JPS5953851A - Electrophotographic receptor - Google Patents

Abstract

PURPOSE:To prevent softening of a photosensitive layer due to temp. rise and to enhance resistance to crystallization, by using Se-As for a lower layer and adding antimony to the surface layer. CONSTITUTION:An Se-As alloy layer 2 is laminated on a conductive substrate 1 in a 20-100mum thickness, and further on this layer an Se-Te-Sb alloy layer is laminated in a <=10mum thickness in contents of <=10% As, <=50% Te, and <=10% Sb, respectively.

Description

【発明の詳細な説明】 本発明は電子写真感光体の構造に関するものである。従
来より電子写真用感光体の感光材料として最も重用され
ているのはセレンであり、基板上に蒸着されたナモルフ
ァスセレンは、くア り返し使用に耐え、高い解像力と疲労の少ない感光体と
して実績を持っている。しかし、セレン単体では、分光
感度が長波長まで延びておらず全色性に欠けている点１
周囲温度の上昇によって容易に結晶化し、感光体として
の機能を失なう点、また、硬度が低い為、複写プロセス
の来ない欠点が存在している。これらの欠点のいくつか
を改善する手段として、各種の添加剤によって、増感を
行ない分光感度を長波長側へ延ばし、全色性にすぐれた
感光体が実用化されている。しかし、この場合、最も一
般的に用いられているテヤルによる増感においては、全
層セ７レ レンーテルル合金の場合も、セレン−セレンテルル合金
の機能分離タイプの場合にも、テルルの添加量が１０％
以上の領域では、結晶転移点がセレンよりも低くなる事
からも分かる様に、より弱い熱的影響（こよって結晶化
が進行する可能性を有する事になり用途によっては、大
きな欠点となり得る。さ・らに他の添加剤を用いた場合
については、製造技術的に困難であったり、感光体とし
ての特性紺持が出来なくなる等の欠点があるが、ヒ素に
ついては、実用化が計られておりその特性は、ヒ素の添
加量が増すに従がって高感度となり、７００ｎｍ付近ま
で有効な感度を有づ〜る事が可能である。また、耐結晶
性硬度ともに良好な値を示す事が知られている。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the structure of an electrophotographic photoreceptor. Selenium has traditionally been the most important photosensitive material for electrophotographic photoreceptors, and the namorphous selenium deposited on the substrate can withstand repeated use and is used as a photoreceptor with high resolution and less fatigue. Has a proven track record. However, with selenium alone, the spectral sensitivity does not extend to long wavelengths and it lacks panchromaticity.
It has the disadvantage that it easily crystallizes when the ambient temperature rises and loses its function as a photoreceptor, and that it cannot be used in the copying process due to its low hardness. As a means to improve some of these drawbacks, photoreceptors with excellent panchromatic properties have been put into practical use by sensitizing them with various additives to extend the spectral sensitivity toward longer wavelengths. However, in this case, in the most commonly used Teyal sensitization, the amount of tellurium added is 10% in both the full-layer selenium-selenium-tellurium alloy and the functionally separated selenium-selenium-tellurium alloy.
In the above range, as can be seen from the fact that the crystal transition point is lower than that of selenium, there is a weaker thermal influence (thereby, there is a possibility that crystallization will proceed), which may be a major drawback depending on the application. In addition, when other additives are used, there are disadvantages such as production technology difficulties and the inability to maintain the characteristics of a photoreceptor, but practical use of arsenic has not been attempted. Its characteristics are that as the amount of arsenic added increases, the sensitivity increases, and it is possible to have effective sensitivity up to around 700 nm.It also shows good values for both crystallization resistance and hardness. things are known.

しかし、他方大川のヒ素の添加は長波長光に大きな疲労
を示す事や、特性の経時変化が大きい事など使用時に障
害を生じる。本発明は前述の欠点を解決し、高感度で耐
環境性、全色性に優れ、且つ疲労及び経時変化を改善し
た電子写真感光体を提供するものである。本発明におい
ては、セレンーヒ素合金の上層にセレン、テルルアンチ
モン合金を積層させている。この構成の場場合、下層に
セレンテルルを用いる事により、温度上昇による感光層
の軟化を防ぎ、表面層にアンチモンを添加する事によっ
て耐結晶性を向上させている。またテルルの添加量を適
時に変える事によって感度の調整も可能となる。この様
な層構成によって、大量のヒ素添加による障害を受けず
に高感度で耐環境性の良い感光体が製造可能となる。第
１図は本発明の実施例による電子写真感光体の構成側図
で図において１はアルミニウム等から成る導電性支持体
、２はセレンーヒ素合金層、３はセレン−テルル−アン
チモン合金層である。ｌの導電性支持体と２のセレン−
−ヒ素合金層 間に電気的又は機械的特性の改善のための中間層を介在
せしめるなどの通常の変更、変形は本発明に含まれるも
のである。又、各合金層において、特性等に重要な影響
を及ぼさない程度の他の不純物の混入等も本発明の範囲
であるのはいうまでもない。However, on the other hand, Okawa's addition of arsenic causes problems during use, such as large fatigue with long wavelength light and large changes in properties over time. The present invention solves the above-mentioned drawbacks and provides an electrophotographic photoreceptor that has high sensitivity, excellent environmental resistance, and excellent all-color properties, and has improved fatigue and aging properties. In the present invention, selenium and tellurium antimony alloy are laminated on top of the selenium-arsenic alloy. In the case of this structure, by using selenium tellurium in the lower layer, softening of the photosensitive layer due to temperature rise is prevented, and by adding antimony to the surface layer, crystallization resistance is improved. It is also possible to adjust the sensitivity by changing the amount of tellurium added at appropriate times. With such a layer structure, it is possible to produce a photoreceptor with high sensitivity and good environmental resistance without being affected by the addition of a large amount of arsenic. FIG. 1 is a side view of the structure of an electrophotographic photoreceptor according to an embodiment of the present invention. In the figure, 1 is a conductive support made of aluminum or the like, 2 is a selenium-arsenic alloy layer, and 3 is a selenium-tellurium-antimony alloy layer. . 1 conductive support and 2 selenium
- Usual changes and modifications such as interposing an intermediate layer between arsenic alloy layers to improve electrical or mechanical properties are included in the present invention. It goes without saying that the scope of the present invention also includes the inclusion of other impurities in each alloy layer to the extent that they do not significantly affect the properties.

以下実施例をもって説明を行なう。外径１２０ｍｍ、長
さ３００　ｍｍの寸法で表面を鏡面仕上げしたアルミニ
ー−ムドラムをトリクロルエチレン等によって、洗浄の
後、適切な表面処理を施した。このドラムを真空蒸着槽
内に設置し、その下方にヒ素５％を含有するセレンーヒ
素合金を入れた−に第１蒸発湘、テルル１０％を含有す
る／セレン・テルル合金を入れた第２蒸発源そしてアン
チモンを入れた第３蒸発源をそれぞれ設置した。さらに
各蒸着源上には、任意に開閉が可能なシャッターを設置
した。アルミドラムの温度を８０℃に保った状態で槽内
を排気し蒸着を開始する。まずｔＦＳ１蒸発源に通電加
熱しセレンーヒ素合金層を５５〃積層させ、シャッター
を／閉じた後、通電を断った。さらに第２蒸発源、第３
蒸発湖に通電加熱を行ない蒸発レートが所望の値に安定
した時点でシャッタを開ける。セヤ／ レン・テルルとアンチモンの共蒸着層を５μ積／層させ
て、シャッターを閉じて通電を断った。The following will be explained using examples. An aluminum neem drum measuring 120 mm in outer diameter and 300 mm in length and having a mirror-finished surface was washed with trichlorethylene or the like and then subjected to an appropriate surface treatment. This drum was placed in a vacuum deposition tank, and below it a selenium-arsenic alloy containing 5% arsenic was placed in the first evaporator, and a second evaporator was placed in which a selenium-tellurium alloy containing 10% tellurium was placed. A third evaporation source containing antimony was installed. Furthermore, a shutter that could be opened and closed at will was installed above each deposition source. While keeping the temperature of the aluminum drum at 80°C, the inside of the tank was evacuated and vapor deposition was started. First, the tFS1 evaporation source was heated by applying electricity to deposit 55 selenium-arsenic alloy layers, and after closing the shutter, the electricity was turned off. Furthermore, a second evaporation source, a third
The evaporation lake is electrically heated and the shutter is opened when the evaporation rate stabilizes to a desired value. A 5μ co-deposited layer of tellurium and antimony was deposited, and the shutter was closed to turn off the electricity.

この後、真空を破って槽内より取り出された感光ドラム
は、セレン・ヒ素・合金上にアンチモン４％を含むセレ
ン・テルル−アンチモン合金層が５μ積層された感光体
である。Thereafter, the vacuum was broken and the photosensitive drum was taken out from the tank, and the photosensitive drum was a photosensitive member in which 5 μm of a selenium-tellurium-antimony alloy layer containing 4% antimony was laminated on a selenium-arsenic alloy.

この本発明による感光ドラムを試料１とし、比較のため
、本発明によらない感光ドラム試料２試料３はアンチモ
ンを用いないで上層をセレンテルルとしたものである。This photosensitive drum according to the present invention is referred to as Sample 1, and for comparison, photosensitive drum samples 2 and 3, which are not according to the present invention, do not use antimony but have selenite as an upper layer.

これ等の試料を５０℃の環境に放置の後、画像テストを
実施した所試料３については、１００時間後に、結晶核
の発生によって、ハーフトーン画像上に白く抜ける点が
発生し、２００時間後には、全面に広がってしまった。After leaving these samples in an environment of 50°C, an image test was performed. Regarding sample 3, after 100 hours, white spots appeared on the halftone image due to the generation of crystal nuclei, and after 200 hours, white spots appeared on the halftone image. has spread all over the place.

これに反して試料１、試料２は、３００時間後も初期画
像と差のない画質であった。さら１こ他の評価方法とし
て、周温３５℃の状況下で複写機１こよる連続画像テス
トを実施した。この際の複写機内の温度変化は、テスト
開始後３０分程度で４２℃まで上昇しその後はぼ安定し
ていた。この事は、複写手内の感光ドラ機 ム温度も除々に上昇する事を示している。On the other hand, samples 1 and 2 had image quality that was the same as the initial image even after 300 hours. As another evaluation method, a continuous image test was conducted using one copying machine at an ambient temperature of 35°C. The temperature change inside the copying machine at this time rose to 42° C. about 30 minutes after the start of the test, and remained fairly stable thereafter. This indicates that the temperature of the photosensitive drum inside the copying machine also gradually rises.

連続画像テストの結果は第１表から分かる様に下層にセ
レンーヒ素合金、上層にセレン・テルル・アンヂモン合
金を積層させた試料１は、５万枚複写後も変化なく、高
温算囲気中で安定して使用出来る事を示している。The results of the continuous image test are as shown in Table 1. Sample 1, which has a selenium-arsenic alloy layered in the lower layer and a selenium-tellurium-andimony alloy layered in the upper layer, remained unchanged even after 50,000 copies were made and was stable in a high-temperature environment. This shows that it can be used.

試料２に傷の発住が大きい事は、感光体が表面だけでな
く、内部の温度による硬度変化に影響を受ける事を示し
ている。以上の説明から明らかなように本発明によれば
高感度で結晶化、硬度などへの４環境性が良く、全色性
に優れ、且つ軒時変化を改善した電子写真感光体が得ら
れその用途は複写機、プリンターなど広く実用上の効果
は大きい。The large number of scratches on Sample 2 indicates that the photoreceptor is affected by changes in hardness due to not only the surface but also the internal temperature. As is clear from the above description, according to the present invention, an electrophotographic photoreceptor can be obtained that has high sensitivity, good resistance to four environmental conditions such as crystallization and hardness, excellent panchromaticity, and improved change over time. It has a wide range of uses, including copying machines and printers, and has great practical effects.

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

第１図は本発明の実施例による電子写真感光体の構成例
図である。１は導電性支持体、２はセレンーヒ素合金層
、３はセレン−テルル−アンチモン合金層である。 新電元工業株式会社FIG. 1 is a diagram showing an example of the structure of an electrophotographic photoreceptor according to an embodiment of the present invention. 1 is a conductive support, 2 is a selenium-arsenic alloy layer, and 3 is a selenium-tellurium-antimony alloy layer. Shindengen Industries Co., Ltd.

Claims (1)

【特許請求の範囲】 ＋１１　　導電性支持体上にセレンーヒ素合金層を積層
し、更にその上層にセレン−テルル−アンチモン合金層
を積層したことを特徴とする電子写真感光体。 （２）　　セレンーヒ素合金層のヒ素濃度を１０％以下
、セレン−テルル−アンチモン合金層のテルル濃度を５
０％以下、アンチモン濃度を１０％以下としたことを特
徴とする特許請求の範囲第１項記載の電子写真感光体。 （３）　セレンーヒ素合金層の膜厚を２０〜１００Ｐセ
レン−テルル−アンチモン合金層の膜厚をＩＯμ以下と
したことを特徴とする特許請求の範囲第１項又は第２項
記載の電子写真感光体。[Claims] +11 An electrophotographic photoreceptor comprising a selenium-arsenic alloy layer laminated on a conductive support, and a selenium-tellurium-antimony alloy layer further laminated on top of the selenium-arsenic alloy layer. (2) The arsenic concentration in the selenium-arsenic alloy layer is 10% or less, and the tellurium concentration in the selenium-tellurium-antimony alloy layer is 5% or less.
The electrophotographic photoreceptor according to claim 1, characterized in that the antimony concentration is 0% or less and the antimony concentration is 10% or less. (3) The electrophotographic photosensitive material according to claim 1 or 2, characterized in that the film thickness of the selenium-arsenic alloy layer is 20 to 100P, and the film thickness of the selenium-tellurium-antimony alloy layer is IOμ or less. body.