JPH06301227A - Laminated electrophotographic sensitive body, its production, and device to remove coating layer of photosensitive body - Google Patents

Laminated electrophotographic sensitive body, its production, and device to remove coating layer of photosensitive body

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Publication number
JPH06301227A
JPH06301227A JP11488393A JP11488393A JPH06301227A JP H06301227 A JPH06301227 A JP H06301227A JP 11488393 A JP11488393 A JP 11488393A JP 11488393 A JP11488393 A JP 11488393A JP H06301227 A JPH06301227 A JP H06301227A
Authority
JP
Japan
Prior art keywords
coating layer
layer
photosensitive
support
photoconductor
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.)
Pending
Application number
JP11488393A
Other languages
Japanese (ja)
Inventor
Yoshihide Shimoda
嘉英 下田
Mitsuhiro Shinobu
充弘 忍
Masayuki Sakamoto
雅遊亀 坂元
Tomoko Otsuki
朋子 大槻
Makoto Kurokawa
誠 黒川
Tatsuhiro Morita
竜廣 森田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sharp Corp
Original Assignee
Sharp Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sharp Corp filed Critical Sharp Corp
Priority to JP11488393A priority Critical patent/JPH06301227A/en
Publication of JPH06301227A publication Critical patent/JPH06301227A/en
Pending legal-status Critical Current

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  • Photoreceptors In Electrophotography (AREA)

Abstract

PURPOSE:To provide a laminated electrophotographic sensitive body having high sensitivity and which can suppresses image faults due to repetition of use, and to provide a production method of a laminated electrophotographic sensitive body and a device to remove a photosensitive coating layer so that the edge part of the coating layer of a photosensitive body formed on a cylindrical conductive supporting body can be revmoved with a simple mechanism while preventing adverse infulence of the solvent used for removing the film. CONSTITUTION:The laminated electrophotographic sensitive body has an under coating layer 1 comprising copolymer nylon resin and titanium oxide without conductivity treatment with >=95wt.% titanium oxide content. When the photosensitive coating layer 5 is formed by dipping on a conductive supporting body 1, the photosensitive coating layer on the lower edge part of the supporting body is removed by attaching a protective member 6 to protect the layer not to be removed and then removing the coating layer in the edge part side of the supporting body from the protective member 6 in the presence of a solvent to remove the film.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、有機光導電性材料を使
用した電子写真感光体に関し、特に、高感度で繰り返し
安定性に優れた積層型電子写真感光体に関するものであ
る。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member using an organic photoconductive material, and more particularly to a laminated electrophotographic photosensitive member having high sensitivity and excellent repeated stability.

【0002】また、本発明は電子写真用感光体の製造方
法並びに製造装置に関し、詳しくは、下端部の塗布層を
除去して成る、電子写真用感光体の製造方法に関する。
The present invention also relates to a method and apparatus for manufacturing an electrophotographic photosensitive member, and more particularly to a method for manufacturing an electrophotographic photosensitive member formed by removing the coating layer at the lower end.

【0003】[0003]

【従来の技術】現在実用化されている電子写真感光体
は、無機系材料を用いたものと有機系材料を用いたもの
に大別できる。無機系の代表的な感光体としては、アモ
ルファスセレン(a−Se)やアモルファスセレンひ素
(a−As7 Se3 )等のセレン系のもの、色素増感し
た酸化亜鉛(ZnO)あるいは、硫化カドミウム(Cd
S)を結着樹脂中に分散したもの、及びアモルファスシ
リコン(a−Si)を使用したもの等が有る。
2. Description of the Related Art Electrophotographic photoreceptors currently in practical use can be roughly classified into those using an inorganic material and those using an organic material. Typical inorganic photoreceptors include selenium-based ones such as amorphous selenium (a-Se) and amorphous selenium arsenic (a-As 7 Se 3 ), dye-sensitized zinc oxide (ZnO), or cadmium sulfide. (Cd
There are those in which S) is dispersed in a binder resin, those in which amorphous silicon (a-Si) is used, and the like.

【0004】これに対して、近年有機系の光導電性材料
は開発が進み、従来より用いられてきた無機系のものよ
りも多く使用されるようになった。有機系の代表的な感
光体としては、2,4,7−トリニトロ−9−フルオレ
ノン(TNF)とポリ−N−ビニルカルバゾール(PV
K)との電荷移動錯体を用いたものなどがある。
On the other hand, in recent years, organic photoconductive materials have been developed and used more than the conventionally used inorganic materials. Typical organic photoreceptors include 2,4,7-trinitro-9-fluorenone (TNF) and poly-N-vinylcarbazole (PV
For example, a charge transfer complex with K) is used.

【0005】これらの感光体は、多くの長所を有すると
同時に欠点も有している。例えば、セレン系及びCdS
を使用した感光体は、耐熱性、保存安定性に問題があ
り、また毒性を有するため簡単に廃棄することができず
回収しなければならないという制約がある。ZnO樹脂
分散系感光体は、低感度及び耐久性の無さから現在ほと
んど使用されなくなりつつある。a−Si感光体は、高
感度、高耐刷性等の優れた長所はもっているものの、そ
の製造プロセスの複雑さに起因する高製造コスト及び成
膜時の欠陥に起因する画像欠陥等の問題を残している。
These photoreceptors have many advantages as well as drawbacks. For example, selenium and CdS
The photoconductor using is problematic in heat resistance and storage stability, and has a limitation that it cannot be easily discarded because it has toxicity and must be recovered. ZnO resin-dispersed photoreceptors are now almost obsolete because of their low sensitivity and lack of durability. Although the a-Si photoconductor has excellent advantages such as high sensitivity and high printing durability, there are problems such as high manufacturing cost due to the complexity of the manufacturing process and image defects due to defects during film formation. Is left.

【0006】一方有機系材料を使用した感光体は、感
度、耐久性及び環境に対する安定性等に若干の問題はあ
るが、毒性、コスト、材料設計の自由度等の点において
無機材料に比べ多くの利点がある。有機材料が多種存在
し合成により多様のアレンジも可能なためそれらを適宜
選択することにより保存安定性、毒性等の問題を回避す
ることができまた低コストで製造することが可能なこと
から、各社精力的に検討している。しかし、有機感光体
もやはり低感度という問題点を有しており、その改良が
進められている。先に記したPVK−TNF電荷移動錯
体もその改良の一つであったが十分な感度を有するまで
には至らなかった。
On the other hand, a photoconductor using an organic material has some problems in sensitivity, durability, environmental stability, etc., but is more common than inorganic materials in terms of toxicity, cost, material design freedom, etc. There are advantages. Since there are various organic materials and various arrangements can be made by synthesis, it is possible to avoid problems such as storage stability and toxicity by appropriately selecting them, and it is possible to manufacture at low cost. We are energetically considering. However, the organic photoreceptor also has a problem of low sensitivity, and its improvement is being promoted. The PVK-TNF charge transfer complex described above was one of the improvements, but it did not reach sufficient sensitivity.

【0007】そこで、各社の精力的な検討の中から、そ
の他種々の増感方法が提案され、中でも図11に示すよ
うな、光を照射したときに電荷担体を発生する物質(以
下「電荷発生物質」と記す)を含む層3(以下「電荷発
生層」と記す)と電荷発生層で発生した電荷担体を受け
入れ、それを輸送する物質(以下電荷輸送物質」と記
す)を主体とする層4(以下「電荷輸送層」を記す)と
を導電性支持体1に積層した積層型の感光体(以下「機
能分離型感光体」と記す)が優れた増感性を示すことか
ら、現在実用化されている有機感光体構成の大部分を占
めてきている。又、近年の耐久性向上から今後感光体の
主流として期待されている。
Therefore, various sensitizing methods have been proposed from the enthusiastic examination of each company, and among them, as shown in FIG. 11, substances that generate charge carriers when irradiated with light (hereinafter referred to as "charge generation"). A layer 3 (hereinafter referred to as “substance”) and a layer mainly composed of a substance (hereinafter referred to as “charge transport substance”) that accepts and transports charge carriers generated in the charge generation layer (hereinafter referred to as “charge generation layer”). 4 (hereinafter referred to as “charge transport layer”) and a conductive type support 1 laminated on the laminated type photoreceptor (hereinafter referred to as “function-separated type photoreceptor”) exhibit excellent sensitization, It has accounted for the majority of the organic photoconductor structures that have been commercialized. Further, it is expected to be the mainstream of photoconductors in the future due to the improvement of durability in recent years.

【0008】さらに、帯電性改善、支持体からの不要な
電荷注入の阻止、支持体上の欠陥の被覆、ピンホール発
生の防止、感光層の接着性の改善等のために下引層を設
けることで、耐久性も向上してきている。
Further, an undercoat layer is provided for the purpose of improving chargeability, preventing unnecessary charge injection from the support, covering defects on the support, preventing pinholes, improving the adhesiveness of the photosensitive layer, and the like. As a result, durability is improving.

【0009】有機電子写真感光体の感光体の塗布方法と
しては、スプレー法、バーコート法、ロールコート法、
ブレード法、リング法、浸漬法等が挙げられる。特に浸
漬塗布方法は、感光体塗布液を満たした塗布槽に導電性
基体を浸漬した後に、一定速度又は逐次変化する速度で
引き上げることにより、感光層を形成する方法である
が、比較的簡単で、生産性及びコストの点で優れている
ため、電子写真感光体を製造する場合に多く利用されて
いる。
The coating method of the organic electrophotographic photoreceptor is a spray method, a bar coating method, a roll coating method,
A blade method, a ring method, a dipping method and the like can be mentioned. In particular, the dip coating method is a method of forming a photosensitive layer by immersing a conductive substrate in a coating tank filled with a photoreceptor coating liquid and then pulling it up at a constant rate or a rate that changes sequentially, but it is relatively simple. Since it is excellent in productivity and cost, it is often used for manufacturing electrophotographic photoreceptors.

【0010】[0010]

【発明が解決しようとする課題】上記機能分離型感光体
にすることにより感度、耐刷性は、向上してきている
が、近年、複写機の高速化、長寿命化が要求されるよう
になり更に感光体の感度の向上が必要となってきてい
る。しかし感度を向上させようとすると帯電性が低く、
暗減衰が大きくなり繰り返し安定性に劣るといった問題
が生じる。また複写機、プリンター等があらゆる環境下
で使用される場合があるため、いかなる環境条件下にお
いても感光体特性が安定であることが要求されている。
Although the sensitivity and printing durability have been improved by using the above-mentioned function-separated type photoreceptor, in recent years, it has been required to increase the speed and life of copying machines. Further, it is necessary to improve the sensitivity of the photoconductor. However, if you try to improve the sensitivity, the chargeability is low,
There is a problem that the dark decay becomes large and the repeated stability becomes poor. Further, since a copying machine, a printer or the like may be used under any environment, it is required that the characteristics of the photoconductor be stable under any environmental conditions.

【0011】これらの問題点を改善する目的で導電性支
持体と電荷発生層との間に下引き層と呼ばれる樹脂層を
設けることが、特開昭51−114132号公報、同5
2−25638号公報、同56−21129号公報、同
58−95351号公報、同60−218655号公
報、同61−163346号公報、同61−17946
4号公報、同61−254951号公報、特開平2−1
81158号公報等で提案されている。
For the purpose of improving these problems, it is known to provide a resin layer called an undercoat layer between the conductive support and the charge generating layer, as disclosed in JP-A-51-114132.
No. 2-25638, No. 56-21129, No. 58-95351, No. 60-218655, No. 61-163346, No. 61-17946.
4, JP-A 61-254951, JP-A 2-1
No. 81158 is proposed.

【0012】該下引層用の樹脂として電荷発生層用塗布
液の溶剤(ハロゲン系、ベンゼン系、エーテル系、エス
テル系、ケトン系など)に不溶であることが望ましく、
一般的にアルコール又は、水溶性の樹脂が使用されてい
る。しかし、このような樹脂層を下引層として設けるだ
けでは、低湿条件下に於ける数万回の繰り返し使用で残
留電位の上昇が著しく、白字部分のカブリなど画像上の
欠陥が発生し、また高湿条件下では、帯電電位の低下に
よる画像濃度不足が生じ鮮明な画像が得られないという
問題があった。また、基板欠陥に起因する塗膜不良の防
止、及び低コスト化のために粗面基板を使用する等の目
的から、下引層の厚膜化が要求されるが、この場合環境
安定性が更に問題となる。
The resin for the undercoat layer is preferably insoluble in the solvent (halogen-based, benzene-based, ether-based, ester-based, ketone-based, etc.) of the charge generation layer coating liquid,
Generally, alcohol or water-soluble resin is used. However, if only such a resin layer is provided as the undercoat layer, the residual potential increases remarkably after repeated use of tens of thousands of times under low humidity conditions, and image defects such as fog in white letters occur. Under high humidity conditions, there is a problem that a clear image cannot be obtained due to insufficient image density due to a decrease in charging potential. In addition, for the purpose of preventing coating film defects due to substrate defects and using a rough substrate for cost reduction, thickening of the undercoat layer is required, but in this case environmental stability is It is even more problematic.

【0013】特開昭58−95351号公報などに記載
のアルコール可溶性樹脂(N−アルコキシメチル化ナイ
ロン樹脂)を下引層に用いた感光体は、湿度の影響は受
けにくいものの、感度が悪く鮮明な画像が得られず、下
引層の厚膜化も難しい。また特開平2−181158号
公報などに記載のアルミナ被覆酸化チタンとポリアミド
系樹脂からなる下引層を用いた感光体は、下引層に酸化
チタンを混合させることで、下引層の厚膜化を可能にし
たが環境条件により繰り返し安定性が左右されるといっ
た問題等を残している。
A photoreceptor using an alcohol-soluble resin (N-alkoxymethylated nylon resin) described in JP-A-58-95351 as an undercoat layer is less susceptible to humidity, but has poor sensitivity and is clear. It is difficult to obtain a thick image for the undercoat layer. Further, a photoreceptor using an undercoat layer made of alumina-coated titanium oxide and a polyamide resin as described in JP-A-2-181158, etc., is a thick film of the undercoat layer by mixing titanium oxide in the undercoat layer. However, there are still problems such as repeated stability depending on environmental conditions.

【0014】上記のような有機電子写真用感光体の性能
向上に伴い、複写機やLBPなどの性能向上、特に現像
特性の良好な安定性、さらには、高速機種への搭載の可
能性が期待されるようになってきた。このような、現像
特性の安定化や高速機種への搭載を考える時、感光体と
現像スリーブの位置関係が非常に重要であり、その間隔
を一定に保った為、現像カラーローラーを用いる方法が
採用されている。その為、前記カラーローラーが接触す
る部分には、大きな応力がかかり、感光体の塗布層が存
在する場は、膜ハガレによる悪影響が生じる。従って、
浸漬塗布により電子写真用感光体の塗布層を形成する場
合、基体下端部の塗布層を除去する必要がある。
With the improvement in the performance of the above-described organic electrophotographic photoreceptor, it is expected that the performance of the copying machine, the LBP and the like will be improved, especially the stability of the developing characteristics will be good, and the possibility of mounting in a high speed model. It has started to be done. The positional relationship between the photoconductor and the developing sleeve is very important when considering the stabilization of the developing characteristics and mounting on high-speed models, and the method of using the developing color roller is recommended because the distance between them is kept constant. Has been adopted. Therefore, a large stress is applied to the portion in contact with the color roller, and in the case where the coating layer of the photoconductor is present, the film peeling has an adverse effect. Therefore,
When the coating layer of the electrophotographic photoreceptor is formed by dip coating, it is necessary to remove the coating layer at the lower end of the substrate.

【0015】従来、基体下端部の塗布層を除去する方法
として、例えば、ブラシで除去する方法(特開昭60−
9731号公報)、掻き取り部材による方法(特開昭6
1−222571号公報)、レーザー光照射により燃
焼、昇華させる方法(特開平3−144458号公報)
などが知られており、特開昭63−27846号公報に
は、遮閉剤を設けて除去を行うことが記載されている。
Conventionally, as a method of removing the coating layer at the lower end of the substrate, for example, a method of removing with a brush (Japanese Patent Laid-Open No. 60-
9731), a method using a scraping member (Japanese Patent Application Laid-Open No. Sho 6-66).
1-222271), a method of burning and sublimating by laser light irradiation (JP-A-3-144458).
Etc. are known, and JP-A-63-27846 describes that a blocking agent is provided for removal.

【0016】しかしながら、従来の方法では、上記塗布
層除去の際、除去溶剤の蒸気やハネにより非除去部がお
かされ、画像欠陥の原因となる問題点があった。一方、
特開昭63−27846号公報に記載されている方法は
機構が複雑になり、操作が容易でないといった欠点があ
る。
However, in the conventional method, when the coating layer is removed, the non-removed portion is left behind by the vapor or the splash of the removing solvent, which causes a problem of image defects. on the other hand,
The method described in Japanese Patent Laid-Open No. 63-27846 has the drawback that the mechanism is complicated and the operation is not easy.

【0017】本発明は、従来技術における上記の問題に
鑑みてなされたものである。
The present invention has been made in view of the above problems in the prior art.

【0018】したがって、本発明の第1の目的は、いか
なる環境条件下においても高感度で繰り返し使用による
画像欠陥を抑制することができる積層型電子写真感光体
を提供することにある。
Therefore, a first object of the present invention is to provide a multi-layer type electrophotographic photosensitive member which has high sensitivity under any environmental conditions and can suppress image defects due to repeated use.

【0019】本発明の第2の目的は、円筒状導電性支持
体上に設けられた感光体の塗布層の端部を、簡単な機構
で、除去溶剤の悪影響を防止しながら除去することがで
きる積層型電子写真用感光体の製造方法及び感光体塗布
層除去装置を提供することにある。
A second object of the present invention is to remove the end portion of the coating layer of the photosensitive member provided on the cylindrical conductive support with a simple mechanism while preventing the removal solvent from being adversely affected. An object of the present invention is to provide a method of manufacturing a laminated type electrophotographic photoconductor and a photoconductor coating layer removing device.

【0020】[0020]

【課題を解決するための手段】前記目的を達成するため
に、本発明では、導電性支持体上に、下引層、電荷発生
層及び電荷輸送層を有する電子写真感光体において、共
重合ナイロン樹脂と導電性処理を施していない酸化チタ
ンとからなり、該酸化チタンの含有量が重量比で95%
以上である下引層を使用する。
To achieve the above object, in the present invention, an electrophotographic photosensitive member having an undercoat layer, a charge generating layer and a charge transporting layer on a conductive support is used as a copolymer nylon. Consists of resin and titanium oxide that has not been subjected to a conductive treatment, and the content of the titanium oxide is 95% by weight.
The above-mentioned undercoat layer is used.

【0021】また、導電性支持体上に浸漬塗布により感
光体塗布層を設けてなる積層型電子写真感光体の製造に
当たり、感光体塗布層を形成した後に支持体下端部の感
光体塗布層を除去する際、非除去層を保護するための保
護部材を支持体下端部に設けて、該保護部材より支持体
端部側の塗布層を除去溶剤存在化にて除去する。
Further, in the production of a laminated electrophotographic photosensitive member having a photosensitive material coating layer provided on a conductive support by dip coating, the photosensitive material coating layer is formed and then the photosensitive material coating layer at the lower end of the support is formed. At the time of removal, a protective member for protecting the non-removed layer is provided at the lower end of the support, and the coating layer on the end of the support with respect to the protective member is removed in the presence of a removal solvent.

【0022】そして、感光体塗布層除去装置を、シャッ
タ機構の保護部材及び溶剤除去部材を備えてなる、導電
性支持体上の感光体塗布層の拭き取り槽で構成した。
The photoconductor coating layer removing device is constituted by a wiping tank for the photoconductor coating layer on the conductive support, which is equipped with a protective member for the shutter mechanism and a solvent removing member.

【0023】シャッタ機構の保護部材は、複数枚の羽根
部材より構成された同心円状に開閉可能な機構のものが
用いられる。
As the protective member of the shutter mechanism, one having a concentric opening / closing mechanism composed of a plurality of blade members is used.

【0024】[0024]

【作用】導電性の酸化チタン[粉体抵抗102 Ωcm以
下(100kg/cm2 圧粉体)]を使用した場合、帯
電電位の不足や繰り返し使用時の帯電電位の低下等の問
題が生じ、その含有量が増えるにつれその現象はが顕著
となるが、本発明で非導電性酸化チタンを使用すること
で、回避することができる。
When conductive titanium oxide [powder resistance 10 2 Ωcm or less (100 kg / cm 2 green powder)] is used, problems such as insufficient charging potential and reduction in charging potential during repeated use occur, Although the phenomenon becomes more remarkable as the content thereof increases, it can be avoided by using the non-conductive titanium oxide in the present invention.

【0025】同心円上に開閉する保護部材の使用によっ
て、感光体塗布層除去の際の溶剤の悪影響を防止すると
共に、径の異なる円筒状導電性支持体に対応可能であ
り、下端部除去装置の交換が不要である。
By using a protective member that opens and closes on a concentric circle, it is possible to prevent the adverse effect of the solvent at the time of removing the photoconductor coating layer, and it is possible to deal with cylindrical conductive supports having different diameters. No replacement required.

【0026】以下本発明を図により更に説明する。The present invention will be further described below with reference to the drawings.

【0027】図1は、本発明の電子写真感光体の模式断
面図であり、1は導電性支持体、2は下引層、3は電荷
発生層、4は電荷輸送層を示す。
FIG. 1 is a schematic sectional view of an electrophotographic photosensitive member of the present invention, in which 1 is a conductive support, 2 is an undercoat layer, 3 is a charge generation layer, and 4 is a charge transport layer.

【0028】本発明において、導電性支持体としては、
基体自体が導電性を持つもの、例えばアルミニウム、ア
ルミニウム合金、銅、亜鉛、ステンレス、ニッケル、チ
タン等を用いる事ができ、その他にアルミニウム、アル
ミニウム合金、酸化インジウム、酸化錫等を蒸着又は、
塗布したプラスチックや紙、導電性粒子を含有したプラ
スチックや紙、及び導電性ポリマーを含有するプラスチ
ック等を用いる事ができ、それらの形状としては、ドラ
ム状、シート状、シームレスベルト状のものなどが使用
できる。
In the present invention, as the conductive support,
The substrate itself having conductivity, for example, aluminum, aluminum alloy, copper, zinc, stainless steel, nickel, titanium or the like can be used, and aluminum, aluminum alloy, indium oxide, tin oxide or the like is vapor-deposited, or
It is possible to use coated plastics and papers, plastics and papers containing conductive particles, and plastics containing conductive polymers, and the shapes thereof include drum shape, sheet shape, seamless belt shape and the like. Can be used.

【0029】次いで、導電性基体表面の傷、凹凸の被
覆、繰り返し使用時の帯電性の劣化防止、低温/低湿環
境下での帯電特性の改善等の理由により、導電性基体と
電荷発生層/電荷輸送層との間に下引層を設ける場合が
ある。
Next, for reasons such as scratches on the surface of the conductive substrate, coating of irregularities, prevention of deterioration of chargeability during repeated use, and improvement of charging characteristics in a low temperature / low humidity environment, the conductive substrate and the charge generating layer / An undercoat layer may be provided between the charge transport layer and the charge transport layer.

【0030】導電性支持体と電荷発生層との間に設けら
れる下引層用の樹脂は、共重合ナイロン樹脂で、酸化チ
タンは、非導電性ものが使用されている。該非導電性酸
化チタンの粒径は1μm以下で、好ましくは、0.01
〜0.2μmであり、その混合比率は、重量比で95%
〜99%が好ましく、これら範囲外の含有量では、環境
安定性及び繰り返し安定性及び膜物性に問題が生じる。
The resin for the undercoat layer provided between the conductive support and the charge generating layer is a copolymer nylon resin, and the titanium oxide is a non-conductive one. The particle diameter of the non-conductive titanium oxide is 1 μm or less, preferably 0.01
~ 0.2 μm, and the mixing ratio is 95% by weight.
It is preferably up to 99%, and if the content is outside these ranges, problems occur in environmental stability, repeated stability and film physical properties.

【0031】下引層の材料としては、従来より、ポリア
ミド、共重合ナイロン、ポリビニルアルコール、ポリウ
レタン、ポリエステル、エポキシ、フェノール樹脂、カ
ゼイン、セルロース、ゼラチン等が知られており、特に
アルコール可溶性の共重合ナイロンが多く用いられてい
る。これらを、水及び各種有機溶剤、特に水、メタノー
ル、エタノール、ブタノールの単独溶剤、又は水/アル
コール、2種以上のアルコールの混合溶剤、又は、ジク
ロロエタン、クロロホルム、トリクロロエタン、トリク
ロロエチレン、パークロルエチレン等の塩素系溶剤とア
ルコールとの混合溶剤に溶解し、導電性基体表面に塗布
する。
As materials for the undercoat layer, polyamide, copolymer nylon, polyvinyl alcohol, polyurethane, polyester, epoxy, phenol resin, casein, cellulose, gelatin and the like have been conventionally known, and particularly alcohol-soluble copolymer. Nylon is often used. These are water and various organic solvents, especially water, methanol, ethanol, butanol as a single solvent, or water / alcohol, a mixed solvent of two or more alcohols, or dichloroethane, chloroform, trichloroethane, trichloroethylene, perchlorethylene, etc. It is dissolved in a mixed solvent of a chlorine-based solvent and alcohol and applied on the surface of the conductive substrate.

【0032】また、必要に応じて、特に下引層の体積抵
抗率の設定、低温/低湿環境下での繰り返しエージング
特性の改善などの理由で、酸化亜鉛、酸化チタン、酸化
スズ、酸化インジウム、シリカ、酸化アンチモン等の無
機顔料を分散含有させることが知られている。
In addition, if necessary, zinc oxide, titanium oxide, tin oxide, indium oxide, zinc oxide, titanium oxide, tin oxide, etc. may be used for reasons such as setting the volume resistivity of the undercoat layer and improving the repeated aging characteristics under low temperature / low humidity environment. It is known to disperse and contain inorganic pigments such as silica and antimony oxide.

【0033】上記のメトキシメチル化ナイロン樹脂と非
導電性酸化チタンの混合物を、メタノール、エタノール
その他の低級アルコール、または水とそれらの混合物、
もしくはアルコール類と、芳香族系、ハロゲン系、エス
テル系溶剤等のいずれかを混合した溶剤にて分散作製
し、該塗布液を導電性支持体上に塗布することにより下
引層が形成される。下引層の膜厚は、0.01〜10μ
m、好ましくは0.05〜5μmの範囲に設定する。該
下引層用塗布液の分散方法としては、ボールミル、サン
ドミル、アトライター、振動ミル、超音波分散機等があ
る。塗布手段としては、ディップコーター、ブレードコ
ーター、アプリケーター、ロッドコーター、ナイフコー
ター、キャスティング、リング及びスプレイ等の塗布方
法がある。次に、本発明をさらに詳細に説明する。
A mixture of the above-mentioned methoxymethylated nylon resin and non-conductive titanium oxide is mixed with methanol, ethanol or other lower alcohol, or water with a mixture thereof,
Alternatively, an undercoat layer is formed by dispersing and preparing with a solvent in which alcohol is mixed with any one of an aromatic solvent, a halogen solvent, an ester solvent and the like, and applying the coating liquid on a conductive support. . The thickness of the undercoat layer is 0.01 to 10 μm.
m, preferably 0.05 to 5 μm. Examples of the method for dispersing the coating liquid for the undercoat layer include a ball mill, a sand mill, an attritor, a vibration mill and an ultrasonic disperser. As the coating means, there are coating methods such as dip coater, blade coater, applicator, rod coater, knife coater, casting, ring and spray. Next, the present invention will be described in more detail.

【0034】下引層の上には、電荷発生層が形成され
る。本発明の電荷発生層は、光照射により電荷を発生す
る電荷発生材料を主成分とし、必要に応じて公知の結合
剤、可塑剤、増感剤を含有する。
A charge generation layer is formed on the undercoat layer. The charge generation layer of the present invention is mainly composed of a charge generation material that generates a charge upon irradiation with light, and optionally contains a known binder, plasticizer and sensitizer.

【0035】電荷発生層に使用される電荷発生材料とし
ては、クロロダイアンブルー等のビスアゾ系化合物、キ
ナクリドン、アントラキノン、ジブロモアンサンスロン
等の多環キノン系化合物、ペリレンイミド、ペリレン酸
無水物等のペリレン系化合物、金属フタロシアニン及び
無金属フタロシアニン、ハロゲン化無金属フタロシアニ
ン等のフタロシアニン系化合物、スクエアリウム色素、
アズレニウム色素、チアピリリウム色素、及びカルバゾ
ール骨格、スチリルスチルベン骨格、トリフェニルアミ
ン骨格、ジベンゾチオフェン骨格、オキサジアゾール骨
格、フルオレノン骨格、ビススチルベン骨格、ジスチリ
ルオキサジアゾール骨格又はジスチリルカルバゾール骨
格を有するアゾ顔料、及びアズレニウム塩系化合物等が
知られている。
Examples of the charge generating material used in the charge generating layer include bisazo compounds such as chlorodian blue, polycyclic quinone compounds such as quinacridone, anthraquinone and dibromoanthanthrone, and perylene compounds such as perylene imide and perylene anhydride. Compounds, metal phthalocyanines and metal-free phthalocyanines, phthalocyanine compounds such as halogenated metal-free phthalocyanines, squarylium dyes,
Azurenium dye, thiapyrylium dye, and azo pigment having a carbazole skeleton, styrylstilbene skeleton, triphenylamine skeleton, dibenzothiophene skeleton, oxadiazole skeleton, fluorenone skeleton, bisstilbene skeleton, distyryloxadiazole skeleton or distyrylcarbazole skeleton , And azurenium salt compounds are known.

【0036】電荷発生層の作成方法としては、真空蒸着
で直接化合物を成膜する方法及び結着性樹脂溶液中に分
散し塗布して成膜する方法があるが一般に後者の方法が
好ましく電荷発生層の膜厚は、0.05〜5μmで好ま
しくは、0.1〜1μmである。塗布による作製の場
合、結着性樹脂溶液中への電荷発生材料の混合分散の方
法並びに、塗布方法としては、下引層と同様の方法が用
いられる。また結着性樹脂溶液用の結着性樹脂として
は、メラミン樹脂、エポキシ樹脂、シリコン樹脂、ポリ
ウレタン樹脂、アクリル樹脂、塩化ビニル−酢酸ビニル
共重合体樹脂、ポリカーボネート樹脂、フェノキシ樹脂
等があり、これらの樹脂を溶解させる溶剤としては、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、酢酸ブチル等のエステル類、テト
ラヒドロフラン、ジオキサン等のエーテル類、ベンゼ
ン、トルエン、キシレン等の芳香族炭化水素類、N,N
−ジメチルホルムアミド、ジメチルスルホキシド等の非
プロトン性極性溶媒等を用いることができる。
As a method for forming the charge generating layer, there are a method of directly forming a film of a compound by vacuum vapor deposition and a method of dispersing and coating the compound in a binder resin solution to form a film, and the latter method is generally preferable. The thickness of the layer is 0.05 to 5 μm, preferably 0.1 to 1 μm. In the case of production by coating, as the method of mixing and dispersing the charge generating material in the binder resin solution and the coating method, the same method as that for the undercoat layer is used. Examples of the binder resin for the binder resin solution include melamine resin, epoxy resin, silicone resin, polyurethane resin, acrylic resin, vinyl chloride-vinyl acetate copolymer resin, polycarbonate resin, and phenoxy resin. As a solvent for dissolving the resin, acetone, methyl ethyl ketone, ketones such as cyclohexanone, ethyl acetate, esters such as butyl acetate, tetrahydrofuran, ethers such as dioxane, benzene, toluene, aromatic hydrocarbons such as xylene, N, N
-Aprotic polar solvents such as dimethylformamide and dimethylsulfoxide can be used.

【0037】電荷発生層の上に設けられる電荷輸送層の
電荷輸送物質としては、ヒドラゾン系化合物、ピラゾリ
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、スチルベン系化合物、オキサジアゾ
ール系化合物等が使用可能であり、電荷輸送液の作製
は、結着剤樹脂溶液中へ電荷輸送物質を溶解して作製す
る。該電荷輸送層の塗布方法としては、下引層と同様の
方法が用いられる。
Examples of the charge transport material of the charge transport layer provided on the charge generation layer include hydrazone compounds, pyrazoline compounds, triphenylamine compounds, triphenylmethane compounds, stilbene compounds, oxadiazole compounds. Etc. can be used, and the charge transport liquid is prepared by dissolving the charge transport substance in the binder resin solution. As the coating method for the charge transport layer, the same method as for the undercoat layer is used.

【0038】該電荷輸送層の膜厚は、5〜50μmで好
ましくは、10〜40μmである。更に本発明の電子写
真用感光体の感光層は、感度の向上、繰返し使用時の残
留電位の上昇や疲労を抑える等の目的のために、一種若
しくは二種以上の電子受容性物質や色素を含有してもよ
い。
The thickness of the charge transport layer is 5 to 50 μm, preferably 10 to 40 μm. Further, the photosensitive layer of the electrophotographic photoreceptor of the present invention contains one or more electron-accepting substances or dyes for the purpose of improving sensitivity, suppressing increase in residual potential during repeated use and suppressing fatigue. May be included.

【0039】ここで用いられる電子受容性物質として
は、例えば無水コハク酸、無水マレイン酸、無水フタル
酸、4−クロルナフタル酸無水物等の酸無水物等の酸無
水物、テトラシアノエチレン、テレフタルマロンジニト
リル等のシアノ化合物、4−ニトロベンズアルデヒド等
のアルデヒド類、アントラキノン、1−ニトロアントラ
キノン等のアントラキノン類、2,4,7−トリニトロ
フルオレノン、2,4,5,7−テトラニトロフルオレ
ノン等の多環若しくは複素環ニトロ化合物を化学増感剤
として用いることができる。
Examples of the electron-accepting substance used here include acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride and 4-chloronaphthalic anhydride, tetracyanoethylene, terephthalmalone. Cyano compounds such as dinitrile, aldehydes such as 4-nitrobenzaldehyde, anthraquinones, anthraquinones such as 1-nitroanthraquinone, 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone and the like A polycyclic or heterocyclic nitro compound can be used as a chemical sensitizer.

【0040】色素としては、例えば、キサンテン系色
素、チアジン色素、トリフェニルメタン色素やキノリン
系顔料、銅フタロシアニン顔料等の有機光導電性化合物
を光学増感剤として用いることができる。
As the dye, for example, an organic photoconductive compound such as a xanthene dye, a thiazine dye, a triphenylmethane dye, a quinoline dye or a copper phthalocyanine pigment can be used as an optical sensitizer.

【0041】更に本発明の電子写真用感光体の感光層
は、成形性、可撓性、機械的強度を向上させるために、
周知の可塑剤を含有してもよい。可塑剤としては、二塩
基酸エステル、脂肪酸エステル、燐酸エステル、フタル
酸エステルや塩素化パラフィン、エポキシ型可塑剤等が
挙げられる。また、必要に応じてレベリング剤、酸化防
止剤や紫外線吸収剤等を含有してもよい。
Further, the photosensitive layer of the electrophotographic photoreceptor of the present invention has the following properties in order to improve moldability, flexibility and mechanical strength.
It may contain a well-known plasticizer. Examples of the plasticizer include dibasic acid ester, fatty acid ester, phosphoric acid ester, phthalic acid ester, chlorinated paraffin, and epoxy type plasticizer. Moreover, you may contain a leveling agent, an antioxidant, an ultraviolet absorber, etc. as needed.

【0042】次に本発明の感光体塗布層除去装置の一例
の断面図及び平面図を各々、図2、図3に示す。
Next, a cross-sectional view and a plan view of an example of the photoconductor coating layer removing device of the present invention are shown in FIGS. 2 and 3, respectively.

【0043】図において、1は円筒状導電性支持体、5
は感光体の塗布層を示し、複数枚の羽根部材7の移動に
より同心円状に開閉可能な保護部材6より支持体端部側
の塗布層を、下端拭き取り槽8の溶剤中にて除去ブラシ
9を用いて除去する構成となっている。円筒状支持体に
当接、もしくは、ごく近傍に接近して非除去部を保護す
る為に、羽根部材は6枚以上であることが望ましく、そ
れ以下では、除去溶剤の影響を防ぐことができない。
In the figure, 1 is a cylindrical conductive support, 5
Is a coating layer of the photoconductor, and the coating layer on the end portion side of the support from the protective member 6 which can be opened and closed concentrically by the movement of a plurality of blade members 7 is removed in a solvent in the lower end wiping tank 8 by a brush 9 It is configured to be removed by using. In order to protect the non-removed part by coming into contact with or close to the cylindrical support, it is desirable that the number of blade members is 6 or more, and if it is less than that, the influence of the removal solvent cannot be prevented. .

【0044】図3においては、円筒状導電性支持体に当
接もしくは、ごく近傍に接近する部分の羽根の形状が直
線的になっているが、該羽根の形状としては、円筒状導
電性支持体との密接性向上の為、適当な曲率を有しても
良い。そのようにして、密接性を向上した装置の一例を
図4、図5に示す。
In FIG. 3, the shape of the blade of the portion which is in contact with or close to the cylindrical conductive support is linear, but the shape of the blade is cylindrical conductive support. It may have an appropriate curvature in order to improve the close contact with the body. An example of a device with improved closeness is shown in FIGS. 4 and 5.

【0045】図6、図7及び図8、図9は、保護部材又
は下端拭き取り槽を、バネ7により、水平方向に移動可
能とした感光体塗布層除去装置の断面図と平面図の一例
である。図6〜9においては、水平方向に移動可能とす
る手段として、バネを用いているが、その他、油圧方
式、空気圧方式等適当な手段を用いてもかまわない。さ
らに、ベアリングその他の手段との組み合せにより、円
滑に移動させる方式を用いても構わない。
FIG. 6, FIG. 7, FIG. 8 and FIG. 9 are examples of a sectional view and a plan view of the photoconductor coating layer removing device in which the protective member or the lower end wiping tank can be moved horizontally by the spring 7. is there. In FIGS. 6 to 9, a spring is used as the means capable of moving in the horizontal direction, but other suitable means such as a hydraulic system or a pneumatic system may be used. Further, a method of smoothly moving may be used in combination with a bearing or other means.

【0046】このように、保護部材及び下端拭き取り槽
を水平移動可能とすることにより、保護部材が同心円状
に開閉可能である為、電子写真用感光体の下端拭き取り
槽の位置決めが可能となり、装置の芯出しが不要とな
る。
As described above, since the protective member and the lower end wiping tank can be moved horizontally, the protective member can be opened and closed concentrically, so that the lower end wiping tank of the electrophotographic photoconductor can be positioned, and the apparatus can be positioned. There is no need for centering.

【0047】図2〜図9においては塗布層の除去方法と
してブラシを用いているが、その他、超音波、ブレー
ド、拭き取りテープ等、いずれの方式を用いてもかまわ
ない。除去用溶剤としては、塗布層を溶解するものであ
っても、溶解しないものであってもよく、如何なるもの
であってもよい。
Although a brush is used as a method for removing the coating layer in FIGS. 2 to 9, any other method such as ultrasonic wave, a blade, a wiping tape or the like may be used. The solvent for removal may be one that dissolves the coating layer, one that does not dissolve it, or any solvent.

【0048】感光体塗布層の除去は、塗布層を設けた円
筒状導電性支持体と除去部材との摺擦によって行われる
ものであれが、その方式としては円筒状導電性支持体が
回転する方式、除去部材が回転する方式、拭き取り槽自
体が回転する方式、さらには、支持体、除去部材が共に
回転する方式のいずれであっても構わない。また、除去
する塗布層は、支持体端部の内外面両面であっても、い
ずれか一方の面だけであっても構わない。
The removal of the photoconductor coating layer is carried out by rubbing the cylindrical conductive support provided with the coating layer and the removing member, but the method is to rotate the cylindrical conductive support. Any of a system, a system in which the removing member rotates, a system in which the wiping tank itself rotates, and a system in which the support and the removing member rotate together may be used. Further, the coating layer to be removed may be on both inner and outer surfaces of the end portion of the support or only one of the surfaces.

【0049】[0049]

【実施例】次に本発明の実施例を説明するが、本発明
は、その要旨をこえない限り以下の実施例に限定される
ものではない。
EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to the following examples unless it exceeds the gist.

【0050】実施例1 メチルアルコール28.7重量部と1,2−ジクロルエ
タン53.3重量部の共沸組成混合溶媒にメトキシメチ
ル化ナイロン樹脂(帝国化学:トレジンEF−30T)
0.9重量部と非導電性酸化チタン(石原産業:TTO
−55A)17.1重量部とを混合したものをペイント
シェーカーにて8時間分散し下引層用塗布液を作製し
た。
Example 1 Methylmethyl alcohol 28.7 parts by weight and 1,2-dichloroethane 53.3 parts by weight in an azeotropic composition mixed solvent were added to a methoxymethylated nylon resin (Teijin Kagaku: Toresin EF-30T).
0.9 parts by weight and non-conductive titanium oxide (Ishihara Sangyo: TTO
A mixture of -55A) and 17.1 parts by weight was dispersed in a paint shaker for 8 hours to prepare an undercoat layer coating solution.

【0051】このようにして作製した塗布液を厚さ1m
mt×80mmφ×340mmのアルミニウム製ドラム
状基板1上に、図9に示した浸漬塗布装置を用いて、基
板上端10mmに感光体の塗布層を設けないようにコー
ティングを行い、図2及び図3に示した装置に、除去溶
剤としてメチルアルコールを用いて、下端部より10m
m巾の感光体の塗布層の除去を行った。その結果、除去
溶剤のハネや蒸気の影響のない、均一で良好な膜厚1.
5μmの下引層が得られた。その上に、メチルイソブチ
ルケトン97重量部に下記構造式(I)のビスアゾ系顔
料(クロルダイアンブルー)1.5重量部とブチラール
樹脂(ユニオンカーバイト社製:XYSG)1.5重量
部を混合したものをペイントシェーカーで8時間分散し
て作製した電荷発生層用塗布液を、前記浸漬塗布装置に
て基板上端10mmに塗布層を設けないようにコーティ
ングを行い、除去溶剤としてジクロルメタンを用いた以
外は、下引層と同様にして塗布層の除去を行った。その
結果、除去溶剤のハネや蒸気の影響のない、均一で良好
な膜厚0.8μmの電荷発生層が得られた。さらにその
上にジクロルメタン8重量部に下記構造式(II)のヒド
ラゾン系化合物(4,−ジエチルアミノベンズアルデヒ
ド−N,N−ジフェニルヒドラゾン)1重量部とポリカ
ーボネイト樹脂(三菱ガス化学社製:ユーピロン)1重
量部を混合したものをマグネティクスタラーにて攪拌溶
解して作製した電荷輸送層用塗布液を用いて、基板上下
端の塗布層を設けない巾を8mmとした以外は、電荷発
生層と同様の方法により、コーティング、塗布層除去を
行い、80℃1時間の熱風乾燥により膜厚20μmの電
荷輸送層を設けた結果、除去溶剤のハネや蒸気の悪影響
を防止した、均一で良好な塗布層をもった積層型電子写
真感光体が得られた。
The coating solution prepared in this manner was applied to a thickness of 1 m.
The aluminum drum-shaped substrate 1 of mt × 80 mmφ × 340 mm was coated with the dip coating apparatus shown in FIG. 9 so that the coating layer of the photoconductor was not provided on the upper end 10 mm of the substrate. 10m from the lower end using methyl alcohol as the removal solvent
The coating layer of the m-width photosensitive member was removed. As a result, a uniform and good film thickness is obtained without the influence of the removing solvent splash or vapor.
An undercoat layer of 5 μm was obtained. On top of that, 97 parts by weight of methyl isobutyl ketone was mixed with 1.5 parts by weight of a bisazo pigment (chlordian blue) represented by the following structural formula (I) and 1.5 parts by weight of butyral resin (manufactured by Union Carbide: XYSG). The coating liquid for the charge generation layer prepared by dispersing the prepared product in a paint shaker for 8 hours was coated by the dip coating device so that the coating layer was not formed on the upper end 10 mm of the substrate, and dichloromethane was used as the removal solvent. The coating layer was removed in the same manner as the undercoat layer. As a result, a uniform and favorable charge generation layer having a film thickness of 0.8 μm was obtained, which was free from the influence of the removing solvent and the vapor. On top of that, 8 parts by weight of dichloromethane, 1 part by weight of a hydrazone compound (4, -diethylaminobenzaldehyde-N, N-diphenylhydrazone) of the following structural formula (II) and 1 part by weight of a polycarbonate resin (Iupilon manufactured by Mitsubishi Gas Chemical Co., Inc.) Similar to the charge generation layer, except that the coating liquid for the charge transport layer, which was prepared by stirring and dissolving a mixture of the parts with a magnetic stirrer, was 8 mm in width without the coating layer at the upper and lower ends of the substrate. The coating and coating layer were removed by the method, and a charge transport layer having a film thickness of 20 μm was provided by hot air drying at 80 ° C. for 1 hour. As a result, a uniform and good coating layer was obtained that prevented the harmful effects of the removal solvent splash and vapor. Thus, a laminated electrophotographic photosensitive member having the above was obtained.

【0052】[0052]

【化1】 [Chemical 1]

【0053】[0053]

【化2】 [Chemical 2]

【0054】このようにして作製した電子写真感光体
を、実際の機器(シャープ(株)製:SF−8100)
に搭載して現像部での感光体表面電位、具体的には帯電
性をみるために、露光プロセスを除いた暗中での感光体
表面電位(VO )と、除電後の感光体表面電位(VR
及び感度をみるために露光を行った時の白地部分の感光
体表面電位(VL )とを測定した。
The electrophotographic photosensitive member thus produced was used as an actual device (SF-8100, manufactured by Sharp Corporation).
In order to check the photoconductor surface potential in the developing unit, specifically, the charging property, the photoconductor surface potential (V O ) in the dark excluding the exposure process and the photoconductor surface potential after static elimination ( V R)
In order to check the sensitivity, the surface potential ( VL ) of the photoconductor on the white background portion when exposed was measured.

【0055】本実施例の電子写真感光体の1万回繰り返
しと、繰り返し前後の電位測定を低温/低湿(5℃/3
0%RH)、常温/常湿(25℃/60%RH)、高温
/高湿(35℃/85%RH)の各環境条件下で測定を
行ったところ、いかなる環境条件においても、安定性に
優れた電子写真感光体を得ることができた。
The electrophotographic photosensitive member of this example was repeated 10,000 times and the potential was measured before and after the repetition at low temperature / low humidity (5 ° C./3).
0% RH), room temperature / normal humidity (25 ° C / 60% RH), high temperature / high humidity (35 ° C / 85% RH) It was possible to obtain an excellent electrophotographic photoreceptor.

【0056】また、実写による画像特性、及び感光体の
接着性不良による膜ハガレ等の問題は生じなかった。以
上の結果を表1に示す。
Further, problems such as image characteristics due to actual photographing and film peeling due to poor adhesion of the photoconductor did not occur. The above results are shown in Table 1.

【0057】[0057]

【表1】 [Table 1]

【0058】実施例2 実施例1の下引層に使用した共重合ナイロン樹脂と非導
電性酸化チタンの混合比率をそれぞれ、共重合ナイロン
樹脂0.18重量部と非導電性酸化チタン17.82重
量部にした以外は、実施例1と同様の方法にて電子写真
感光体を作製し、電子写真特性の測定及び実写実験を実
施例1と同様の方法にて行ったところ、実施例1と同様
の結果が得られた。以上の測定結果を表2に示す。
Example 2 The mixing ratio of the copolymerized nylon resin used in the undercoat layer of Example 1 and the non-conductive titanium oxide was 0.18 parts by weight of the copolymerized nylon resin and 17.82 of the non-conductive titanium oxide, respectively. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the weight part was used, and the electrophotographic characteristics were measured and the actual copying experiment was conducted in the same manner as in Example 1. Similar results were obtained. Table 2 shows the above measurement results.

【0059】[0059]

【表2】 [Table 2]

【0060】比較例1 実施例1の下引層を、共重合ナイロン樹脂18重量部に
し非導電性酸化チタンを除いた以外は、実施例1と同様
の方法にて電子写真感光体を作製し、電子写真特性の測
定を実施例1と同様の方法にて行ったところ、繰り返し
により帯電電位(VO )、残留電位(VR )の上昇及び
感度(VL )の劣化が著しく、良好な電子写真感光体
は、得られなかった。以上の測定結果を表3に示す。
Comparative Example 1 An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the undercoat layer of Example 1 was changed to 18 parts by weight of copolymerized nylon resin and the non-conductive titanium oxide was removed. When the electrophotographic characteristics were measured by the same method as in Example 1, the charging potential (V O ), the residual potential (V R ) increased and the sensitivity (V L ) deteriorated repetitively, resulting in good results. No electrophotographic photoreceptor was obtained. Table 3 shows the above measurement results.

【0061】[0061]

【表3】 [Table 3]

【0062】比較例2 実施例1の下引層に使用した共重合ナイロン樹脂、非導
電性酸化チタンの混合比率をそれぞれ、共重合ナイロン
樹脂3.6重量部と非導電性酸化チタン14.4重量部
にした以外は、実施例1と同様の方法にて電子写真感光
体を作製し、電子写真特性の測定を実施例1と同様の方
法にて行ったところ、比較例1と同様に、良好な電子写
真感光体は、得られなかった。以上の測定結果を表4に
示す。
Comparative Example 2 The mixing ratios of the copolymerized nylon resin and the non-conductive titanium oxide used in the undercoat layer of Example 1 were 3.6 parts by weight of the copolymerized nylon resin and 14.4 of the non-conductive titanium oxide, respectively. An electrophotographic photosensitive member was produced by the same method as in Example 1 except that the weight part was used, and the electrophotographic characteristics were measured by the same method as in Example 1. As in Comparative Example 1, No good electrophotographic photoreceptor was obtained. Table 4 shows the above measurement results.

【0063】[0063]

【表4】 [Table 4]

【0064】比較例3 実施例1の下引層に使用した非導電性酸化チタンを導電
性酸化チタン(石原産業:500W)にした以外は、実
施例1と同様の方法にて電子写真感光体を作製し、電子
写真特性の測定を実施例1と同様の方法にて行ったとこ
ろ、初期の帯電電位不足と、繰り返しによる帯電電位
(Vo )の低下が著しく、良好な電位写真感光体は得ら
れなかった。以上の測定結果を表5に示す。
Comparative Example 3 An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the non-conductive titanium oxide used in the undercoat layer of Example 1 was replaced with conductive titanium oxide (Ishihara Sangyo: 500 W). Was prepared, and the electrophotographic characteristics were measured by the same method as in Example 1. As a result, the initial charging potential was insufficient and the charging potential (V o ) was remarkably lowered due to repetition. I couldn't get it. Table 5 shows the above measurement results.

【0065】[0065]

【表5】 [Table 5]

【0066】比較例4 図2、3において、保護部材3を用いずに塗布層除去を
行った以外は、実施例1と同様にして電子写真用感光体
を作製したところ、下引層、電荷発生層、電荷輸送層各
層の下端部除去の際、除去溶剤による塗布層の欠陥が発
生し、画像評価においても、斑点や濃度ムラといった問
題点が生じていた。
Comparative Example 4 An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the coating layer was removed without using the protective member 3 in FIGS. When removing the lower end of each of the generation layer and the charge transport layer, defects in the coating layer due to the removal solvent occurred, and problems such as spots and uneven density occurred in image evaluation.

【0067】実施例3、4 塗布層除去方式として、ブラシの代りに、ブレード及び
超音波を用いた以外は、実施例1と同様にして電子写真
用感光体を作製し評価を行ったところ、いずれの電子写
真用感光体も、塗布層及び画像に欠陥のない良好な特性
が得られた。
Examples 3 and 4 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that a blade and ultrasonic waves were used instead of the brush as the coating layer removing method. All the electrophotographic photoconductors had good characteristics without defects in the coating layer and images.

【0068】実施例5 下端拭き取り槽として、図4と図5に示された下端拭き
取り槽を用いた以外は、実施例1と同様にして電子写真
用感光体を作製し評価を行ったところ、塗布層及び画像
に欠陥のない良好な特性の電子写真用感光体が得られ
た。
Example 5 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the lower end wiping tank shown in FIGS. 4 and 5 was used as the lower end wiping tank. An electrophotographic photosensitive member having good characteristics with no defects in the coating layer and the image was obtained.

【0069】実施例6 下端拭き取り槽として、図8と図9に示された下端拭き
取り槽を用い、更に、円筒状導電性支持体と下端拭き取
り槽の中心軸を5mmずらした状態に設置した以外は、
実施例1と同様にして電子写真用感光体を作製し評価を
行ったところ、塗布層及び画像に欠陥のない良好な特性
の電子写真用感光体が得られた。
Example 6 The lower end wiping tank shown in FIGS. 8 and 9 was used as the lower end wiping tank, and the cylindrical conductive support and the lower end wiping tank were placed with their central axes displaced by 5 mm. Is
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1. As a result, an electrophotographic photosensitive member having good characteristics with no defects in the coating layer and the image was obtained.

【0070】比較例5 下端拭き取り槽として、図2と図3に示された下端拭き
取り槽を用いた以外は、実施例6と同様にして電子写真
用感光体を作製し評価を行ったところ、除去すべき塗布
層への拭き取りブラシの当接の度合が支持体周方向で不
均一となったり、保護部材による塗布層の保護が十分で
ない部分ができてしまった為に、塗布層端部の処理が十
分にできず、溶剤のハネによる画像欠陥が発生した。
Comparative Example 5 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 6 except that the lower end wiping tank shown in FIGS. 2 and 3 was used as the lower end wiping tank. The degree of contact of the wiping brush with the coating layer to be removed becomes uneven in the circumferential direction of the support, or the coating layer is not sufficiently protected by the protective member, so that the edge of the coating layer is The processing could not be performed sufficiently, and image defects due to solvent splash occurred.

【0071】以上から明らかなように、本発明による支
持体下端部の感光体塗布層除去方法を用いて作製した積
層型電子写真用感光体は、良品率にすぐれ、均一で良好
な特性を有するもので、その方法についても容易に実施
できるものである。
As is apparent from the above, the laminated electrophotographic photoconductor prepared by using the method for removing the photoconductor coating layer at the lower end of the support according to the present invention has a good yield rate and uniform and good characteristics. However, the method can be easily implemented.

【0072】[0072]

【発明の効果】以上のように本発明によれば、導電性支
持体と電荷発生層との間に、共重合ナイロン樹脂と非導
電性酸化チタンとからなる下引層を設けることにより、
いかなる環境下においても繰り返し安定性に優れた電子
写真感光体を得ることが可能となった。
As described above, according to the present invention, by providing the undercoat layer comprising the copolymerized nylon resin and the non-conductive titanium oxide between the conductive support and the charge generating layer,
It has become possible to obtain an electrophotographic photosensitive member having excellent repeated stability under any environment.

【0073】その他、下記の効果を奏した。In addition, the following effects were exhibited.

【0074】1.感光体塗布層除去の際の溶剤の悪影響
防止。
1. Prevents the adverse effects of solvents when removing the photoconductor coating layer.

【0075】2.保護部材が同心円上に開閉することか
ら、装置の位置決め(芯だし)の必要がない。
2. Since the protective member opens and closes concentrically, there is no need to position (center) the device.

【0076】3.保護部材が同心円上に開閉することか
ら、径の異なる円筒状導電性支持体に対応可能であり、
下端部除去装置の交換が不要であり、設備も簡単であ
る。
3. Since the protective member opens and closes concentrically, it is possible to support cylindrical conductive supports with different diameters.
There is no need to replace the lower end removal device, and the equipment is simple.

【図面の簡単な説明】[Brief description of drawings]

【図1】本発明の積層型電子写真感光体の断面図であ
る。
FIG. 1 is a cross-sectional view of a laminated electrophotographic photosensitive member of the present invention.

【図2】本発明の積層型電子写真感光体の感光体塗布層
除去装置の断面図である。
FIG. 2 is a cross-sectional view of a photoconductor coating layer removing device for a laminated electrophotographic photoconductor of the present invention.

【図3】図2の平面図である。FIG. 3 is a plan view of FIG.

【図4】本発明の別の積層型電子写真感光体の感光体塗
布層除去装置の断面図である。
FIG. 4 is a cross-sectional view of another photoconductor coating layer removing device for a laminated electrophotographic photoconductor of the present invention.

【図5】図4の平面図である。FIG. 5 is a plan view of FIG.

【図6】本発明の別の積層型電子写真感光体の感光体塗
布層除去装置の断面図である。
FIG. 6 is a cross-sectional view of another apparatus for removing a photoreceptor coating layer of a laminated electrophotographic photoreceptor of the present invention.

【図7】図6の平面図である。FIG. 7 is a plan view of FIG.

【図8】本発明の別の積層型電子写真感光体の感光体塗
布層除去装置の断面図である。
FIG. 8 is a cross-sectional view of another apparatus for removing a photoreceptor coating layer of a laminated electrophotographic photoreceptor of the present invention.

【図9】図8の平面図である。9 is a plan view of FIG. 8. FIG.

【図10】本発明の積層型電子写真感光体の製造に用い
る塗布装置である。
FIG. 10 shows a coating apparatus used for manufacturing the laminated electrophotographic photosensitive member of the present invention.

【図11】従来の積層型電子写真感光体の断面図であ
る。
FIG. 11 is a cross-sectional view of a conventional laminated electrophotographic photosensitive member.

【符号の説明】[Explanation of symbols]

1 導電性支持体 2 下引層 3 電荷発生層 4 電荷輸送層 5 塗布層 6 保護部材 7 羽根部材 8 下端拭き取り層 9 除去ブラシ 10 バネ 11 支柱 12 モータ 13 塗布槽 14 塗布液 15 ポンプ 16補助タンク DESCRIPTION OF SYMBOLS 1 Conductive support 2 Undercoat layer 3 Charge generation layer 4 Charge transport layer 5 Coating layer 6 Protective member 7 Blade member 8 Bottom wiping layer 9 Removal brush 10 Spring 11 Strut 12 Motor 13 Coating tank 14 Coating liquid 15 Pump 16 Auxiliary tank

───────────────────────────────────────────────────── フロントページの続き (72)発明者 大槻 朋子 大阪府大阪市阿倍野区長池町22番22号 シ ャープ株式会社内 (72)発明者 黒川 誠 大阪府大阪市阿倍野区長池町22番22号 シ ャープ株式会社内 (72)発明者 森田 竜廣 大阪府大阪市阿倍野区長池町22番22号 シ ャープ株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Tomoko Otsuki, 22-22 Nagaike-cho, Abeno-ku, Osaka, Osaka Incorporated (72) Inventor Ryuhiro Morita 22-22 Nagaike-cho, Abeno-ku, Osaka City, Osaka Prefecture

Claims (6)

【特許請求の範囲】[Claims] 【請求項1】 導電性支持体上に、下引層、電荷発生層
及び電荷輸送層を有する電子写真感光体において、該下
引層が共重合ナイロン樹脂と導電性処理を施していない
酸化チタンとからなり、該酸化チタンの含有量が重量比
で95%以上であることを特徴とする積層型電子写真感
光体。
1. An electrophotographic photoreceptor having an undercoat layer, a charge generation layer and a charge transport layer on a conductive support, wherein the undercoat layer is a copolymerized nylon resin and titanium oxide not subjected to a conductive treatment. And a titanium oxide content of 95% or more by weight.
【請求項2】 導電性支持体上に浸漬塗布により感光体
塗布層を設けてなる積層型電子写真感光体の製造方法に
おいて、感光体塗布層を形成した後に支持体下端部の感
光体塗布層を除去する際、非除去層を保護するための保
護部材を支持体下端部に設けて、該保護部材より支持体
端部側の塗布層を除去溶剤存在化にて除去することを特
徴とする積層型電子写真感光体の製造方法。
2. A method for manufacturing a laminated electrophotographic photosensitive member comprising a photosensitive support and a photosensitive coating layer provided on the conductive support by dip coating, wherein the photosensitive coating layer is formed on the lower end of the support after the photosensitive coating layer is formed. When removing, the protective member for protecting the non-removed layer is provided on the lower end of the support, and the coating layer on the end side of the support with respect to the protective member is removed by the presence of a removing solvent. Manufacturing method of laminated electrophotographic photoreceptor.
【請求項3】 シャッタ機構の保護部材及び溶剤除去部
材を備えてなる、導電性支持体上の感光体塗布層の拭き
取り槽で構成されていることを特徴とする積層型電子写
真感光体の感光体塗布層除去装置。
3. A photosensitive member for a multi-layer electrophotographic photosensitive member, comprising a wiping tank for wiping off a photosensitive member coating layer on a conductive support, comprising a shutter mechanism protecting member and a solvent removing member. Body coating layer removal device.
【請求項4】 シャッタ機構の保護部材が、複数枚の羽
根部材より構成された同心円状に開閉可能な機構を有し
ていることを特徴とする請求項3記載の感光体塗布層除
去装置。
4. The photoconductor coating layer removing apparatus according to claim 3, wherein the protective member of the shutter mechanism has a concentric opening / closing mechanism composed of a plurality of blade members.
【請求項5】 シャッタ機構の保護部材及び塗布層の拭
き取り槽の少なくとも一方を水平方向に移動自在とした
ことを特徴とする請求項3記載の感光体塗布層除去装
置。
5. The photoconductor coating layer removing device according to claim 3, wherein at least one of the protective member of the shutter mechanism and the coating layer wiping tank is movable in the horizontal direction.
【請求項6】 導電性支持体に当接もしくは接近する羽
根部材の内側形状を、導電性支持体の外形とほぼ等しく
したことを特徴とする請求項4記載の感光体塗布層除去
装置。
6. The photoconductor coating layer removing device according to claim 4, wherein the inner shape of the blade member which comes into contact with or approaches the conductive support is made substantially equal to the outer shape of the conductive support.
JP11488393A 1993-02-19 1993-05-17 Laminated electrophotographic sensitive body, its production, and device to remove coating layer of photosensitive body Pending JPH06301227A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP11488393A JPH06301227A (en) 1993-02-19 1993-05-17 Laminated electrophotographic sensitive body, its production, and device to remove coating layer of photosensitive body

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP3007593 1993-02-19
JP5-30075 1993-02-19
JP11488393A JPH06301227A (en) 1993-02-19 1993-05-17 Laminated electrophotographic sensitive body, its production, and device to remove coating layer of photosensitive body

Publications (1)

Publication Number Publication Date
JPH06301227A true JPH06301227A (en) 1994-10-28

Family

ID=26368362

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JPH06301227A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006259765A (en) * 2006-05-11 2006-09-28 Mitsubishi Chemicals Corp Electrophotographic receptor and image forming apparatus using same
JP2007004089A (en) * 2005-06-27 2007-01-11 Fuji Xerox Co Ltd Method for manufacturing electrophotographic photoreceptor and apparatus for removing excess coating film
JP2007178483A (en) * 2005-12-27 2007-07-12 Fuji Xerox Co Ltd Electrophotographic photoreceptor, manufacturing method therefor, manufacturing equipment, and image forming apparatus
JP5257534B1 (en) * 2012-07-12 2013-08-07 富士ゼロックス株式会社 Electrophotographic photosensitive member coating film removing apparatus and electrophotographic photosensitive member manufacturing method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007004089A (en) * 2005-06-27 2007-01-11 Fuji Xerox Co Ltd Method for manufacturing electrophotographic photoreceptor and apparatus for removing excess coating film
JP2007178483A (en) * 2005-12-27 2007-07-12 Fuji Xerox Co Ltd Electrophotographic photoreceptor, manufacturing method therefor, manufacturing equipment, and image forming apparatus
JP2006259765A (en) * 2006-05-11 2006-09-28 Mitsubishi Chemicals Corp Electrophotographic receptor and image forming apparatus using same
JP5257534B1 (en) * 2012-07-12 2013-08-07 富士ゼロックス株式会社 Electrophotographic photosensitive member coating film removing apparatus and electrophotographic photosensitive member manufacturing method

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