JP2001242656A - Electrophotographic photoreceptor - Google Patents
Electrophotographic photoreceptorInfo
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- JP2001242656A JP2001242656A JP2000054341A JP2000054341A JP2001242656A JP 2001242656 A JP2001242656 A JP 2001242656A JP 2000054341 A JP2000054341 A JP 2000054341A JP 2000054341 A JP2000054341 A JP 2000054341A JP 2001242656 A JP2001242656 A JP 2001242656A
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Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、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の画像形
成装置に用いられる電子写真感光体と、それを用いた画
像形成方法とに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member used for an image forming apparatus such as an electrophotographic copying machine, a facsimile, a laser beam printer, and the like, and an image forming method using the same.
【0002】より詳細には、転写メモリーが非常に小さ
く、且つ、オゾン、NOx等の耐ガス性に優れた正帯電
単層型電子写真感光体と、それを用いた反転現像式デジ
タル画像形成方法に関するものである。More specifically, a positively charged single-layer type electrophotographic photoreceptor having a very small transfer memory and having excellent resistance to gases such as ozone and NOx, and a reversal developing digital image forming method using the same. It is about.
【0003】[0003]
【従来の技術】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。2. Description of the Related Art Organic photoreceptors are easier to manufacture than conventional inorganic photoreceptors, are inexpensive, and have a wide variety of photoreceptor materials such as charge transport agents, charge generators and binder resins. In recent years, it has been widely used because it has an advantage that the degree of freedom in functional design is high.
【0004】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る。The organic photoreceptor includes a single-layer type photoreceptor in which a charge transporting agent (a hole transporting agent and an electron transporting agent) is dispersed in the same photosensitive layer together with a charge generating agent, and a charge generating agent containing a charge generating agent. There is a laminated photoconductor in which a layer and a charge transport layer containing a charge transport agent are laminated.
【0005】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), forms an electrostatic latent image by exposing the image (exposure step), and develops the electrostatic latent image. The toner is developed with a bias voltage applied (developing step), the formed toner image is transferred onto a transfer sheet (transfer step), and fixed to form an image. Further, 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).
【0006】また、前記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。Image forming apparatuses utilizing the electrophotographic method include digital and analog copying machines, facsimile machines, laser beam printers, and the like. In particular, toner having the same polarity as a charging voltage applied to a photosensitive member in a charging step is used. The reversal developing method of developing by using is widely used in digital image forming apparatuses.
【0007】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。When an electrophotographic photoreceptor is used in a reversal developing digital image forming apparatus, the transfer voltage applied to the photoreceptor in the transfer step is not directly applied to the photoreceptor but via a transfer medium (paper). It is applied and is not applied when the transfer medium does not pass through the transfer process.
【0008】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、当該部分は前記感光体に転写電圧が直接
印加されるのである。However, it is very difficult to turn on and off the transfer voltage, and the front and rear ends of the transfer medium often have portions directly applied to the photosensitive member. That is, before the leading end of the transfer medium covers the transfer device, the transfer voltage starts to be applied, and the transfer voltage continues to be applied even when a part of the transfer device is exposed by the passage of the rear end of the transfer medium. In this portion, a transfer voltage is directly applied to the photosensitive member.
【0009】正帯電単層型電子写真感光体の場合、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
印加された感光体表面には負の空間電荷が残存する、い
わゆる転写メモリーが発生する。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。In the case of a positively charged single-layer type electrophotographic photosensitive member, since the polarity of the voltage applied by the transfer device is negative, a negative space charge remains on the surface of the photosensitive member to which the negative voltage is applied, so-called, Transfer memory occurs. In general, since the single-layer type photoconductor has sensitivity to both polarities, negative space charges are erased in the next neutralization step.
【0010】ところが、前記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(半減露光量が非常に大き
い)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、いわゆる転写メ
モリー画像が発生する。すなわち、転写メモリーを発生
させないようにするためには正負の感度差が少ないほど
好ましい。However, if the sensitivity of the positively charged single-layer type photoreceptor to the negative polarity is very low (the half-exposure amount is very large), the negative space charge is not sufficiently erased and the next charging step is not performed. However, even if the surface is positively charged, a potential drop is caused by the effect of space charge, and furthermore, it appears as a difference in sensitivity in the developing process, and a so-called transfer memory image occurs in which the portion becomes black in the image. That is, in order to prevent transfer memory from being generated, it is preferable that the difference in positive / negative sensitivity be as small as possible.
【0011】一方、前記正帯電単層型感光体を使用した
反転現像式デジタル画像形成装置は、一般的にオゾンの
発生は少ない。しかし、前述のように転写装置で印加さ
れる電圧の極性は負であるため、転写装置付近ではオゾ
ンの発生があり、特に大型画像形成装置においては顕著
となる。また、特に帯電装置付近ではNOxの発生が多
い。On the other hand, a reversal-developing digital image forming apparatus using the positively charged single-layer type photoreceptor generally generates less ozone. However, as described above, since the polarity of the voltage applied in the transfer device is negative, ozone is generated in the vicinity of the transfer device, and is particularly remarkable in a large-sized image forming apparatus. In particular, NOx is frequently generated near the charging device.
【0012】感光体表面が前記のオゾン、NOx等のガ
スに暴露されると、当該部分の帯電電位が低下し、画像
かぶりや黒筋の発生原因となることが知られている。It is known that when the surface of the photoreceptor is exposed to the above-mentioned gases such as ozone and NOx, the charged potential of the portion is reduced, which causes image fogging and black streaks.
【0013】[0013]
【発明が解決しようとする課題】そこで、本発明の目的
は、反転現像式デジタル画像形成装置に使用しても転写
メモリーが非常に小さく、且つ、オゾン、NOx等の耐
ガス性に優れた正帯電単層型電子写真感光体を提供する
ことである。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a reversible development type digital image forming apparatus which has a very small transfer memory and excellent resistance to gas such as ozone and NOx. An object of the present invention is to provide a charged single-layer type electrophotographic photosensitive member.
【0014】更には、本発明の正帯電単層型電子写真感
光体を使用した反転現像式デジタル画像形成装置を提供
することである。Still another object of the present invention is to provide a reversal-developing digital image forming apparatus using the positively charged single-layer type electrophotographic photosensitive member of the present invention.
【0015】[0015]
【課題を解決するための手段】本発明者らは鋭意研究の
結果、上記目的を達成するために、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、電子輸送剤として一般式(1)、
(2)または(3)で示される化合物を少なくとも1
種、及び、一般式(4)で示されるターフェニル化合物
を含有することを特徴とする正帯電単層型電子写真感光
体は、転写メモリーが非常に小さく、且つ、オゾン等の
耐ガス性に優れている事実を見出した。Means for Solving the Problems As a result of intensive studies, the present inventors have formed a photosensitive layer on a conductive substrate to achieve the above object, and the photosensitive layer is a phthalocyanine compound as a charge generating agent. General formula (1) as an electron transport agent,
At least one compound represented by (2) or (3)
The positively-charged single-layer type electrophotographic photoreceptor, which is characterized by containing a seed and a terphenyl compound represented by the general formula (4), has a very small transfer memory and is resistant to gas such as ozone. I found the fact that it is excellent.
【0016】[0016]
【発明の実施形態】正帯電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。DESCRIPTION OF THE PREFERRED EMBODIMENTS A positively charged single-layer type electrophotographic photosensitive member has a single photosensitive layer provided on a conductive substrate. This photosensitive layer is formed by dissolving or dispersing a charge generating agent, a hole transporting agent, an electron transporting agent, a binder resin, and the like in an appropriate solvent, applying the obtained coating solution on a conductive substrate, and drying. You.
【0017】次に、本発明の正帯電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。Next, various materials used for the positively charged single-layer type electrophotographic photosensitive member of the present invention will be described in detail.
【0018】<電荷発生剤>デジタル画像形成装置の光
源としては、現在、LED、半導体レーザが使用されて
いるが、その発振波長は約740nm以上であり、赤外
領域に限定されている。従って、少なくとも700〜8
50nm付近の波長領域に感度を有する有機感光体が必
要である。<Charge Generating Agent> At present, LEDs and semiconductor lasers are used as the light source of the digital image forming apparatus, but the oscillation wavelength thereof is about 740 nm or more and is limited to the infrared region. Therefore, at least 700-8
An organic photoreceptor having sensitivity in a wavelength region around 50 nm is required.
【0019】前記要求を満たす、有機感光体に使用され
る電荷発生剤として、例えば、多環キノン系化合物、ピ
リリウム系化合物、スクエアリウム系化合物、フタロシ
アニン系化合物、アゾ系化合物等が提案または実用化さ
れているが、本発明の正帯電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。As the charge generator used in the organic photoreceptor satisfying the above requirements, for example, polycyclic quinone compounds, pyrylium compounds, squarium compounds, phthalocyanine compounds, azo compounds and the like are proposed or put into practical use. However, various phthalocyanine compounds are used in the positively charged single-layer type electrophotographic photoreceptor of the present invention.
【0020】一般的にフタロシニン系化合物には、中心
金属を有さないメタルフリーフタロシニン(CGM−
1)と、近年研究開発が活発に行われているアルミニウ
ムフタロシアニン、バナジウムフタロシニン、カドミウ
ムフタロシアニン、アンチモンフタロシニン、クロムフ
タロシニン、銅4−フタロシニン、ゲルマニウムフタロ
シニン、鉄フタロシニン、クロロアルミニウムフタロシ
ニン、チタニルフタロシニン、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ニン、マグネシウム
フタロシニン、ジアルキルフタロシニン、テトラメチル
フタロシニン、テトラフェニルフタロシニン等の中心金
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型等、種々の結晶型の
ものがあり、何れも使用可能である。また、これらのフ
タロシアニン化合物は単独または二種以上をブレンドし
て使用できる。In general, phthalosinine-based compounds include metal-free phthalosinins having no central metal (CGM-
1) and aluminum phthalocyanine, vanadium phthalosinine, cadmium phthalocyanine, antimony phthalosinine, chromium phthalosinine, copper 4-phthalosinine, germanium phthalosinine, iron phthalosinine, chloroaluminum phthalosinine, titanyl Phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalosinine, magnesium phthalosinine, dialkylphthalosinine, tetramethylphthalosinine, metal phthalocyanines having a central metal such as tetraphenylphthalosinine, and α-type, β
There are various crystal types such as type, γ-type, δ-type, ε-type, σ-type, and x-type, and any of them can be used. These phthalocyanine compounds can be used alone or as a blend of two or more.
【0021】(CGM−1)(CGM-1)
【化7】 Embedded image
【0022】上記フタロシアニン系化合物は、バインダ
ー樹脂重量に対して0.1〜20wt%、特に0.5〜
10wt%含有することが好ましい。The phthalocyanine compound is used in an amount of 0.1 to 20% by weight, especially 0.5 to 20% by weight, based on the weight of the binder resin.
It is preferable to contain 10 wt%.
【0023】<電子輸送剤>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、転写メモリー低
減のため、電子の移動度が大きい請求項1記載の一般式
(1)、(2)または(3)で示される化合物が使用さ
れる。<Electron transporting agent> The electron transporting agent used in the single-layer type electrophotographic photoreceptor of the present invention has a high electron mobility to reduce transfer memory, and has the general formula (1) according to claim 1, The compound represented by (2) or (3) is used.
【0024】また電子輸送剤として、前記化合物を使用
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。すなわち前記化合物と共に、種々の電子輸送剤を含
有していてもよい。When the above compounds are used as the electron transporting agent, they may be used alone or in at least one kind. That is, various electron transporting agents may be contained together with the compound.
【0025】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 transporting agents include pyrene compounds, carbazole compounds, hydrazone compounds, N, N-dialkylaniline compounds, diphenylamine compounds, triphenylamine compounds, triphenylmethane compounds, tetraphenylmethane compounds, Cyanoethyl, tetracyanoquinodimethane, chloranil, bromoanil, 2,
4,7-trinitro-9-fluorenone, 2,4,5,7-
Tetranitro-9-fluorenone, 2,4,7-trinitro-9-dicyanomethylenefluorenone, 2,4,5,7
And electron-withdrawing substances such as -tetranitroxanthone, 2,4,8-trinitrothioxanthone, and those obtained by polymerizing these electron-withdrawing substances.
【0026】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。The content of the electron transporting agent is 5 to 100% by weight, more preferably 10 to 80% by weight based on the weight of the binder resin.
Is preferred.
【0027】<ホール輸送剤>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、転写メモリ
ー低減のため、特に、請求項2記載の一般式(6)また
は(7)で示される化合物が好適に使用される。<Hole transporting agent> The hole transporting agent used in the single-layer type electrophotographic photoreceptor of the present invention is preferably a compound represented by the general formula (6) or (7) according to claim 2 for reducing transfer memory. The compounds shown are preferably used.
【0028】またホール輸送剤として、前記化合物を使
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。すなわち前記化合物と共に、種々のホール輸送剤
を含有していてもよい。When the above compounds are used as the hole transporting agent, they may be used alone or in at least one kind. That is, various hole transporting agents may be contained together with the compound.
【0029】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。ま
た、これらのホール輸送剤は単独または二種以上をブレ
ンドして使用できる。Oxadiazole compounds such as 2,5-di (4-methylaminophenyl) -1,3,4-oxadiazole, styryl compounds such as 9-4 (-diethylaminostyryl) 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, oxazole compounds, iso Examples thereof include nitrogen-containing cyclic compounds such as oxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, and triazole compounds. These hole transporting agents can be used alone or as a blend of two or more.
【0030】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25〜200w
t%が好ましい。The content of the hole transporting agent is 5 to 500 wt% based on the weight of the binder resin, and more preferably 25 to 200 watts.
t% is preferred.
【0031】<結着樹脂>前記各成分を分散させるため
の結着樹脂は、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> As the binder resin for dispersing the above components, various resins conventionally used in the photosensitive layer can be used.
【0032】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。また、これ
らのバインダー樹脂は単独または二種以上をブレンドし
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, Thermoplastic resin such as vinyl chloride-vinyl acetate copolymer, polyester, alkyd resin, polyamide, polyurethane, polycarbonate, polyarylate, polysulfone, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, silicone resin, epoxy resin , Phenolic resin,
Resins such as urea resins, melamine resins, other cross-linkable thermosetting resins, and photo-curing resins such as epoxy acrylate and urethane-acrylate can be used. These binder resins can be used alone or as a blend of two or more.
【0033】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 preferred resins are bisphenol Z-type polycarbonates derived from bisphenol Z-type monomers and phosgene, such as Panlite manufactured by Teijin Chemicals Limited and PCZ manufactured by Mitsubishi Gas Chemical Company, Ltd.
【0034】前記例の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 of the above example is from 5,000 to 200,000, and more preferably from 15,000 to
100,000 is preferred.
【0035】<添加剤>本発明の正帯電単層型電子写真
感光体には、特に、請求項1記載のターフェニル化合物
を、オゾン等の耐ガス性向上の目的で含有させることを
特徴とする。詳細は明らかでないが、前記ターフェニル
化合物を含有させると、感光層表面の微細な空隙に分子
が入り込み、感光層表面へのガスの侵入を阻害するので
はないかと考えられる。<Additive> The positively charged single-layer type electrophotographic photoreceptor of the present invention is characterized in that the terphenyl compound according to claim 1 is particularly contained for the purpose of improving gas resistance such as ozone. I do. Although the details are not clear, it is considered that when the terphenyl compound is contained, molecules enter into fine voids on the surface of the photosensitive layer and hinder gas from entering the surface of the photosensitive layer.
【0036】前記ターフェニル化合物の含有量は、バイ
ンダー樹脂重量に対して0.5〜30wt%、更には1
〜10wt%が好ましい。The content of the terphenyl compound is 0.5 to 30% by weight, more preferably 1 to 30% by weight, based on the weight of the binder resin.
-10 wt% is preferred.
【0037】本発明の正帯電単層型電子写真感光体の膜
厚は5〜50μm、特に15〜35μmが好ましい。The thickness of the positively charged single-layer type electrophotographic photosensitive member of the present invention is preferably 5 to 50 μm, particularly preferably 15 to 35 μm.
【0038】本発明の正帯電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 positively charged single-layer type 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.
【0039】上記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。As the conductive base on which the photosensitive layer is formed, various conductive materials can be used.
For example, simple metals such as iron, aluminum, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, and brass, and plastic materials on which the above metals are deposited or laminated , Aluminum iodide, tin oxide,
Glass coated with indium oxide or the like can be given.
【0040】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。The conductive substrate may be in the form of a sheet, a drum, or the like, depending on the structure of the image forming apparatus to be used. The substrate itself has conductivity or the surface of the substrate is conductive. What is necessary is just to have the property. The conductive substrate preferably has a sufficient mechanical strength when used.
【0041】前記感光層を塗布の方法により形成する場
合には、前記例示のホール輸送剤、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
トシエーカー、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 above-described hole transporting agent, charge generating agent, electron acceptor, binder resin, etc., together with a suitable solvent, may be used in a known method.
For example, a dispersion may be prepared by dispersing and mixing using a roll mill, a ball mill, an attritor, a paint shaker, an ultrasonic disperser, or the like, and the dispersion may be applied by a known means and dried.
【0042】上記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。Various organic solvents can be used as a solvent for preparing the dispersion, for example, alcohols such as methanol, ethanol, isopropanol and butanol, and aliphatic solvents such as n-hexane, octane and cyclohexane. Hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, and chlorobenzene; dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. Ethers, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate and methyl acetate, dimethylformaldehyde, dimethylformamide, dimethyls Rufoxide and the like. These solvents are used alone or in combination of two or more.
【0043】更に、感光層表面の平滑性を良くするため
に、シリコンオイル等のレベリング剤を使用してもよ
い。Further, in order to improve the smoothness of the surface of the photosensitive layer, a leveling agent such as silicone oil may be used.
【0044】一方、本発明の画像形成装置は、請求項1
記載の正帯電単層型電子写真感光体を使用し、該感光体
の進行方向に沿って、少なくとも主帯電工程、露光工
程、現像工程、転写工程、除電工程及びクリーニング工
程とを備え、前記転写工程で印加される電圧は、帯電工
程で印加される電圧とは逆極性であることを特徴とする
反転現像式デジタル画像形成装置であり、例えば、デジ
タル複写機、ファクシミリ、レーザービームプリンタ等
が挙げられる。On the other hand, the image forming apparatus of the present invention has the following features.
Using the positively charged single-layer type electrophotographic photoreceptor described in the above, and including at least a main charging step, an exposure step, a development step, a transfer step, a charge removal step, and a cleaning step along a traveling direction of the photoreceptor; The voltage applied in the process is a reversal-developed digital image forming apparatus, which has a polarity opposite to that of the voltage applied in the charging process, and examples thereof include a digital copying machine, a facsimile, and a laser beam printer. Can be
【0045】本発明の正帯電単層型電子写真感光体は、
前述のように転写メモリーが非常に小さいため、前記画
像形成装置に使用してもメモリー画像が発生することは
ない。また、オゾン、NOx等の耐ガス性に優れている
ため、前記ガスが大量に発生する大型画像形成装置にお
いても、画像かぶりや黒筋が発生することはない。The positively charged single-layer type electrophotographic photoreceptor of the present invention comprises:
As described above, since the transfer memory is very small, no memory image is generated even when used in the image forming apparatus. Further, since it has excellent resistance to gases such as ozone and NOx, even in a large-sized image forming apparatus in which a large amount of the gas is generated, image fogging and black stripes do not occur.
【0046】[0046]
【実施例】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。The present invention will be described below with reference to examples and comparative examples. Note that the following embodiments are merely examples embodying the present invention, and do not limit the technical scope of the present invention.
【0047】<実施例1〜12>電荷発生剤としてX型
無金属フタロシアニン(CGM−1)2.2重量部、電
子輸送剤として、一般式(1)[ET−101、−10
2]、一般式(2)[ET−201、−202]、一般
式(3)[ET−301、−302]から選ばれた1種
(30重量部)、ホール輸送剤として、一般式(5)
[HT−501]、一般式(6)[HT−601]から
選ばれた1種(60重量部)、ターフェニル化合物とし
て、一般式(4)[AD−401、−402]から選ば
れた1種(3重量部)、及びバインダー樹脂として重量
平均分子量50,000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750重
量部を、ボールミル中で20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、130℃、45分間の熱風乾燥を
行い、膜厚22.5μmの単一感光層を有する正帯電単
層型感光体を作製した。<Examples 1 to 12> 2.2 parts by weight of an X-type metal-free phthalocyanine (CGM-1) as a charge generating agent and the general formula (1) [ET-101, -10] as an electron transporting agent
2), one kind (30 parts by weight) selected from general formulas (2) [ET-201, -202] and general formula (3) [ET-301, -302]; 5)
[HT-501], one kind (60 parts by weight) selected from the general formula (6) [HT-601], and a terphenyl compound selected from the general formula (4) [AD-401, -402] One type (3 parts by weight), 100 parts by weight of a bis-Z type polycarbonate resin having a weight average molecular weight of 50,000 as a binder resin, and 750 parts by weight of tetrahydrofuran are dispersed or dissolved in a ball mill for 20 hours to obtain a single-layer type photosensitive material. A coating solution for a layer was prepared. Then, this coating solution is applied on an aluminum tube as a support by a dip coating method, and dried with hot air at 130 ° C. for 45 minutes to obtain a positively charged unit having a single photosensitive layer having a thickness of 22.5 μm. A layer type photoreceptor was prepared.
【0048】表1〜3に、実施例に使用した前記化合物
の構造式を示した。Tables 1 to 3 show the structural formulas of the compounds used in the examples.
【0049】<電子輸送剤><Electron transport agent>
【表1】 [Table 1]
【0050】<ホール輸送剤><Hole transport agent>
【表2】 [Table 2]
【0051】<ターフェニル化合物><Terphenyl compound>
【表3】 [Table 3]
【0052】<比較例1、2>電子輸送剤としてET−
1、−2を使用した以外は実施例1〜12と同様に正帯
電単層型感光体を作製した。<Comparative Examples 1 and 2> ET- as an electron transporting agent
A positively charged single-layer type photoreceptor was produced in the same manner as in Examples 1 to 12, except that Examples 1 and 2 were used.
【0053】<比較例3〜14>ターフェニル化合物を
添加しない以外は実施例1〜12と同様に正帯電単層型
感光体を作製した。<Comparative Examples 3 to 14> Positively charged single-layer type photoconductors were prepared in the same manner as in Examples 1 to 12, except that no terphenyl compound was added.
【0054】表4に、比較例1、2に使用した化合物の
構造式を示した。Table 4 shows the structural formulas of the compounds used in Comparative Examples 1 and 2.
【0055】<電子輸送剤><Electron transport agent>
【表4】 [Table 4]
【0056】上記各実施例、比較例の正帯電単層型電子
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5、6に示した。The following characteristics were evaluated for the positively charged single-layer type electrophotographic photoreceptors of the above Examples and Comparative Examples. The evaluation results are shown in Tables 5 and 6.
【0057】<光感度評価>ジェンテック(GENTE
C)社製のドラム感度試験機(ジェンテックシンシア3
0M)を使用して、各実施例、比較例の感光体に印加電
圧を加えて、その表面を+700Vに帯電させた。<Evaluation of Light Sensitivity>
C) Drum sensitivity tester (Gentec Cynthia 3)
0M), an applied voltage was applied to the photoreceptors of the examples and comparative examples to charge the surfaces thereof to +700 V.
【0058】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使用して
取り出した波長780nmの単色光(半値幅20nm、
光強度15μW)を、上記帯電状態の感光体表面に露光
(露光時間40msec)した。そして、露光開始時点
から330msec経過した時点での表面電位を露光後
電位VL(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。Next, monochromatic light having a wavelength of 780 nm (half-width 20 nm, extracted from white light of a halogen lamp, which is an exposure light source of the tester, using a band-pass filter).
A light intensity of 15 μW) was applied to the charged surface of the photoreceptor (exposure time: 40 msec). Then, the surface potential at the point when 330 msec had elapsed from the start of exposure was measured as the post-exposure potential VL (V). That is, the smaller the potential after exposure, the higher the sensitivity of the photoconductor.
【0059】<転写メモリー評価>京セラミタ(株)社
製デジタル複写機Creage630を使用して、各実
施例、比較例の感光体に、主帯電器により+850Vに
均一に帯電し、反射光学濃度が約0.5のハーフトーン
を出力し画像露光を行った後、+650Vの現像バイア
スを印加して、正帯電トナーを使用した二成分現像剤に
て反転現像を行った。次いで転写出力6kVで転写紙に
転写を行い、定着後、評価用画像を得た。<Evaluation of Transfer Memory> Using a digital copying machine CREAGE630 manufactured by Kyocera Mita Co., Ltd., the photoconductors of the respective examples and comparative examples were uniformly charged to +850 V by a main charger, and the reflection optical density was reduced. After outputting a halftone of about 0.5 and performing image exposure, a developing bias of +650 V was applied, and reversal development was performed with a two-component developer using positively charged toner. Then, the image was transferred to a transfer sheet at a transfer output of 6 kV, and after fixing, an image for evaluation was obtained.
【0060】前記評価用画像の、感光体ドラム長手方向
に帯状に出現する画像の濃い部分(転写メモリー画像)
と、その他の部分との画像濃度差(ΔID)が0.2以
上を不可とした。A dark portion (transfer memory image) of the evaluation image, which appears in a band shape in the longitudinal direction of the photosensitive drum.
And an image density difference (ΔID) between the other portion and the other portion is not allowed to be 0.2 or more.
【0061】<耐オゾン性評価>各実施例、比較例の感
光体の表面電位を京セラミタ(株)社製デジタル複写機
Creage7320を使用して測定し、次いで、前記
感光体を、暗所にてオゾン濃度10ppmの雰囲気中
に、常温にて10時間暴露させ、暴露直後の表面電位を
同様にして測定した。<Evaluation of Ozone Resistance> The surface potentials of the photoreceptors of the examples and comparative examples were measured using a digital copier CREAGE 7320 manufactured by Kyocera Mita Corporation, and then the photoreceptors were placed in a dark place. Then, it was exposed to an atmosphere having an ozone concentration of 10 ppm at room temperature for 10 hours, and the surface potential immediately after the exposure was measured in the same manner.
【0062】(初期表面電位)−(暴露直後の表面電
位)=ΔV0とし、ΔV0が60V以上を不可とした。(Initial surface potential)-(surface potential immediately after exposure) =. DELTA.V0, and .DELTA.V0 was not allowed to be 60 V or more.
【0063】[0063]
【表5】 [Table 5]
【0064】[0064]
【表6】 [Table 6]
【0065】表5、表6から明らかなように、請求項1
記載の電子輸送剤の存在が画像濃度差、すなわち耐メモ
リー性に、また、ターフェニル化合物の存在が耐オゾン
性に大きく影響することが理解できる。As apparent from Tables 5 and 6, claim 1
It can be understood that the presence of the electron transporting agent greatly affects the difference in image density, that is, memory resistance, and the presence of the terphenyl compound greatly affects ozone resistance.
【0066】[0066]
【発明の効果】本発明の電子写真感光体は、反転現像方
式のデジタル画像形成装置に使用しても、転写メモリー
が非常に小さく、転写メモリー画像が発生しない。ま
た、オゾン、NOx等の耐ガス性に優れているため、前
記ガスが大量に発生する大型画像形成装置においても、
画像かぶりや黒筋が発生することはない。The electrophotographic photoreceptor of the present invention has a very small transfer memory and does not generate a transfer memory image even when used in a digital image forming apparatus of a reversal developing system. Further, because of its excellent gas resistance such as ozone and NOx, even in a large-sized image forming apparatus in which the gas is generated in a large amount,
No image fogging or black streaks occur.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) G03G 5/06 315 G03G 5/06 315Z 319 319 5/05 104 5/05 104B Fターム(参考) 2H068 AA14 AA19 AA20 AA31 BA12 BA13 BA14 BA16 BA38 BA60 BA63 BA64 BB26 FA02 FC02──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) G03G 5/06 315 G03G 5/06 315Z 319 319 5/05 104 5/05 104B F-term (reference) 2H068 AA14 AA19 AA20 AA31 BA12 BA13 BA14 BA16 BA38 BA60 BA63 BA64 BB26 FA02 FC02
Claims (3)
層が電化発生剤としてフタロシアニン系化合物、電子輸
送剤として一般式(1)、(2)または(3)で示され
る化合物を少なくとも1種、及び、一般式(4)で示さ
れるターフェニル化合物を含有することを特徴とする正
帯電単層型電子写真感光体。 一般式(1): 【化1】 (一般式(1)中、R1、R2は同一または異なって、置
換基を有してもよい1価の炭化水素基を示す。) 一般式(2): 【化2】 (一般式(2)中、R3、R4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(3): 【化3】 (一般式(3)中、R5、R6は同一または異なって、置
換基を有してもよい1価の炭化水素基を示す。) 一般式(4): 【化4】 (一般式(4)中、R7、R8、R9は同一または異なっ
て、水素原子、あるいは置換基を有してもよいアルキル
基、アリール基、アミノ基を示す。)1. A photosensitive layer is formed on a conductive substrate. The photosensitive layer comprises a phthalocyanine compound as an electrification generator and a compound represented by the general formula (1), (2) or (3) as an electron transporting agent. A positively charged single-layer type electrophotographic photoreceptor comprising at least one kind and a terphenyl compound represented by the general formula (4). General formula (1): (In the general formula (1), R 1 and R 2 are the same or different and represent a monovalent hydrocarbon group which may have a substituent.) The general formula (2): (In the general formula (2), R 3 and R 4 are the same or different and are an alkyl group, a halogenated alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, an alkoxycarbonyl group. , An aryloxycarbonyl group, an aralkyloxycarbonyl group or a nitro group, and n represents an integer of 0 to 3.) General formula (3): (In the general formula (3), R 5 and R 6 are the same or different and represent a monovalent hydrocarbon group which may have a substituent.) A general formula (4): (In the general formula (4), R 7 , R 8 , and R 9 are the same or different and each represent a hydrogen atom or an alkyl group, an aryl group, or an amino group which may have a substituent.)
(6)で示される化合物を少なくとも1種含有すること
を特徴とする請求項1記載の正帯電単層型電子写真感光
体。 一般式(5): 【化5】 (一般式(5)中、R10およびR12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、R11およびR13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、R11およびR
13の置換位置がパラ位の場合、R11およびR13は水素原
子である。) 一般式(6): 【化6】 (一般式(6)中、R14及びR16は同一または異な
るアルキル基を示し、R 15、R17は同一または異なって
水素原子またはアルキル基を示す。)2. A compound represented by the following general formula (5) or (2):
Contains at least one compound represented by (6)
The positively charged single-layer type electrophotographic photosensitive member according to claim 1, wherein
body. General formula (5):(In the general formula (5), RTenAnd R12Are the same or different
An alkyl group which may have a substituent,
Aryl groups, which may have a substituent, aralkyl
A group or an alkoxy group;11And R13Is the same
Or differently, a hydrogen atom, which may have a substituent,
Represents a kill group or an alkoxy group. Where R11And R
13Is substituted at the para position,11And R13Is hydrogen field
I am a child. General formula (6):(In the general formula (6), R14 and R16 are the same or different.
R represents an alkyl group Fifteen, R17Are the same or different
Shows a hydrogen atom or an alkyl group. )
体を使用し、前記電子写真感光体の進行方向に沿って、
少なくとも主帯電工程、露光工程、現像工程、転写工
程、除電工程及びクリーニング工程とを備え、前記転写
工程で印加される電圧の極性が負で、帯電工程で印加さ
れる電圧の極性が正であることを特徴とする反転現像式
デジタル画像形成装置。3. The method according to claim 1, wherein the positively charged single-layer type electrophotographic photoreceptor is used along a traveling direction of the electrophotographic photoreceptor.
It comprises at least a main charging step, an exposure step, a developing step, a transferring step, a discharging step and a cleaning step, wherein the polarity of the voltage applied in the transferring step is negative and the polarity of the voltage applied in the charging step is positive. A reversal-developing digital image forming apparatus.
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