JP2598100B2 - Electrophotographic photoreceptor - Google Patents
Electrophotographic photoreceptorInfo
- Publication number
- JP2598100B2 JP2598100B2 JP63215252A JP21525288A JP2598100B2 JP 2598100 B2 JP2598100 B2 JP 2598100B2 JP 63215252 A JP63215252 A JP 63215252A JP 21525288 A JP21525288 A JP 21525288A JP 2598100 B2 JP2598100 B2 JP 2598100B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- layer
- group
- charge
- photoreceptor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/142—Inert intermediate layers
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、複写機、プリンターとして用いられる電子
写真装置において静電潜像を形成するために用いられる
電子写真感光体に関し、特に、耐久安定性に優れた電子
写真感光体に関する。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member used for forming an electrostatic latent image in an electrophotographic device used as a copying machine or a printer, The present invention relates to an electrophotographic photosensitive member having excellent properties.
従来より、複写機、プリンターとして用いられる電子
写真装置に投載される電子写真感光体としてCdS,ZnO,Ti
O,Se,Se−Te,a−Si等の無機系感光体が知られている。
近年、複写機、プリンター市場の拡大に伴ない、安価で
量産性に優れた有機系の感光体が注目されており、感度
等の初期特性は無機系のものを上回るまでに進歩して来
た。また、有機系の材料の特徴として、さまざまな化学
修飾により機能付加できる範囲が広い点が挙げられ、特
性の向上や最適化が容易に行なえる利点を有する。Conventionally, CdS, ZnO, Ti has been used as an electrophotographic photoreceptor mounted on electrophotographic devices used as copiers and printers.
Inorganic photoconductors such as O, Se, Se-Te, and a-Si are known.
In recent years, with the expansion of the copier and printer markets, inexpensive and highly mass-producible organic photoconductors have been attracting attention, and their initial characteristics such as sensitivity have progressed beyond inorganic ones. . In addition, as a feature of the organic material, there is a wide range in which functions can be added by various chemical modifications, and there is an advantage that characteristics can be easily improved or optimized.
有機系感光体の一般的な形態は、導電性基体上に、有
機材料である電荷輸送材及び電荷発生材を樹脂等により
成膜させたものである。また、特性上、電荷輸送層と電
荷発生層とを分離積層した機能分離型の感光層が特に優
れており、その実用例が多い。また、有機系感光体にお
いて、導電性基板と感光層との密着性、電荷の注入性制
御等の向上のために導電性基体と感光層との間に中間層
を設ける場合が多い。In a general form of the organic photoreceptor, a charge transporting material and a charge generating material, which are organic materials, are formed on a conductive substrate using a resin or the like. Further, in terms of characteristics, a function-separated type photosensitive layer in which a charge transport layer and a charge generation layer are separated and laminated is particularly excellent, and there are many practical examples. Further, in the organic photoreceptor, an intermediate layer is often provided between the conductive substrate and the photosensitive layer in order to improve adhesion between the conductive substrate and the photosensitive layer, control of charge injection property, and the like.
以上の様な特徴、利点を有する有機系感光体である
が、無機系感光体に比べて劣る点として耐久性が挙げら
れる。無機材料に比べ柔軟であるため、物理的な摩耗や
傷に弱い。また、化学的安定性も無機材料に比べて低
く、特に耐久時に帯電プロセスによて生成するオゾン等
の活性なコロナ生成物の影響が大きい。有機感光体を形
成する有機光導電材料や樹脂は、前記活性なコロナ生成
物により、酸化、付加、解裂等の化学的変化を生じ易
い。このような変化を受けた有機感光体においては、感
度の低下、残留電位の蓄積、キャリア移動度の低下、帯
電能の低下等を引き起こす。また、コロナ生成物もしく
は有機感光体とコロナ生成物との反応複合物等が電荷受
容体もしくは電荷供与体として作用する場合、キャリア
の生成や注入による感度増加や帯電能低下や暗減衰の増
加等を引き起こす。Although the organic photoreceptor has the features and advantages as described above, it is inferior to the inorganic photoreceptor in durability. Because it is more flexible than inorganic materials, it is vulnerable to physical abrasion and scratches. In addition, the chemical stability is lower than that of the inorganic material, and the effect of an active corona product such as ozone generated by a charging process during durability is particularly large. The organic photoconductive material and resin forming the organic photoreceptor are liable to undergo chemical changes such as oxidation, addition, and cleavage due to the active corona product. In the organic photoreceptor subjected to such a change, the sensitivity is reduced, the residual potential is accumulated, the carrier mobility is reduced, and the charging ability is reduced. When a corona product or a reaction complex of an organic photoreceptor and a corona product acts as a charge acceptor or a charge donor, sensitivity increases due to generation or injection of carriers, charging ability decreases, dark decay increases, etc. cause.
以上に述べたコロナ生成物による有機感光体の劣化
は、装置動作時のコロナ生成物が発生している間は感光
体全面への影響として現れてくる。また、装置停止時に
おいても、コロナ帯電器には、NOx,HNO3等のコロナ生成
物が残留しており、帯電器近傍の感光体の部分的劣化と
して現れてくる。いずれの場合も複写もしくはプリント
画像に変動を生じるが、感光体全面の劣化時には、画像
全面の濃度変化や画像ボケを生じ、部分的劣化時には、
部分的濃度ムラ等を生じてしまう。このような化学的劣
化を生じた有機感光体は交換しなければならず、複写機
もしくはプリンターのランニングコストの増加やサービ
ス性、メインテナンス性の低下として反映されてしま
う。The deterioration of the organic photoconductor due to the corona product described above appears as an influence on the entire surface of the photoconductor while the corona product is generated during operation of the apparatus. Further, even when the apparatus is stopped, corona products such as NO x and HNO 3 remain in the corona charger and appear as partial deterioration of the photoconductor near the charger. In either case, the copy or print image fluctuates, but when the entire photoconductor is deteriorated, a change in the density of the entire image or image blur occurs.
This causes partial density unevenness and the like. The organic photoreceptor that has undergone such chemical deterioration must be replaced, and this is reflected as an increase in the running cost of a copier or a printer, and a decrease in serviceability and maintainability.
この事実は有機感光体本来の利点である低コストや扱
い易さといった点と相反する問題であり、そのために従
来から数々の解決法が提案されている。例えば特開昭57
−122444号公報、特開昭58−120260号公報に示された劣
化防止剤を感光層に添加する方法等がある。しかし、い
ずれの方法においても完全な対策とはなっておらず、特
に高画質を要求されるグラフィック画像や写真画像を複
写もしくはプリントする装置においては、実用性の高い
有機感光体は得られていなかった。This fact conflicts with the inherent advantages of the organic photoreceptor, such as low cost and ease of handling, and various solutions have been proposed for this purpose. For example, JP-A-57
JP-A-122444 and JP-A-58-120260, in which a deterioration inhibitor is added to a photosensitive layer. However, neither method is a complete countermeasure, and a highly practical organic photoreceptor has not been obtained, particularly in an apparatus for copying or printing a graphic image or a photographic image requiring high image quality. Was.
我々の研究から得られた知見により以下の事実が判明
した。すなわち、前記コロナ生成物が有機感光体を劣化
させる理由として、コロナ生成物自体、もしくは、感光
層を構成する有機材料とコロナ生成物との間で生成した
反応物、複合体が電子受容体または電子供与体として作
用することが含まれる。有機感光体中にこれらの電子受
容体または電子供与体が生成、混入すると、それらはキ
ャリアの発生能や注入性を発揮するため、感光体の感度
変化や暗減衰の増加、帯電能の低下等を起こす。また、
以上に述べたキャリアの発生、注入は、特に、感光層と
導電性基体との界面において著しい弊害を与えることが
示唆された。The findings obtained from our study revealed the following facts. That is, as the reason that the corona product deteriorates the organic photoreceptor, the corona product itself, or a reactant generated between the organic material constituting the photosensitive layer and the corona product, the complex is an electron acceptor or Acting as an electron donor is included. When these electron acceptors or electron donors are generated or mixed in the organic photoreceptor, they exhibit carrier generation ability and injection property, so that the sensitivity of the photoreceptor changes, dark decay increases, charging ability decreases, etc. Cause Also,
It has been suggested that the generation and injection of carriers described above have a significant adverse effect particularly at the interface between the photosensitive layer and the conductive substrate.
本発明の目的は、コロナ生成物に起因する有機感光体
の劣化を防止することであり、特に、キャリアの増加に
よる帯電能低下や画像ムラを防止することである。An object of the present invention is to prevent deterioration of an organic photoreceptor caused by a corona product, and in particular, to prevent a decrease in charging ability and an uneven image due to an increase in carriers.
そこで、本発明の目的を効果的に達成するために感光
層と導電性基体との界面において、侵入してきたコロナ
生成物を不活性化する方法を選択した。Therefore, in order to effectively achieve the object of the present invention, a method of inactivating corona products that have entered at the interface between the photosensitive layer and the conductive substrate has been selected.
本発明の電子写真感光体は導電性基体及び有機系感光
層を有する電子写真感光体において、該導電性基体と該
感光層との間に、下記式（１）で表わされる化合物の層
又は該化合物を含有する中間層を有することを特徴とす
る。The electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a conductive substrate and an organic photosensitive layer, wherein a layer of a compound represented by the following formula (1) or the compound is provided between the conductive substrate and the photosensitive layer. It is characterized by having an intermediate layer containing a compound.
上記式において、X3、X4、X5及びX6はそれぞれ独自に
水素原子、アルキル基、置換又は非置換のアリール基、
アラルキル基又は複素環式化合物基、OH,NO2,COOR（こ
の場合にＲは水素原子、アルキル基、アリール基又はア
ラルキル基である）、 （この場合にR1及びR2はそれぞれ独自に水素原子、アル
キル基、アリール基又はアラルキル基である）、Cl,Br,
F又はCNであり、ＹはCH2 ｎ、CH＝CHｎ、 −Ｓ−、−Ｏ−、CH2 nSCH2 ｎ又はCH2 nOC
H2 ｎであり、 はそれぞれ独自に これら含窒素複素環式化合物の特徴としては、窒素原
子上の不対電子対が、共役二重結合をもつ環構造中で非
局在化する傾向に有るため、通常の窒素原子より電子密
度が低いことが挙げられる。このような化合物は、電荷
のトラップとなりづらいため、導電性基板と感光層との
間に添加しても、感度低下や残留電位上昇が少ないこと
が判った。また、弱塩基性もしくは弱いドナー性を有す
るために、コロナ生成物等の酸もしくは受容体等と複合
体を形成し、不活性化させることができる。 In the above formula, X 3 , X 4 , X 5 and X 6 are each independently a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group,
An aralkyl group or a heterocyclic compound group, OH, NO 2 , COOR (where R is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group), (Where R 1 and R 2 are each independently a hydrogen atom, an alkyl group, an aryl group or an aralkyl group), Cl, Br,
F or CN, Y is CH 2 n , CH = CH n , -S -, - O-, CH 2 n SCH 2 n or CH 2 n OC
H 2 n , Each independently One of the characteristics of these nitrogen-containing heterocyclic compounds is that the unpaired electron pair on the nitrogen atom tends to delocalize in the ring structure having a conjugated double bond. Low. It has been found that such a compound is unlikely to become an electric charge trap, so that even if it is added between the conductive substrate and the photosensitive layer, a decrease in sensitivity and an increase in residual potential are small. Further, since it has a weak basicity or a weak donor property, it can be inactivated by forming a complex with an acid such as a corona product or an acceptor.
本発明において、有窒素複素環式化合物の層を導電性
基板と感光層との間に設けるには、前記含窒素複素環化
合物を適当な有機溶剤に溶かしたものを塗布法により成
膜する。単独で成膜しづらい化合物は、適当な樹脂を結
着剤とした中間層として塗布・成膜する。In the present invention, in order to provide a nitrogen-containing heterocyclic compound layer between the conductive substrate and the photosensitive layer, a film obtained by dissolving the nitrogen-containing heterocyclic compound in an appropriate organic solvent is formed by a coating method. A compound that is difficult to form a film by itself is applied and formed as an intermediate layer using an appropriate resin as a binder.
含窒素複素環式化合物の導入量は、感光体単位面積当
りで0.1〜300mg/m2である。この数値は化合物の窒素原
子上の電子密度にもよるが、より好ましくは、１〜100m
g/m2である。少ない場合はコロナ生成物等の不活性化能
が不足するし、多い場合は感度劣化や残留電位上昇等の
弊害を生ずる。The amount of the nitrogen-containing heterocyclic compound to be introduced is 0.1 to 300 mg / m 2 per unit area of the photoreceptor. Although this value depends on the electron density on the nitrogen atom of the compound, more preferably 1 to 100 m
g / m 2 . If the amount is small, the ability to deactivate corona products or the like is insufficient. If the amount is large, adverse effects such as sensitivity deterioration and increase in residual potential occur.
結着樹脂と共に中間層として成膜する際には、以下の
様な結着樹脂が用いられる。ポリエステル樹脂、ポリカ
ーボネート樹脂、ポリアリレート樹脂、ポリウレタン樹
脂、フェノール樹脂、エポキシ樹脂、アルキッド樹脂、
メラミン樹脂、ポリスチレン樹脂、ポリビニルブチラー
ル樹脂、ポリアミド樹脂、アクリル樹脂、スチレン−ブ
タジエン共重合体、スチレン−アクリル共重合体、セル
ロース、変性セルロース樹脂、ポリアミノ酸、カゼイ
ン、ゼラチン等が挙げられる。また、これら中間層の厚
さは、0.01〜10μさらに好ましくは0.1〜３μである。
また、中間層は導電性顔料、酸化防止剤、界面活性剤等
を含んでいても良い。When a film is formed as an intermediate layer together with a binder resin, the following binder resin is used. Polyester resin, polycarbonate resin, polyarylate resin, polyurethane resin, phenol resin, epoxy resin, alkyd resin,
Examples include melamine resin, polystyrene resin, polyvinyl butyral resin, polyamide resin, acrylic resin, styrene-butadiene copolymer, styrene-acryl copolymer, cellulose, modified cellulose resin, polyamino acid, casein, gelatin and the like. Further, the thickness of these intermediate layers is 0.01 to 10 μm, more preferably 0.1 to 3 μm.
Further, the intermediate layer may contain a conductive pigment, an antioxidant, a surfactant and the like.
本発明で用いることのできる電荷輸送材料は、有機感
光体に一般に用いられている多環芳香族化合物や、含窒
素化合物であり、フェナンスレン誘導体、アントラセン
誘導体、トリフェニルメタン誘導体、トリフェニルアミ
ン誘導体、カルバゾール誘導体、フルオレノン誘導体、
ピラゾリン誘導体、ヒドラゾン誘導体、トリアゾール誘
導体、オキサゾール誘導体、イミダゾール誘導体、オキ
サジアゾール誘導体、スチルベン誘導体等が挙げられ、
具体的には以下のものがある。各式においてＸは水素原
子、アルキル基、アリール基、ハロアルキル基又はハロ
ゲン原子である。The charge transporting material that can be used in the present invention is a polycyclic aromatic compound or a nitrogen-containing compound generally used for an organic photoreceptor, and includes a phenanthrene derivative, an anthracene derivative, a triphenylmethane derivative, a triphenylamine derivative, Carbazole derivatives, fluorenone derivatives,
Pyrazoline derivatives, hydrazone derivatives, triazole derivatives, oxazole derivatives, imidazole derivatives, oxadiazole derivatives, stilbene derivatives and the like,
Specifically, there are the following. In each formula, X is a hydrogen atom, an alkyl group, an aryl group, a haloalkyl group, or a halogen atom.
本発明で用いることのできる電荷発生材料は、有機感
光体に一般に用いられているものであり、フタロシアニ
ン顔料、多環キノン顔料、トリスアゾ顔料、ジスアゾ顔
料、アゾ顔料、インジコ顔料、キナクリドン顔料、アス
レニウム塩染料、スクワリリウム染料、シアニン染料、
ピリリウム染料、チオピリリウム染料、キサンテン色
素、キノンアミン色素、トリフェニルメタン色素、スチ
リル色素、セレン、セレン・テルル、アモルファスシリ
コン、硫化カドミウム等が挙げられ、具体的には以下の
ものがある： M:Al,Ca,Si,Sn,Ge,V,Cu,Co X:Cl,F,O アゾ顔料 （以下の各式において、ＸはH,F,Cl,Br,NO2,CN等であ
り、Arは置換又は非置換の芳香環であり、Ｒはアルキル
基、アラルキル基又は水素原子である） 本発明の電子写真感光体は、導電性基体及び感光層を
有している。感光層は、前記電荷輸送材料及び電荷発生
材料とそれらを成膜するための結着樹脂が基本的構成要
素である。層構成は、単層型と積層型があるが後者がよ
り一般的である。単層型の場合は、前記電荷輸送材料、
電荷発生材料及び結着樹脂を適切な割合で混合する。積
層型の場合は、電荷輸送材及び電荷発生材をそれぞれ別
個に結着樹脂で成膜、積層し、電荷輸送層及び電荷発生
層を形成する。この際、導電性基体側にどちらの層が形
成されても良いが、電荷発生層を先に形成するのが一般
的である。さらに電荷輸送層に更に電荷発生材、電荷発
生層に更に電荷輸送材が含有されていても良い。 Charge generation materials that can be used in the present invention are those generally used in organic photoreceptors, and include phthalocyanine pigments, polycyclic quinone pigments, trisazo pigments, disazo pigments, azo pigments, indico pigments, quinacridone pigments, and athrenium salts. Dyes, squarylium dyes, cyanine dyes,
Examples include pyrylium dyes, thiopyrylium dyes, xanthene dyes, quinoneamine dyes, triphenylmethane dyes, styryl dyes, selenium, selenium / tellurium, amorphous silicon, cadmium sulfide, and the like, and specifically include the following: M: Al, Ca, Si, Sn, Ge, V, Cu, Co X: Cl, F, O Azo pigment (In the following formulas, X is H, F, Cl, Br, NO 2 , CN, etc. , Ar is a substituted or unsubstituted aromatic ring, and R is an alkyl group, an aralkyl group, or a hydrogen atom) The electrophotographic photoreceptor of the present invention has a conductive substrate and a photosensitive layer. The photosensitive layer is basically composed of the charge transporting material and the charge generating material and a binder resin for forming them. The layer configuration includes a single-layer type and a laminated type, the latter being more common. In the case of a single-layer type, the charge transport material,
The charge generating material and the binder resin are mixed in an appropriate ratio. In the case of a stacked type, the charge transporting material and the charge generating material are separately formed with a binder resin and laminated to form a charge transporting layer and a charge generating layer. At this time, either layer may be formed on the conductive substrate side, but generally, the charge generation layer is formed first. The charge transport layer may further contain a charge generating material, and the charge generating layer may further contain a charge transport material.
成膜のための結着樹脂としては、ポリエステル樹脂、
ポリアリレート樹脂、アクリル樹脂、アクリロニトリル
樹脂、メタクリル樹脂、ポリカーボネート樹脂、ポリア
ミド樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、エポキシ
樹脂、フェノール樹脂、ポリウレタン樹脂、スチレン−
ブタジエン共重合体、スチレン−アクリル共重合体など
が用いらる。As a binder resin for film formation, polyester resin,
Polyarylate resin, acrylic resin, acrylonitrile resin, methacrylic resin, polycarbonate resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, phenol resin, polyurethane resin, styrene
Butadiene copolymers, styrene-acrylic copolymers and the like are used.
積層型の場合、電荷発生材の結着樹脂に対する比率は
0.5/1〜10/1であり、好ましくは1/1〜5/1である。また
電荷発生層の膜厚は、0.01〜５μであり、好ましくは0.
05〜３μである。同様に電荷輸送層の電荷輸送材と結着
樹脂との比率は、5/10〜50/10であるが、好ましくは7/1
0〜30/10である。また電荷輸送層の厚さは５〜50μ、好
ましくは、10〜30μである。In the case of the multilayer type, the ratio of the charge generation material to the binder resin is
It is 0.5 / 1 to 10/1, preferably 1/1 to 5/1. The thickness of the charge generation layer is 0.01 to 5 μm, preferably 0.1 μm.
05 to 3μ. Similarly, the ratio of the charge transport material of the charge transport layer and the binder resin is 5/10 to 50/10, preferably 7/1.
0 to 30/10. The thickness of the charge transport layer is 5 to 50 μm, preferably 10 to 30 μm.
本発明で用いることのできる感光体の導電性基体とし
ては、アルミニウム、鉄、銅、亜鉛、ニッケル、クロ
ム、チタン、インジウム等の金属及びそれらの合金や、
プラスチック、紙、金属等に導電処理したものを用いる
ことができる。導電処理としては、導電材料を蒸着する
方法、結着樹脂に含有または分散させて成膜する方法等
が一般的である。結着樹脂に含有、分散させる導電材料
としては、上記金属または合金の粉末、カーボン、酸化
スズ、酸化亜鉛、酸化アンチモン、酸化ケイ素等の粉末
や導電性プラスチック等が用いられる。また導電性基体
の形状は、フィルム、シート、ベルト状のものや、円筒
状、円柱状のものなどがある。As the conductive substrate of the photoreceptor that can be used in the present invention, aluminum, iron, copper, zinc, nickel, chromium, titanium, metals such as indium and alloys thereof,
Plastics, paper, metal, or the like that has been subjected to conductive treatment can be used. As the conductive treatment, a method of vapor deposition of a conductive material, a method of containing or dispersing in a binder resin, and forming a film are common. As the conductive material contained and dispersed in the binder resin, powders of the above metals or alloys, powders of carbon, tin oxide, zinc oxide, antimony oxide, silicon oxide, and the like, conductive plastics, and the like are used. The conductive substrate may be in the form of a film, a sheet, a belt, a cylinder, a column, or the like.
本発明の電子写真感光体における成膜法は、一般の塗
布方法が用いられる。すなわち、前記感光体材料を結着
樹脂などと共に適当な溶剤に分散もしくは溶解させ、液
状にして用いる。これらの液は、スプレー塗布、浸漬塗
布、ブレード塗布、マイヤーバー塗布、ローラー塗布、
スピンナー塗布、カーテン塗布などの塗布方法により成
膜される。As a film forming method in the electrophotographic photoreceptor of the present invention, a general coating method is used. That is, the photoreceptor material is dispersed or dissolved in an appropriate solvent together with a binder resin and the like, and used in a liquid state. These liquids are applied by spray coating, dip coating, blade coating, Meyer bar coating, roller coating,
The film is formed by a coating method such as spinner coating or curtain coating.
実施例１ 構造式 で表わされる含窒素複素環式化合物９重量部、可溶性ポ
リアミド（トレジンEF−30:帝国化学製）91重量部、メ
タノール800重量部及び、イソプロパノール400重量部を
撹拌溶解した。Example 1 Structural formula 9 parts by weight of a nitrogen-containing heterocyclic compound represented by the following formula, 91 parts by weight of a soluble polyamide (Toresin EF-30: manufactured by Teikoku Chemicals), 800 parts by weight of methanol and 400 parts by weight of isopropanol were dissolved by stirring.
径80mm、長さ375mm、厚さ1.0mmの鏡面アルミニウムシ
リンダー上に、前記溶液をスプレー塗布し、50℃で30分
間の乾燥の後に、厚さ0.7μの中間層を得た。The solution was spray-coated on a mirror-finished aluminum cylinder having a diameter of 80 mm, a length of 375 mm, and a thickness of 1.0 mm. After drying at 50 ° C. for 30 minutes, an intermediate layer having a thickness of 0.7 μ was obtained.
次に、構造式 で表わされるアゾ顔料10重量部、ポリカーポネート樹脂
（ビスフェノールＡ型：分子量Mn＝13,000）20重量部及
びシクロヘキサノン1,000重量部を、1mm径ガラスビーズ
を用いたサンドミルによって25℃で2,000rpmの分散を50
時間行った。シクロヘキサノン500重量部により洗い出
し、ガラスビーズを除去し、10,000rpmの遠心分離処理
後、テトラヒドロフラン500重量部、シクロヘキサノン2
00重量部で希釈した。この分散液を前記中間層上にスプ
レー塗布した後、70℃で10分間の乾燥により、0.15μの
電荷発生層とした。Next, the structural formula Is dispersed at 2,000 rpm at 25 ° C. by a sand mill using 1 mm diameter glass beads in an amount of 10 parts by weight of an azo pigment represented by the following formula, 20 parts by weight of a polycarbonate resin (bisphenol A type: molecular weight Mn = 13,000) and 1,000 parts by weight of cyclohexanone. 50
Time went. After washing with 500 parts by weight of cyclohexanone, removing glass beads and centrifuging at 10,000 rpm, 500 parts by weight of tetrahydrofuran, cyclohexanone 2
It was diluted with 00 parts by weight. This dispersion was spray-coated on the intermediate layer, and then dried at 70 ° C. for 10 minutes to form a 0.15 μ charge-generating layer.
さらに、構造式 で表わされるスチレベン化合物20重量部、ポリカーボネ
ート樹脂（ビスフェノールＺ型:mn＝14,000）25重量
部、及び、ベンゼン200重量部を混合、溶解した。この
溶液を、前記電荷発生層上に浸漬塗布した後、110℃で8
0分間の乾燥により膜厚17μの電荷輸送層とし、それに
より感光体ドラムを得た。In addition, the structural formula Were mixed and dissolved in 20 parts by weight of a styrene compound represented by the following formula, 25 parts by weight of a polycarbonate resin (bisphenol Z type: mn = 14,000), and 200 parts by weight of benzene. After dip coating this solution on the charge generation layer,
By drying for 0 minutes, a charge transporting layer having a film thickness of 17 μm was obtained, whereby a photosensitive drum was obtained.
比較例１ 中間層に前記含窒素複素環式化合物を含まない点以外
は実施例１と同様にして感光体ドラムを得た。Comparative Example 1 A photoconductor drum was obtained in the same manner as in Example 1 except that the intermediate layer did not contain the nitrogen-containing heterocyclic compound.
耐久にはキャノン製複写機NP−3525を用いた。NP−35
25に前記感光体ドラムをセットして駆動させ、現像位置
に配置した電位測定センサーによって、感光体の暗電位
（Vd）が−800Vとなる様に一次帯電グリッドバイアスを
調整した。さらに、ベタ白原稿を用いた際の感光体の明
電位（Ve）が、−100Vになる様に原稿読み取り用ハロゲ
ンランプの電圧を調整した。For durability, a Canon copier NP-3525 was used. NP-35
The photosensitive drum was set at 25 and driven, and the primary charging grid bias was adjusted by a potential measurement sensor arranged at the developing position so that the dark potential (Vd) of the photosensitive member became -800 V. Further, the voltage of the document reading halogen lamp was adjusted such that the light potential (Ve) of the photoconductor when using a solid white document was -100V.
以上の初期設定後、ベタ白原稿を用いてA4サイズ横流
しの連続耐久を10,000毎行った。耐久後、Vd,Veを再測
定し、さらにVd＝−800Vにグリッドバイアスを再調整し
た時のVeを測定した。After the initial setting described above, continuous durability of A4 size horizontal flow was performed every 10,000 using a solid white original. After endurance, Vd and Ve were measured again, and Ve was measured when the grid bias was readjusted to Vd = -800V.
その結果、比較例１の感光体は、Vdが40V、Veが50V低
下したが、実施例１の感光体では、Vdが15V、Veが10Vの
低下と、電位の変動が少ないことが判った。また初期の
Ve設定に必要な光量も比較例１より大きく変化せず感度
低下も少ないことが判明し、良好な感光体が得られたと
言える。以上の結果を第１表にまとめた。As a result, in the photoconductor of Comparative Example 1, Vd was reduced by 40 V and Ve was reduced by 50 V. However, in the photoconductor of Example 1, Vd was reduced by 15 V and Ve was reduced by 10 V, indicating that there was little change in potential. . Also early
It was found that the amount of light required for setting Ve did not change much as compared with Comparative Example 1, and that the decrease in sensitivity was small, indicating that a good photoconductor was obtained. Table 1 summarizes the above results.
また、上記耐久試験前後において、ハーフトーン画像
の濃度変化、画像ムラの発生を評価した。比較例１にお
いては、耐久後の画像濃度の低下及び濃度ムラが生じた
が、実施例１においては耐久後でも安定したハーフトー
ン画像が得られた。その結果を第１表にまとめた。Before and after the durability test, a change in density of a halftone image and occurrence of image unevenness were evaluated. In Comparative Example 1, a decrease in image density and density unevenness after durability occurred, but in Example 1, a stable halftone image was obtained even after durability. The results are summarized in Table 1.
実施例２ 中間層に構造式 で表わされる含窒素複素環式化合物を用いた以外は実施
例１と同様にして感光体ドラムを作成し、耐久を行っ
た。その結果を第１表にまとめた。Example 2 Structural formula for intermediate layer A photosensitive drum was prepared and durable in the same manner as in Example 1 except that the nitrogen-containing heterocyclic compound represented by the following formula was used. The results are summarized in Table 1.
実施例３ 中間層として次の熱硬化性ポリウレタンを用いた。す
なわちポリオール（３官能ポリエーテルポリオールタイ
プ、ニッポラン800）50重量部、イソシアネート（ブロ
ックイソシアネートタイプ、コロネート2540）50重量
部、構造式 で表わされる含窒素複素環式化合物５重量部及びシクロ
ヘキサノン895重量部からなる溶液を用いて浸漬塗布に
よりアルミニウムシリンダー上に塗布し、150℃で60分
間処理した後に0.6μの中間層を得た。以後は実施例１
と同様にして感光体を作成し、耐久を行った。その結果
を第１表にまとめた。Example 3 The following thermosetting polyurethane was used as the intermediate layer. That is, 50 parts by weight of polyol (trifunctional polyether polyol type, Nipporan 800), 50 parts by weight of isocyanate (block isocyanate type, Coronate 2540), structural formula Was applied onto an aluminum cylinder by dip coating using a solution comprising 5 parts by weight of a nitrogen-containing heterocyclic compound represented by the following formula and 895 parts by weight of cyclohexanone, and treated at 150 ° C. for 60 minutes to obtain a 0.6 μm intermediate layer. Hereinafter, Example 1
A photoreceptor was prepared in the same manner as described above, and durability was performed. The results are summarized in Table 1.
比較例２ 中間層に含窒素複素環式化合物を含まないこと以外は
実施例１と同様にして感光体を作成し、耐久を行った。
その結果を第１表にまとめた。Comparative Example 2 A photoconductor was prepared and durable in the same manner as in Example 1 except that the nitrogen-containing heterocyclic compound was not contained in the intermediate layer.
The results are summarized in Table 1.
実施例４ 構造式 で表わされる含窒素複素環式化合物８重量部、メタノー
ル50重量部、及びプロパノール40重量部の溶液を用いて
アルミニウムシリンダーを浸漬塗布し、100℃で10分間
の乾燥を行った。アルミニウムシリンダーへの付着固型
分は75mg/m2であった。以後は他の実施例と同様にして
感光体ドラムを作成し、耐久を行った。その結果を第１
表にまとめた。Example 4 Structural formula An aluminum cylinder was dip-coated with a solution of 8 parts by weight of a nitrogen-containing heterocyclic compound represented by the following formula, 50 parts by weight of methanol, and 40 parts by weight of propanol, and dried at 100 ° C. for 10 minutes. The solid content attached to the aluminum cylinder was 75 mg / m 2 . Thereafter, a photosensitive drum was prepared in the same manner as in the other examples, and durability was performed. The result is
It is summarized in the table.
比較例３ 中間層及び含窒素複素環式化合物を含まないこと以外
は実施例１と同様にして感光体を作成し、耐久を行っ
た。その結果を第１表にまとめた。Comparative Example 3 A photoconductor was prepared and durable in the same manner as in Example 1 except that the intermediate layer and the nitrogen-containing heterocyclic compound were not contained. The results are summarized in Table 1.
表中、○は目視にて表中項目が全く見い出されない場
合、×は、表中項目が明白に見い出される場合、××は
さらに程度が悪い場合、△は、あまり明白ではなくと
も、全く見い出されないとは言い切れない場合を意味す
る。 In the table, ○ indicates that no item in the table is found visually, × indicates that the item is clearly found in the table, XX indicates that the degree is worse, and Δ indicates that the item is not so obvious, even if it is not so obvious. Not being found means not being able to say.
以上、第１表にもまとめた様に、含窒素複素環式化合
物、特に窒素原子及び共役二重結合を環構造中にもつ含
窒素複素環式化合移を感光層と導電性基体との間、もし
くは、中間層に含ませることにより、SP2混成窒素原子
上の電子により、キャリアのトラップ等の弊害がなく、
なおかつ耐久時に感光層と基板との間に電子受容性物
質、もしくは電子供与性物質が生成し、電位の低下等を
引き起こすのを防止することを可能とした感光体ドラム
が得られた。As summarized in Table 1 above, nitrogen-containing heterocyclic compounds, in particular, nitrogen-containing heterocyclic compounds having a nitrogen atom and a conjugated double bond in a ring structure are formed between the photosensitive layer and the conductive substrate. Or, by including it in the intermediate layer, there is no adverse effect such as carrier trapping due to electrons on the SP 2 hybrid nitrogen atom,
In addition, a photoreceptor drum capable of preventing generation of an electron-accepting substance or an electron-donating substance between the photosensitive layer and the substrate at the time of durability and causing a decrease in potential or the like was obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 永原 晋 東京都大田区下丸子３丁目30番２号 キ ヤノン株式会社内 (56)参考文献 特開 昭63−125944（ＪＰ，Ａ) 特開 昭58−187931（ＪＰ，Ａ) 特開 昭58−17450（ＪＰ，Ａ) 特開 平１−314253（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Susumu Nagahara 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-63-125944 (JP, A) JP-A-58 JP 187931 (JP, A) JP-A-58-17450 (JP, A) JP-A-1-314253 (JP, A)
Claims (1)
写真感光体において、該導電性基体と該感光層との間
に、下記式（１）で表わされる化合物の層又は該化合物
を含有する中間層を有することを特徴とする電子写真感
光体。 上記式において、X3、X4、X5及びX6はそれぞれ独自に水
素原子、アルキル基、置換又は非置換のアリール基、ア
ラルキル基又は複素環式化合物基、OH,NO2,COOR（この
場合にＲは水素原子、アルキル基、アリール基又はアラ
ルキル基である）、 （この場合にR1及びR2はそれぞれ独自に水素原子、アル
キル基、アリール基又はアラルキル基である）、Cl,Br,
F又はCNであり、ＹはCH2 ｎ、CH＝CHｎ、 −Ｓ−、−Ｏ−、CH2 nSCH2 ｎ又はCH2 nOC
H2 ｎであり、 はそれぞれ独自に 1. An electrophotographic photoreceptor having a conductive substrate and an organic photosensitive layer, wherein a layer of the compound represented by the following formula (1) or the compound is contained between the conductive substrate and the photosensitive layer. An electrophotographic photoreceptor, comprising an intermediate layer. In the above formula, X 3 , X 4 , X 5 and X 6 each independently represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, an aralkyl group or a heterocyclic compound group, OH, NO 2 , COOR R is a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), (Where R 1 and R 2 are each independently a hydrogen atom, an alkyl group, an aryl group or an aralkyl group), Cl, Br,
F or CN, Y is CH 2 n , CH = CH n , -S -, - O-, CH 2 n SCH 2 n or CH 2 n OC
H 2 n , Each independently
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63215252A JP2598100B2 (en) | 1988-08-31 | 1988-08-31 | Electrophotographic photoreceptor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63215252A JP2598100B2 (en) | 1988-08-31 | 1988-08-31 | Electrophotographic photoreceptor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0264553A JPH0264553A (en) | 1990-03-05 |
| JP2598100B2 true JP2598100B2 (en) | 1997-04-09 |
Family
ID=16669239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63215252A Expired - Fee Related JP2598100B2 (en) | 1988-08-31 | 1988-08-31 | Electrophotographic photoreceptor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2598100B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7074534B2 (en) | 2002-07-10 | 2006-07-11 | E. I. Du Pont De Nemours And Company | Polymeric charge transport compositions and electronic devices made with such compositions |
| KR20070011458A (en) | 2004-04-08 | 2007-01-24 | 탈자진 인코포레이티드 | Benzotriazine inhibitors of kinases |
| RU2597364C2 (en) | 2005-11-01 | 2016-09-10 | Таргеджен, Инк. | Bi-aryl-meta-pyrimidine kinase inhibitors |
| NZ603789A (en) * | 2010-05-26 | 2015-03-27 | Sunovion Pharmaceuticals Inc | Heteroaryl compounds and methods of use thereof |
| WO2012060847A1 (en) | 2010-11-07 | 2012-05-10 | Targegen, Inc. | Compositions and methods for treating myelofibrosis |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5817450A (en) * | 1981-07-24 | 1983-02-01 | Mitsubishi Paper Mills Ltd | Electrophotographic receptor |
| JPS58187931A (en) * | 1982-04-28 | 1983-11-02 | Canon Inc | Electrophotographic receptor |
| JPS63125944A (en) * | 1986-11-17 | 1988-05-30 | Canon Inc | Electrophotographic sensitive body |
| JPH01314253A (en) * | 1988-06-14 | 1989-12-19 | Fujitsu Ltd | Electrophotographic sensitive body |
-
1988
- 1988-08-31 JP JP63215252A patent/JP2598100B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0264553A (en) | 1990-03-05 |
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