having a transport property and a cross-linked structure.
[0015]
(2) The image forming method according to (1), wherein the inorganic particles have an average particle size of 70 to 300 nm.
[0016]
(3) The image forming method according to the above (1) or (2), wherein the inorganic particles are made of calcium carbonate.
[0017]
(4) The image forming method according to any one of (1) to (3), wherein the toner has a shape having an average shape index SF1 of 100 to 140.
(Equation 1)
SF1 = (ML ² / A) × (π / 4) × 100
Here, ML: the absolute maximum length of the particle, A: the projected area of the particle, and these are quantified mainly by analyzing a microscope image or a scanning electron microscope image with an image analyzer.
[0018]
(5) The transfer / separation unit develops each color toner on a latent image carrier, transfers the toner to a transfer belt or a transfer drum, and then transfers each color toner to the transfer body at once. The color image forming method according to any one of the above (1) to (4).
[0019]
(6) The color image forming method according to any one of (1) to (5), wherein the fixing unit is a fixing unit that does not substantially supply a release agent.
[0020]
(7) charging means for charging the latent image carrier, latent image forming means for exposing the charged latent image carrier to form an electrostatic latent image, and developing the electrostatic latent image using toner Developing means for transferring the formed toner image to a recording material and separating the toner image from a latent image carrier, which is a toner image carrier, and cleaning for removing toner remaining on the toner image carrier after the transfer Means for forming an image using an image forming apparatus having a toner image and a fixing means for thermally fixing the transferred toner image on a recording material, wherein the toner has a Mohs hardness of at least 2 to 4.5. Wherein the surface layer of the latent image carrier has a charge transporting property and is made of a siloxane resin having a crosslinked structure, and the cleaning means does not rub the latent image carrier with a blade. Using an electrostatic brush Image forming method characterized by recovering the residual toner on the image bearing member.
[0021]
(8) The image forming method according to the above (7), wherein the inorganic particles have an average particle diameter of 70 to 300 nm.
[0022]
(9) The image forming method as described in (7) or (8) above, wherein the inorganic particles are made of calcium carbonate.
[0023]
(10) The image forming method as described in any one of (7) to (9) above, wherein the toner has a shape having an average shape index SF1 of 100 to 140.
[0024]
BEST MODE FOR CARRYING OUT THE INVENTION
(toner)
Next, the toner in the present invention will be described.
[0025]
The toner must contain at least inorganic particles having a Mohs hardness of 2 to 4.5.
[0026]
As described above, it is necessary to control the toner extremely high in consideration of not only transportability, developability, transferability, chargeability, etc., but also cleaning characteristics. Cleaning is a function mainly required to remove toner remaining on the photoconductor after transfer. As a cleaning method, there are a blade method and a brush method. In both cases, mechanical force is applied to the photoconductor to remove toner, but at this time, the surface of the photoconductor is worn due to the blade or brush itself and the toner material interposed. , May cause scratches. For example, toner particles enter between the blade and the photoreceptor pressed against the photoreceptor, and silica, titania, alumina and the like constituting the toner surface act on the photoreceptor as an abrasive to cause abrasion and scratches. This is because silica, titania, and alumina are excellent in transportability, developability, and transferability, but partly because they are much harder than the material of the surface of the toner photoreceptor. In particular, when a photoreceptor having a hard surface is used, scratches are suppressed and durability is increased, but uneven wear occurs. Such uneven wear causes discharge products and deteriorated portions to remain, resulting in image quality deterioration. Therefore, uneven wear and scratches of the photoreceptor can be improved by using relatively low hardness inorganic particles among the inorganic particles.
[0027]
Further, if the photoreceptor is used repeatedly, even though it has been cleaned, the photoreceptor is also contaminated by components constituting the toner. In this respect, cleaning is required not only to remove toner particles but also to suppress contamination as much as possible. From this point, it is necessary that inorganic particles capable of polishing and removing contaminants formed of the toner material on the photoconductor are added to the toner.
[0028]
As a result of intensive studies, the present inventors have found that by adding inorganic particles having a Mohs' hardness of 2 to 4.5 to a toner and using the same, it is possible to suppress abrasion and scratches on the photoreceptor and to suppress contamination.
[0029]
Further, when spherical toner is used, the packing property is inevitably increased in the conveyance regulating portion in the developing device, and accordingly, a strong force is applied not only to the toner surface but also to the carrier. Therefore, by dispersing and containing a conductive material in the resin coating layer of the carrier, even if the resin coating layer peels off, it does not significantly change the volume resistivity, and as a result, it is possible to realize long-term high image quality. I can do it.
[0030]
Hereinafter, the present invention will be described in detail.
[0031]
Examples of the inorganic particles having a Mohs hardness of 2 to 4.5 include, but are not limited to, hydrous aluminum silicate (2 to 2.5), mica (2.8), and calcium carbonate (3). (The value in the parenthesis is Mohs hardness).
[0032]
In the present invention, calcium carbonate particles can be suitably used because they are relatively advantageous in terms of negative charge control.
[0033]
Mohs hardness is obtained using a Mohs hardness tester. F. Mohs devised the following ten kinds of minerals, and if they were scratched and damaged sequentially, they would have lower hardness than the minerals. Minerals in order of hardness are: 1: talc, 2: gypsum, 3: calcite, 4: fluorite, 5: apatite, 6: feldspar, 7: quartz, 8: yellow ore, 9: steel ball, 10: diamond. ,.
[0034]
As a method for producing the above-mentioned inorganic particles, calcium carbonate is produced by blowing carbon dioxide gas into lime milk which is an aqueous suspension of calcium hydroxide (JP-B-37-519, JP-B-47-22944, Japanese Patent Publication No. 56-40118) is known.
[0035]
For hydrous aluminum silicate, a hydrothermal synthesis method is used, which is obtained by maintaining a raw material at a high temperature and a high pressure for a certain period of time in the presence of moisture. Spherical synthetic hydrous aluminum silicates and their preparation have been reported by Shibasaki and Watari (1983, Clays & Clay minerals) et al. Also, a homogeneous mixed silica-alumina gel at temperatures below 220 ° C. and above 220 ° C. (Japanese Unexamined Patent Publication (Kokai) No. 6-191829).
[0036]
As mica, any natural mica such as natural muscovite, phlogopite, sericite, biotite and the like can be used. As the synthetic mica, a melt synthesis method is known, and examples thereof include synthetic fluorine tetrasilicic mica and synthetic phlogopite.
[0037]
A specific embodiment of the method for producing calcium carbonate used in the present invention will be described.
[0038]
Synthesis of calcium carbonate:
Methods for producing calcium carbonate by blowing carbon dioxide gas into ash milk can be classified into two types according to the conditions of carbonation. As a general condition, one is cubic particles called colloidal calcium carbonate having an average particle size of 0.1 μm or less, and is usually formed into lime milk having a calcium hydroxide concentration of 15% or less at a compounding start temperature of 25 ° C. or less. Carbon dioxide gas at a blowing rate of 2.0 L / min or more in terms of 100% carbon dioxide gas per kg of calcium hydroxide. The other is spindle-shaped particles called light calcium carbonate having an average particle diameter of 0.5 μm or more. The calcium hydroxide concentration is added to lime milk having a concentration of 15% or more. The reaction is performed at a blowing rate of 2.0 L / min or less in terms of 100% carbon dioxide gas per kg to obtain a desired particle size and particle shape.
[0039]
As for the average particle size of the calcium carbonate particles, the primary particle size is 70 to 300 nm, preferably 100 to 200 μm. If it is less than 70 nm, not only the effect of polishing and removing contaminants on the photoreceptor surface cannot be obtained, but also toner transferability cannot be obtained. If it is larger than 300 nm, an excessive amount must be added to the toner to obtain transferability. This has an adverse effect on the charging characteristics.
[0040]
Further, a surface treatment may be performed for adjusting fluidity and charging characteristics. Although the surface treatment is not limited to the case where the following surface treatment compounds are used, examples of the surface treatment compound include a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, various silicone oils, A treatment using a fatty acid, a fatty acid metal salt, its esterified product, rosin acid or the like can be exemplified. Particularly preferably, silane coupling agents, fatty acids and rosin acids can be used.
[0041]
Also, the surface treatment amount is not limited to the following, but may be 0.1 to 30 wt%, preferably 0.2 to 20 wt%, more preferably 0.2 to 10 wt%. . If it is less than 0.1 wt%, no surface treatment effect can be obtained, and if it is more than 30 wt%, aggregated particles will be generated. In the present invention, by using a material in the above range, uneven wear due to being too hard can be prevented, and durability can be improved by moderate wear.
[0042]
As the inorganic particles, those having a small shape distribution (uniform shape) such as a cube, a spindle, and a hexahedron are preferable. By using particles having a uniform shape, the particles are uniformly dispersed on the toner surface, and a stable spacer effect can be obtained. Furthermore, since the contact area is large and wear can be performed uniformly, uneven wear can be further prevented.
[0043]
The amount of the inorganic particles added is 0.1 to 5 wt%, more preferably 0.3 to 2 wt%. If it is less than 0.1 wt%, the effect of adding the inorganic particles is not sufficient. If it is more than 5 wt%, the influence on the fluidity and charging characteristics of the toner is large, and it is difficult to control the toner.
[0044]
The electrostatic latent image developing toner includes a binder resin, a colorant, and a release agent, and may have a volume average particle diameter of 2 to 10 μm.
[0045]
Further, by using a toner having an average shape index SF1 of 100 to 140, it is possible to obtain an image having high development, transferability and high quality.
[0046]
The toner used in the present invention is not particularly limited by a manufacturing method as long as it satisfies the above-mentioned shape index and particle diameter, and a known method can be used.
[0047]
The toner is produced by, for example, kneading, pulverizing and classifying a binder resin and a colorant, a release agent, and, if necessary, a charge controlling agent, and the like. A method of changing the shape by force or thermal energy, emulsion polymerization of the polymerizable monomer of the binder resin, dispersion of the formed dispersion, dispersion of a colorant, a release agent, and if necessary, a charge control agent, etc. Emulsion polymerization agglomeration method to obtain toner particles by mixing and aggregating, heating and fusing liquid, polymerizable monomer and colorant for obtaining binder resin, mold release agent, charge control agent if necessary A suspension polymerization method in which the solution is suspended in an aqueous solvent and polymerized, a solution in which a solution of a binder resin and a colorant, a release agent, and, if necessary, a charge control agent is suspended in an aqueous solvent and granulated. A suspension method or the like can be used. Alternatively, a production method may be performed in which the toner obtained by the above method is used as a core, and aggregated particles are further adhered and fused to form a core-shell structure.
[0048]
As the binder resin used, styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl acetate, vinyl propionate, vinyl benzoate and vinyl esters such as vinyl butyrate, Α-methylene aliphatic monocarboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate And homopolymers and copolymers of vinyl ethers such as vinyl methyl ketone, vinyl ethyl ether and vinyl butyl ether, and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone. Particularly typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, and styrene-anhydride. Maleic acid copolymer, polyethylene, polypropylene and the like can be mentioned. Furthermore, polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like can be mentioned. Further, a resin having a softening point of 90 to 150 ° C., a glass transition point of 50 to 75 ° C., and a Mw (weight average molecular weight) of 8,000 to 150,000 can be particularly preferably used.
[0049]
Examples of toner colorants include magnetic powders such as magnetite and ferrite, carbon black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, Dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, and malachite green oxalate. Rate, lamp black, rose bengal, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 17, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 3 and the like can be exemplified.
[0050]
Representative examples of the release agent include low-molecular polyethylene, low-molecular polypropylene, Fischer-Tropsch wax, montan wax, carnauba wax, rice wax, candelilla wax and the like.
[0051]
Further, a charge controlling agent may be added to the electrostatic latent image developing toner of the present invention as needed. As the charge control agent, known ones can be used, and an azo metal complex compound, a metal complex compound of salicylic acid, and a resin type charge control agent containing a polar group can be used. When a toner is manufactured by a wet manufacturing method, it is preferable to use a material that is hardly dissolved in water in terms of controlling ionic strength and reducing wastewater contamination. The toner in the present invention may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.
[0052]
Further, in order to further improve the long-term storage properties, fluidity, developability, and transferability of the toner, the toner used in the present invention is made of an inorganic powder other than the inorganic particles used in the present invention and a resin powder on the toner surface. You may add together. Examples of the inorganic powder include carbon black, silica, alumina, titania, zinc oxide, strontium titanate, and cerium oxide. Examples of the resin powder include polystyrene, polymethyl methacrylate (PMMA), nylon, melamine, benzoguanamine, and spherical spherical particles of fluorine. And amorphous powders such as vinylidene chloride and fatty acid metal salts. When added to the surface, each is added in an amount of 0.1 to 4% by weight, more preferably 0.2 to 3% by weight. The mixing can be performed by a known mixer such as a V-type blender, a Henschel mixer or a Loedige mixer.
[0053]
In addition, it does not matter if the sieving process is performed after the external addition and mixing.
[0054]
(Developer)
The developer according to the present invention includes the above-described toner composition and a carrier described below. The carrier constituting the developer together with the toner is a resin-coated carrier having a resin coating layer in which a conductive material is dispersed and contained in a matrix resin in order to stably control toner charging and stably control electric resistance on a core material. Preferably, there is.
[0055]
As the matrix resin, polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid copolymer Examples include polymers, straight silicone resins comprising organosiloxane bonds or modified products thereof, fluororesins, polyesters, polyurethanes, polycarbonates, phenolic resins, amino resins, melamine resins, benzoguanamine resins, urea resins, amide resins, epoxy resins and the like. However, the present invention is not limited to these.
[0056]
Examples of the conductive material include metals such as gold, silver, and copper, and titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate, tin oxide, and carbon black, but are not limited thereto. It is not done.
[0057]
The content of the conductive material is preferably 1 to 50 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the resin.
[0058]
Examples of the core material of the carrier include magnetic metals such as iron, nickel, and cobalt; magnetic oxides such as ferrite and magnetite; and glass beads.A magnetic material is used to adjust the volume resistivity by using a magnetic brush method. Preferably, there is.
[0059]
The average particle size of the core material is generally from 10 to 500 μm, preferably from 30 to 100 μm.
[0060]
As a method of forming a resin coating layer on the surface of a carrier core material, a carrier core material is immersed in a coating layer forming solution containing a matrix resin, a conductive material and a solvent. Spray method for spraying on the surface of the core material, fluidized bed method for spraying the coating layer forming solution in a state where the carrier core material is suspended by flowing air, mixing the carrier core material and the coating layer forming solution in a kneader coater, A kneader coater method for removing the solvent may be used.
[0061]
The solvent used in the coating layer forming solution is not particularly limited as long as it dissolves the matrix resin, and examples thereof include aromatic hydrocarbons such as toluene and xylene, and ketones such as acetone and methyl ethyl ketone. And ethers such as tetrahydrofuran and dioxane.
[0062]
The average thickness of the resin coating layer is usually 0.1 to 10 μm, but in the present invention, it is preferably in the range of 0.5 to 3 μm in order to develop a stable volume resistivity of the carrier over time. .
[0063]
In order to achieve high image quality, the volume resistivity of the carrier formed as described above is equivalent to the upper and lower limits of a normal developing contrast potential. ³ -10 ⁴ In the range of V / cm, 10 ⁶ -10 ¹⁴ It is preferably Ωcm. Carrier volume resistivity is 10 ⁶ If it is less than Ωcm, reproducibility of fine lines is poor, and toner fogging on the background due to injection of electric charge is likely to occur. Further, the volume resistivity of the carrier is 10 ¹⁴ If it is larger than Ωcm, reproduction of solid black and halftone becomes poor. Further, the amount of carrier transferred to the photoconductor increases, and the photoconductor is easily damaged. As the electrostatic brush, a resin containing a conductive filler such as carbon black or a metal oxide or a fibrous substance coated on the surface can be used, but the present invention is not limited thereto.
[0064]
(Image forming method)
The image forming method according to the present invention is a method for forming an image on both sides of a recording material using an image forming apparatus described below.
[0065]
The image forming apparatus includes a charging unit that charges the latent image carrier, a latent image forming unit that exposes the charged latent image carrier to form an electrostatic latent image, and a toner that uses the electrostatic latent image with toner. Developing means for transferring the formed toner image to a recording material and separating the toner image from a latent image carrier, which is a toner image holding member; and a roll or belt for transferring the transferred toner image onto the recording material. The image forming method includes a charging step of charging the latent image carrier, and a latent image forming an electrostatic latent image by exposing the latent image carrier on the charged latent image carrier. An image forming step, a developing step of developing the electrostatic latent image using toner, a transfer separating step of transferring the formed toner image to a recording material, and separating the toner image from a latent image carrier that is a toner image holding body; And transfer the toner image onto the recording material using a roll or belt. A fixing step of, a.
[0066]
The image forming apparatus may further include a cleaning unit that removes toner remaining on the toner image holding member after the transfer, between the transfer separation unit and the charging unit. There is a cleaning step between the transfer separation step and the charging step for removing the toner remaining on the toner image carrier after the transfer.
[0067]
Further, in the image forming apparatus used in another image forming method of the present invention, the transfer / separation unit develops each color toner on the latent image carrier, transfers the toner to the transfer belt or the transfer drum, and then transfers each color toner at once. It may transfer to a transfer body.
[0068]
Further, in the image forming apparatus used in another image forming method of the present invention, the fixing unit is a fixing unit that does not substantially supply a release agent, and may be oilless.
[0069]
The cleaning unit may recover the residual toner on the latent image carrier using an electrostatic brush without rubbing the latent image carrier with a blade. Although the blade cleaning method is generally used because of its high performance stability, the use of the toner of the present invention makes it possible to collect the residual toner on the latent image carrier using an electrostatic brush, The wear Life of the latent image carrier can be greatly extended.
[0070]
The electrostatic brush is, for example, a cleaning brush provided with a shaft member provided around the surface of the latent image carrier and driven to rotate, and a brush fiber member provided around the shaft member. The resistance value of the fiber member may be insulating or conductive. When the fiber member is conductive, a voltage may be applied as necessary. Specific examples of the material include polypropylene, nylon, rayon, polyester and the like. The thickness, length, etc. of such a bristle agent can be appropriately selected basically in the same manner as that of a well-known cleaning device, but the thickness of the brush fiber member is 15 to 19 [denier], and The thickness is 6 to 12 [mm] and the density is 1 to 3 [1000 pieces / cm. ² Is preferred.
[0071]
As the latent image carrier, a known photoconductor can be used without any particular limitation. From the viewpoint of sensitivity and stability, an organic photoconductor having a so-called function-separated structure in which a charge generation layer and a charge transport layer are separated from each other. Can be preferably used. Further, a photoreceptor whose surface layer has a charge transporting property and is made of a siloxane-based resin having a crosslinked structure is used. This photoreceptor surface layer is excellent in thermal and mechanical strength and relatively abrasion-resistant. By combining with the toner of the present invention, development and cleaning can be stably maintained for a long time.
[0072]
In another image forming method of the present invention, the siloxane-based resin having a charge transporting property and having a crosslinked structure has the following G and F.
G: Inorganic glass network subgroup
F: charge transporting subunit
[0073]
Further, in another image forming method of the present invention, the siloxane-based resin having a charge transporting property and having a crosslinked structure has the following D.
D: Flexible organic subunit
[0074]
<Photoreceptor used in the present invention>
1 to 5 are schematic views showing a cross section of the electrophotographic photoreceptor of the present invention. The photosensitive layer having a laminated structure is shown in FIGS. 1 to 3, and the photosensitive layer having a single layer structure is shown in FIGS. In FIG. 1, an undercoat layer 1 is provided on a conductive support 4, and a charge generation layer 2 and a charge transport layer 3 are provided thereon. In FIG. 2, a protective layer 5 is further provided on the surface. Is provided. In FIG. 3, an undercoat layer 1 is provided on a conductive support 4, a charge transport layer 3 and a charge generation layer 2 are provided thereon, and a protective layer 5 is provided on the surface. . 1 to 3, the undercoat layer may or may not be provided. 4, an undercoat layer 1 is provided on a conductive support 4, and a charge generation / transport layer 6 is provided thereon. In FIG. 5, a protective layer 5 is further provided on the surface. Is provided.
[0075]
Conductive support
As the conductive support, aluminum is used in an appropriate shape such as a drum shape, a sheet shape, and a plate shape, but is not limited thereto.
[0076]
When the photosensitive drum is used in a laser printer, the surface of the support has a center line average roughness Ra of 0.04 μm to 0.5 μm in order to prevent interference fringes generated when irradiating laser light. Preferably, it is planarized. As a method of surface roughening, wet honing performed by suspending an abrasive in water and spraying the support on the support, or centerless grinding in which the support is pressed against a rotating grindstone and grinding is performed continuously is preferable. . If Ra is smaller than 0.04 μm, the effect of preventing interference cannot be obtained because the surface is close to a mirror surface, and if Ra is larger than 0.5 μm, even if the coating according to the present invention is formed, the image quality becomes coarse and unsuitable. When non-interfering light is used as a light source, roughening for preventing interference fringes is not particularly necessary, and generation of defects due to irregularities on the surface of the base material can be prevented, which is more suitable for extending the life.
[0077]
Undercoat layer
If desired, an intermediate layer (undercoat layer) can be formed between the substrate and the photosensitive layer. Materials used include zirconium chelate compounds, zirconium alkoxide compounds, organic zirconium compounds such as zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, organic titanium compounds such as titanate coupling agents, aluminum chelate compounds, and aluminum coupling agents. In addition to such organic aluminum compounds, antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxide compounds, aluminum titanium alkoxide compounds, Aluminum zirconium alkoxide compounds, etc. Organometallic compounds, particularly organic zirconium compound, an organic titanyl compound and an organic aluminum compound since residual potential show good electrophotographic properties lower, be mentioned as preferable examples. Further, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3,4-epoxy A silane coupling agent such as cyclohexyltrimethoxysilane may be contained and used. Furthermore, polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinyl imidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, polyester conventionally used for the undercoat layer Known binder resins such as phenol resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, polyvinylpyrrolidone, polyvinylpyridine, polyurethane, polyglutamic acid, and polyacrylic acid can also be used. These mixing ratios can be appropriately set as needed.
[0078]
Further, an electron transporting pigment can be mixed / dispersed in the undercoat layer. Examples of the electron transporting pigment include organic pigments such as perylene pigments described in JP-A-47-30330, bisbenzimidazole perylene pigments, polycyclic quinone pigments, indigo pigments, quinacridone pigments, and cyano groups, nitro groups, Organic pigments such as bisazo pigments and phthalocyanine pigments having an electron-withdrawing substituent such as a nitroso group and a halogen atom, and inorganic pigments such as zinc oxide and titanium oxide are exemplified. Among these pigments, perylene pigments, bisbenzimidazole perylene pigments and polycyclic quinone pigments are preferably used because of their high electron mobility. If the amount of the electron transporting pigment is too large, the strength of the undercoat layer is reduced and a coating defect is caused. As a mixing / dispersing method, an ordinary method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave or the like is applied. The mixing / dispersion is performed in an organic solvent. As the organic solvent, any solvent that dissolves a term metal compound or resin and does not cause gelation or aggregation when mixing / dispersing an electron transporting pigment is used. Anything can be used. For example, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene And ordinary organic solvents such as toluene and the like can be used alone or in combination of two or more. The thickness of the undercoat layer is generally from 0.1 to 20 μm, preferably from 0.2 to 10 μm. In addition, as an application method used when providing the undercoat layer, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like. No. The applied material is dried to obtain an undercoat layer. Usually, the drying is performed at a temperature at which a solvent can be evaporated and a film can be formed. In particular, it is preferable to form an intermediate layer on a substrate that has been subjected to an acidic solution treatment or a boehmite treatment, since the defect concealing power of the substrate tends to be insufficient.
[0079]
Surface layer
Next, the surface layer will be described. The surface layer has a siloxane-based resin having a charge transporting property and a crosslinked structure. A siloxane-based resin having a crosslinked structure is particularly preferable in terms of transparency, dielectric breakdown resistance, light stability, and the like. Hereinafter, the siloxane-based resin having a crosslinked structure used in the present invention will be described.
[0080]
The siloxane-based resin having a crosslinked structure is a resin obtained by three-dimensionally crosslinking siloxane, dimethylsiloxane, methylphenylsiloxane, and other necessary components. In the present invention, the resin has a crosslinked structure containing the following G and F: A siloxane-based resin (hereinafter sometimes referred to as “compound (I)”) is particularly excellent in terms of abrasion resistance, charge transporting properties, and the like, in addition to the above-mentioned features, and is preferred.
G: Inorganic glass network subgroup
F: charge transporting subunit
[0081]
Further, the following D can be interposed between G and F to connect G and F. D: Flexible organic subunit
[0082]
Among the above-mentioned G, particularly preferred are reactive Si groups, which cause a cross-linking reaction with each other to form a three-dimensional Si—O—Si bond, that is, an inorganic glassy network. Specifically, G is -Si (R ₁ ) _(3-a) Q _a And a substituted silicon group having a hydrolyzable group represented by ₁ Represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, and Q represents a hydrolyzable group. a represents an integer of 1 to 3). b represents an integer of 1 to 4.
[0083]
D is for linking F for imparting charge transport properties to the three-dimensional inorganic glassy network G. In addition, it also has a function of imparting appropriate flexibility to an inorganic vitreous network having fragility on the other hand, and improving the strength as a film. Specifically, -C when n is an integer of 1 to 15 _n H _2n -, C _n H _(2n-2) -, -C _n H _(2n-4) A divalent hydrocarbon group represented by-, -COO-, -S-, -O-, -CH ₂ -C ₆ H ₄ -, -N = CH-,-(C ₆ H ₄ )-(C ₆ H ₄ )-, And combinations thereof, and those having a substituent introduced thereinto, and the like.
[0084]
The above F has a structure having a photocarrier transport property as a triarylamine-based compound, a benzidine-based compound, an arylalkane-based compound, an aryl-substituted ethylene-based compound, a stilbene-based compound, an anthracene-based compound, a hydrazone-based compound, and a quinone-based compound. Compounds, fluorenone compounds, xanthone compounds, benzophenone compounds, cyanovinyl compounds, ethylene compounds and the like.
Further, the compound in which F is represented by the general formula (II) exhibits particularly excellent hole transport properties and mechanical properties. Ar in the general formula (II) ₁ ~ Ar ₄ Each independently represents a substituted or unsubstituted aryl group, and specific examples are preferably those listed in Structural Group 1 below.
[0085]
Embedded image

[0086]
In the general formula (II), Ar ₁ ~ Ar ₄ Each independently represents a substituted or unsubstituted aryl group, and Ar ₅ Represents a substituted or unsubstituted aryl group or an arylene group. Where Ar ₁ ~ Ar ₅ 1 to 4 have a bond capable of bonding to the bonding group represented by -DG. k represents 0 or 1.
[0087]
Embedded image

[0088]
In the above, Ar is preferably those listed in Structural Group 2 below.
[0089]
Embedded image

[0090]
Further, it is preferable that Z ′ be one listed in Structural Group 3 below.
[0091]
Embedded image

[0092]
Where R ₆ Is a phenyl group substituted with hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or an unsubstituted phenyl group; Represents an aralkyl group. R ₇ ~ R _Thirteen Is a phenyl group substituted by hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, or an unsubstituted phenyl group; Represents an aralkyl group and halogen. m and s each independently represent 0 or 1, q and r each independently represent an integer of 1 to 10, and t and t 'each independently represent an integer of 1 to 3. Here, X is the same as defined for -DA in the definition of compound (I).
[0093]
Further, the above W is preferably those listed below in Structural Group 4.
[0094]
Embedded image

[0095]
Here, s ′ represents an integer of 0 to 3.
[0096]
Ar in the general formula (II) ₅ As a specific structure, when k = 0, the above Ar ₁ ~ Ar ₄ When the structure of m = 1 is k = 1, the above Ar ₁ ~ Ar ₄ M = 0. Specific examples of the compound (II) are shown in Tables 1 to 55, but are not limited thereto.
[0097]
[Table 1]

[0098]
[Table 2]

[0099]
[Table 3]

[0100]
[Table 4]

[0101]
[Table 5]

[0102]
[Table 6]

[0103]
[Table 7]

[0104]
[Table 8]

[0105]
[Table 9]

[0106]
[Table 10]

[0107]
[Table 11]

[0108]
[Table 12]

[0109]
[Table 13]

[0110]
[Table 14]

[0111]
[Table 15]

[0112]
[Table 16]

[0113]
[Table 17]

[0114]
[Table 18]

[0115]
[Table 19]

[0116]
[Table 20]

[0117]
[Table 21]

[0118]
[Table 22]

[0119]
[Table 23]

[0120]
[Table 24]

[0121]
[Table 25]

[0122]
[Table 26]

[0123]
[Table 27]

[0124]
[Table 28]

[0125]
[Table 29]

[0126]
[Table 30]

[0127]
[Table 31]

[0128]
[Table 32]

[0129]
[Table 33]

[0130]
[Table 34]

[0131]
[Table 35]

[0132]
[Table 36]

[0133]
[Table 37]

[0134]
[Table 38]

[0135]
[Table 39]

[0136]
[Table 40]

[0137]
[Table 41]

[0138]
[Table 42]

[0139]
[Table 43]

[0140]
[Table 44]

[0141]
[Table 45]

[0142]
[Table 46]

[0143]
[Table 47]

[0144]
[Table 48]

[0145]
[Table 49]

[0146]
[Table 50]

[0147]
[Table 51]

[0148]
[Table 52]

[0149]
[Table 53]

[0150]
[Table 54]

[0151]
[Table 55]

[0152]
Compound (I) may be used alone or in combination of two or more. In forming the surface layer, it is preferable to add at least one compound having a group that can bind to the compound (I) for the purpose of further improving the mechanical strength of the cured film.
[0153]
The group capable of bonding to the compound (I) means a group capable of bonding to a silanol group generated when the compound (I) is hydrolyzed, and specifically, -Si (R ₁ ) _(3-a) Q _a , An epoxy group, an isocyanate group, a carboxyl group, a hydroxy group, a halogen, and the like. Of these, -Si (R ₁ ) _(3-a) Q _a Compounds having a hydrolyzable group, an epoxy group or an isocyanate group represented by are preferred because they have higher mechanical strength. Further, as the compound having a group capable of bonding to the compound (I), a compound having two or more of these groups in a molecule makes the crosslinked structure of the cured film three-dimensional and gives the film a stronger mechanical strength. Therefore, it is preferable. Among these, the most preferred example of the compound is a compound represented by the general formula (III).
[0154]
Embedded image

[0155]
In the general formula (III), A ′ is —Si (R ₁ ) _(3-a) Q _a A substituted silicon group having a hydrolyzable group represented by: B is at least a group selected from an n-valent hydrocarbon group which may contain a branch, an n-valent phenyl group, -NH-, -O-Si- It consists of one or a combination of these. a represents an integer of 1 to 3, and n represents an integer of 2 or more.
[0156]
The compound represented by the general formula (III) is represented by —Si (R ₁ ) _(3-a) Q _a Is a compound having two or more substituted silicon groups A ′ having a hydrolyzable group represented by The portion of the Si group contained in A ′ reacts with the compound (I) or the compound (III) itself to form a Si—O—Si bond to form a three-dimensional cross-linked cured film. Since the compound (I) also has the same Si group, it is possible to form a cured film by itself, but since the compound (III) has two or more A ′, the cured film is formed. It is considered that the cross-linked structure becomes three-dimensional and has higher mechanical strength. Further, similarly to the D portion in the compound (I), it also has a role of imparting appropriate flexibility to the crosslinked cured film. As the compound (III), those represented by the following structural group 5 are more preferred.
[0157]
Embedded image

[0158]
In the above formula, T ₁ , T ₂ Represents a divalent or trivalent hydrocarbon group which may be independently branched, and A ′ represents the substituent described above. h, i, and j are integers of 1 to 3, and are selected such that the number of A ′ in the molecule is 2 or more.
[0159]
Specific examples of the compound of the general formula (III) represented by these formulas are shown below, but are not limited thereto.
[0160]
Embedded image

[0161]
The compound (I) may be used alone, or may be a compound represented by the general formula (III), another coupling agent, or a fluorine compound for the purpose of adjusting the film-forming property and flexibility of the film. May be used in combination. As such a compound, various silane coupling agents and commercially available silicone hard coat agents can be used.
[0162]
Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrisilane. Methoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, tetramethoxysilane, methyltrimethoxysilane , Dimethyldimethoxysilane, and the like. Commercially available silicone hard coat agents include KP-85, X-40-9740, X-40-2239 (all manufactured by Shin-Etsu Silicone Co., Ltd.), and AY42-440, AY42-441, AY49-208 (all manufactured by Toray) Dow Corning). In order to impart water repellency and the like, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, and 3- (hepta Fluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyl A fluorine-containing compound such as triethoxysilane may be added.
[0163]
The silane coupling agent can be used in any amount, but the amount of the fluorine-containing compound is desirably 25 wt% or less based on the fluorine-free compound. Exceeding this may cause a problem in the film formability of the crosslinked film.
[0164]
When a crosslinked film is formed as a surface protective layer, it is preferable to add an organometallic compound or a curable matrix.
[0165]
Examples of the organic metal compound include zirconium chelate compounds, zirconium alkoxide compounds, organic zirconium compounds such as zirconium coupling agents; titanium chelate compounds, titanium alkoxide compounds, organic titanium compounds such as titanate coupling agents; aluminum chelate compounds, aluminum coupling agents Organic aluminum compounds such as antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxide compounds, aluminum titanium alkoxide compounds , Aluminum zirconium alkoxide compounds, Organometallic compounds, in particular organic zirconium compound, an organic titanyl compound, an organic aluminum compound to show the good electrophotographic properties low residual potential, be mentioned as preferred.
[0166]
Curable matrices include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxy Silane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3 Silane coupling agents such as 1,4-epoxycyclohexyltrimethoxysilane and the like can be used.
[0167]
Adjustment of these coating liquids is carried out without solvent or, if necessary, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, diethyl ether and dioxane. Although it can be used, it preferably has a boiling point of 100 ° C. or lower, and can be used by optionally mixing. The amount of the solvent can be set arbitrarily. However, if the amount is too small, the compound (I) tends to precipitate. You.
[0168]
In the preparation of the coating solution, the compound (I) and, if necessary, another compound are brought into contact with a solid catalyst to cause a reaction. The reaction temperature and time vary depending on the type of the raw material, and are usually 0 to 100 ° C. And more preferably at 0 to 70 ° C, particularly preferably at a temperature of 10 to 35 ° C. Although the reaction time is not particularly limited, gelation is likely to occur when the reaction time is long, so that the reaction is preferably performed in the range of 10 minutes to 100 hours.
[0169]
When a polymer having a group capable of binding to the compound (I) is added, if the solid catalyst and the polymer are present at the same time, gelation is remarkably promoted and coating may be difficult. It is preferred to add. Such a solid catalyst is not particularly limited as long as the catalyst component is insoluble in the compound (I) solution, other compounds, solvents and the like. As the solid catalyst insoluble in the system, the following catalysts can be used and hydrolyzed in advance.
[0170]
-Cation exchange resin: Amberlite 15, Amberlite 200C, Amberlyst 15 (manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (Novel, Dow) -Chemicals); Levatit SPC-108, Levatit SPC-118 (all manufactured by Bayer); Diaion RCP-150H (Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duolite C- 433, Duolite-464 (manufactured by Sumitomo Chemical Co., Ltd.); Nafion-H (manufactured by DuPont) and the like.
-Anion exchange resin: Amberlite IRA-400, Amberlite IRA-45 (all manufactured by Rohm and Haas) and the like.
Inorganic solid having a group containing a protonic acid group bonded to the surface: Zr (O ₃ PCH ₂ CH ₂ SO ₃ H) ₂ , Th (O ₃ PCH ₂ CH ₂ COOH) ₂ Such.
-Polyorganosiloxane having a protonic acid group: such as a polyorganosiloxane having a sulfonic acid group.
-Heteropoly acid: cobalt tungstic acid, phosphomolybdic acid, etc.
-Isopoly acid: niobic acid, tantalic acid, molybdic acid, etc.
-Single metal oxide: silica gel, alumina, chromia, zirconia, CaO, MgO, etc.
-Composite metal oxides: silica-alumina, silica-magnesia, silica-zirconia, zeolites and the like.
-Clay minerals: acid clay, activated clay, montmorillonite, kaolinite, etc.
-Metal sulfate: LiSO ₄ , MgSO ₄ Such.
-Metal phosphate: zirconia phosphate, lanthanum phosphate and the like.
-Metal nitrate: LiNO ₃ , Mn (NO ₃ ) ₂ Such.
-An inorganic solid having a group containing an amino group bonded to the surface: a solid obtained by reacting aminopropyltriethoxysilane on silica gel.
-Polyorganosiloxane containing an amino group: amino-modified silicone resin and the like.
[0171]
The hydrolysis and condensation reaction is performed using at least one of these catalysts. These catalysts can be placed in a fixed bed and the reaction can be carried out by a flow system, or can be carried out by a batch system. The amount of the catalyst used is not particularly limited, but is preferably 0.1 to 20% by weight based on the total amount of the material containing a hydrolyzable silicon substituent.
[0172]
The amount of water to be added during the hydrolytic condensation is not particularly limited, but preferably affects the storage stability of the product and the suppression of gelation when the product is subjected to polymerization. Is preferably used at a ratio in the range of 30 to 500%, more preferably 50 to 300%, based on the theoretical amount necessary for hydrolyzing all the compounds. When the amount of water is more than 500%, the storage stability of the product is deteriorated or the product is easily precipitated. On the other hand, when the amount of water is less than 30%, unreacted substances increase, which tends to cause phase separation at the time of application of the coating liquid and at the time of curing, and to decrease the strength of the coating film.
[0173]
Further, as the curing catalyst, protonic acids such as hydrochloric acid, acetic acid, phosphoric acid, and sulfuric acid; bases such as ammonia and triethylamine; organic tin compounds such as dibutyltin diacetate, dibutyltin dioctoate, and stannous octoate; Organic titanium compounds such as -butyl titanate and tetraisopropyl titanate; organic aluminum compounds such as aluminum tributoxide and aluminum triacetylacetonate; iron salts, manganese salts, cobalt salts, zinc salts, zirconium salts and the like of organic carboxylic acids. However, a metal compound is preferable in terms of storage stability, and a metal acetylacetonate or acetylacetate is more preferable.
The amount of the curing catalyst used can be arbitrarily set, but is preferably 0.1 to 20% by weight based on the total amount of the material containing a hydrolyzable silicon substituent in terms of storage stability, properties, strength, and the like. 0.3-10 wt% is more preferable.
[0174]
The curing temperature can be set arbitrarily, but is set to 60 ° C. or higher, more preferably 80 ° C. or higher, to obtain a desired strength. The curing time can be arbitrarily set as required, but is preferably 10 minutes to 5 hours. It is also effective to maintain the high humidity state after the curing reaction to stabilize the characteristics. Further, depending on the use, the surface may be treated with hexamethyldisilazane, trimethylchlorosilane, or the like to make the surface hydrophobic.
[0175]
It is preferable to add an antioxidant to the surface crosslinked cured film of the photoreceptor in order to prevent deterioration due to oxidizing gas such as ozone generated in the charger. If the mechanical strength of the surface of the photoreceptor is increased and the life of the photoreceptor is extended, the photoreceptor comes into contact with an oxidizing gas for a long time.
[0176]
As the antioxidant, hindered phenol-based or hindered amine-based antioxidants are desirable, and organic sulfur-based antioxidants, phosphite-based antioxidants, dithiocarbamate-based antioxidants, thiourea-based antioxidants, and benzimidazole-based antioxidants And other known antioxidants. The addition amount of the antioxidant is desirably 15 wt% or less based on the entire cured film, and more desirably 10 wt% or less.
[0177]
Hindered phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butylhydroquinone, N, N′-hexamethylenebis (3,5-di- -T-butyl-4-hydroxyhydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 2,4-bis [(octylthio) methyl] -o-cresol , 2,6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol) ), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2,5-di-t-amylhydroquinone, 2-t-butyl-6- (3-butyl-2- (Hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 4,4'-butylidenebis (3-methyl-6-t-butylphenol), and the like.
[0178]
A siloxane-based resin having a charge-transporting property and having a crosslinked structure has excellent mechanical strength and sufficient photoelectric properties, and thus can be used as it is as a charge-transporting layer of a laminated photoreceptor.
[0179]
As a coating method, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like can be used. However, when the required film thickness cannot be obtained by a single application, the required film thickness can be obtained by performing multiple coatings. In the case where multiple coatings are performed, the heat treatment may be performed for each coating, or may be performed after multiple coatings.
[0180]
The degree of crosslinking of the surface layer can be known from the hardness of the surface layer, and this hardness can be determined as the hardness of the photoconductor. The photoreceptor has a dynamic hardness of 15 to 35 mN / μm. ² Is preferable. In addition, dynamic hardness can be measured by Shimadzu dynamic hardness meter DUH-201.
[0181]
In the case of a single-layer type photosensitive layer, it is formed containing the above-mentioned charge generating substance and a binder resin. As the binder resin, those similar to the binder resins used for the charge generation layer and the charge transport layer can be used. The content of the charge generating substance in the single-layer type photosensitive layer is about 10 to 85 wt%, preferably 20 to 50 wt%. A charge transporting material or a polymer charge transporting material may be added to the single-layer type photosensitive layer for the purpose of improving the photoelectric characteristics. The addition amount is preferably 5 to 50 wt%. Further, compound (I) may be added. The same solvent and the same coating method as described above can be used. The thickness is preferably about 5 to 50 μm, more preferably 10 to 40 μm.
[0182]
Charge generation layer
Next, the charge generation layer will be described.
[0183]
As the charge generating material, all known materials such as azo pigments such as bisazo and trisazo, fused aromatic pigments such as dibromoanthanthrone, perylene pigments, pyrrolopyrrole pigments, and furatocyanin pigments can be used. Metal phthalocyanine pigments are preferred. Among them, hydroxygallium phthalocyanine, chlorogallium phthalocyanine, dichlorotin phthalocyanine and titanyl phthalocyanine having specific crystals are particularly preferable. The chlorogallium phthalocyanine used in the present invention is, as disclosed in JP-A-5-98181, a chlorogallium phthalocyanine crystal produced by a known method, an automatic mortar, a planetary mill, a vibration mill, a CF mill, a roller mill, It can be manufactured by mechanical dry pulverization with a sand mill, kneader or the like, or wet pulverization using a ball mill, mortar, sand mill, kneader or the like together with a solvent after the dry pulverization. Solvents used in the above treatment include aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), aliphatic polyvalent Alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.), aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.), esters (acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide , Ethers (diethyl ether, tetrahydrofuran, etc.), a mixture of several kinds, and a mixture of water and these organic solvents. The solvent used is used in an amount of 1 to 200 parts, preferably 10 to 100 parts, based on chlorogallium phthalocyanine. The treatment temperature is in the range of 0 ° C. to the boiling point of the solvent or lower, preferably 10 to 60 ° C. In addition, at the time of pulverization, a grinding aid such as salt and sodium sulfate can be used. The grinding aid is used 0.5 to 20 times, preferably 1 to 10 times the pigment.
[0184]
As disclosed in JP-A-5-140472 and JP-A-5-140473, dichlorotin phthalocyanine is obtained by pulverizing a dichlorotin phthalocyanine crystal produced by a known method in the same manner as the above-mentioned chlorogallium phthalocyanine and treating with a solvent. Can be obtained.
[0185]
As described in JP-A-5-263007 and JP-A-5-279951, hydroxygallium phthalocyanine is obtained by hydrolyzing chlorogallium phthalocyanine crystals produced by a known method in an acid or alkaline solution. By performing acid pasting to synthesize hydroxygallium phthalocyanine crystal and directly performing a solvent treatment, or by using a hydroxygallium phthalocyanine crystal obtained by synthesis with a solvent in a ball mill, mortar, sand mill, kneader, or the like, using a wet process. It can be produced by performing a pulverizing treatment or performing a dry pulverizing treatment without using a solvent followed by a solvent treatment. Solvents used in the above treatment include aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), aliphatic polyvalent Alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.), aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.), esters (acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide , Ethers (diethyl ether, tetrahydrofuran, etc.), a mixture of several kinds, and a mixture of water and these organic solvents. The solvent used is used in an amount of 1 to 200 parts, preferably 10 to 100 parts, based on hydroxygallium phthalocyanine. The treatment temperature is in the range of 0 to 150 ° C, preferably room temperature to 100 ° C. In addition, at the time of pulverization, a grinding aid such as salt and sodium sulfate can be used. The grinding aid is used 0.5 to 20 times, preferably 1 to 10 times the pigment.
[0186]
Oxytitanyl phthalocyanine is disclosed in JP-A-4-189873 and JP-A-5-43813.Acid pasting of an oxytitanyl phthalocyanine crystal produced by a known method, or Salt milling with an inorganic salt using a ball mill, mortar, sand mill, kneader, or the like is performed to obtain relatively low-crystallinity oxytitanyl phthalocyanine crystal having a peak at 27.2 in the X-ray diffraction spectrum, and then directly subjected to solvent treatment Or a wet pulverization treatment using a ball mill, a mortar, a sand mill, a kneader or the like together with a solvent. As the acid used for the acid pasting, sulfuric acid is preferable, and one having a concentration of 70 to 100%, preferably 95 to 100% is used. You. The amount of concentrated sulfuric acid is set in the range of 1 to 100 times, preferably 3 to 50 times, the weight of the oxytitanyl phthalocyanine crystal. As a solvent to be precipitated, water or a mixed solvent of water and an organic solvent is used in an arbitrary amount, and water and an alcohol-based solvent such as methanol and ethanol, or a mixture of water and an aromatic-based solvent such as benzene and toluene are used. Solvents are particularly preferred. The temperature for the precipitation is not particularly limited, but is preferably cooled with ice or the like in order to prevent heat generation. The weight ratio of the oxytitanyl phthalocyanine crystal to the inorganic salt is 1 / 0.1 to 1/20, preferably 1 / 0.5 to 1/5. Solvents used in the above solvent treatment include aromatics (toluene, chlorobenzene, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), halogenated hydrocarbons (dichloromethane, chloroform, trichloroethane, etc.), and furthermore There are several types of mixed systems, such as a mixed system of water and these organic solvents. The solvent used is used in an amount of 1 to 100 parts, preferably 5 to 50 parts, based on oxytitanyl phthalocyanine. The treatment temperature is in the range of room temperature to 100 ° C, preferably 50 to 100 ° C. The grinding aid is used 0.5 to 20 times, preferably 1 to 10 times the pigment.
[0187]
The binder resin can be selected from a wide range of insulating resins, and can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin And insulating resins such as polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin and polyvinyl pyrrolidone resin, but are not limited thereto. These binder resins can be used alone or in combination of two or more.
[0188]
The compounding ratio (weight ratio) of the charge generating material and the binder resin is preferably in the range of 10: 1 to 1:10. As a method for dispersing these, a normal method such as a ball mill dispersion method, an attritor dispersion method, and a sand mill dispersion method can be used. In this case, conditions are required in which the crystal form is not changed by the dispersion. . Incidentally, it has been confirmed that the crystal form does not change from that before the dispersion in any of the above-mentioned dispersion methods. Further, at the time of this dispersion, it is effective to make the particles have a particle size of 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less. The solvents used for these dispersions include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, and tetrahydrofuran. Ordinary organic solvents such as methylene chloride, chloroform, chlorobenzene and toluene can be used alone or as a mixture of two or more.
[0189]
The thickness of the charge generation layer used in the present invention is generally from 0.1 to 5 μm, preferably from 0.2 to 2.0 μm. In addition, as a coating method used when providing the charge generation layer, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like. Can be used. Further, a pigment treated with compound (I) for the purpose of increasing the dispersion stability of the pigment, the photosensitivity, or the purpose of stabilizing the electrical characteristics may be used. May be.
[0190]
Charge transport layer
As the charge transport layer in the photoreceptor of the present invention, those formed by a known technique can be used. These charge transport layers are formed containing a charge transport material and a binder resin, or are formed containing a polymer charge transport material.
[0191]
Examples of the charge transport material include quinone compounds such as p-benzoquinone, chloranil, bromanyl, and anthraquinone; tetracyanoquinodimethane compounds; fluorenone compounds such as 2,4,7-trinitrofluorenone; xanthone compounds; and benzophenone compounds. And electron transporting compounds such as cyanovinyl compounds and ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds and hydrazone compounds. Hole transporting compounds. These charge transporting materials can be used alone or in combination of two or more, but are not limited thereto. These charge transporting materials can be used alone or in combination of two or more. Charge transporting materials, in particular, the triphenylamine-based compound represented by the structural formula (IV) and the benzidine-based compound represented by the structural formula (V) have high charge (hole) transporting ability and excellent stability. Therefore, it can be particularly preferably used.
[0192]
Embedded image

[0193]
(Where R ₁₄ Represents a hydrogen atom or a methyl group. Further, n means 1 or 2. Ar ₆ And Ar ₇ Represents a substituted or unsubstituted aryl group, and as the substituent, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 1 to 3 carbon atoms A substituted amino group substituted with a range of alkyl groups is shown. )
[0194]
Embedded image

[0195]
(Where R _Fifteen And R _Fifteen May be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. R ₁₆ , R _{16 '} , R ₁₇ And R _{17 '} May be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an amino group substituted with an alkyl group having 1 to 2 carbon atoms; And n are integers from 0 to 2. )
[0196]
Examples of each compound are shown in Tables 56 to 61.
[0197]
[Table 56]

[0198]
[Table 57]

[0199]
[Table 58]

[0200]
[Table 59]

[0201]
[Table 60]

[0202]
[Table 61]

[0203]
These can be used alone or in combination of two or more. Further, a polymer charge transport material can also be used. As the polymer charge transporting material, a known charge transporting material such as poly-N-vinylcarbazole and polysilane can be used. In particular, polyester-based polymer charge transporting materials disclosed in JP-A-8-176293 and JP-A-8-208820 have high charge transporting properties and are particularly preferable. The polymer charge transporting material alone can form a film, but it may be mixed with the binder resin to form a film.
[0204]
Further, the binder resin used for the charge transport layer is a polycarbonate resin, a polyester resin, a methacrylic resin, an acrylic resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polystyrene resin, a polyvinyl acetate resin, a styrene-butadiene copolymer, and a vinylidene chloride resin. Acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicon-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N- Polymer charge transport materials such as vinyl carbazole, polysilane, and polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 can also be used. Further, organic zirconium compounds such as zirconium chelate compounds, zirconium alkoxide compounds, and zirconium coupling agents, organic titanium compounds such as titanium chelate compounds, titanium alkoxide compounds, titanate coupling agents, and organic aluminum compounds such as aluminum chelate compounds and aluminum coupling agents. In addition to compounds, antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxide compounds, aluminum titanium alkoxide compounds, aluminum zirconium alkoxide compounds , And other organometallic compounds Especially organic zirconium compound, an organic titanyl compound, since the organic aluminum compound to residual potential indicates a satisfactory electrophotographic properties lower, are preferably used. Further, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3,4-epoxy A silane coupling agent such as cyclohexyltrimethoxysilane or the like, or a curable matrix such as a photocurable resin may be used, and a charge transporting agent such as compound (I) curable with these may be used. These binder resins can be used alone or in combination of two or more. The mixing ratio (weight ratio) of the charge transport material and the binder resin is preferably from 10: 1 to 1: 5.
[0205]
The thickness of the charge transport layer used in the present invention is generally 5 to 50 μm, preferably 10 to 30 μm. As a coating method, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like can be used.
[0206]
Further, as a solvent used when providing the charge transport layer, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; ketones such as acetone and 2-butanone; and halogenated solvents such as methylene chloride, chloroform, and ethylene chloride. Normal organic solvents such as aliphatic hydrocarbons, cyclic or linear ethers such as tetrahydrofuran and ethyl ether can be used alone or in combination of two or more.
[0207]
Further, in order to prevent the deterioration of the photoconductor due to ozone or oxidizing gas generated in the image forming apparatus, or light or heat, additives such as an antioxidant, a light stabilizer, and a heat stabilizer are added to the photosensitive layer. Can be added. For example, examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, organic phosphorus compounds and the like. Examples of the light stabilizer include derivatives such as benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine.
[0208]
Further, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, reducing fatigue when repeatedly used, and the like. Examples of the electron acceptor usable in the photoreceptor of the present invention include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, and o. -Dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid and the like, and compound (I). Of these, fluorenone type, quinone type, Cl, CN, NO ₂ A benzene derivative having an electron-withdrawing substituent such as
[0209]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. In the description of the toner composition and the carrier, all “parts” mean “parts by weight” unless otherwise specified.
[0210]
In the production of the toner composition, the carrier, and the electrostatic latent image developer, each measurement was performed by the following methods.
[0211]
<Measurement of volume average particle diameter of calcium compound particles>
The particles are embedded in a curable resin, sliced thinly with a diamond cutter, and observed with a TEM. The image was printed and 50 samples of primary particles were arbitrarily extracted as a sample, and the diameter of the circular particles corresponding to the image area was defined as the volume average particle diameter.
[0212]
<Electrical resistance measurement>
As shown in FIG. 6, the measurement sample 33 is sandwiched between the lower electrode 34 and the upper electrode 32 as a thickness H, and the thickness is measured with a dial gauge while pressing from above, and the electric resistance of the measurement sample 33 is measured with a high-voltage resistance meter. Was measured. Specifically, a sample of a specific titanium oxide is 500 kg / cm ² Was applied to produce a measurement disc. Next, the surface of the disk was cleaned with a brush, sandwiched between the upper electrode 32 and the lower electrode 34 in the cell, and the thickness was measured with a dial gauge. Next, a voltage was applied, and the current value of the electrometer 36 was read to determine the volume resistivity.
[0213]
Further, a carrier sample was filled in a lower electrode 4 of 100φ, an upper electrode 2 was set, a load of 3.43 kg was applied from above, and the thickness was measured with a dial gauge. Next, a voltage was applied, and the current value of the electrometer 5 was read to determine the volume resistivity.
[0214]
<Toner average shape index SF1>
In the present invention, the average shape index SF1 of the toner means a value calculated by the following equation. In the case of a true sphere, SF1 = 100.
(Equation 2)
SF1 = (ML ² / A) × (π / 4) × 100
Here, ML: the absolute maximum length of the particle, A: the projected area of the particle, and these are quantified mainly by analyzing a microscope image or a scanning electron microscope image with an image analyzer.
[0215]
As a specific method for obtaining the average shape index, a toner image is taken from an optical microscope into an image analyzer (LUZEX III, manufactured by Nireco Co., Ltd.), and the equivalent circle diameter is measured. Of the above formula for the particles of ² Find the value of / A.
[0216]
<Measurement of charge amount>
The charge amount in the evaluation test of the actual machine was measured using a TB200 manufactured by Toshiba Corporation under the conditions of 25 ° C. and 55% RH by collecting the developer on the mag sleeve in the developing device.
[0219]
[Adjustment of inorganic particles]
(A) Preparation of calcium carbonate particles
Particle preparation: In a 2 L stainless steel beaker, 30% concentration of carbon dioxide gas is blown into 1000 g of 15% by weight lime milk at a compounding start temperature of 25 ° C. at a rate of 2.0 L / min, and the conductivity of the suspension is increased. The reaction was performed until the second drop was made stable. The reaction solution was suction-filtered with a Nutsche, and the mother liquor was separated and dried and pulverized to obtain calcium carbonate particles.
[0218]
Surface treatment: Next, calcium carbonate particles are dispersed in a toluene solution, silicone oil is added, ultrasonic waves are applied, toluene is distilled off by an evaporator, and the mixture is further heated at 150 ° C. for 1 hour and then pulverized. Surface-treated calcium carbonate particles A having an average particle size of 150 nm were obtained.
[0219]
(B) Preparation of calcium carbonate particles
In the preparation of the calcium carbonate particles, the “particle preparation” was performed by the “surface treatment” in the same manner as the calcium carbonate particles A as described below.
[0220]
Surface treatment: A slurry of calcium carbonate particles having a solid content of 10% by weight was adjusted to 65 ° C. While stirring the slurry with a dispersing machine, a fatty acid mixture having a sodium oleate content of 60% by weight, a sodium stearate content of 20% by weight, and a sodium palmitate content of 20% by weight was added and stirred. Press dewatering. The obtained filter cake was dried with a box drier, and then crushed to obtain surface-treated calcium carbonate particles B having an average particle diameter of 150 nm and treated with the fatty acid mixture.
[0221]
(C) Preparation of calcium carbonate particles
Particle preparation: In a 2 L stainless steel beaker, 30% concentration of carbon dioxide gas is blown into 1000 g of 10% by weight lime milk at a compounding start temperature of 20 ° C. at a rate of 2.0 L / min, and the conductivity of the suspension is increased. The reaction was performed until the second descent was stabilized. The reaction solution was suction-filtered with a Nutsche, and the mother liquor was separated and dried and pulverized to obtain calcium carbonate particles. The surface treatment was performed in the same manner as in the preparation of the calcium carbonate particles A to obtain surface-treated calcium carbonate particles C having an average particle diameter of 70 nm.
[0222]
(D) Preparation of calcium carbonate particles
Particle preparation: In a 2 L stainless steel beaker, 30% concentration of carbon dioxide gas is blown into 1000 g of 20% by weight lime milk at a compounding start temperature of 25 ° C. at a rate of 2.0 L / min, and the conductivity of the suspension is increased. The reaction was performed until the second drop was made stable. The reaction solution was suction-filtered with a Nutsche, and the mother liquor was separated and dried and pulverized to obtain calcium carbonate particles. The surface treatment was performed in the same manner as in the preparation of the calcium carbonate particles A to obtain the surface-treated calcium carbonate particles D having an average particle diameter of 200 nm.
[0223]
(E) Preparation of hydrous aluminum silicate particles
Sodium silicate and aluminum sulfate were used as raw materials, and the raw materials were continuously mixed while stirring so that the molar ratio was Si / Al = 1. At the same time, a silica-alumina gel was prepared by adding and neutralizing sodium hydroxide so that the reaction pH became 10 to 12. Next, an aqueous solution of ammonium nitrate was used at twice the amount of sodium in the gel, and sodium was ion-exchanged with ammonium at room temperature. Then, the exchanged ammonium was removed by calcination at 600 ° C. for 2 hours. Further, dry pulverization was performed to obtain a raw material powder. The raw material powder was charged into an autoclave so as to have a slurry concentration of 10 wt%, and a hydrothermal reaction was performed at 200 ° C. for 1 day, further at 250 ° C. for 3 days. After cooling, the reaction solution was subjected to suction filtration with a Nutsche, and the mother liquor was separated and dried and pulverized to obtain hydrous aluminum silicate particles E having an average particle diameter of 200 nm.
[0224]
(F) Preparation of unsurfaced calcium carbonate particles
In the preparation of the calcium carbonate particles, “preparation of particles” was performed in the same manner as in the above-mentioned calcium carbonate particles A to obtain unsurfaced calcium carbonate particles F having an average particle diameter of 140 nm.
[0225]
(G) Preparation of calcium carbonate particles
Particle preparation: In a 2 L stainless steel beaker, 30% concentration of carbon dioxide gas is blown into 1000 g of 22% by weight lime milk at a compounding start temperature of 28 ° C. at a rate of 2.0 L / min, and the conductivity of the suspension is increased. The reaction was performed until the second descent was stabilized. The reaction solution was suction-filtered with a Nutsche, and the mother liquor was separated and dried and pulverized to obtain calcium carbonate particles. The surface treatment was performed in the same manner as the preparation of the calcium carbonate particles A, to obtain surface-treated calcium carbonate particles G having an average particle diameter of 260 nm.
[0226]
[Method for producing colored particles]
(I) Method for producing colored particles A
Styrene-n-butyl acrylate resin 100 parts
(Tg = 61 ° C., Mn = 6000, Mw = 35000)
3 parts carbon black
(Mogal L: made by Cabot)
[0227]
The mixture was kneaded with an extruder, pulverized with a jet mill, and dispersed with an air classifier to obtain a black toner A having D50 = 5.0 μm and SF1 = 148.8.
[0228]
(Ii) Method for producing colored particles B
<Preparation of resin dispersion liquid (1)>
Styrene 370 parts by mass
30 parts by mass of n-butyl acrylate
Acrylic acid 8 parts by mass
Dodecanethiol 24 parts by mass
Carbon tetrabromide 4 parts by mass
[0229]
6 parts by mass of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) and an anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ) 10 parts by mass of a solution prepared by dissolving 10 parts by mass in 550 parts by mass of ion-exchanged water were emulsified and dispersed in a flask, and while slowly mixing for 10 minutes, 50 parts by mass of ion-exchanged water in which 4 parts by mass of ammonium persulfate was dissolved was added. After purging with nitrogen, the contents in the flask were heated in an oil bath until the temperature reached 70 ° C. while stirring, and the emulsion polymerization was continued for 5 hours. As a result, a resin dispersion (1) in which resin particles having an average particle size of 155 nm, Tg = 59 ° C., and a weight average molecular weight Mw = 12000 were dispersed was obtained.
[0230]
<Preparation of resin dispersion (2)>
Styrene 280 parts by mass
120 parts by mass of n-butyl acrylate
Acrylic acid 8 parts by mass
[0231]
6 parts by mass of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) and an anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ) 12 parts by mass of a solution prepared by dissolving 12 parts by mass in 550 parts by mass of ion-exchanged water were emulsified and dispersed in a flask, and while slowly mixing for 10 minutes, 50 parts by mass of ion-exchanged water in which 3 parts by mass of ammonium persulfate was dissolved was added. After purging with nitrogen, the contents in the flask were heated in an oil bath until the temperature reached 70 ° C. while stirring, and the emulsion polymerization was continued for 5 hours. As a result, a resin dispersion (2) in which resin particles having an average particle diameter of 105 nm, Tg = 53 ° C., and a weight average molecular weight Mw = 550,000 were dispersed was obtained.
[0232]
[Colorant dispersion]
<Preparation of Colorant Dispersion (1)>
50 parts by mass of carbon black
(Mogal L: made by Cabot)
Nonionic surfactant 5 parts by mass
(Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.)
200 parts by mass of ion-exchanged water
[0233]
The above components are mixed, dissolved and dispersed using a homogenizer (Ultra Turrax T50: manufactured by IKA) for 10 minutes, and a colorant dispersion in which colorant (carbon black) particles having an average particle size of 250 nm are dispersed. Liquid (1) was prepared.
[0234]
<Preparation of Colorant Dispersion (2)>
Cyan pigment C.I. I. Pigment Blue 15: 3 70 parts by mass
Nonionic surfactant 5 parts by mass
(Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.)
200 parts by mass of ion-exchanged water
[0235]
The above components are mixed, dissolved, and dispersed using a homogenizer (Ultra Turrax T50: manufactured by IKA) for 10 minutes, and a colorant dispersion in which colorant (Cyan pigment) particles having an average particle size of 250 nm are dispersed. Liquid (2) was prepared.
[0236]
<Preparation of colorant dispersion liquid (3)>
Magenta pigment C.I. I. Pigment Red 122 70 parts by mass
Nonionic surfactant 5 parts by mass
(Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.)
200 parts by mass of ion-exchanged water
[0237]
The above components are mixed, dissolved, and dispersed using a homogenizer (Ultra Turrax T50: manufactured by IKA) for 10 minutes, and a colorant (Magenta pigment) having an average particle diameter of 250 nm is dispersed therein. Liquid (3) was prepared.
[0238]
<Preparation of Colorant Dispersion (4)>
Yellow pigment C.I. I. Pigment Yellow 180 100 parts by mass
Nonionic surfactant 5 parts by mass
(Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.)
200 parts by mass of ion-exchanged water
[0239]
The above components are mixed, dissolved, and dispersed using a homogenizer (Ultra Turrax T50: manufactured by IKA) for 10 minutes, and a colorant dispersion in which colorant (Yellow pigment) particles having an average particle size of 250 nm are dispersed. Liquid (4) was prepared.
[0240]
[Preparation of release agent dispersion liquid (1)]
Paraffin wax 50 parts by mass
(HNP0190: Nippon Seiro Co., Ltd., melting point 85 ° C)
5 parts by mass of cationic surfactant
(Sanisol B50: manufactured by Kao Corporation)
[0241]
The above components were dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA) for 10 minutes, and then dispersed using a pressure discharge type homogenizer to obtain a separation having an average particle size of 550 nm. A release agent dispersion liquid (1) in which mold particles were dispersed was prepared.
[0242]
[Adjustment of aggregated particles]
Resin dispersion liquid (1) 120 parts by mass
80 parts by mass of resin dispersion liquid (2)
200 parts by mass of colorant dispersion liquid (1)
Release dispersion liquid (1) 40 parts by mass
1.5 parts by mass of cationic surfactant
(Sanisol B50: manufactured by Kao Corporation)
[0243]
The above components were mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), and then heated to 50 ° C. while stirring the inside of the flask in a heating oil bath. . After holding at 45 ° C. for 20 minutes, it was confirmed by an optical microscope that aggregated particles having an average particle size of about 5.0 μm were formed. Further, 60 parts by mass of the resin dispersion (1) was slowly added to the above dispersion as a resin-containing fine particle dispersion. Then, the temperature of the heating oil bath was raised to 50 ° C. and maintained for 30 minutes. Observation with an optical microscope confirmed that adhering particles having an average particle size of about 5.6 μm were formed.
[0244]
[Preparation of colored particles B]
After adding 3 parts by mass of an anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) to the dispersion of the aggregated particles, the inside of the stainless steel flask is closed, and the mixture is stirred with a magnetic seal. Heated to 105 ° C and held for 4 hours. After cooling, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried to obtain colored particles B for developing an electrostatic image.
[0245]
<Generation of colored particles KuroB>
Using the colorant dispersion liquid (1), a Kuro toner having an SF1 of 128.5 and a particle size D50 of 5.8 μm was obtained by the method of adjusting the aggregated particles and preparing the colored particles.
[0246]
<Generation of colored particles CyanB>
In the preparation of the aggregated particles, the colorant dispersion liquid (2) is used in place of the colorant dispersion liquid (1), and the cyan toner having a SF1 of 130 and a particle diameter D50 of 5.6 μm is further obtained by the above-described method of producing the colored particles. Got.
[0247]
<Generation of colored particles Magenta B>
In the preparation of the agglomerated particles, the colorant dispersion liquid (3) was used in place of the colorant dispersion liquid (1), and SF1 was 132.5 and the particle diameter D50 was 5.5 μm by the method of producing the colored particles. Magenta toner was obtained.
[0248]
<Generation of Colored Particles YellowB>
In the preparation of the agglomerated particles, the colorant dispersion liquid (4) was used in place of the colorant dispersion liquid (1), and further, SF1 = 127 and a particle diameter D50 = 5.9 μm Yellow by the above-described method of preparing the colored particles. A toner was obtained.
[0249]
[Generation of carrier]
100 parts of ferrite particles (average particle size: 50 μm)
14 parts of toluene
Styrene-methyl methacrylate copolymer 2 parts
(Ingredient ratio: 90/10, Mw = 75,000)
Carbon black (R330: manufactured by Cabot Corporation) 0.2 parts
[0250]
First, the above-mentioned components excluding the ferrite particles are stirred with a stirrer for 10 minutes to prepare a dispersed coating solution. Next, the coating solution and the ferrite particles are placed in a vacuum degassing kneader and stirred at 60 ° C. for 30 minutes. After that, the carrier was degassed under reduced pressure while further heating, and dried to obtain a carrier. This carrier has a volume resistivity of 10 at an applied electric field of 1000 V / cm. ¹¹ Ωcm.
[0251]
<Manufacture of photoconductor 1>
An example of the production of a photoreceptor in which the photoreceptor surface layer has a charge transporting property and is made of a siloxane-based resin having a crosslinked structure will be described below.
[0252]
A drawn tube made of JIS A3003 alloy and having a diameter of 84 mm was prepared and polished by a centerless polishing device, and the surface roughness was set to Rz = 0.5 μm. As a cleaning step, the cylinder was subjected to a degreasing treatment, an etching treatment with a 2 wt% sodium hydroxide solution for 1 minute, a neutralization treatment, and a cleaning with pure water in order. Next, as a step of anodizing treatment, an anodic oxide film (current density 1.0 A / dm) was formed on the cylinder surface with a 10 wt% sulfuric acid solution. ² ) Was formed. After washing with water, the resultant was immersed in a 1 wt% nickel acetate solution at 80 ° C. for 20 minutes to perform sealing treatment. Further, pure water washing and drying were performed. Thus, a 7 μm anodic oxide film was formed on the surface of the aluminum cylinder.
[0253]
Chlorogallium having strong diffraction peaks at 7.4 °, 16.6 °, 25.5 °, and 28.3 ° in the X-ray diffraction spectrum on this aluminum substrate at Bragg angles (2θ ± 0.2 °). 1 part of phthalocyanine was mixed with 1 part of polyvinyl butyral (Eslec BM-S, Sekisui Chemical) and 100 parts of n-butyl acetate, and the mixture was treated with glass beads for 1 hour using a paint shaker and dispersed. Was dip-coated on the undercoat layer and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.
[0254]
A coating solution obtained by dissolving 2 parts of a benzidine compound having the following structure and 3 parts of a polymer compound (viscosity average molecular weight of 40,000) in 20 parts of chlorobenzene is applied on the charge generation layer by a dip coating method. Was carried out to form a charge transport layer having a thickness of 20 μm. This is designated as Photoconductor 1.
[0255]
Embedded image

The constituent materials shown below are dissolved in 5 parts of isopropyl alcohol, 3 parts of tetrahydrofuran, and 0.3 parts of distilled water, and 0.5 parts of an ion exchange resin (Amberlyst 15E) is added. Decomposition was performed.
[0256]
Constituent materials
Exemplified compound 261 2 parts
Methyltrimethoxysilane 2 parts
0.5 parts of tetramethoxysilane
0.3 parts of colloidal silica
[0257]
0.04 parts of aluminum trisacetylacetonate and 0.1 part of 3,5-di-t-butyl-4-hydroxytoluene (BHT) were added to 2 parts of the liquid obtained by filtering and separating the ion exchange resin from the hydrolyzed product. The coating solution is applied on the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then heat-treated at 170 ° C. for 1 hour to be cured. Was formed.
[0258]
(Example 1)
100 parts each of Kuro, Cyan, Magenta, and Yellow toners of the colored particles B are 0.8 parts of hydrophobic titania having an average particle diameter of 15 nm and surface-treated with decylsilane, and hydrophobic silica having an average particle diameter of 40 nm (RX50, manufactured by Nippon Aerosil Co., Ltd.) 1.2 parts) and 0.6 parts of calcium carbonate particles A were blended using a Henschel mixer at a peripheral speed of 32 m / s for 10 minutes, and then coarse particles were removed using a 45 μm mesh sieve to obtain a toner. Was. A developer was obtained by stirring 100 parts of the above carrier and 5 parts of the above toner at 40 rpm for 20 minutes using a V-blender and sieving through a sieve having a mesh of 177 μm.
[0259]
(Example 2)
0.8 parts of hydrophobic titania having an average particle size of 15 nm, surface-treated with decylsilane, 1.2 parts of hydrophobic silica (RX50, manufactured by Nippon Aerosil Co., Ltd.) having an average particle size of 40 nm, and 100 parts of the colored particles KuroB, calcium carbonate particles B1. 0 parts were blended at a peripheral speed of 32 m / s for 10 minutes using a Henschel mixer, and then coarse particles were removed using a 45-μm mesh sieve to obtain a toner. A developer was obtained by stirring 100 parts of the carrier and 5 parts of the toner at 40 rpm for 20 minutes using a V-blender and sieving through a sieve having a mesh of 177 μm.
[0260]
(Example 3)
0.8 parts of hydrophobic titania having an average particle size of 15 nm, surface-treated with decylsilane, 1.2 parts of hydrophobic silica (RX50, manufactured by Nippon Aerosil Co., Ltd.) having an average particle size of 40 nm, and 100 parts of the colored particles KuroB, calcium carbonate particles C0. Six parts were blended at a peripheral speed of 32 m / s for 10 minutes using a Henschel mixer, and then coarse particles were removed using a sieve having a mesh of 45 μm to obtain a toner. A developer was obtained by stirring 100 parts of the carrier and 5 parts of the toner at 40 rpm for 20 minutes using a V-blender and sieving through a sieve having a 177 μm mesh.
[0261]
(Example 4)
0.8 parts of hydrophobic titania having an average particle diameter of 15 nm, surface-treated with decylsilane, 1.2 parts of hydrophobic silica (RX50, manufactured by Nippon Aerosil Co., Ltd.) having an average particle diameter of 40 nm, and 100 parts of the colored particles KuroB, calcium carbonate particles D1. After blending 3 parts for 10 minutes at a peripheral speed of 32 m / s using a Henschel mixer, coarse particles were removed using a sieve having a mesh of 45 μm to obtain a toner. A developer was obtained by stirring 100 parts of the carrier and 5 parts of the toner at 40 rpm for 20 minutes using a V-blender and sieving through a sieve having a mesh of 177 μm.
[0262]
(Example 5)
0.9 parts of hydrophobic titania having an average particle diameter of 15 nm, surface-treated with decylsilane, 1.3 parts of hydrophobic silica (RX50, manufactured by Nippon Aerosil Co., Ltd.) having an average particle diameter of 40 nm, and calcium carbonate particles A1. After blending 3 parts for 10 minutes at a peripheral speed of 32 m / s using a Henschel mixer, coarse particles were removed using a sieve having a mesh of 45 μm to obtain a toner. A developer was obtained by stirring 100 parts of the carrier and 5 parts of the toner at 40 rpm for 20 minutes using a V-blender and sieving through a sieve having a mesh of 177 μm.
[0263]
(Example 6)
0.8 parts of hydrophobic titania having an average particle size of 15 nm, surface-treated with decylsilane, 1.2 parts of hydrophobic silica having an average particle size of 40 nm, surface-treated with silicone oil, and 1.0 part of calcium carbonate particles B were added to 100 parts of the colored particles KuroB. Was blended at a peripheral speed of 32 m / s for 10 minutes using a Henschel mixer, and coarse particles were removed using a sieve having a mesh of 45 μm to obtain a toner. A developer was obtained by stirring 100 parts of the carrier and 5 parts of the toner at 40 rpm for 20 minutes using a V-blender and sieving through a sieve having a mesh of 177 μm.
[0264]
(Example 7)
0.8 parts of hydrophobic titania having an average particle diameter of 15 nm treated with decylsilane on 1.2 parts of the colored particles KuroB, 1.2 parts of hydrophobic silica having an average particle diameter of 40 nm treated with silicone oil, and 0.6 parts of calcium carbonate particles F Was blended at a peripheral speed of 32 m / s for 10 minutes using a Henschel mixer, and coarse particles were removed using a sieve having a mesh of 45 μm to obtain a toner. A developer was obtained by stirring 100 parts of the carrier and 5 parts of the toner at 40 rpm for 20 minutes using a V-blender and sieving through a sieve having a mesh of 177 μm.
[0265]
(Example 8)
A developer was obtained in the same manner as in Example 7, except that the calcium carbonate particles F were changed to hydrous aluminum silicate particles.
[0266]
(Comparative Example 1)
A developer was obtained in the same manner as in Example 2, except that the calcium carbonate particles B were omitted. (The Mohs hardness of silica is 7, Mohs hardness of titania is 6.5 to 7)
[0267]
(Comparative Example 2)
0.8 parts of hydrophobic titania having an average particle diameter of 15 nm treated with decylsilane and 1.2 parts of hydrophobic silica having an average particle diameter of 40 nm treated with silicone oil, and cerium oxide having an average particle diameter of 650 nm were added to 100 parts of the colored particles KuroB. (Mohs hardness 7) 0.6 parts were blended at a peripheral speed of 32 m / s for 10 minutes using a Henschel mixer, and then coarse particles were removed using a sieve of 45 μm mesh to obtain a toner. A developer was obtained by stirring 100 parts of the carrier and 5 parts of the toner at 40 rpm for 20 minutes using a V-blender and sieving through a sieve having a mesh of 177 μm.
[0268]
(Comparative Example 3)
A developer was obtained in the same manner as in Example 4, except that the calcium carbonate particles D were changed to alumina having an average particle diameter of 200 nm (Mohs hardness 9).
[0269]
[Evaluation]
Using the developer described in the above Examples and Comparative Examples, charging means for charging the latent image carrier, and a latent image forming means for exposing the charged latent image carrier to form an electrostatic latent image, Developing means for developing the electrostatic latent image using toner, transfer separating means for transferring the formed toner image to a recording material and separating it from a latent image carrier as a toner image holding body, and transferred toner A long-term running test of 20,000 copies is performed using a modified Docu Center Color 500 manufactured by Fuji Xerox Co., Ltd., which carries out an image forming method having a fixing means for performing roll image fixing of an image on a recording material. Photoconductor contamination and scratches were evaluated. The photoconductor was replaced with the photoconductor 1 composed of a siloxane-based resin having a cross-linked surface layer from the Docu Center Color 500 original photoconductor (organic photoconductor).
[0270]
The toner charge amount and transfer efficiency are the results of the initial test, and the photoconductor contamination and the photoconductor scratches are the results of observation of the photoconductor after 20,000 copies.
[0271]
The transferability was evaluated by performing a hard stop at the end of the transfer process, determining the amount of the transferred toner a from the measurement of the toner weight of the transfer material before and after the toner was removed, and similarly calculating the amount b of the toner remaining on the photoreceptor. To determine the transfer efficiency.
[Equation 3]
Transfer efficiency η (%) = a * 100 / (a + b)
And he made the following judgment.
η ≧ 90% ・ ・ ・ ○, η <90% ・ ・ ・ ×
[0272]
Regarding the photoreceptor contamination and the photoreceptor scratch, ○ indicates no contamination, X indicates contamination, ○ indicates no damage, and X indicates damage.
[0273]
The results are shown in Table 62.
[0274]
[Table 62]

[0275]
The developer of the toner using the inorganic particles having a Mohs hardness of 2 to 4.5 according to the present invention has good charge retention properties as shown in the results of Examples 1 to 8, and has good transferability even after long-term repeated use. It was good. Further, in each evaluation of the developer, the photoreceptor was extracted after copying 20,000 sheets, and the surface was observed. As a result, scratches / uneven wear and contamination were slight. Further, in Example 2, there was no problem with the photoreceptor even after 40,000 copies.
[0276]
On the other hand, as for the developer of the toner not using inorganic particles having a Mohs hardness of 2 to 4.5, the photoreceptor was extracted after 20,000 sheets were copied and the surface thereof was observed as shown in the results of Comparative Example 1-3. The contamination was clearly confirmed. Further, as shown in the results of Comparative Examples 2 and 3, scratches / uneven wear were clearly confirmed.
[0277]
【The invention's effect】
According to the image forming method of the present invention, contamination of the latent image carrier, damage to the latent image carrier and uneven wear can be prevented, and good image quality can be obtained stably for a long period of time.
[Brief description of the drawings]
FIG. 1 is an enlarged sectional view illustrating an example of a photoconductor used in the present invention.
FIG. 2 is an enlarged cross-sectional view illustrating another example of the photoconductor used in the present invention.
FIG. 3 is an enlarged cross-sectional view illustrating another example of the photoconductor used in the present invention.
FIG. 4 is an enlarged cross-sectional view showing another example of the photoconductor used in the present invention.
FIG. 5 is an enlarged sectional view showing another example of the photoconductor used in the present invention.
FIG. 6 is a schematic diagram showing a configuration of an apparatus for obtaining a volume resistivity of a carrier used in Examples and Comparative Examples of the present invention.
[Explanation of symbols]
Reference Signs List 1 Undercoat layer, 2 charge generation layer, 3 charge transport layer, 4 conductive support, 5 surface protective layer, 6 monolayer type photosensitive layer, 31 guard electrode, 32 upper electrode, 33 measurement sample, 34 lower electrode, 35 Sample retaining ring, 36 electrometer.

Claims (2)

Charging means for charging the latent image carrier, latent image forming means for exposing the charged latent image carrier to form an electrostatic latent image, and developing means for developing the electrostatic latent image using toner A transfer separation unit that transfers the formed toner image to a recording material and separates the toner image from a latent image carrier that is a toner image holding body, and a fixing unit that thermally fixes the transferred toner image on the recording material by contact heat. An image forming method for forming an image using an image forming apparatus having
The toner contains at least inorganic particles having a Mohs hardness of 2 to 4.5,
An image forming method, wherein the surface layer of the latent image carrier is made of a siloxane-based resin having a charge transporting property and a crosslinked structure. Charging means for charging the latent image carrier, latent image forming means for exposing the charged latent image carrier to form an electrostatic latent image, and developing means for developing the electrostatic latent image using toner A transfer separation unit that transfers the formed toner image to a recording material and separates the toner image from a latent image carrier that is a toner image holder, and a cleaning unit that removes toner remaining on the toner image holder after the transfer, A fixing unit for thermally fixing the transferred toner image on the recording material, and an image forming method for forming an image using an image forming apparatus having the fixing unit.
The toner contains at least inorganic particles having a Mohs hardness of 2 to 4.5,
The surface layer of the latent image carrier has a charge transporting property, and is made of a siloxane-based resin having a crosslinked structure,
The image forming method according to claim 1, wherein the cleaning unit collects residual toner on the latent image carrier using an electrostatic brush without rubbing the latent image carrier with a blade.

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