JP3748452B2 - Single layer type electrophotographic photoreceptor - Google Patents

Single layer type electrophotographic photoreceptor Download PDF

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JP3748452B2
JP3748452B2 JP2005177261A JP2005177261A JP3748452B2 JP 3748452 B2 JP3748452 B2 JP 3748452B2 JP 2005177261 A JP2005177261 A JP 2005177261A JP 2005177261 A JP2005177261 A JP 2005177261A JP 3748452 B2 JP3748452 B2 JP 3748452B2
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photosensitive member
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electrophotographic photosensitive
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JP2005331965A (en
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之勝 今中
宏昭 岩崎
裕二 田中
政克 林
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Kyocera Document Solutions Inc
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Kyocera Mita Corp
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Description

本発明は、単層型電子写真感光体に関し、特に、電子写真式複写機、ファクシミリ、レーザービームプリンタ等に用いられる単層型電子写真感光体に関する。The present invention relates to a single layer type electrophotographic photosensitive member, and more particularly to a single layer type electrophotographic photosensitive member used for an electrophotographic copying machine, a facsimile, a laser beam printer, and the like.

より詳細には、除電工程を有さない反転現像式デジタル画像形成装置において使用してもメモリー画像が発生しない単層型電子写真感光体に関するものである。  More specifically, the present invention relates to a single-layer electrophotographic photosensitive member that does not generate a memory image even when used in a reversal development type digital image forming apparatus that does not have a charge eliminating step.

有機感光体は、従来の無機感光体に比べて製造が容易であり、コストが安く、電荷輸送剤、電荷発生剤、結着樹脂等の感光体材料の選択肢が多様で、機能設計の自由度が高いという利点を有することから、近年、広く用いられている。   Organic photoconductors are easier to manufacture than conventional inorganic photoconductors, are less expensive, have a wide range of options for photoconductor materials such as charge transport agents, charge generators, and binder resins. Has been widely used in recent years.

有機感光体には、電荷輸送剤(ホール輸送剤、電子輸送剤)を電荷発生剤とともに同一の感光層中に分散させた単層型感光体と、電荷発生剤を含有する電荷発生層と電荷輸送剤を含有する電荷輸送層とを積層した積層型感光体とがあり、層構成が簡単で生産性に優れている、層間の界面が少ないので光学的特性を向上できる、といった利点を有するため、近年、脚光を浴びつつある。   The organic photoreceptor includes a single-layer type photoreceptor in which a charge transport agent (a hole transport agent, an electron transport agent) is dispersed in the same photosensitive layer together with a charge generator, a charge generation layer containing the charge generator, and a charge. There are laminated photoconductors with a charge transport layer containing a transport agent, which has advantages such as a simple layer structure and excellent productivity, and improved optical characteristics because there are few interfaces between layers. In recent years, it has been in the spotlight.

一方、電子写真方式を利用した画像形成装置は、感光体を帯電し(主帯電工程)、画像露光して静電潜像を形成し(露光工程)、この静電潜像を現像バイアス電圧が印加された状態でトナー現像し(現像工程)、形成されるトナー像を転写紙に転写し(転写工程)、定着して画像形成を行う。また、感光体上の残留トナーはウレタンブレード等によりクリーニングされ(クリーニング工程)、感光体上の残留電荷はLED等により消去される(除電工程)。   On the other hand, an image forming apparatus using an electrophotographic system charges a photosensitive member (main charging step), exposes an image to form an electrostatic latent image (exposure step), and develops the electrostatic latent image with a developing bias voltage. The toner is developed in the applied state (development process), and the formed toner image is transferred to transfer paper (transfer process) and fixed to perform image formation. The residual toner on the photoconductor is cleaned by a urethane blade or the like (cleaning process), and the residual charge on the photoconductor is erased by an LED or the like (static elimination process).

そして、画像形成装置の小型化やイニシャルコストダウン等のために、上述のクリーニング工程と除電工程については省略される試みが種々なされている。   Various attempts have been made to omit the above-described cleaning process and static elimination process in order to reduce the size of the image forming apparatus and reduce the initial cost.

また、電子写真方式を利用した画像形成装置には、デジタル及びアナログ複写機、ファクシミリ、レーザービームプリンタ等があり、特に帯電工程で感光体に印加される帯電電圧と同極性のトナーを使用して現像する反転現像方式は、デジタル画像形成装置に広く使用されている。   In addition, image forming apparatuses using electrophotography include digital and analog copying machines, facsimiles, laser beam printers, and the like, and in particular, using toner having the same polarity as the charging voltage applied to the photoreceptor in the charging process. A reversal developing method for developing is widely used in digital image forming apparatuses.

<転写メモリー>
電子写真感光体を反転現像式デジタル画像形成装置に使用した場合、転写工程で感光体に印加される転写電圧は、通常、感光体に直接印加せず転写媒体(紙)を介して印加され、転写媒体が転写工程を通過しないときは印加されない。
<Transfer memory>
When the electrophotographic photosensitive member is used in a reversal development type digital image forming apparatus, the transfer voltage applied to the photosensitive member in the transfer step is usually applied via a transfer medium (paper) without being directly applied to the photosensitive member, It is not applied when the transfer medium does not pass through the transfer process.

しかしながら、転写電圧の入切タイミングは非常に困難で、転写媒体の先後端部については感光体に直接印加される部分が発生してしまうことが多い。すなわち、転写媒体の先端が転写装置を覆う前に、転写電圧が印加され始め、また、転写媒体の後端の通過により転写装置の一部が露出されてもなお、転写電圧が印加され続けるため、当該部分は感光体に転写電圧が直接印加されるのである。   However, the transfer voltage on / off timing is very difficult, and a portion that is directly applied to the photoreceptor often occurs at the front and rear end portions of the transfer medium. That is, the transfer voltage starts to be applied before the leading edge of the transfer medium covers the transfer device, and the transfer voltage continues to be applied even if a part of the transfer device is exposed due to the passage of the rear end of the transfer medium. In this portion, the transfer voltage is directly applied to the photoconductor.

このため、例えば正帯電単層型感光体の場合、転写装置で印加される電圧の極性は負であるため、負電圧が印加された感光体部分には負の空間電荷が残存してしまう。一般に、単層型感光体は両極性に感度を有するため、次の除電工程において負の空間電荷が消去される。   For this reason, for example, in the case of a positively charged single layer type photoreceptor, since the polarity of the voltage applied by the transfer device is negative, negative space charges remain on the photoreceptor portion to which a negative voltage is applied. In general, a single-layer type photoreceptor has sensitivity in both polarities, so that negative space charges are erased in the next static elimination step.

ところが、上述の正帯電単層型感光体の負極性に対する感度が非常に悪い(電子輸送剤の移動度が極端に小さい)場合や、除電工程を有さない画像形成装置において使用する場合には、負の空間電荷が十分に消去されず、次の帯電工程で正帯電されても空間電荷の影響で電位低下が引き起こされ、更に現像工程においては感度差となって現れ、画像中では当該部分が黒くなる(メモリー画像)という問題が発生する。   However, when the above-mentioned positively charged single-layer type photoreceptor is very insensitive to the negative polarity (the mobility of the electron transfer agent is extremely small), or when used in an image forming apparatus that does not have a charge eliminating step. The negative space charge is not sufficiently erased, and even if it is positively charged in the next charging step, the potential drop is caused by the effect of the space charge, and further, a sensitivity difference appears in the development step, and the portion in the image The problem arises that the image becomes black (memory image).

<露光メモリー>
例えば、正帯電単層型感光体は、露光工程、現像工程を経て、通常は、除電工程で一様に感光体表面の正電荷が消去された後、次帯電工程において均一に正帯電される。
<Exposure memory>
For example, a positively charged single layer type photoreceptor is normally positively charged in the next charging step after the positive charge on the surface of the photosensitive member is erased uniformly in the static elimination step after the exposure step and the development step. .

しかし、転写メモリーの場合と同様に、上述の正帯電単層型感光体の負極性に対する感度が悪い場合や、除電工程を有さない画像形成装置において使用する場合には、露光部分の方が非露光部分に比較して負の空間電荷密度が大きく、次帯電工程で電位差が生じ、メモリー画像が発生し易くなる。   However, as in the case of the transfer memory, when the sensitivity to the negative polarity of the positively charged single layer type photoreceptor described above is poor, or when used in an image forming apparatus that does not have a charge eliminating step, the exposed portion is better. Compared with the non-exposed portion, the negative space charge density is large, a potential difference is generated in the next charging step, and a memory image is easily generated.

そこで、本発明の目的は、除電工程を有さない反転現像式デジタル画像形成装置において使用してもメモリー画像が発生しない単層型電子写真感光体を提供することにある。 SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a single-layer electrophotographic photosensitive member that does not generate a memory image even when used in a reversal development type digital image forming apparatus that does not have a charge eliminating step.

本発明者らは鋭意研究の結果、上述の目的を達成するために、除電工程を有さない反転現像式デジタル画像形成装置において、プラス極性に帯電させて用いる単層型電子写真感光体であって、導電性基体上に感光層を形成し、感光層が電荷発生剤としてのフタロシアニン系化合物、及びホール輸送剤、電子輸送剤をバインダー樹脂中に含有し、フタロシアニン系化合物の含有量がバインダー樹脂重量に対して0.1〜4wt%であり、感光層の膜厚が10〜35μmであって、且つ、帯電電位を800Vに設定し、露光波長780nm、露光エネルギー1.0μJ/cm  As a result of diligent research, the inventors of the present invention have found a single-layer type electrophotographic photosensitive member that is used by being charged to a positive polarity in a reversal development type digital image forming apparatus that does not have a static elimination process in order to achieve the above-described object. A photosensitive layer is formed on a conductive substrate, the photosensitive layer contains a phthalocyanine compound as a charge generator, a hole transport agent, and an electron transport agent in a binder resin, and the content of the phthalocyanine compound is a binder resin. The photosensitive layer thickness is 10 to 35 μm, the charging potential is set to 800 V, the exposure wavelength is 780 nm, and the exposure energy is 1.0 μJ / cm. 22 の条件で、500msec経過後に測定したプラス極性とマイナス極性の感度の絶対値差が312V以下であるとともに、プラス極性感度の絶対値が、マイナス極性感度の絶対値より小さい単層型電子写真感光体が、露光メモリー及び転写メモリーが非常に小さく、除電工程を有さない反転現像デジタル式画像形成システムにおいてもメモリー画像が発生しない事実を見出した。Single layer type electrophotographic photosensitive member in which the absolute value difference between the positive and negative polarities measured after elapse of 500 msec is 312 V or less and the absolute value of the positive polarity is smaller than the absolute value of the negative polarity However, the present inventors have found that a memory image is not generated even in a reversal development digital image forming system that has very small exposure memory and transfer memory and does not have a charge eliminating step.

すなわち、露光波長780nm、露光エネルギー1.0μJ/cm2の条件で、500msec経過後に測定したプラス極性とマイナス極性の感度の絶対値差が312V以下であるとともに、プラス極性感度の絶対値が、マイナス極性感度の絶対値より小さい単層型電子写真感光体を使用すると、露光メモリー及び転写メモリーが非常に小さい。これは、プラス極性とマイナス極性の感度の絶対値差が小さいほど、感光層中で発生したホールと電子の輸送バランスが良好となりメモリーが小さくなるためと考えられる。 That is, the absolute value difference between the positive polarity and negative polarity sensitivity measured after elapse of 500 msec under the conditions of the exposure wavelength of 780 nm and the exposure energy of 1.0 μJ / cm 2 is 312 V or less, and the absolute value of the positive polarity sensitivity is negative. When a single layer type electrophotographic photosensitive member having a smaller polarity sensitivity is used , the exposure memory and the transfer memory are very small. This is presumably because the smaller the absolute value difference between the positive and negative polarities, the better the transport balance between holes and electrons generated in the photosensitive layer and the smaller the memory.

また、本発明の単層型電子写真感光体において、電荷発生剤であるフタロシアニン系化合物の含有量は、バインダー樹脂重量に対して0.1〜4wt%の範囲が好ましい。フタロシアニン系化合物の含有量が4wt%を超えるとメモリーが大きくなる。すなわち、メモリーが、感光層中のトラップにキャリアが入りこみ残存キャリアとなって発生すると考えられるため、発生するキャリア数が過剰となり、残存キャリア数も多くなるためである。一方、含有量が0.1wt%未満の場合は光感度不足となり実使用が困難となる。   In the single-layer electrophotographic photosensitive member of the present invention, the content of the phthalocyanine compound as a charge generator is preferably in the range of 0.1 to 4 wt% with respect to the binder resin weight. When the content of the phthalocyanine compound exceeds 4 wt%, the memory becomes large. That is, since it is considered that the memory is generated as a residual carrier by entering the trap in the photosensitive layer, the number of generated carriers becomes excessive and the number of remaining carriers also increases. On the other hand, when the content is less than 0.1 wt%, the photosensitivity is insufficient and actual use becomes difficult.

また、本発明の単層型電子写真感光体において、感光層の膜厚は10〜35μmの範囲が好ましい。膜厚が35μmを超えるとメモリーが大きくなる。すなわち、感光層膜厚が大きくなるほど、暗減衰が大きくなり帯電能力が低下し、メモリーの影響を受け易くなること、または感光層構成材料の絶対量が増大することによりトラップが増えることに起因していると考えられる。一方、膜厚が10μm未満の場合、膜削れによる感度悪化が著しくなり実使用が困難となる。   In the single-layer electrophotographic photoreceptor of the present invention, the thickness of the photosensitive layer is preferably in the range of 10 to 35 μm. When the film thickness exceeds 35 μm, the memory becomes large. That is, as the photosensitive layer thickness increases, the dark decay increases and the charging ability decreases, making it more susceptible to memory, or the increase in the absolute amount of photosensitive layer constituent material increases traps. It is thought that. On the other hand, when the film thickness is less than 10 μm, the sensitivity is greatly deteriorated due to film shaving, and actual use becomes difficult.

また、本発明の単層型電子写真感光体として、移動度の大きい電子輸送剤の材料設計が困難で、電子輸送剤の移動度がホール輸送剤の移動度に比較して小さいこと、画像形成装置内でのオゾンの発生が極めて少ないこと等の理由により、プラス極性感度の絶対値がマイナス極性感度の絶対値より小さい、すなわち正帯電型を用いることが好ましい。   In addition, as a single-layer electrophotographic photosensitive member of the present invention, it is difficult to design a material for an electron transport agent having a high mobility, and the mobility of the electron transport agent is small compared to the mobility of a hole transport agent. It is preferable to use a positively charged type because the absolute value of the positive polarity sensitivity is smaller than the absolute value of the negative polarity sensitivity, for example, because ozone generation in the apparatus is extremely small.

また、本発明の単層型電子写真感光体において、ホール輸送剤として、一般式(1)で示される化合物を含有することが好ましい。これは、メモリー低減のためフタロシアニン系化合物含有量や膜厚を減少させることが、正帯電単層型電子写真感光体の初期感度を悪化させるため、ホール輸送能力の高い上述の化合物を使用することにより十分な初期感度を得ることができるためである。   In the single-layer electrophotographic photosensitive member of the present invention, it is preferable to contain a compound represented by the general formula (1) as a hole transport agent. This is because reducing the content of phthalocyanine compounds and the film thickness to reduce memory deteriorates the initial sensitivity of the positively charged single-layer type electrophotographic photosensitive member. This is because sufficient initial sensitivity can be obtained.

また、本発明の単層型電子写真感光体において、電子輸送剤として、一般式(2)、(3)、(4)または(5)で示される化合物を、少なくとも1種以上含有することが好ましい。これは、電子輸送能力の高い上述の化合物を使用することにより、十分な初期感度が得られるとともに、メモリー低減に非常に効果的なためである。   The single-layer electrophotographic photosensitive member of the present invention may contain at least one compound represented by the general formula (2), (3), (4) or (5) as an electron transport agent. preferable. This is because the use of the above-described compound having a high electron transporting capability provides a sufficient initial sensitivity and is very effective in reducing memory.

[第1の実施形態]
第1の実施形態は、除電工程を有さない反転現像式デジタル画像形成装置において、プラス極性に帯電させて用いる単層型電子写真感光体であって、導電性基体上に感光層を形成し、感光層が電荷発生剤としてのフタロシアニン系化合物、及びホール輸送剤、電子輸送剤をバインダー樹脂中に含有し、フタロシアニン系化合物の含有量がバインダー樹脂重量に対して0.1〜4wt%であり、感光層の膜厚が10〜35μmであって、且つ、帯電電位を800Vに設定し、露光波長780nm、露光エネルギー1.0μJ/cm 2 の条件で、500msec経過後に測定したプラス極性とマイナス極性の感度の絶対値差が312V以下であるとともに、プラス極性感度の絶対値が、マイナス極性感度の絶対値より小さい単層型電子写真感光体である。
本発明の単層型電子写真感光体に用いられる種々の材料について詳細に説明する。
[First Embodiment]
The first embodiment is a single-layer electrophotographic photosensitive member that is used by being charged with a positive polarity in a reversal development type digital image forming apparatus that does not have a static elimination step, and a photosensitive layer is formed on a conductive substrate. The photosensitive layer contains a phthalocyanine compound as a charge generator, a hole transport agent, and an electron transport agent in a binder resin, and the content of the phthalocyanine compound is 0.1 to 4 wt% with respect to the binder resin weight. The positive polarity and the negative polarity measured after 500 msec have elapsed under the conditions that the photosensitive layer thickness is 10 to 35 μm, the charging potential is set to 800 V, the exposure wavelength is 780 nm, and the exposure energy is 1.0 μJ / cm 2. In the single-layer type electrophotographic photosensitive member, the absolute value difference of the sensitivity is 312 V or less and the absolute value of the positive polarity sensitivity is smaller than the absolute value of the negative polarity sensitivity. That.
Various materials used for the single-layer electrophotographic photosensitive member of the present invention will be described in detail.

<電荷発生剤>
デジタル画像形成装置において、レーザを光源とする場合、小型・安価・簡便さ等の点から、多くは半導体レーザ、LEDが使用される。従って、少なくとも700〜850nmの波長領域に感度を有する有機感光体が必要である。かかる要求を満たす、有機感光体に使用される電荷発生剤として、例えば、多環キノン化合物、ピリリウム化合物、スクエアリウム化合物、フタロシアニン系化合物、アゾ化合物等が提案または実用化されているが、本発明の画像形成方法において使用される単層型電子写真感光体には、種々のフタロシアニン系化合物が使用される。
<Charge generator>
In a digital image forming apparatus, when a laser is used as a light source, semiconductor lasers and LEDs are often used from the viewpoints of small size, low cost, and simplicity. Therefore, an organic photoreceptor having sensitivity in a wavelength region of at least 700 to 850 nm is necessary. As charge generators used in organic photoreceptors that satisfy such requirements, for example, polycyclic quinone compounds, pyrylium compounds, squalium compounds, phthalocyanine compounds, azo compounds and the like have been proposed or put into practical use. Various phthalocyanine compounds are used for the single-layer electrophotographic photoreceptor used in the image forming method.

一般的にフタロシアニン系化合物には、中心金属を有さないメタルフリーフタロシアニン(CGM−1)と、近年研究開発が活発に行われているチタニルフタロシアニン(CGM−2)、及び、アルミニウムフタロシアニン、バナジウムフタロシアニン、カドミウムフタロシアニン、アンチモンフタロシアニン、クロムフタロシアニン、銅4−フタロシアニン、ゲルマニウムフタロシアニン、鉄フタロシアニン、クロロアルミニウムフタロシアニン、クロロインジウムフタロシアニン、クロロガリウムフタロシアニン、マグネシウムフタロシアニン、ジアルキルフタロシアニン、テトラメチルフタロシアニン、テトラフェニルフタロシアニン等の中心金属を有する金属フタロシアニンとがあり、またα型、β型、γ型、δ型、ε型、σ型、x型、τ型等の結晶型のものがある。   In general, phthalocyanine compounds include metal-free phthalocyanine (CGM-1) having no central metal, titanyl phthalocyanine (CGM-2), which has been actively researched and developed in recent years, and aluminum phthalocyanine and vanadium phthalocyanine. Central metals such as cadmium phthalocyanine, antimony phthalocyanine, chromium phthalocyanine, copper 4-phthalocyanine, germanium phthalocyanine, iron phthalocyanine, chloroaluminum phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalocyanine, magnesium phthalocyanine, dialkyl phthalocyanine, tetramethyl phthalocyanine, tetraphenyl phthalocyanine Metal phthalocyanines having α-type, β-type, γ-type, δ-type, ε-type, σ-type, x-type, τ There is a thing of the crystal type and the like.

<CGM−1>

Figure 0003748452
<CGM-1>
Figure 0003748452

<CGM−2>

Figure 0003748452
<CGM-2>
Figure 0003748452

また、本発明の画像形成方法において使用される単層型電子写真感光体には、フタロシアニン系化合物として、メタルフリーフタロシアニン、またはチタニルフタロシアニンが好適に使用される。また、フタロシアニン系化合物は、前述のようにバインダー樹脂重量に対して0.1〜4wt%含有することが好ましい。   In addition, metal-free phthalocyanine or titanyl phthalocyanine is preferably used as the phthalocyanine compound in the single-layer electrophotographic photosensitive member used in the image forming method of the present invention. Moreover, it is preferable to contain 0.1-4 wt% of phthalocyanine type compounds with respect to the binder resin weight as mentioned above.

<ホール輸送剤>
また、本発明の単層型電子写真感光体に用いられるホール輸送剤としては、特に一般式(1)で示されるスチルベン系化合物が好適に使用される。
<Hole transport agent>
As the hole transporting agent used in the single layer type electrophotographic photosensitive member of the present invention, a stilbene compound represented by the general formula (1) is particularly preferably used.

また、ホール輸送剤として、該スチルベン系化合物を使用する場合、単独、または少なくとも1種以上含有すればよい。すなわち該スチルベン系化合物と共に、種々のホール輸送剤を含有していてもよい。   Moreover, when using this stilbene type compound as a hole transport agent, what is necessary is just to contain individually or at least 1 sort (s) or more. That is, various hole transport agents may be contained together with the stilbene compound.

また、種々のホール輸送剤としては、例えば2,5−ジ(4−メチルアミノフェニル)−1,3,4−オキサジアゾール等のオキサジアゾール系の化合物、9−4(−ジエチルアミノスチリル)アントラセン等のスチリル系化合物、ポリビニルカルバゾール等のカルバゾール系化合物、有機ポリシラン化合物、1−フェニル−3(p−ジメチルアミノフェニル)ピラゾリン等のピラゾリン系化合物、ヒドラゾン系化合物、トリフェニルアミン系化合物、インドール系化合物、オキサゾール系化合物、イソオキサゾール系化合物、チアゾール系化合物、チアジアゾール系化合物、イミダゾール系化合物、ピラゾール系化合物、トリアゾール系化合物等の含窒素環式化合物等があげられる。   Examples of various hole transport agents include oxadiazole compounds such as 2,5-di (4-methylaminophenyl) -1,3,4-oxadiazole, and 9-4 (-diethylaminostyryl). Styryl compounds such as anthracene, carbazole compounds such as polyvinyl carbazole, organic polysilane compounds, pyrazoline compounds such as 1-phenyl-3 (p-dimethylaminophenyl) pyrazoline, hydrazone compounds, triphenylamine compounds, indole compounds Examples thereof include nitrogen-containing cyclic compounds such as compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, and triazole compounds.

また、ホール輸送剤の含有量は、バインダー樹脂重量に対して5〜500wt%、更には25〜200wt%が好ましい。   Further, the content of the hole transport agent is preferably 5 to 500 wt%, more preferably 25 to 200 wt%, based on the weight of the binder resin.

<電子輸送剤>
また、本発明の単層型電子写真感光体に用いられる電子輸送剤としては、特に一般式(2)、(3)、(4)または(5)で示されるキノン系化合物が好適に使用される。
<Electron transport agent>
In addition, as the electron transfer agent used in the single-layer electrophotographic photosensitive member of the present invention, a quinone compound represented by the general formula (2), (3), (4) or (5) is particularly preferably used. The

また、電子輸送剤として、該キノン系化合物を使用する場合、単独、または少なくとも1種以上含有すればよい。すなわち該キノン系化合物と共に、種々の電子輸送剤を含有していてもよい。   Moreover, when using this quinone type compound as an electron transport agent, what is necessary is just to contain individually or at least 1 sort (s) or more. That is, various electron transport agents may be contained together with the quinone compound.

また、種々の電子輸送剤としては、例えばピレン系化合物、カルバゾール系化合物、ヒドラゾン系化合物、N,N−ジアルキルアニリン系化合物、ジフェニルアミン系化合物、トリフェニルアミン系化合物、トリフェニルメタン系化合物、テトラシアノエチル、テトラシアノキノジメタン、クロルアニル、ブロモアニル、2,4,7−トリニトロ−9−フルオレノン、2,4,5,7−テトラニトロ−9−フルオレノン、2,4,7−トリニトロ−9−ジシアノメチレンフルオレノン、2,4,5,7−テトラニトロキサントン、2,4,8−トリニトロチオキサントン等の電子吸引性物質、あるいはこれらの電子吸引性物質を高分子化したもの等があげられる。   Examples of various electron transfer agents include pyrene compounds, carbazole compounds, hydrazone compounds, N, N-dialkylaniline compounds, diphenylamine compounds, triphenylamine compounds, triphenylmethane compounds, tetracyanoethyl. Tetracyanoquinodimethane, chloroanil, bromoanil, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,7-trinitro-9-dicyanomethylenefluorenone Examples thereof include electron-withdrawing substances such as 2,4,5,7-tetranitroxanthone and 2,4,8-trinitrothioxanthone, or polymers obtained by polymerizing these electron-withdrawing substances.

また、電子輸送剤の含有量は、バインダー樹脂重量に対して5〜100wt%、更には10〜80wt%が好ましい。   Further, the content of the electron transport agent is preferably 5 to 100 wt%, more preferably 10 to 80 wt%, based on the weight of the binder resin.

<バインダー樹脂>
また、上述の各成分を分散させるためのバインダー樹脂は、従来から感光層に使用されている種々の樹脂を使用することができる。
<Binder resin>
In addition, as the binder resin for dispersing the above-described components, various resins conventionally used in the photosensitive layer can be used.

例えば、スチレン−ブタジエン共重合体、スチレン−アクリロニトリル共重合体、スチレン−マレイン酸共重合体、アクリル共重合体、スチレン−アクリル酸共重合体、ポリエチレン、エチレン−酢酸ビニル共重合体、塩素化ポリエチレン、ポリ塩化ビニル、ポリプロピレン、アイオノマー、塩化ビニル−酢酸ビニル共重合体、ポリエステル、アルキド樹脂、ポリアミド、ポリウレタン、ポリカーボネート、ポリアリレート、ポリスルホン、ジアリルフタレート樹脂、ケトン樹脂、ポリビニルブチラール樹脂、ポリエーテル樹脂等の熱可塑性樹脂、シリコーン樹脂、エポキシ樹脂、フェノール樹脂、尿素樹脂、メラミン樹脂、その他架橋性の熱硬化性樹脂、エポキシアクリレート、ウレタン−アクリレート等の光硬化型樹脂等の樹脂が使用可能である。これらのバインダー樹脂は単独または二種類以上をブレンドして使用できる。   For example, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylic copolymer, styrene-acrylic acid copolymer, polyethylene, ethylene-vinyl acetate copolymer, chlorinated polyethylene , Polyvinyl chloride, polypropylene, ionomer, vinyl chloride-vinyl acetate copolymer, polyester, alkyd resin, polyamide, polyurethane, polycarbonate, polyarylate, polysulfone, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, etc. Resin such as thermoplastic resin, silicone resin, epoxy resin, phenol resin, urea resin, melamine resin, other cross-linkable thermosetting resin, epoxy acrylate, urethane acrylate, etc. It is. These binder resins can be used alone or in combination of two or more.

また、特に好適な樹脂は、帝人化成(株)社製パンライト、三菱瓦斯化学(株)社製PCZ等のビスフェノールZ型モノマーとホスゲンとから誘導されるビスフェノールZ型ポリカーボネートである。   Particularly suitable resins are bisphenol Z-type polycarbonates derived from bisphenol Z-type monomers and phosgene such as Panlite manufactured by Teijin Chemicals Ltd. and PCZ manufactured by Mitsubishi Gas Chemical Company, Inc.

また、上述の例に挙げたバインダー樹脂の重量平均分子量は5,000〜200,000、更には15,000〜100,000が好ましい。   The weight average molecular weight of the binder resin mentioned in the above example is preferably 5,000 to 200,000, more preferably 15,000 to 100,000.

また、本発明の単層型電子写真感光体には、上述の各成分のほかに、電子写真特性に悪影響を与えない範囲で、従来公知の種々の添加剤、例えば、酸化防止剤、ラジカル補足剤、一重項クエンチャー、紫外線吸収剤等の劣化防止剤、軟化剤、可塑剤、表面改質剤、増量剤、増粘剤、分散安定剤、ワックス、アクセプター、ドナー等を配合することができる。また、感光層の感度を向上させるために、例えば、テルフェニル、ハロナフトナフトキノン類、アセナフチレン等の公知の増感剤を電荷発生剤と併用してもよい。   In addition to the above-described components, the single-layer type electrophotographic photosensitive member of the present invention includes various conventionally known additives such as antioxidants and radical scavengers as long as the electrophotographic characteristics are not adversely affected. Agent, singlet quencher, anti-degradation agent such as UV absorber, softener, plasticizer, surface modifier, extender, thickener, dispersion stabilizer, wax, acceptor, donor, etc. . In order to improve the sensitivity of the photosensitive layer, for example, a known sensitizer such as terphenyl, halonaphthoquinone, and acenaphthylene may be used in combination with the charge generator.

また、本発明の単層型電子写真感光体においては、導電性基体と感光層との間に、感光体の特性を阻害しない範囲でバリア層が形成されていてもよい。   In the single-layer electrophotographic photosensitive member of the present invention, a barrier layer may be formed between the conductive substrate and the photosensitive layer as long as the characteristics of the photosensitive member are not impaired.

また、本発明の単層型電子写真感光体は、導電性基体上に単一の感光層を設けたものである。この感光層は、電荷発生剤、ホール輸送剤、電子輸送剤、バインダー樹脂等を適当な溶媒に溶解または分散させ、得られた塗布液を導電性基体上に塗布し、乾燥させることで形成される。   The single-layer type electrophotographic photosensitive member of the present invention has a single photosensitive layer provided on a conductive substrate. This photosensitive layer is formed by dissolving or dispersing a charge generator, a hole transport agent, an electron transport agent, a binder resin, etc. in an appropriate solvent, coating the resulting coating solution on a conductive substrate, and drying. The

また、上述の感光層が形成される導電性基体としては、導電性を有する種々の材料を使用することができ、例えば、鉄、アルミニウム、銅、スズ、白金、銀、バナジウム、モリブデン、クロム、カドミウム、チタン、ニッケル、パラジウム、インジウム、ステンレス鋼、真鍮等の金属単体や、上記金属が蒸着またはラミネートされたプラスチック材料、ヨウ化アルミニウム、酸化スズ、酸化インジウム等で被覆されたガラス等があげられる。   In addition, as the conductive substrate on which the above-described photosensitive layer is formed, various conductive materials can be used. For example, iron, aluminum, copper, tin, platinum, silver, vanadium, molybdenum, chromium, Examples thereof include simple metals such as cadmium, titanium, nickel, palladium, indium, stainless steel, and brass, plastic materials on which the above metals are deposited or laminated, glass coated with aluminum iodide, tin oxide, indium oxide, and the like. .

また、導電性基体の形状は、使用する画像形成装置の構造に合わせて、シート状、ドラム状等のいずれであってもよく、基体自体が導電性を有するか、あるいは基体の表面が導電性を有していればよい。また、導電性基体は、使用に際して十分な機械的強度を有するものが好ましい。   Further, the shape of the conductive substrate may be any of a sheet shape, a drum shape, or the like in accordance with the structure of the image forming apparatus to be used. The substrate itself is conductive or the surface of the substrate is conductive. As long as it has. The conductive substrate preferably has sufficient mechanical strength when used.

また、上述の感光層を塗布の方法により形成する場合には、先に例示したホール輸送剤、電荷発生剤、電子受容体、結着樹脂等を適当な溶剤とともに、公知の方法、例えば、ロールミル、ボールミル、アトライタ、ペイントシェーカー、超音波分散機等を用いて分散混合して分散液を調整し、これを公知の手段により塗布して乾燥させればよい。   When the photosensitive layer is formed by a coating method, the hole transporting agent, charge generating agent, electron acceptor, binder resin, and the like exemplified above together with an appropriate solvent are combined with a known method such as a roll mill. A dispersion is prepared by dispersing and mixing using a ball mill, an attritor, a paint shaker, an ultrasonic disperser or the like, and this is applied by a known means and dried.

また、上述の分散液を作製するための溶剤としては、種々の有機溶剤が使用可能であり、例えば、メタノール、エタノール、イソプロパノール、ブタノール等のアルコール類、n−ヘキサン、オクタン、シクロヘキサン等の脂肪族系炭化水素、ベンゼン、トルエン、キシレン等の芳香族系炭化水素、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素、クロロベンゼン等のハロゲン化炭化水素、ジメチルエーテル、ジエチルエーテル、テトラヒドロフラン、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル等のエーテル類、アセトン、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、酢酸メチル等のエステル類、ジメチルホルムアルデヒド、ジメチルホルムアミド、ジメチルスルホキシド等があげられる。これらの溶剤は単独で、または2種以上混合して用いられる。   Moreover, as a solvent for producing the above-mentioned dispersion liquid, various organic solvents can be used, for example, alcohols such as methanol, ethanol, isopropanol and butanol, and aliphatics such as n-hexane, octane and cyclohexane. Hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. Ethers, acetone, methyl ethyl ketone, cyclohexanone and other ketones, ethyl acetate, methyl acetate and other esters, dimethylformaldehyde, dimethylformamide, dimethylsulfone Examples include xoxide. These solvents are used alone or in combination of two or more.

更に、ホール輸送剤、電荷発生剤、電子受容体の分散性、感光層表面の平滑性を良くするために、界面活性剤、レベリング剤等を使用してもよい。   Further, a surfactant, a leveling agent or the like may be used in order to improve the dispersibility of the hole transporting agent, charge generating agent, electron acceptor, and surface of the photosensitive layer.

以下、実施例、比較例をあげて本発明を説明する。なお、以下の実施形態は本発明を具体化した一例であって、本発明の技術的範囲を限定するものではない。   Hereinafter, the present invention will be described with reference to examples and comparative examples. The following embodiment is an example embodying the present invention, and does not limit the technical scope of the present invention.

[実施例1〜7、参考例8
電荷発生剤としてX型無金属フタロシアニン(CGM−1)2.0重量部、一般式(1)で示されるホール輸送剤(HTM−1)70重量部、一般式(2)、(3)、(4)、(5)で示される電子輸送剤(ETM−1〜ETM−8)40重量部、及びバインダー樹脂として重量平均分子量30,000のbis−Z型ポリカーボネート樹脂100重量部、及びテトラヒドロフラン800重量部を、ボールミル中で24時間分散あるいは溶解させ、単層型感光層用塗布液を調合した。そして、この塗布液を、支持体としてのアルミニウム素管上にディップコート法にて塗布し、125℃、30分間の熱風乾燥を行い、膜厚20μmの単一感光層を有する単層型感光体を作製した。
[Examples 1-7 , Reference Example 8 ]
As a charge generating agent, 2.0 parts by weight of X-type metal-free phthalocyanine (CGM-1), 70 parts by weight of a hole transport agent (HTM-1) represented by the general formula (1), general formulas (2) and (3), (4), 40 parts by weight of the electron transporting agent (ETM-1 to ETM-8) shown in (5), 100 parts by weight of a bis-Z type polycarbonate resin having a weight average molecular weight of 30,000 as a binder resin, and tetrahydrofuran 800 Weight parts were dispersed or dissolved in a ball mill for 24 hours to prepare a single-layer photosensitive layer coating solution. Then, this coating solution is applied on an aluminum base tube as a support by a dip coating method, followed by hot air drying at 125 ° C. for 30 minutes, and a single-layer photoreceptor having a single photosensitive layer with a thickness of 20 μm. Was made.

[比較例1〜3]
電子輸送剤としてETM−9〜ETM−11を使用した以外は実施例1〜7と同様に単層型感光体を作製した。
[Comparative Examples 1-3]
Single layer type photoreceptors were prepared in the same manner as in Examples 1 to 7 except that ETM-9 to ETM-11 were used as the electron transporting agent.

<HTM−1>

Figure 0003748452
<HTM-1>
Figure 0003748452

<ETM−1>

Figure 0003748452
<ETM-1>
Figure 0003748452

<ETM−2>

Figure 0003748452
<ETM-2>
Figure 0003748452

<ETM−3>

Figure 0003748452
<ETM-3>
Figure 0003748452

<ETM−4>

Figure 0003748452
<ETM-4>
Figure 0003748452

<ETM−5>

Figure 0003748452
<ETM-5>
Figure 0003748452

<ETM−6>

Figure 0003748452
<ETM-6>
Figure 0003748452

<ETM−7>

Figure 0003748452
<ETM-7>
Figure 0003748452

<ETM−8>

Figure 0003748452
<ETM-8>
Figure 0003748452

<ETM−9>

Figure 0003748452
<ETM-9>
Figure 0003748452

<ETM−10>

Figure 0003748452
<ETM-10>
Figure 0003748452

<ETM−11>

Figure 0003748452
<ETM-11>
Figure 0003748452

[実施例9〜15、参考例16
電荷発生剤としてチタニルフタロシアニン(CGM−2)を使用した以外は、実施例1〜7、及び参考例8と同様に単層型感光体を作製した。
[Examples 9 to 15, Reference Example 16 ]
Single layer type photoreceptors were prepared in the same manner as in Examples 1 to 7 and Reference Example 8 except that titanyl phthalocyanine (CGM-2) was used as the charge generating agent.

[比較例4〜6]
電荷発生剤としてチタニルフタロシアニン(CGM−2)を使用した以外は、比較例1〜3と同様に単層型感光体を作製した。
[Comparative Examples 4 to 6]
Single layer type photoreceptors were prepared in the same manner as in Comparative Examples 1 to 3, except that titanyl phthalocyanine (CGM-2) was used as the charge generator.

[比較例7]
電荷発生剤としてX型無金属フタロシアニン(CGM−1)を4.5重量部含有させた以外は、実施例1と同様に単層型感光体を作製した。
[Comparative Example 7]
A single-layer photoreceptor was prepared in the same manner as in Example 1 except that 4.5 parts by weight of X-type metal-free phthalocyanine (CGM-1) was contained as a charge generator.

[比較例8]
膜厚40μmの感光層を得た以外は、実施例1と同様に単層型感光体を作製した。
[Comparative Example 8]
A single layer type photoreceptor was prepared in the same manner as in Example 1 except that a photosensitive layer having a thickness of 40 μm was obtained.

[比較例9]
電荷発生剤としてチタニルフタロシアニン(CGM−2)を4.5重量部含有させた以外は、実施例9と同様に単層型感光体を作製した。
[Comparative Example 9]
A monolayer type photoreceptor was produced in the same manner as in Example 9 except that 4.5 parts by weight of titanyl phthalocyanine (CGM-2) was contained as a charge generating agent.

[比較例10]
膜厚40μmの感光層を得た以外は、実施例9と同様に単層型感光体を作製した。
[Comparative Example 10]
A single-layer type photoreceptor was produced in the same manner as in Example 9 except that a photosensitive layer having a thickness of 40 μm was obtained.

上記各実施例、比較例の単層型電子写真感光体について、下記の各特性を評価した。評価結果を表1、2に示した。また、これらのデータのうち、転写メモリー電位・露光メモリー電位と、プラス極性感度とマイナス極性感度の絶対値差との関係を図1に示した。   The following characteristics were evaluated for the single-layer electrophotographic photoreceptors of the above Examples and Comparative Examples. The evaluation results are shown in Tables 1 and 2. Of these data, the relationship between the transfer memory potential / exposure memory potential and the absolute value difference between the positive polarity sensitivity and the negative polarity sensitivity is shown in FIG.

<プラス極性感度評価>
ジェンテック(GENTEC)社製のドラム感度試験機(商品名ジェンテックシンシア30M)を用いて、各実施例、比較例の電子写真感光体に印加電圧を加えて、その表面を+800Vに帯電させた。次に、上記試験機の露光光源であるハロゲンランプの白色光からバンドパスフィルターを用いて取り出した波長780nmの単色光(半値幅20nm,光強度20μW)を、上記帯電状態の感光体の表面に露光(露光時間100msec)した(露光エネルギーは1.0μJ/cm2)。そして、露光開始時点から500msec経過した時点での表面電位を露光後電位VLP(V)として測定した。すなわち、露光後電位が小さいほど感光体は高感度である。
<Positive polarity sensitivity evaluation>
An applied voltage was applied to the electrophotographic photosensitive member of each example and comparative example using a drum sensitivity tester (product name Gentec Cynthia 30M) manufactured by GENTEC, and the surface was charged to + 800V. . Next, monochromatic light having a wavelength of 780 nm (half-value width 20 nm, light intensity 20 μW) extracted from the white light of a halogen lamp, which is an exposure light source of the testing machine, using a band-pass filter is applied to the surface of the charged photoreceptor. Exposure (exposure time 100 msec) was performed (exposure energy was 1.0 μJ / cm 2 ). Then, the surface potential after 500 msec from the exposure start time was measured as a post-exposure potential V LP (V). That is, the smaller the post-exposure potential, the higher the sensitivity of the photoreceptor.

<マイナス極性感度評価>
ジェンテック(GENTEC)社製のドラム感度試験機(商品名ジェンテックシンシア30M)を用いて、各実施例、比較例の電子写真感光体に印加電圧を加えて、その表面を−800Vに帯電させた以外は、上述の<プラス極性感度評価>と同様に、露光開始時点から500msec経過した時点での表面電位を露光後電位VLN(V)として測定した。
<Negative polarity sensitivity evaluation>
Using a drum sensitivity testing machine (product name Gentec Cynthia 30M) manufactured by GENTEC, an applied voltage is applied to the electrophotographic photosensitive member of each example and comparative example, and the surface is charged to -800V. Except for the above, the surface potential at the time when 500 msec had elapsed from the start of exposure was measured as the post-exposure potential V LN (V) in the same manner as in the above <Positive polarity sensitivity evaluation>.

<転写メモリー電位評価>
除電ランプを取除いた京セラミタ(株)社製マルチファンクションプリンタAntico40に、各実施例、比較例の電子写真感光体を搭載し、転写バイアスを印加しない時の表面電位、及び転写バイアス印加時の次帯電工程後の表面電位を測定し、その差異を転写メモリー電位とした。転写メモリー電位については、転写メモリー画像の発生しない45V以下を可、45Vより大きい場合を不可とした。
<Evaluation of transfer memory potential>
The multi-function printer Antico40 manufactured by Kyocera Mita Co., Ltd., from which the static elimination lamp has been removed, is mounted with the electrophotographic photosensitive member of each example and comparative example, and the surface potential when no transfer bias is applied, and when the transfer bias is applied. The surface potential after the next charging step was measured, and the difference was taken as the transfer memory potential. As for the transfer memory potential, 45 V or less at which no transfer memory image was generated was allowed, and when it was greater than 45 V, it was not allowed.

<露光メモリー電位評価>
除電ランプを取除いた京セラミタ(株)社製マルチファンクションプリンタAntico40に、各実施例、比較例の電子写真感光体を搭載し、未露光時の表面電位、及び露光時の次帯電工程後の表面電位を測定し、その差異を露光メモリー電位とした。露光メモリー電位については、転写メモリー電位と同様、露光メモリー画像の発生しない45V以下を可、45Vより大きい場合を不可とした。
<Evaluation of exposure memory potential>
The multi-function printer Antico40 manufactured by Kyocera Mita Co., Ltd., from which the static elimination lamp has been removed, is mounted with the electrophotographic photosensitive member of each example and comparative example, and the surface potential at the time of unexposed and after the next charging step at the time of exposure. The surface potential was measured and the difference was taken as the exposure memory potential. As for the exposure memory potential, 45 V or less at which no exposure memory image is generated is allowed, and when it is higher than 45 V, the transfer memory potential is not allowed.

<転写メモリー画像評価>
除電ランプを取除いた京セラミタ(株)社製マルチファンクションプリンタAntico40に、各実施例、比較例の電子写真感光体を搭載し、印写試験を実施し、転写メモリー画像が発生しているか否かを目視により判断した。転写メモリー画像とは、図6に示すように、前面グレー(マンセル値:N=6.5)原稿を使用し印写試験を実施した場合、転写バイアスが印加された部分の感光体表面電位の低下により、ドラム長手方向に黒横帯が発生した画像を示す。
<Evaluation of transfer memory image>
Whether or not a transfer memory image is generated by mounting the electrophotographic photosensitive member of each example and comparative example on the multi-function printer Antico40 manufactured by Kyocera Mita Co., Ltd., from which the static elimination lamp has been removed, and performing a printing test. It was judged visually. As shown in FIG. 6, the transfer memory image means that the surface potential of the photosensitive member at the portion to which the transfer bias is applied when a printing test is performed using a front gray (Munsell value: N = 6.5) document. An image in which a black horizontal band is generated in the drum longitudinal direction due to the decrease is shown.

<露光メモリー画像評価>
除電ランプを取除いた京セラミタ(株)社製マルチファンクションプリンタAntico40に、各実施例、比較例の電子写真感光体を搭載し、印写試験を実施し、露光メモリー画像が発生しているか否かを目視により判断した。露光メモリー画像とは、図7に示すような原稿を使用し印写試験を実施した場合、強い露光部分(黒ベタ部)の感光体表面電位の低下により、露光部分のゴースト画像がグレー部に発生した画像を示す。
<Exposure memory image evaluation>
Whether or not an exposure memory image is generated by mounting the electrophotographic photosensitive member of each example and comparative example on the multifunction printer Antico40 manufactured by Kyocera Mita Co., Ltd., from which the static elimination lamp has been removed, and performing a printing test. It was judged visually. The exposure memory image means that when a printing test is carried out using a document as shown in FIG. 7, the ghost image of the exposed portion is changed to a gray portion due to a decrease in the photosensitive member surface potential of the strongly exposed portion (solid black portion). The generated image is shown.

Figure 0003748452
Figure 0003748452

Figure 0003748452
Figure 0003748452

表1、2、図1より、プラス極性とマイナス極性の感度の絶対値差が500V以下である場合、転写メモリー電位及び露光メモリー電位の両方が45V以下となり、メモリー画像が発生しないことが明らかとなった。   From Tables 1 and 2 and FIG. 1, it is clear that when the absolute value difference between the positive and negative polarities is 500 V or less, both the transfer memory potential and the exposure memory potential are 45 V or less, and no memory image is generated. became.

図2には、実施例6で作製した単層型電子写真感光体のX型無金属フタロシアニン添加量と、転写メモリー電位・露光メモリー電位との関係を、図3には、感光体のX型無金属フタロシアニン添加量と、プラス極性とマイナス極性の感度の絶対値差との関係を示した。   FIG. 2 shows the relationship between the X-type metal-free phthalocyanine addition amount of the single-layer electrophotographic photosensitive member produced in Example 6 and the transfer memory potential / exposure memory potential, and FIG. 3 shows the X-type photosensitive member. The relationship between the addition amount of metal-free phthalocyanine and the absolute difference in sensitivity between positive polarity and negative polarity was shown.

図2、3より、X型無金属フタロシアニン添加量がバインダー樹脂重量に対して4wt%以下の場合、プラス極性とマイナス極性の感度の絶対値差が500V以下、転写メモリー電位及び露光メモリー電位の両方が45V以下となった。   2 and 3, when the X-type metal-free phthalocyanine addition amount is 4 wt% or less with respect to the binder resin weight, the absolute value difference between the positive polarity and the negative polarity sensitivity is 500 V or less, both the transfer memory potential and the exposure memory potential. Became 45V or less.

図4には、実施例6に準じて作製した単層型電子写真感光体の感光層膜厚と、転写メモリー電位・露光メモリー電位との関係を、図5には感光体の感光層膜厚と、プラス極性とマイナス極性の感度の絶対値差との関係を示した。   4 shows the relationship between the photosensitive layer thickness of the single-layer electrophotographic photosensitive member produced according to Example 6 and the transfer memory potential / exposure memory potential, and FIG. 5 shows the photosensitive layer thickness of the photosensitive member. And the relationship between the positive and negative polarity sensitivity difference.

図4、5より、感光層膜厚が35μm以下の場合、プラス極性とマイナス極性の感度の絶対値差が500V以下、転写メモリー電位及び露光メモリー電位の両方が45V以下となった。   4 and 5, when the film thickness of the photosensitive layer is 35 μm or less, the absolute value difference between the positive polarity and the negative polarity sensitivity is 500 V or less, and both the transfer memory potential and the exposure memory potential are 45 V or less.

各実施例、比較例の単層型電子写真感光体の転写メモリー電位・露光メモリー電位と、プラス極性とマイナス極性の感度の絶対値差との関係を示すグラフである。6 is a graph showing the relationship between the transfer memory potential / exposure memory potential of single layer type electrophotographic photosensitive member of each example and comparative example, and the absolute value difference in sensitivity between positive polarity and negative polarity. 単層型電子写真感光体のX型無金属フタロシアニン添加量と、転写メモリー電位・露光メモリー電位との関係を示すグラフである。6 is a graph showing the relationship between the addition amount of X-type metal-free phthalocyanine and the transfer memory potential / exposure memory potential of a single layer type electrophotographic photosensitive member. 単層型電子写真感光体のX型無金属フタロシアニン添加量と、プラス極性とマイナス極性の感度の絶対値差との関係を示すグラフである。It is a graph which shows the relationship between the addition amount of X-type metal-free phthalocyanine of a single layer type electrophotographic photosensitive member, and the absolute value difference of the sensitivity of positive polarity and negative polarity. 単層型電子写真感光体の感光層膜厚と、転写メモリー電位・露光メモリー電位との関係を示すグラフである。6 is a graph showing the relationship between the photosensitive layer thickness of a single-layer type electrophotographic photosensitive member and the transfer memory potential and exposure memory potential. 単層型電子写真感光体の感光層膜厚と、プラス極性とマイナス極性の感度の絶対値差との関係を示すグラフである。It is a graph which shows the relationship between the photosensitive layer film thickness of a single layer type electrophotographic photosensitive member, and the absolute value difference of the sensitivity of plus polarity and minus polarity. 転写メモリー画像評価用原稿と転写メモリー画像を示す図である。It is a figure which shows the original for transfer memory image evaluation, and a transfer memory image. 露光メモリー画像評価用原稿と露光メモリー画像を示す図である。It is a figure which shows the original for exposure memory image evaluation, and an exposure memory image.

Claims (6)

除電工程を有さない反転現像式デジタル画像形成装置において、プラス極性に帯電させて用いる単層型電子写真感光体であって、  In a reversal development type digital image forming apparatus having no charge eliminating step, a single layer type electrophotographic photosensitive member used by being charged to a positive polarity,
導電性基体上に感光層を形成し、前記感光層が電荷発生剤としてのフタロシアニン系化合物、及びホール輸送剤、電子輸送剤をバインダー樹脂中に含有し、前記フタロシアニン系化合物の含有量がバインダー樹脂重量に対して0.1〜4wt%であり、前記感光層の膜厚が10〜35μmであって、且つ、帯電電位を800Vに設定し、露光波長780nm、露光エネルギー1.0μJ/cm  A photosensitive layer is formed on a conductive substrate, and the photosensitive layer contains a phthalocyanine compound as a charge generator, a hole transport agent, and an electron transport agent in a binder resin, and the content of the phthalocyanine compound is a binder resin. The photosensitive layer thickness is 10 to 35 μm, the charging potential is set to 800 V, the exposure wavelength is 780 nm, the exposure energy is 1.0 μJ / cm. 22 の条件で、500msec経過後に測定したプラス極性とマイナス極性の感度の絶対値差が312V以下であるとともに、プラス極性感度の絶対値が、マイナス極性感度の絶対値より小さいことを特徴とする単層型電子写真感光体。The absolute value difference between the positive polarity and negative polarity sensitivity measured after elapse of 500 msec is 312 V or less, and the absolute value of the positive polarity sensitivity is smaller than the absolute value of the negative polarity sensitivity. Type electrophotographic photoreceptor.
前記単層型電子写真感光体におけるフタロシアニン系化合物として、中心金属を有さないメタルフリーフタロシアニン、またはチタニルフタロシアニンを含有することを特徴とする請求項1に記載の単層型電子写真感光体。 2. The monolayer electrophotographic photoreceptor according to claim 1, wherein the phthalocyanine compound in the monolayer electrophotographic photoreceptor contains metal-free phthalocyanine having no central metal or titanyl phthalocyanine . 前記単層型電子写真感光体におけるホール輸送剤として、一般式(1)で示される化合物を含有することを特徴とする請求項1または2に記載の単層型電子写真感光体。
一般式(1):
Figure 0003748452

(一般式(1)中、R1およびR3は同一または異なって、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよい、アラルキル基またはアルコキシ基を示し、R2およびR4は同一または異なって、水素原子、置換基を有してもよい、アルキル基またはアルコキシ基を示す。但し、R2およびR4の置換位置がパラ位の場合、R2およびR4は水素原子である。)
3. The single-layer electrophotographic photosensitive member according to claim 1, comprising a compound represented by the general formula (1) as a hole transport agent in the single-layer electrophotographic photosensitive member.
General formula (1):
Figure 0003748452

(In the general formula (1), R 1 and R 3 are the same or different, and may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An aralkyl group or an alkoxy group, wherein R 2 and R 4 are the same or different and each represents a hydrogen atom, an alkyl group or an alkoxy group which may have a substituent, provided that the substitution positions of R 2 and R 4 are In the para position, R 2 and R 4 are hydrogen atoms.)
前記単層型電子写真感光体における電子輸送剤として、一般式(2)、(3)、(4)または(5)で示される化合物を、少なくとも1種以上含有することを特徴とする請求項1〜3のいずれか一項に記載の単層型電子写真感光体。
一般式(2):
Figure 0003748452

(一般式(2)中、R5はハロゲン原子、置換基を有してもよい、アルキル基またはアリール基を示し、R6は置換基を有してもよい、アルキル基またはアリール基、または基:−O−R6aを示す。R6aは、置換基を有してもよい、アルキル基またはアリール基を示す。)
一般式(3):
Figure 0003748452

(一般式(3)中、R7およびR8は同一または異なって、アルキル基、ハロゲン化アルキル基、アリール基、アラルキル基、アルコキシ基、アリールオキシ基、アラルキルオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アラルキルオキシカルボニル基またはニトロ基を示す。nは0〜3の整数を表わす。)
一般式(4):
Figure 0003748452

(一般式(4)中、R9a、R9b、R9c、およびR9dは同一または異なって、水素原子、置換基を有してもよい、アルキル基またはアリール基を示す。)
一般式(5):
Figure 0003748452

(一般式(5)中、R10およびR11は同一または異なって、アルキル基、ハロゲン化アルキル基、アリール基、アラルキル基、アルコキシ基、アリールオキシ基、アラルキルオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アラルキルオキシカルボニル基またはニトロ基を示す。nは0〜3の整数を表わす。)
The electron transport agent in the single-layer type electrophotographic photosensitive member contains at least one compound represented by the general formula (2), (3), (4) or (5). The single-layer electrophotographic photosensitive member according to any one of 1 to 3 .
General formula (2):
Figure 0003748452

(In the general formula (2), R 5 represents a halogen atom, an alkyl group or an aryl group which may have a substituent, and R 6 may have an alkyl group or an aryl group, or group: .R 6a showing a -O-R 6a may have a substituent, an alkyl group or an aryl group).
General formula (3):
Figure 0003748452

(In the general formula (3), R 7 and R 8 are the same or different and are an alkyl group, halogenated alkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group, acyl group, alkoxycarbonyl group. An aryloxycarbonyl group, an aralkyloxycarbonyl group or a nitro group, n represents an integer of 0 to 3.)
General formula (4):
Figure 0003748452

(In the general formula (4), R 9a , R 9b , R 9c and R 9d are the same or different and each represents a hydrogen atom or an alkyl group or an aryl group which may have a substituent.)
General formula (5):
Figure 0003748452

(In the general formula (5), R 10 and R 11 are the same or different and are an alkyl group, halogenated alkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group, acyl group, alkoxycarbonyl group. An aryloxycarbonyl group, an aralkyloxycarbonyl group or a nitro group, n represents an integer of 0 to 3.)
前記単層型電子写真感光体におけるバインダー樹脂として、重量平均分子量が15,000〜100,000のビスフェノールZ型ポリカーボネートを含有することを特徴とする請求項1〜4のいずれか一項に記載の単層型電子写真感光体。 5. The bisphenol Z-type polycarbonate having a weight average molecular weight of 15,000 to 100,000 is contained as a binder resin in the single-layer type electrophotographic photosensitive member. Single layer type electrophotographic photoreceptor. 前記単層型電子写真感光体における露光メモリーおよび転写メモリーを45V以下の値とすることを特徴とする請求項1〜5のいずれか一項に記載の単層型電子写真感光体。 6. The single-layer electrophotographic photosensitive member according to claim 1, wherein an exposure memory and a transfer memory in the single-layer electrophotographic photosensitive member have a value of 45 V or less .
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