JPS61269162A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To increase a sensitivity of the titled body in a long wavelength range, and to improve a heat stability and a durability and also a residual potential of the titled body by laminating a surface layer contg. at least a selenium and an arsenic directly or through an electric charge generating layer composed of a selenide alloy on the electric charge holding layer contg. the selenium, the arsenic and a halogen. CONSTITUTION:The electric charge holding layer 2 composed of the selenium.tellurium.arsenic.chlorine alloy, the electric charge generating layer 3 composed of a selenium.telluriom alloy and the surface layer 4 composed of a selenium.arsenic alloy are formed on an electroconductive substrate 1 composed of an aluminium. Preferably, the additional amount of the tellurium is 2-10wt%, the additional amount of the arsenic is 0.2-5wt% and the additional amount of the chlorine is 5-200ppm, 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。　
　　　　　　　　　　　　　・安キ専キ去ネ。いわゆる
電子写真用感光体として従来から使用されているものは
、酸化亜鉛系ＯＰＣ系、セレン系などであるが、これ等
の中でセレン系は最も重用されており、その解像力、耐
久力、電気安定性共他の材料と比べて優秀である。しか
しながらセレンは、結晶セレンによる長波長感度域を除
けば５５０ｎｍ程度までの短波長域までしか有効な感度
を持たないこと、また装置内のわずかな温度上昇によっ
ても感光体表面が結晶化して使用出来なくなるなどの欠
点を持っている。この為に各種の添加物を用いることに
よって、これらの欠点を解消する事が提案されている。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the structure of an electrophotographic photoreceptor.
・Anki Senki left. Photoreceptors traditionally used for electrophotography include zinc oxide, OPC, and selenium, but of these, selenium is the most heavily used, with its high resolution, durability, and electrical properties. It has excellent stability compared to other materials. However, selenium has an effective sensitivity only in the short wavelength range of about 550 nm, excluding the long wavelength sensitivity range due to crystalline selenium, and even a slight temperature rise inside the device will cause the surface of the photoreceptor to crystallize, making it unusable. It has drawbacks such as being lost. For this reason, it has been proposed to eliminate these drawbacks by using various additives.

この中で最も一般的に用いられているのがテルル増感で
ある。テルル添加によって、感度は増大し、結晶化の抑
制にも若干は寄与している。しかしながら、可視光全域
に十分な感度を持たせるには、テルル添加量は大量とな
り、結晶化への移行はより起り易くなる。Among these, tellurium sensitization is the most commonly used. The addition of tellurium increases sensitivity and also contributes to some extent to suppress crystallization. However, in order to provide sufficient sensitivity in the entire visible light range, the amount of tellurium added must be large, making the transition to crystallization more likely.

さらに、電位保持率が低下し、疲労が増大するなど、電
気特性的にも不安定となり、実用上きめ細かい注意が必
要となる。これに反してヒ素を添加して増感を行なう場
合には、感度及び耐熱性が同時に向上する為に、高感度
で熱安定性に優れた感光体の提供が可能である。しかし
、セレン・ヒ素感光体は疲労特性、経時特性に難点があ
り、有効感度域も７００ｎｍまでである。Furthermore, electrical properties become unstable, such as a decrease in potential holding rate and an increase in fatigue, which requires careful attention in practice. On the other hand, when sensitization is carried out by adding arsenic, sensitivity and heat resistance are simultaneously improved, making it possible to provide a photoreceptor with high sensitivity and excellent thermal stability. However, the selenium-arsenic photoreceptor has drawbacks in fatigue characteristics and aging characteristics, and its effective sensitivity range is limited to 700 nm.

さらに高濃度のヒ素添加は製造上困難な点が多い。本発
明は前述の欠点を解消し、長波長領域の感度を増大化し
、熱的安定性及び耐久性を向上し、併せて電気特性特に
残留電位を改善した電子写真感光体を提供する。第１図
（ａｌ及び（ｂ）は本発明の実施例による電子写真感光
体の構成図である。図において１はアルミニウム等から
なる導電性支持体である。２はセレン・テルル・１、　
　　　　　　ヒ素・塩素合金であり、感光体の電荷保持
層を形成する。３はセレン・テルル合金であり、感光体
の電荷発生層を形成する。又、４はセレン・ヒ素合金で
あり、感光体の表面層を形成するＯなお、１の導電性支
持体と２の電荷保持層の間に電気的又は機械的特性の改
善のための中間層を必要に応じて設けたりその他、通常
の付加、変更、変形等はなし得るものである。第１図（
ａ）においては２の電荷保持層上に直接表面層４を積層
しており、この表面層４は高感度層を形成し、増感作用
をなす。もちろん、表面層４は光の照射等により電荷発
生機能を有するものである。第１図（ａ）では高感度に
するためテルル、ヒ素等の過剰な添加を必要とし、その
結果として電気抵抗の低下をまねき、表面電位の保持が
困難になることがある。第１図（ｂ）は表面層４と電荷
保持層２との間に高濃度テルルを含むセレン化合金から
なる電荷発生１３を別に形成するものであり、第１図（
ａ）の構成による感光体を改善し、併せて長波長領域を
より高感度にするものである。前記する電荷保持層２、
電荷発生層３及び表面層４のセレン化合金における不純
物添加量は感光体の電気的又は機械的特性を決定するの
に重要な役割をなす。第２図は本発明の電荷保持層２の
セレン・テルル・ヒ素・塩素合金の各元素の添加量が電
子写真特性特に残留電位及び繰返し使用における表面電
位の変動に及ぼす影響を示している。即ち実線によって
テルルの載加量との関係を示し、その増加は残留電位を
減少せしめ、繰返し使用における表面降下電位を増大せ
しめる傾向を示す。　、７又、鎖線によりヒ素の添加量
との関係を示し、その添加による効果はテルルによる影
響を更に増大せしむる方向にある。更に、点線によりて
塩素の添加量との関係を示し、前二者より効果の大きい
ことがわかる。従って、表面降下電位の増大を適当に押
えて残留電位を減少させる改善点を見出し得る。更に耐
熱性等を考慮し、実験によってテルルの添加量は２〜１
０重量％、ヒ素の添加量０．２〜５重量％、塩素の添加
量５〜２００ｐｐｍが好ましいことがわかった。なお、
電荷保持層２の塩素のかわりに他のハロゲン元素、よう
素臭素、フッ素等を用いてもよい。第１図（ｂ）の電荷
発生層３のセレン・テルル合金についてのテルルの添加
量は２０〜５０重量％、厚さ０．１〜１μｍが好ましい
値であった。又、表面ＷＩ４のセレン・ヒ素合金は感度
及び耐熱性からヒ素の添加！１〜２０重景％、厚さ１〜
１０μｍにすることが好ましい。なお、本明細書におい
てセレン・テルルφヒ素・塩素合金、セレン・ヒ素合金
、セレン・テルル合金等の表現は特性を決定する主成分
によつてあられしており、除去し得ないか又は除去する
必要のない微量の不純物については含有してもよい。次
に実験例によ」 り本発明を説明する。真空蒸着機構内に温媒体１３よ５
−Ｃ＠　！１！　’Ｗｌヮヵ３□ヶ、５４□□□　　　
　　１設置し、その下方に３台の蒸発源を設置した。Furthermore, adding arsenic at a high concentration poses many manufacturing difficulties. The present invention eliminates the above-mentioned drawbacks, and provides an electrophotographic photoreceptor which has increased sensitivity in the long wavelength range, improved thermal stability and durability, and improved electrical properties, particularly residual potential. Figures 1 (al and b) are block diagrams of an electrophotographic photoreceptor according to an embodiment of the present invention. In the figures, 1 is a conductive support made of aluminum or the like. 2 is selenium tellurium 1,
It is an arsenic-chlorine alloy and forms the charge retention layer of the photoreceptor. 3 is a selenium-tellurium alloy, which forms the charge generation layer of the photoreceptor. Further, 4 is a selenium-arsenic alloy, which forms the surface layer of the photoreceptor. Furthermore, an intermediate layer is provided between the conductive support 1 and the charge retention layer 2 to improve electrical or mechanical properties. may be provided as necessary, and other usual additions, changes, modifications, etc. may be made. Figure 1 (
In a), a surface layer 4 is directly laminated on the charge retention layer 2, and this surface layer 4 forms a high-sensitivity layer and has a sensitizing effect. Of course, the surface layer 4 has a charge generation function when irradiated with light or the like. In FIG. 1(a), it is necessary to add excessive amounts of tellurium, arsenic, etc. to achieve high sensitivity, which may result in a decrease in electrical resistance and make it difficult to maintain the surface potential. FIG. 1(b) shows a method in which a charge generating layer 13 made of a selenide alloy containing a high concentration of tellurium is separately formed between the surface layer 4 and the charge retention layer 2.
This is to improve the photoreceptor having the configuration a) and also to make it more sensitive in the long wavelength region. The charge retention layer 2 described above,
The amount of impurities added to the selenide alloy of the charge generation layer 3 and the surface layer 4 plays an important role in determining the electrical or mechanical properties of the photoreceptor. FIG. 2 shows the influence of the amount of each element added in the selenium-tellurium-arsenic-chlorine alloy in the charge retention layer 2 of the present invention on the electrophotographic properties, particularly on the residual potential and the variation in surface potential during repeated use. That is, the solid line shows the relationship with the loading amount of tellurium, and its increase tends to decrease the residual potential and increase the surface potential drop during repeated use. , 7, and the chain line shows the relationship with the amount of arsenic added, and the effect of its addition tends to further increase the influence of tellurium. Furthermore, the dotted line shows the relationship with the amount of chlorine added, and it can be seen that the effect is greater than the former two. Therefore, it is possible to find an improvement point for appropriately suppressing the increase in the surface potential drop and reducing the residual potential. Furthermore, considering heat resistance, etc., the amount of tellurium added was determined by experiment to be 2 to 1.
It was found that 0% by weight, an amount of arsenic added of 0.2 to 5% by weight, and an amount of chlorine added of 5 to 200 ppm are preferable. In addition,
In place of chlorine in the charge retention layer 2, other halogen elements, iodine, bromine, fluorine, etc. may be used. The preferred amount of tellurium added to the selenium-tellurium alloy of the charge generating layer 3 in FIG. 1(b) was 20 to 50% by weight and the thickness was 0.1 to 1 μm. Also, arsenic is added to the selenium-arsenic alloy with surface WI4 for sensitivity and heat resistance! 1~20% heavy background, thickness 1~
Preferably, the thickness is 10 μm. In addition, in this specification, expressions such as selenium/tellurium φ arsenic/chlorine alloy, selenium/arsenic alloy, selenium/tellurium alloy, etc. are used depending on the main component that determines the characteristics and cannot be removed or removed. A trace amount of unnecessary impurities may be included. Next, the present invention will be explained with reference to experimental examples. A heating medium 13 to 5 is placed inside the vacuum evaporation mechanism.
-C@! 1! 'Wlヮka 3□ months, 54□□□
1 was installed, and three evaporation sources were installed below it.

第一の蒸発源にはセレン・テルル・ヒ素・塩素合金（テ
ルル・ヒ素・塩素各々５重量％、１重量％、１５０ｐｐ
ｍ　）を入れ、第二の蒸発源にはセレン・テルル合金（
テルル２０重量％）を入れた。更に第三の蒸発源にはセ
レン・ヒ素合金（ヒ素７重量％）を入れた。又、各蒸発
源上には任意に開閉が可能なシャッターを設けた。表面
を鋺面仕上げした１２０〆ｘ３００Ｉのアルミニウムド
ラムに適切な表面処理を施して真空蒸着機槽内の回転支
持台に固定し、ドラムを８０℃に保って排気を行ない蒸
着を開始した。各蒸発源を加熱→蒸着→シャ、ター→閉
→加熱終了の順序で操作して感光層を積層した。各蒸発
源による積層嗅厚と所要時間は第一蒸発源が５５μｍを
３０分で積層し、第二蒸発源は１μｍを３分で積層し、
第三蒸発源は２１）ｍを２分間で積層した。この感光ド
ラムを試料袋して更に第三蒸発源を用いないで蒸着を行
なって試料２を試作した。更に第一蒸発源にセレン・ヒ
素・塩素合金（ヒ素２重量％、塩素１）００ｐｐ　）を
用いて他は試料１と同仕様の試料３を蒸着した。The first evaporation source is a selenium-tellurium-arsenic-chlorine alloy (tellurium, arsenic, chlorine each 5% by weight, 1% by weight, 150pp).
m), and the second evaporation source is a selenium-tellurium alloy (
20% by weight of tellurium) was added. Further, a selenium-arsenic alloy (7% by weight of arsenic) was added to the third evaporation source. Moreover, a shutter that can be opened and closed arbitrarily was provided above each evaporation source. A 120 x 300 I aluminum drum with a rough surface finish was subjected to appropriate surface treatment and fixed to a rotating support in a vacuum evaporator tank, and the drum was kept at 80° C. and evacuated to start vapor deposition. The photosensitive layers were laminated by operating each evaporation source in the order of heating→evaporation→opening→close→end of heating. The laminated thickness and time required for each evaporation source are as follows: The first evaporation source laminates 55 μm in 30 minutes, the second evaporation source laminates 1 μm in 3 minutes,
The third evaporation source stacked 21) m in 2 minutes. This photosensitive drum was placed in a sample bag, and evaporation was further performed without using a third evaporation source to prepare sample 2. Furthermore, Sample 3 having the same specifications as Sample 1 was deposited using a selenium-arsenic-chlorine alloy (2% by weight of arsenic, 00pp of chlorine) as the first evaporation source.

又、比較のため本発明によらない試料として第−蒸発源
にセレン・テルル合金（テルル５重量％）を入れて、他
は試料１と同仕様の試料４を蒸着した。試料１、試料３
及び試料４は三層構造を形成しており、分光感度につい
て長波長領域で十分高度感度であり特性も安定している
ことがわかった。次いで実機によって装置内温度を４５
℃にして画像テストを行い、耐久性について第１表のご
とき結果を得た。For comparison, as a sample not according to the present invention, a selenium-tellurium alloy (tellurium 5% by weight) was placed in the first evaporation source, and sample 4 having the same specifications as sample 1 was evaporated. Sample 1, sample 3
Sample 4 and Sample 4 formed a three-layer structure, and were found to have sufficiently high spectral sensitivity in the long wavelength region and stable characteristics. Next, the temperature inside the device was set to 45% using the actual machine.
An image test was conducted at 0.degree. C., and the durability results shown in Table 1 were obtained.

＠１表 試料４の結晶化は支持体であるアルミニウムドラムの表
面まで達していることがｍｆＲ鋼での観察で確認された
。このことは結晶化がアルミニウムドラム側から発生し
ていると考えられる。It was confirmed by observation using mfR steel that the crystallization of Sample 4 in Table 1 reached the surface of the aluminum drum that was the support. This is considered to be because crystallization occurs from the aluminum drum side.

なお、試料１〜３の表面＠（第１図（ａ）　（ｂ）の４
に相当）としてセレン・テルル・ヒ素合金（テルル０．
５〜６重量％、ヒ素１〜２０％）を用いても耐久テスト
にセいて第１表と同様の好結果を得ることができた。Note that the surfaces of samples 1 to 3 (4 in Figure 1 (a) and (b))
) as a selenium-tellurium-arsenic alloy (tellurium 0.
5 to 6% by weight and 1 to 20% arsenic), good results similar to those shown in Table 1 could be obtained in the durability test.

以上のごとく１本発明の電子写真感光体は長波長領域の
感度を増大し、熱的安定性及び耐久性を向上し、併せて
残留電位を改善することから複写機、プリンタ等に利用
して極めて効果大なるものである。As described above, the electrophotographic photoreceptor of the present invention increases sensitivity in the long wavelength region, improves thermal stability and durability, and improves residual potential, so it can be used in copiers, printers, etc. This is extremely effective.

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

第１図（ａ）及び（ｂ）は本発明の実施例による電子写
真感光体の構成図であり、ｌは導電性支持体２は電荷保
持層、３は電荷発生層、４は表面層である。第２図は電
気的特性図を示す。 特許出願人　新電元工業株式会社 山梨電子工業株式会社 （（：Ｌ）（り 算１図 第２図FIGS. 1(a) and 1(b) are structural diagrams of an electrophotographic photoreceptor according to an embodiment of the present invention, in which l represents a conductive support 2, a charge retention layer, 3 a charge generation layer, and 4 a surface layer. be. FIG. 2 shows an electrical characteristic diagram. Patent applicant Shindengen Kogyo Co., Ltd. Yamanashi Electronics Kogyo Co., Ltd.

Claims (4)

【特許請求の範囲】[Claims] （１）少くともセレン、ヒ素及びハロゲンを含む電荷保
持層上に直接もしくはセレン化合金からなる電荷発生層
を介して少くともセレン、ヒ素を含む表面層を積層した
ことを特徴とする電子写真感光体。(1) An electrophotographic photosensitive material characterized in that a surface layer containing at least selenium and arsenic is laminated on a charge retention layer containing at least selenium, arsenic, and halogen, either directly or via a charge generation layer made of a selenized alloy. body. （２）テルル濃度２〜１０重量％、ヒ素濃度０．２〜５
重量％、塩素濃度５〜２００ｐｐｍを含む電荷保持層か
らなる特許請求の範囲第（１）項の電子写真感光体。(2) Tellurium concentration 2-10% by weight, arsenic concentration 0.2-5
The electrophotographic photoreceptor according to claim 1, comprising a charge retention layer containing a chlorine concentration of 5 to 200 ppm by weight. （３）テルル濃度１０〜５０重量％を含む電荷発生層か
らなる特許請求の範囲第（１）項、第（２）項記載の電
子写真感光体。(3) An electrophotographic photoreceptor according to claims (1) and (2), which comprises a charge generation layer containing a tellurium concentration of 10 to 50% by weight. （４）ヒ素濃度１〜２０重量％を含む表面層からなる特
許請求の範囲第（１）項、第（２）項、第（３）項記載
の電子写真感光体。(4) An electrophotographic photoreceptor according to claims (1), (2), and (3), comprising a surface layer containing an arsenic concentration of 1 to 20% by weight.