JPH05158251A - Electrophotographic sensitive body - Google Patents
Electrophotographic sensitive bodyInfo
- Publication number
- JPH05158251A JPH05158251A JP35015691A JP35015691A JPH05158251A JP H05158251 A JPH05158251 A JP H05158251A JP 35015691 A JP35015691 A JP 35015691A JP 35015691 A JP35015691 A JP 35015691A JP H05158251 A JPH05158251 A JP H05158251A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- transport layer
- charge
- charge transport
- layer
- 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
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、複写機、プリンター、
ファクシミリなどの装置に使用される電子写真感光体に
関する。BACKGROUND OF THE INVENTION The present invention relates to a copying machine, a printer,
The present invention relates to an electrophotographic photosensitive member used in a device such as a facsimile.
【０００２】[0002]
【従来の技術】従来、導電性基体上に、電荷発生層と電
荷輸送層とが設けられてなる積層型感光体において、上
記電荷輸送層が結着樹脂として、下記構造式（II）で示
される繰返し単位からなるポリカーボネート樹脂を使用
している。2. Description of the Related Art Conventionally, in a laminated type photoreceptor having a charge generation layer and a charge transport layer provided on a conductive substrate, the charge transport layer is represented by the following structural formula (II) as a binder resin. Polycarbonate resin consisting of repeating units is used.
【化１】 また、前記電荷輸送層は、一般にテトラヒドロフラン、
塩化メチレン等の有機溶剤を用いて前記電荷発生層上に
形成されている。このようにして作られた積層型感光体
では帯電、露光を長時間繰り返す事により、残留電位が
上昇してくる。[Chemical 1] Further, the charge transport layer is generally tetrahydrofuran,
It is formed on the charge generation layer using an organic solvent such as methylene chloride. In the laminated photoconductor thus manufactured, the residual potential is increased by repeating charging and exposure for a long time.
【０００３】そこで、結着樹脂を構造式（I）で示され
る繰り返し単位からなるポリカーボネート樹脂を用いる
と、常温常湿下（22℃40％RH）では残留電位の上昇は見
られないものの高温高湿下（30℃90％RH）では残留電位
が上昇してくる問題がなお存在する。Therefore, when a polycarbonate resin comprising a repeating unit represented by the structural formula (I) is used as the binder resin, the residual potential does not rise at room temperature and normal humidity (22 ° C. 40% RH), but the high temperature is high. There is still a problem that the residual potential rises under humidity (30 ℃ 90% RH).
【化２】 （式中Ｘ及びＸ1は水素原子、ハロゲン原子、またはメ
チル基を表わし、Ｒは水素原子、ハロゲン原子、水酸
基、カルボキシル基、アセチル基、または炭素数1〜5の
アルキル基を表わす）[Chemical 2] (In the formulas, X and X 1 represent a hydrogen atom, a halogen atom, or a methyl group, and R represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, an acetyl group, or an alkyl group having 1 to 5 carbon atoms.)
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、上記
欠点を改良した長期の繰り返し使用によっても残留電位
が上昇せず、高感度、高耐久で信頼性の高い電子写真感
光体を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member which is improved in the above-mentioned drawbacks and which does not raise the residual potential even after repeated use over a long period of time, and which has high sensitivity, high durability and high reliability. That is.
【０００５】[0005]
【課題を解決しようとする手段】導電性基体上に電荷発
生層と電荷輸送層とが設けられてなる積層型感光体にお
いて、上記電荷発生層の結着樹脂がブチラール樹脂、あ
るいはビスフェノールＡ型ポリカーボネート樹脂から構
成され、前記電荷発生層上に該電荷発生層を実質的に溶
解しない溶剤よりなる電荷輸送層塗工液を用いて電荷輸
送層を形成することにより課題を達成した。さらに前記
電荷輸送層が、結着樹脂として前記構造式（I）で示さ
れる繰り返し単位からなるポリカーボネート樹脂を含有
させることにより、さらに効果が促進される。In a laminated type photoreceptor having a charge generation layer and a charge transport layer provided on a conductive substrate, the binder resin of the charge generation layer is butyral resin or bisphenol A type polycarbonate. The object is achieved by forming a charge transport layer on the charge generation layer by using a charge transport layer coating liquid which is composed of a resin and which does not substantially dissolve the charge generation layer. Further, the effect is further promoted when the charge transport layer contains a polycarbonate resin composed of the repeating unit represented by the structural formula (I) as a binder resin.
【０００６】本発明者らは、電荷発生層の結着樹脂がブ
チラール樹脂、ビスフェノールＡ型ポリカーボネート樹
脂等から構成されている場合、この電荷発生層上に塩化
メチレン、塩化エチレン、テトラヒドロフラン等の有機
容媒を用いて電荷輸送層を形成すると、これらの有機溶
媒に電荷発生層の結着樹脂が溶解されるため電荷発生層
と電荷輸送層との界面が混じり合い静電特性に影響を及
ぼしている事を見出した。つまり、電荷輸送層の有機溶
剤を電荷発生層の結着樹脂に対して不溶な溶剤を用いる
ことにより、電荷発生層と電荷輸送層との界面がほとん
ど混じり合う事なくシャープな界面が形成され、高温高
湿下でも残留電位の上昇がなく高耐久、高信頼性の感光
体を得ることができる。The present inventors have found that when the binder resin of the charge generating layer is composed of butyral resin, bisphenol A type polycarbonate resin, etc., organic charge of methylene chloride, ethylene chloride, tetrahydrofuran or the like is formed on the charge generating layer. When the charge transport layer is formed by using a medium, the binder resin of the charge generation layer is dissolved in these organic solvents, so that the interface between the charge generation layer and the charge transport layer mixes and affects the electrostatic characteristics. I found a thing. That is, by using an organic solvent of the charge transport layer that is insoluble in the binder resin of the charge generation layer, a sharp interface is formed without the interfaces of the charge generation layer and the charge transport layer being mixed with each other. Even under high temperature and high humidity, the residual potential does not increase, and a highly durable and highly reliable photoreceptor can be obtained.
【０００７】なお、本発明はブチラール樹脂、あるいは
ビスフェノールＡ型ポリカーボネート樹脂を結着樹脂と
する電荷発生層上に、電荷発生層を実質的に溶解させな
い有機溶媒剤からなる電荷輸送層塗工液により電荷輸送
層を設けるものであるが、該有機溶媒剤としてはトルエ
ン、ジオキサン、キシレン、ベンゼン及びこれらの有機
溶媒剤を２種以上混合したものが好適である。According to the present invention, a charge transport layer coating liquid comprising an organic solvent agent which does not substantially dissolve the charge generation layer is formed on the charge generation layer containing butyral resin or bisphenol A type polycarbonate resin as a binder resin. Although the charge transport layer is provided, the organic solvent agent is preferably toluene, dioxane, xylene, benzene, or a mixture of two or more of these organic solvent agents.
【０００８】[0008]
実施例１ 厚み75μｍのポリエチレンテレフタレートフィルム上に
厚み500ÅのAl層を真空蒸着法により成膜した導電性基
材上に以下の如く感光層を設けて、本発明の電子写真感
光体を作製した。 トリスアゾ顔料（化合物１）（リコー製） 15g ブチラール樹脂（ＫＹＨＬ：ＵＣＣ社製） 5g シクロヘキサノン（関東化学社製） 150g からなる混合物をガラス製ポットと10mmφの大きさのメ
ノウボールを用いて、48時間ボールミリングした後シク
ロヘキサノン300ｇを追加してさらに1時間ミリングし
た。このミリング液にさらにシクロヘキサノンを添加し
て固形分濃度が2wt％の電荷発生層用途布液を作成、膜
厚0.2μmの電荷発生層を設けた。Example 1 An electrophotographic photoreceptor of the present invention was prepared by providing a photosensitive layer as described below on a conductive base material obtained by forming an Al layer having a thickness of 500 Å on a polyethylene terephthalate film having a thickness of 75 μm by a vacuum deposition method. Trisazo pigment (Compound 1) (manufactured by Ricoh) 15 g Butyral resin (KYHL: manufactured by UCC) 5 g Cyclohexanone (manufactured by Kanto Chemical Co., Ltd.) A mixture of 150 g was used for 48 hours using a glass pot and an agate ball of 10 mmφ. After ball milling, 300 g of cyclohexanone was added and milling was performed for another hour. Cyclohexanone was further added to this milling solution to prepare a charge generation layer application liquid having a solid content concentration of 2 wt%, and a charge generation layer having a thickness of 0.2 μm was provided.
【化３】 ついでこの電荷発生層上に下記組成からなる電荷輸送層
用塗工液をノズルコート法により塗工し、130℃で15分
間乾燥して膜厚20μｍの電荷輸送層を設けて感光層を形
成した。 電荷輸送物質（化合物２）（リコー製） 9ｇ ポリカーボネート（樹脂１）（ＴＳ2050:帝人化成社製）10ｇ トルエン 90ｇ [Chemical 3] Then, a charge transport layer coating solution having the following composition was applied onto this charge generation layer by a nozzle coating method, and dried at 130 ° C. for 15 minutes to form a charge transport layer having a thickness of 20 μm to form a photosensitive layer. .. Charge transport material (compound 2) (manufactured by Ricoh) 9g Polycarbonate (resin 1) (TS2050: manufactured by Teijin Chemicals) 10g Toluene 90g
【化４】 [Chemical 4]
【化５】 [Chemical 5]
【０００９】実施例２ 実施例１においてトルエンをジオキサンにした以外は、
実施例１と同様にして電子写真感光体を作製した。Example 2 Except that toluene was changed to dioxane in Example 1,
An electrophotographic photosensitive member was produced in the same manner as in Example 1.
【００１０】実施例３ 実施例１においてトルエンをベンゼンにした以外は、実
施例１と同様にして電子写真感光体を作製した。Example 3 An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that benzene was used instead of toluene.
【００１１】実施例４ 実施例１においてトルエンをキシレンにした以外は、実
施例１と同様にして電子写真感光体を作製した。Example 4 An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that xylene was used instead of toluene.
【００１２】比較例１ 実施例１においてポリカーボネート樹脂１を構造式（I
I）で示されるビスフェノールＡ型のポリカーボネート
（樹脂）（C-1400帝人化成社製）にした以外は、実施例
１と同様にして電子写真感光体を作製した。Comparative Example 1 Polycarbonate resin 1 in Example 1 was replaced with a structural formula (I
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the bisphenol A type polycarbonate (resin) represented by I) (C-1400 manufactured by Teijin Chemicals Ltd.) was used.
【００１３】比較例２ 実施例１においてトルエンをテトラヒドロフランにした
以外は、実施例１と同様にして比較用の電子写真感光体
を作製した。Comparative Example 2 An electrophotographic photosensitive member for comparison was prepared in the same manner as in Example 1 except that tetrahydrofuran was used instead of toluene.
【００１４】比較例３ 比較例１においてトルエンをテトラヒドロフランにした
以外は、比較例１と同様にして電子写真感光体を作製し
た。Comparative Example 3 An electrophotographic photosensitive member was produced in the same manner as in Comparative Example 1 except that tetrahydrofuran was used instead of toluene in Comparative Example 1.
【００１５】このようにして作製した感光体を静電特性
測定装置SP-428（川口電機製作所製）を用い、ダイナミ
ック方式にて測定した。まづ印加電圧−６KVにて20秒間
帯電し、ついで20秒間暗減衰させ、さらにタングステン
ランプで感光体表面の照度が4.5luxになるように30秒間
露光を行った。感度は露光後、表面電位が-800V→-80V
となるに要する露光量Ｅ1/10(lux.sec）を残留電位V30
は露光30秒後の表面電位を測定することにより各々評価
した。また強制疲労テスト（感光体を1000rpmで回転さ
せながら感光体表面が-800V、9.6μAとなうようにコロ
ナ帯電とタングステンランプによる露光を繰り返し続け
る）をおこなった後の感度と残留電位も測定した。その
結果を下記表１に示す。The photoconductor thus manufactured was measured by a dynamic method using an electrostatic characteristic measuring device SP-428 (manufactured by Kawaguchi Denki Seisakusho). First, it was charged with an applied voltage of -6 KV for 20 seconds, then dark-decayed for 20 seconds, and further exposed with a tungsten lamp for 30 seconds so that the illuminance on the surface of the photoreceptor was 4.5 lux. After exposure, the surface potential is -800V → -80V after exposure.
Exposure dose E1 / 10 (lux.sec) required to obtain
Was evaluated by measuring the surface potential after 30 seconds of exposure. The sensitivity and residual potential were also measured after a forced fatigue test (while the photoreceptor was rotated at 1000 rpm, corona charging and exposure with a tungsten lamp were repeated until the photoreceptor surface was -800 V and 9.6 μA). .. The results are shown in Table 1 below.
【００１６】[0016]
【表１】 [Table 1]
【００１７】一方実施例１の感光体を電子写真方式のレ
−ザ−ビ−ムプリンタ−（RICOH LP2310-SP5）改造機に
搭載し画像出しテストを行ったところ、50,000枚まで画
像欠陥のない鮮明な画像が得られた。また比較例２．３
の感光体を同じように画像出しテストを行ったところ、
それぞれ35,000枚、20,000枚付近より地肌部の汚れが認
められるようになった。On the other hand, the photoconductor of Example 1 was mounted on a modified electrophotographic laser beam printer (RICOH LP2310-SP5) and subjected to an image output test. A clear image was obtained. Comparative Example 2.3
When the image output test was performed on the photoconductor of
Dirt on the background became visible from around 35,000 and 20,000 sheets, respectively.
【００１８】また透過型電子顕微鏡（日立製 H-500H）
で、実施例１、比較例２の感光体の断面を観察したとこ
ろ、実施例１の感光体では電荷発生層と電荷輸送層との
界面がはっきりしているのに対し、比較例２では界面が
はっきりせず両層が混じっているように見えた。A transmission electron microscope (Hitachi H-500H)
When the cross sections of the photoconductors of Example 1 and Comparative Example 2 were observed, the interface between the charge generation layer and the charge transport layer was clear in the photoconductor of Example 1, whereas the interface in Comparative Example 2 was clear. It was not clear, and it seemed that both layers were mixed.
【００１９】[0019]
【発明の効果】電荷発生層の結着樹脂がブチラ−ル樹
脂、あるいはビスフェノ−ルＡ型ポリカ−ボネ−ト樹脂
から構成される電荷発生層上に該電荷発生層を実質的に
溶解しない溶剤よりなる電荷輸送層塗工液を用いて電荷
輸送層を形成することにより、さらにまた、前記電荷輸
送層の結着樹脂として構造式（Ｉ）で示される繰り返し
単位からなるポリカ−ボネ−ト樹脂を含有させることに
より、長期の繰り返し使用によっても残留電位が上昇せ
ず画像欠陥のない良好な画像が得られ高感度、高耐久
で、信頼性の高い電子写真感光体が得られる。The binder resin of the charge generating layer is a butyral resin or a solvent which does not substantially dissolve the charge generating layer on the charge generating layer composed of a bisphenol A type polycarbonate resin. A charge transporting layer coating solution is used to form a charge transporting layer, and a polycarbonate resin comprising a repeating unit represented by the structural formula (I) as a binder resin for the charge transporting layer. By containing, the residual potential does not rise even after repeated use for a long time, a good image without image defects can be obtained, and a highly sensitive, highly durable and highly reliable electrophotographic photoreceptor can be obtained.
Claims (2)
とが設けられてなる積層型感光体において、上記電荷発
生層の結着樹脂がブチラール樹脂、あるいはビスフェノ
ールＡ型ポリカーボネート樹脂から構成され、前記電荷
発生層上に該電荷発生層を実質的に溶解しない溶剤によ
りなる電荷輸送層塗工液を用いて電荷輸送層を形成する
ことを特徴とする電子写真感光体。1. A laminate-type photoreceptor having a charge generation layer and a charge transport layer provided on a conductive substrate, wherein the binder resin of the charge generation layer is made of butyral resin or bisphenol A type polycarbonate resin. An electrophotographic photoreceptor comprising a charge transport layer formed on the charge generation layer by using a charge transport layer coating liquid comprising a solvent that does not substantially dissolve the charge generation layer.
記構造式（Ｉ）で示される繰返し単位からなるポリカー
ボネート樹脂を含有する請求項１に記載の電子写真感光
体。 （式中、Ｘ及びＸ1は水素原子、ハロゲン原子、また
は、メチル基を表わし、Ｒは水素原子、ハロゲン原子、
水酸基、カルボキシル基、アセチル基、または炭素数1
〜5のアルキル基を表わす）2. The electrophotographic photosensitive member according to claim 1, wherein the charge transport layer contains, as a binder resin, a polycarbonate resin including a repeating unit represented by the following structural formula (I). (In the formula, X and X 1 represent a hydrogen atom, a halogen atom, or a methyl group, and R represents a hydrogen atom, a halogen atom,
Hydroxyl group, carboxyl group, acetyl group, or carbon number 1
~ Represents an alkyl group of 5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35015691A JPH05158251A (en) | 1991-12-10 | 1991-12-10 | Electrophotographic sensitive body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35015691A JPH05158251A (en) | 1991-12-10 | 1991-12-10 | Electrophotographic sensitive body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05158251A true JPH05158251A (en) | 1993-06-25 |
Family
ID=18408607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35015691A Pending JPH05158251A (en) | 1991-12-10 | 1991-12-10 | Electrophotographic sensitive body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05158251A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100421403B1 (en) * | 2000-02-29 | 2004-03-09 | 캐논 가부시끼가이샤 | Process for Producing Electrophotographic Photosensitive Member and Electrophotographic Photosensitive Member Produced thereby |
-
1991
- 1991-12-10 JP JP35015691A patent/JPH05158251A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100421403B1 (en) * | 2000-02-29 | 2004-03-09 | 캐논 가부시끼가이샤 | Process for Producing Electrophotographic Photosensitive Member and Electrophotographic Photosensitive Member Produced thereby |
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