JP3707111B2 - Electrophotographic photoreceptor - Google Patents

Description

【００１２】
式中、Ｑ₁、Ｑ₂、Ｑ₃、Ｑ₄、Ｑ₅は酸素原子、＝ＣＸ₁Ｘ₂または＝Ｎ−ＣＮを表す。Ａｒ₁、Ａｒ₂、Ａｒ₃、Ａｒ₄は各々置換、未置換の芳香族炭化水素環基、複素環基の二価の基を表すＲ₁、Ｒ₂は水素原子または各々置換、未置換の芳香族炭化水素環基を表す。Ａｒ₅、Ａｒ₆、Ａｒ₇は各々置換、未置換の芳香族炭化水素環基、複素環基を表す。Ｒ₃は水素原子、置換または未置換のアルキル基、置換または未置換のアルコキシ基、ハロゲン原子またはアルコキシカルボニル基を表す。Ｘ₁及びＸ₂は各々独立にシアノ基、アルコキシカルボニル基を表す。
【００１３】
２） 前記感光層にキャリア発生物質を含有することを特徴とする前記１記載の電子写真感光体。
【００１４】
３） 導電性支持体上にキャリア発生物質を含有するキャリア発生層と前記一般式（１）、一般式（２）または一般式（３）で示されるキャリア輸送物質の少なくとも１種を含有するキャリア輸送層を表記の順に積層した感光層を有することを特徴とする前記１記載の電子写真感光体。
【００１５】
本発明を更に詳しく説明する。一般式（１）、（２）中、Ａｒ₁、Ａｒ₂、Ａｒ₃、Ａｒ₄の置換または未置換の芳香族炭化水素環、複素環の具体例としては、ベンゼン環、ナフタレン環、フラン環、チオフェン環、ピロール環、ピリジン環などを挙げることができるが、特にはベンゼン環の二価の基が好ましい。またこれらの環にはアルキル基、アルコキシ基、ハロゲン原子、ニトロ基、シアノ基、アルコキシカルボニル基、アミド基等の置換基を有していても良い。
【００１６】
Ｒ₁、Ｒ₂、Ａｒ₅、Ａｒ₆、Ａｒ₇における芳香族炭化水素環基、複素環基の具体例としてはフェニル、ナフチル、ピリジル、ピロリル、フリル、チエニル基等を挙げることができる。またこれらの各環基にはメチル、エチル、トリフルオロメチル等のアルキル基、メトキシ、エトキシ等のアルコキシ基、フッ素、塩素等のハロゲン原子、ニトロ基、シアノ基、アルコキシカルボニル基、アミド基等の置換基を有していても良い。
【００１７】
Ｘ₁、Ｘ₂におけるアルコキシカルボニル基の具体例としては、メトキシカルボニル、エトキシカルボニル、ブトキシカルボニル、オクチルカルボニル基等を挙げることができる。
【００１８】
次に、本発明の電子輸送性物質の具体例について述べるがこれによって本発明の電子輸送性物質が限定されるものではない。
【００１９】
【化３】

【００２０】
【化４】

【００２１】
【化５】

【００２２】
【化６】

【００２３】
【化７】

【００２４】
【化８】

【００２５】
（合成例１ 例示化合物Ａ−３の合成）
２，６−（ｐ−ホルミルフェニル）−４−（シアノ（エトキシカルボニル）メチレン）−２，５−シクロヘキサジエン−１−オン（０．０１モル；４．１ｇ）をトルエン１２０ｍｌに加え、次いでシアノ酢酸エチル（０．０２４モル；２．７ｇ）とピペリジン０．５ｍｌを加えて撹拌下、５時間加熱還流する。放冷後、トルエン層を水洗し、無水硫酸マグネシウムにて乾燥後、トルエンを除去して、残った残査をシリカゲルカラムにて分離し、目的物Ａ−３を４．２ｇ得た。
【００２６】
（合成例２ Ｂ−３の合成）
ｔ−ブトキシドカリウム（０．０２４モル；２．７ｇ）をＤＭＦ５０ｍｌに加え、窒素雰囲気中５０℃にて撹拌しておく。ついで本液に２，６−（ｐ−ホルミルフェニル）−４−（シアノ（エトキシカルボニル）メチレン）−２，５−シクロヘキサジエン−１−オン（０．０１モル；４．１ｇ）／ジフェニルメチルホスホン酸ジエチル（０．０２４モル；７．３ｇ）／ＤＭＦ５０ｍｌの溶液を反応温度を５０〜７０℃に保ちながら滴下する。滴下終了後、同温度にて２時間反応させる。反応終了後、反応液を水に注ぎ、有機物をトルエンにて抽出する。トルエン層を水洗し、無水硫酸マグネシウムにて乾燥後、トルエンを除去して、残った残査をシリカゲルカラムにて分離し、目的物Ｂ−３を５．４ｇ得た。
【００２７】
（合成例３ Ｃ−１の合成）
２−フェニルチオクロモン−１，１−ジオキシド（０．０１モル；２．７ｇ）を塩化メチレン８０ｍｌに溶解し、窒素雰囲気中にて撹拌下０℃〜５℃にて四塩化チタン／塩化メチレン溶液２ｍｌ／１０ｍｌを滴下する。３０分間同温度で撹拌後、次いでビストリメチルカルボジイミド（３．５ｇ；０．０１８モル）を滴下する。滴下終了後室温にて５時間反応させる。反応後、塩化メチレンを増量して析出物を溶解抽出してから、塩化メチレン層を水洗し、無水硫酸マグネシウムにて乾燥後、塩化メチレンを除去して、残った残査をシリカゲルカラムにて分離し、目的物Ｃ−１を２．２ｇ得た。
【００２８】
本発明の前記物質は優れた電子輸送性を有し、これをバインダー中に分子分散した感光層を導電性支持体上に設けることにより本発明の電子写真感光体を製造することができる。本発明の電子輸送性物質はその優れた電子輸送能を利用して、これをキャリア輸送物質として用い、これと組み合わせて有効に作用し得るキャリア発生物質を共に用いることにより、いわゆる機能分離型の感光体とすることができる。前記機能分離型感光体は前記両物質の混合分散単層構成の感光体であってもよいが、キャリア発生層を下層としと本発明の電子輸送性物質からなるキャリア輸送層を上層とする積層型感光体とすることがより好ましい。いずれの層構成においても、支持体と感光層の間にバリア機能と接着性を持つ下引層（中間層）を設けても良く、感光層の上に保護層を設けても良い。
【００２９】
電子輸送層は本発明の電子輸送物質を適当な溶媒に単独であるいはバインダ樹脂と共に溶解分散せしめたものをアプリケーター、バーコーター、ディップコーター等を用いて塗布、乾燥して形成することができる。
【００３０】
電子輸送層に使用可能なバインダー樹脂としては、例えばポリスチレン、アクリル樹脂、メタクリル樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、ポリビニルブチラール樹脂、エポキシ樹脂、ポリウレタン樹脂、フェノール樹脂、ポリエステル樹脂、アルキッド樹脂、ポリカーボネート樹脂、シリコン樹脂、メラミン樹脂ならびに、これらの樹脂の繰り返し単位のうちの２つ以上を含む共重合体樹脂。またこれらの絶縁性樹脂の他、ポリ−Ｎ−ビニルカルバゾール等の高分子有機半導体が挙げられる。電子輸送性物質の分散媒としては、例えばトルエン、キシレン等の炭化水素類；メチレンクロライド、１，２−ジクロルエタン等のハロゲン化炭化水素；メチルエチルケトン、シクロヘキサノン等のケトン類；酢酸エチル、酢酸ブチル等のエステル類；メタノール、エタノール、プロパノール、ブタノール、メチルセルソルブ、エチルセルソルブ等のアルコール類及びこの誘導体；テトラヒドロフラン、１，４−ジオキサン等のエーテル類；ピリジンやジエチルアミン等のアミン類；Ｎ，Ｎ−ジメチルホルムアミド等のアミド類等の窒素化合物；その他脂肪酸及びフェノール類；二硫化炭素や燐酸トリエチル等の硫黄、燐化合物等の１種又は２種以上を用いることができる。
【００３１】
電子輸送層中のバインダ樹脂１００重量部当り電子輸送物質は２０〜２００重量部が好ましく、特に好ましくは５０〜１５０重量部である。形成される電子輸送層の膜厚は、好ましくは５〜３０μｍである。また単層機能分離型の電子写真感光体の場合のバインダ：電子輸送物質：キャリア発生物質の割合は１〜１００：１〜５００：１〜５００が好ましく、形成される感光層の膜厚は５〜５０μｍである
次にキャリア発生層はキャリア発生物質を適当な溶媒に単独であるいは上述の電子輸送層に用いたものと同様なバインダ樹脂と共に分散せしめた分散液をディップ塗布、スプレイ塗布、ブレード塗布、ロール塗布等によって支持体または下引層上に塗布して乾燥させる方法により設けるもの、またはキャリア発生物質を支持体または下引層上に蒸着したものが用いられる。分散塗布の場合、用いられる溶媒としても前記電子輸送物質の分子分散において用いた分散媒を用いることができる。分散にはボールミル、ホモミキサ、サンドミル、超音波分散機、アトライタ等が用いられる。
【００３２】
用いられるキャリア発生物質としては公知のどのようなものでも使用できるが、例えばセレン系の無機半導体、種々のフタロシアニン化合物、アゾ化合物、ピリリウム化合物、ペリレン系化合物、シアニン系化合物、スクアリウム化合物、多環キノン化合物が使用できる。
【００３３】
本発明の感光体が積層型構成の場合、キャリア発生層中のバインダ：キャリア発生物質の重量比は０〜１０：１〜５０である。以上のようにして形成されるキャリア発生層の膜厚は、好ましくは０．０１〜１０μｍ、特に好ましくは０．１〜５μｍである。
【００３４】
次に前記感光層を支持する導電性支持体としては、アルミニウム、ニッケルなどの金属板・金属ドラム、またはアルミニウム、酸化錫、酸化インジュウムなどを蒸着したプラスチックフィルム、または導電性物質を塗布した紙・プラスチックフィルム・ドラムを使用することができる。
【００３５】
また本発明の感光層においては、オゾン劣化防止の目的で以下に示すような酸化防止剤を添加することができる。
【００３６】
（１）ヒンダードフェノール類
（２）ヒンダートアミン類
（３）パラフェニレンジアミン類
（４）ハイドロキノン類
（５）有機燐化合物類
これらの化合物はゴム、プラスチック、油脂類等の酸化防止剤として知られており、市販品を容易に入手できる。
【００３７】
また本発明の感光体には、その他、必要により感光層を保護する目的で紫外線吸収剤また感色性補正の染料を含有してもよい。
【００３８】
【実施例】
実施例１〜１０
アルミニウムを蒸着したＰＥＴフィルム上にポリアミド樹脂「ＣＭ８０００」（東レ社製）からなる厚さ０．５μｍの中間層を設けた。その上に、Ｘ線回折におけるブラッグ角２θの９．５°、２４．１°、２７．２°にピークを有するチタニルフタロシアニン１部、シリコーン−ブチラール樹脂０．５部、分散媒として酢酸ｔ−ブチル／メトキシメチルペンタノン＝９／１ ５０部をサンドグラインダーを用いて分散した液をワイヤーバーを用いて塗布し膜厚０．３μｍのキャリア発生層を形成した。次いで表１に示す例示化合物１部とポリカーボネート樹脂「ユーピロンＺ−２００」（三菱瓦斯化学社製）１．５部をＴＨＦ１０部に溶解し、キャリア発生層上にドクターブレードを用いて塗布し膜厚２０μｍのキャリア輸送層を形成し、実施例感光体１〜１０を作製した。
【００３９】
比較例１
実施例１の例示化合物Ａ−３を下記比較化合物Ｎ−１に変えた他は実施例１と同様にして比較例感光体１を作成した。
【００４０】
比較例２
実施例１の例示化合物Ａ−３を下記比較化合物Ｎ−２に変えた他は実施例１と同様にして比較例感光体２を作成した。
【００４１】
【化９】

【００４２】
評価方法
実施例１〜１０及び比較例１〜２により得られた電子写真感光体サンプルについて静電複写試験装置ＥＰＡ−８１００（川口電気社製）を用いて、＋６ｋＶにて５秒帯電させ、その後暗所にて１０秒放置した後の受容電位Ｖａを測定した。次に１０ｌｕｘの白色光を露光し、表面電位が半分になるまでの露光量Ｅ１／２（ｌｕｘ．ｓｅｃ）を求めて感度とした。また２０秒露光した後の残留電位Ｖｒを求めた。結果を表１に示す。
【００４３】
【表１】

【００４４】
表１から、本発明の電子写真感光体は、残留電位が小さく、高感度であることが解る。
【００４５】
実施例１１
円筒形アルミ基体上にポリアミド樹脂「ＣＭ８０００」（東レ社製）からなる厚さ０．５μｍの中間層を設け、その上にＸ線回折におけるブラッグ角２θの９．５°、２４．１°、２７．２°にピークを有するチタニルフタロシアニン１部、シリコーン−ブチラール樹脂０．５部、分散媒として酢酸ｔ−ブチル／メトキシメチルペンタノン＝９／１ ５０部をサンドミルを用いて分散した液をディップ塗布して膜厚０．３μｍのキャリア発生層を形成した。次いで例示化合物Ａ−３ １部とポリカーボネート樹脂「ユーピロンＺ−２００」（三菱瓦斯化学社製）１．５部をＴＨＦ１０部に溶解し、キャリア発生層上にディップ塗布して膜厚２０μｍのキャリア輸送層を形成し、実施例感光体１１を作製した。
【００４６】
実施例１２
実施例１１における例示化合物Ａ−３をＢ−３に変えた他は、実施例１１と同様にして実施例感光体１２を作製した。
【００４７】
実施例１３
実施例１１における例示化合物Ａ−３をＣ−１に変えた他は、実施例１１と同様にして実施例感光体１３を作製した。
【００４８】
評価方法
実施例１１、１２、１３で得られた感光体について、コニカ（株）社製デジタルコピー「Ｋｏｎｉｃａ９０２８」改造機（帯電極性：正、反転現像）に装着し画像を複写したところ、コントラストが高く原画に忠実でかつ鮮明な複写画像を得た。また５、０００回の繰り返しでもコントラストが高く鮮明な複写画像を得られた。
【００４９】
【発明の効果】
以上のように、本発明の電子輸送物質を用いた電子写真感光体は、従来の電子輸送物質を用いた電子写真感光体と比較して、感度が高く、繰り返し使用時の感光体特性も安定していることがわかる。[0001]
[Industrial application fields]
The present invention relates to an electrophotographic photosensitive member for forming an electrostatic latent image. Specifically, the present invention relates to an electrophotographic photosensitive member having a layer containing a compound having an electron transporting ability.
[0002]
[Prior art]
Conventionally, as an electrophotographic photoreceptor, an inorganic photoreceptor having a photosensitive layer mainly composed of an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide, and silicon has been widely used. However, these are not always satisfactory in terms of sensitivity, thermal stability, moisture resistance, durability, etc., and some inorganic photoreceptors contain substances harmful to the human body. There is.
[0003]
In order to overcome the drawbacks of these inorganic photoreceptors, research and development of organic photoreceptors having a photosensitive layer mainly composed of various organic photoconductive compounds have been actively conducted in recent years. In particular, the function-separated type photoconductor, in which the carrier generation function and the carrier transport function are each assigned to different materials, each material can be selected from a wide range, and a photoconductor with arbitrary performance can be created relatively easily. Therefore, many studies have been made, and some have been put into practical use. For example, US Pat. No. 3,871,882 uses a perylene derivative as a carrier generation layer and an oxadiazole derivative as a carrier transport layer, and JP-A 55-84943 discloses a distyrylbenzene bisazo compound as a carrier generation material. Those using hydrazone compounds as compounds and carrier transporting materials are known.
[0004]
As such a substance having a carrier transport function, compounds such as pyrazoline, hydrazone, and triphenylamine derivatives are known, and these are substances having a hole transport ability, and are layers containing a carrier generating substance. In the case of a function-separated type photoconductor having a lower layer as a lower layer and a layer containing a carrier transport material as an upper layer, it is necessary to take a method of negatively charging the surface of the photoconductor. For this reason, it is impossible to use the developer used in the conventional inorganic photoconductor, and the amount of ozone generated when the photoconductor is charged by corona discharge is larger than that in the positive charging performed by the inorganic photoconductor. There is. In particular, the large amount of ozone generated is a problem in terms of the influence on the human body and the environment in addition to the deterioration of the photoreceptor due to the generated ozone.
[0005]
As a positively charged type photoconductor using an organic photoconductor, a conventional positive hole transport material is used, and a reverse layer structure photoconductor with a carrier generation layer as an upper layer and a carrier transport layer as a lower layer, a carrier generation material and a carrier transport material. In the same layer, a photoconductor having a single layer structure has been studied. However, a photoconductor having sufficient performance to be compatible with a high-speed machine in terms of durability and environmental characteristics has not been obtained.
[0006]
Therefore, in order to solve the above problems, it is required to apply a substance having an electron transporting ability as a carrier transporting substance to the carrier transporting layer. 2,4,7-trinitrofluorenone is known as such an electron transporting material, but this material is poorly soluble and compatible with the polymer used for the solvent and binder, and constitutes an actual photosensitive layer. However, its use has been discontinued because it does not have sufficient characteristics and has carcinogenic properties.
[0007]
In recent years, several electron transporting substances in which a soluble group is introduced into an electron accepting structure have been proposed. Examples thereof include JP-A-1-206349, JP-A-2-135362, JP-A-2-214866, JP-A-3-290666, “Japan Hard Copy '92”, P173 (1992). However, none of the compounds have sufficient sensitivity and potential characteristics in combination with existing carrier generating substances, and presently have problems in practical use.
[0008]
[Problems to be solved by the invention]
In view of the above-mentioned problems, an object of the present invention is an electrophotography having excellent durability that uses an electron transport material having an electron transport ability, has high sensitivity, has a small residual potential, and does not change their characteristics even when used repeatedly. The object is to provide a photoreceptor.
[0009]
[Means for Solving the Problems]
The above object of the present invention is achieved by the following configurations.
[0010]
1) In an electrophotographic photosensitive member in which a photosensitive layer is provided on a conductive support, at least one compound represented by the general formula (1), the general formula (2) or the general formula (3) is contained in the photosensitive layer. An electrophotographic photosensitive member containing the electrophotographic photosensitive member.
[0011]
[Chemical formula 2]

[0012]
In the formula, Q ₁ , Q ₂ , Q ₃ , Q ₄ and Q _{5 each} represents an oxygen atom, ═CX ₁ X ₂ or ═N—CN. Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ are each a substituted, unsubstituted aromatic hydrocarbon ring group, or a divalent group of a heterocyclic group, R ₁ , R ₂ are hydrogen atoms or each substituted, unsubstituted Represents an aromatic hydrocarbon ring group . Ar ₅ , Ar ₆ and Ar ₇ each represent a substituted or unsubstituted aromatic hydrocarbon ring group or heterocyclic group. R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a halogen atom or an alkoxycarbonyl group . X ₁ and X ₂ each independently represent a cyano group or an alkoxycarbonyl group.
[0013]
2) The electrophotographic photosensitive member according to 1 above, wherein the photosensitive layer contains a carrier generating substance.
[0014]
3) A carrier containing a carrier generating layer containing a carrier generating material on a conductive support and at least one carrier transporting material represented by the general formula (1), general formula (2) or general formula (3). 2. The electrophotographic photosensitive member according to 1 above, further comprising a photosensitive layer in which transport layers are laminated in the order of description.
[0015]
The present invention will be described in more detail. In the general formulas (1) and (2), Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ substituted or unsubstituted aromatic hydrocarbon rings and heterocyclic rings are exemplified by benzene ring, naphthalene ring, furan ring. , A thiophene ring, a pyrrole ring, a pyridine ring, and the like, among which a divalent group of a benzene ring is particularly preferable. These rings may have a substituent such as an alkyl group, an alkoxy group, a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, and an amide group.
[0016]
Specific examples of the aromatic hydrocarbon ring group and heterocyclic group in R ₁ , R ₂ , Ar ₅ , Ar ₆ and Ar ₇ include phenyl, naphthyl, pyridyl, pyrrolyl, furyl, and thienyl groups. These ring groups include alkyl groups such as methyl, ethyl and trifluoromethyl, alkoxy groups such as methoxy and ethoxy, halogen atoms such as fluorine and chlorine, nitro groups, cyano groups, alkoxycarbonyl groups and amide groups. It may have a substituent.
[0017]
Specific examples of the alkoxycarbonyl group in X ₁ and X ₂ include methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octylcarbonyl group and the like.
[0018]
Next, specific examples of the electron transporting material of the present invention will be described, but the electron transporting material of the present invention is not limited thereby.
[0019]
[Chemical 3]

[0020]
[Formula 4]

[0021]
[Chemical formula 5]

[0022]
[Chemical 6]

[0023]
[Chemical 7]

[0024]
[Chemical 8]

[0025]
(Synthesis Example 1 Synthesis of Exemplary Compound A-3)
2,6- (p-formylphenyl) -4- (cyano (ethoxycarbonyl) methylene) -2,5-cyclohexadien-1-one (0.01 mol; 4.1 g) was added to 120 ml of toluene and then cyano. Add ethyl acetate (0.024 mol; 2.7 g) and 0.5 ml piperidine, and heat to reflux for 5 hours with stirring. After allowing to cool, the toluene layer was washed with water, dried over anhydrous magnesium sulfate, toluene was removed, and the remaining residue was separated on a silica gel column to obtain 4.2 g of the desired product A-3.
[0026]
(Synthesis Example 2 Synthesis of B-3)
t-Butoxide potassium (0.024 mol; 2.7 g) is added to 50 ml of DMF and stirred at 50 ° C. in a nitrogen atmosphere. Subsequently, 2,6- (p-formylphenyl) -4- (cyano (ethoxycarbonyl) methylene) -2,5-cyclohexadien-1-one (0.01 mol; 4.1 g) / diphenylmethylphosphonic acid was added to this solution. A solution of diethyl (0.024 mol; 7.3 g) / DMF (50 ml) is added dropwise while maintaining the reaction temperature at 50 to 70 ° C. After completion of the dropwise addition, the reaction is carried out at the same temperature for 2 hours. After completion of the reaction, the reaction solution is poured into water, and the organic matter is extracted with toluene. The toluene layer was washed with water, dried over anhydrous magnesium sulfate, toluene was removed, and the remaining residue was separated with a silica gel column to obtain 5.4 g of the desired product B-3.
[0027]
(Synthesis Example 3 Synthesis of C-1)
2-Phenylthiochromone-1,1-dioxide (0.01 mol; 2.7 g) is dissolved in 80 ml of methylene chloride and stirred in a nitrogen atmosphere at 0 ° C. to 5 ° C. with a titanium tetrachloride / methylene chloride solution. 2 ml / 10 ml is added dropwise. After stirring at the same temperature for 30 minutes, bistrimethylcarbodiimide (3.5 g; 0.018 mol) is then added dropwise. After completion of dropping, the reaction is allowed to proceed at room temperature for 5 hours. After the reaction, the amount of methylene chloride was increased and the precipitate was dissolved and extracted. The methylene chloride layer was washed with water, dried over anhydrous magnesium sulfate, methylene chloride was removed, and the remaining residue was separated on a silica gel column. As a result, 2.2 g of the target product C-1 was obtained.
[0028]
The substance of the present invention has an excellent electron transporting property, and the electrophotographic photosensitive member of the present invention can be produced by providing a photosensitive layer in which this is molecularly dispersed in a binder on a conductive support. The electron transporting substance of the present invention utilizes the excellent electron transporting ability, uses it as a carrier transporting substance, and uses a carrier generating substance that can act effectively in combination with this so-called function separation type. It can be a photoconductor. The function-separated type photoreceptor may be a photoreceptor having a mixed-dispersed single layer structure of the two substances. However, a laminate in which the carrier generation layer is a lower layer and the carrier transport layer made of the electron transport material of the present invention is an upper layer. It is more preferable to use a type photoreceptor. In any layer configuration, an undercoat layer (intermediate layer) having a barrier function and adhesion may be provided between the support and the photosensitive layer, and a protective layer may be provided on the photosensitive layer.
[0029]
The electron transport layer can be formed by applying and drying a material obtained by dissolving and dispersing the electron transport material of the present invention alone or together with a binder resin using an applicator, bar coater, dip coater or the like.
[0030]
Examples of binder resins that can be used in the electron transport layer include polystyrene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, and polycarbonate resin. , Silicone resins, melamine resins, and copolymer resins containing two or more of the repeating units of these resins. In addition to these insulating resins, polymer organic semiconductors such as poly-N-vinylcarbazole can be used. Examples of the electron transport material dispersion medium include hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane; ketones such as methyl ethyl ketone and cyclohexanone; ethyl acetate and butyl acetate; Esters; alcohols such as methanol, ethanol, propanol, butanol, methyl cellosolve, ethyl cellosolve and derivatives thereof; ethers such as tetrahydrofuran and 1,4-dioxane; amines such as pyridine and diethylamine; N, N- One or more of nitrogen compounds such as amides such as dimethylformamide; other fatty acids and phenols; sulfur such as carbon disulfide and triethyl phosphate, and phosphorus compounds can be used.
[0031]
The electron transporting material is preferably 20 to 200 parts by weight, particularly preferably 50 to 150 parts by weight per 100 parts by weight of the binder resin in the electron transporting layer. The film thickness of the formed electron transport layer is preferably 5 to 30 μm. The ratio of binder: electron transport material: carrier generating material in the case of a single layer function separation type electrophotographic photosensitive member is preferably 1-100: 1-500: 1-500, and the film thickness of the formed photosensitive layer is 5 Next, the carrier generation layer having a thickness of ˜50 μm is formed by dip coating, spray coating or blade coating of a dispersion in which the carrier generating material is dispersed in an appropriate solvent alone or together with the same binder resin as that used in the above electron transport layer. For example, a material provided by a method such as roll coating or the like applied on a support or an undercoat layer and dried, or a carrier generation material deposited on a support or an undercoat layer is used. In the case of dispersion coating, the dispersion medium used in the molecular dispersion of the electron transport material can also be used as the solvent used. A ball mill, a homomixer, a sand mill, an ultrasonic disperser, an attritor or the like is used for dispersion.
[0032]
Any known carrier generating material can be used. For example, selenium inorganic semiconductors, various phthalocyanine compounds, azo compounds, pyrylium compounds, perylene compounds, cyanine compounds, squalium compounds, polycyclic quinones. Compounds can be used.
[0033]
When the photoreceptor of the present invention has a laminated structure, the weight ratio of binder: carrier generating substance in the carrier generating layer is 0-10: 1-50. The film thickness of the carrier generation layer formed as described above is preferably 0.01 to 10 μm, particularly preferably 0.1 to 5 μm.
[0034]
Next, as the conductive support for supporting the photosensitive layer, a metal plate / metal drum such as aluminum or nickel, or a plastic film deposited with aluminum, tin oxide, indium oxide, or the like, or paper coated with a conductive substance, Plastic film drums can be used.
[0035]
In the photosensitive layer of the present invention, an antioxidant as shown below can be added for the purpose of preventing ozone deterioration.
[0036]
(1) Hindered phenols (2) Hindered amines (3) Paraphenylenediamines (4) Hydroquinones (5) Organophosphorus compounds These compounds are known as antioxidants for rubber, plastics, oils and fats, etc. It is easy to obtain a commercial product.
[0037]
In addition, the photoreceptor of the present invention may contain an ultraviolet absorber or a dye for correcting color sensitivity for the purpose of protecting the photosensitive layer, if necessary.
[0038]
【Example】
Examples 1-10
An intermediate layer having a thickness of 0.5 μm made of polyamide resin “CM8000” (manufactured by Toray Industries, Inc.) was provided on a PET film on which aluminum was deposited. Furthermore, 1 part of titanyl phthalocyanine having peaks at 9.5 °, 24.1 ° and 27.2 ° of Bragg angle 2θ in X-ray diffraction, 0.5 part of silicone-butyral resin, t-acetate as a dispersion medium A liquid in which 50 parts of butyl / methoxymethylpentanone = 9/1 was dispersed using a sand grinder was applied using a wire bar to form a carrier generation layer having a thickness of 0.3 μm. Next, 1 part of the exemplary compound shown in Table 1 and 1.5 parts of polycarbonate resin “Iupilon Z-200” (manufactured by Mitsubishi Gas Chemical Co., Inc.) are dissolved in 10 parts of THF, and coated on the carrier generation layer using a doctor blade. A carrier transport layer having a thickness of 20 μm was formed, and Example photoreceptors 1 to 10 were produced.
[0039]
Comparative Example 1
A comparative photoreceptor 1 was prepared in the same manner as in Example 1 except that the exemplified compound A-3 in Example 1 was changed to the following comparative compound N-1.
[0040]
Comparative Example 2
A comparative photoreceptor 2 was prepared in the same manner as in Example 1 except that the exemplified compound A-3 in Example 1 was changed to the following comparative compound N-2.
[0041]
[Chemical 9]

[0042]
Evaluation Method The electrophotographic photosensitive member samples obtained in Examples 1 to 10 and Comparative Examples 1 and 2 were charged at +6 kV for 5 seconds using an electrostatic copying test apparatus EPA-8100 (manufactured by Kawaguchi Electric Co., Ltd.), and thereafter The acceptance potential Va after being left for 10 seconds in a dark place was measured. Next, 10 lux of white light was exposed, and the exposure amount E1 / 2 (lux.sec) until the surface potential was reduced to half was determined as the sensitivity. Further, the residual potential Vr after exposure for 20 seconds was obtained. The results are shown in Table 1.
[0043]
[Table 1]

[0044]
From Table 1, it can be seen that the electrophotographic photosensitive member of the present invention has a small residual potential and high sensitivity.
[0045]
Example 11
An intermediate layer made of polyamide resin “CM8000” (manufactured by Toray Industries Inc.) having a thickness of 0.5 μm is provided on a cylindrical aluminum substrate, and a Bragg angle 2θ in X-ray diffraction of 9.5 °, 24.1 °, 2 parts of titanyl phthalocyanine having a peak at 27.2 °, 0.5 parts of silicone-butyral resin, and tert-butyl acetate / methoxymethylpentanone = 9/1 50 parts as a dispersion medium were dispersed using a sand mill. This was applied to form a carrier generation layer having a thickness of 0.3 μm. Next, 1 part of Exemplified Compound A-3 and 1.5 parts of polycarbonate resin “Iupilon Z-200” (manufactured by Mitsubishi Gas Chemical Co., Inc.) are dissolved in 10 parts of THF, and dip-coated on the carrier generating layer to transport the carrier with a thickness of 20 μm. A layer was formed to prepare Example Photoreceptor 11.
[0046]
Example 12
Example Photoconductor 12 was prepared in the same manner as Example 11 except that Example Compound A-3 in Example 11 was changed to B-3.
[0047]
Example 13
Example Photoreceptor 13 was produced in the same manner as Example 11 except that Example Compound A-3 in Example 11 was changed to C-1.
[0048]
Evaluation Method The photoconductors obtained in Examples 11, 12, and 13 were mounted on a digital copy “Konica 9028” modified machine (charged polarity: positive, reverse development) manufactured by Konica Corporation. A high-fidelity copy of the original image was obtained. In addition, a clear copy image with high contrast was obtained even after 5,000 repetitions.
[0049]
【The invention's effect】
As described above, the electrophotographic photoreceptor using the electron transport material of the present invention has higher sensitivity than the conventional electrophotographic photoreceptor using the electron transport material, and the photoreceptor characteristics during repeated use are also stable. You can see that

Claims (3)

In the electrophotographic photosensitive member in which a photosensitive layer is provided on a conductive support, the photosensitive layer contains at least one compound represented by the general formula (1), the general formula (2), or the general formula (3). An electrophotographic photosensitive member characterized by the above.

In the formula, Q ₁ , Q ₂ , Q ₃ , Q ₄ and Q _{5 each} represents an oxygen atom, ═CX ₁ X ₂ or ═N—CN. Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ are each a substituted, unsubstituted aromatic hydrocarbon ring group, or a divalent group of a heterocyclic group, R ₁ , R ₂ are hydrogen atoms or each substituted, unsubstituted Represents an aromatic hydrocarbon ring group . Ar ₅ , Ar ₆ and Ar ₇ each represent a substituted or unsubstituted aromatic hydrocarbon ring group or heterocyclic group. R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a halogen atom or an alkoxycarbonyl group . X ₁ and X ₂ each independently represent a cyano group or an alkoxycarbonyl group.   2. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer contains a carrier generating substance.   A carrier generating layer containing a carrier generating material on a conductive support and a carrier transporting layer containing at least one of the carrier transporting materials represented by the general formula (1), general formula (2) or general formula (3) The electrophotographic photosensitive member according to claim 1, further comprising a photosensitive layer in which the layers are laminated in the order of description.