JPH04124672A - Manufacture of as-se alloy and electrophotographic sensitive body using same and manufacture of said body - Google Patents

Abstract

PURPOSE:To obtain the electrophotographic sensitive body superior in acceptance and stability of potential and image quality, such as color reproducibility, and not causing deterioration of oxygen concentration by executing distillation and melting in the material purification process of the As-Se alloy under an oxygen atmosphere specified in pressure and temperature. CONSTITUTION:The distillation and melting are carried out in the material purification process of the As-Se alloy in an oxygen atmosphere under the conditions of a vacuum of 10<-1> - 10 Torr and a temperature of 550 - 600 deg.C and a maintenance time of >=15hr, thus permitting the As-Se alloy to be stably doped with oxygen of >=100ppm concentration, and the photosensitive layer of the As-Se alloy formed under said vacuum deposition conditions to contain oxygen in an amount of 130 - 500ppm by weight and the obtained photosensitive body to be superior in potential acceptance and its maintenance.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to an As-Se electrophotographic photoreceptor used in electrophotographic copying machines, laser beam printers, facsimile machines, etc., a manufacturing method thereof, and an As-Se electrophotographic photoreceptor used therein. -Relating to a method for producing a Se alloy.

[Conventional technology]

An As-Se electrophotographic photoreceptor is an electrophotographic photoreceptor in which As-S is used as a photoconductive material on a conductive substrate made of an aluminum alloy or the like.
It is equipped with a photosensitive layer made of e-alloy, and has been used mainly in high-speed printers and copying machines due to its excellent rigidity and environmental resistance.

In recent years, high resolution has been required due to the colorization of these counterfeits and the 04 compatibility of facsimile machines. However, when such a device is equipped with an As-Se photoconductor with low charging and holding capacity, the charging and holding capacity tends to fluctuate, resulting in poor color reproducibility.B) The charge holding capacity is low, resulting in poor image quality. There are problems such as shading in density, and a photoreceptor with good charging and holding ability has been desired. As such a photoreceptor, oxygen is added to the photosensitive layer made of As-Se alloy ^S20. lppm in the form of
The one containing ~500 ppm is published in JP-A-58-1235.
43, and methods for obtaining such a photoreceptor include (a) a method of doping Se02 when forming a photosensitive layer by vacuum evaporating an As-Se alloy (Japanese Unexamined Patent Publication No. 54993;
(C) As-Se alloy^S20. A method of vapor depositing a photosensitive layer using a raw material doped with
Publication No. 3) is known.

[Problem to be solved by the invention]

However, in method (a) above, it is necessary to perform vapor deposition while controlling the vapor pressure of each of the As-Se alloy and Se02, and it is difficult to uniformly and stably contain oxygen in the photosensitive layer. I felt dizzy.

Furthermore, in the method (b), the amount of oxygen doped in the As-Se alloy raw material is only about 5 ppm to 10 ρρm by weight, as is also known in JP-A-47-26071; There has been a problem in that it is extremely difficult to stably dope several hundred ppm of oxygen into the Se alloy raw material and into the photosensitive layer.

The present invention solves the above-mentioned problems and provides a manufacturing method capable of containing 100 ppm or more of oxygen in the ^s -Se alloy raw material, and also provides a method for producing 5-Se The problem to be solved is to fabricate a photoreceptor by vacuum-depositing an alloy raw material under predetermined conditions, and to provide a photoreceptor with excellent charging and holding ability.

[Means to solve the problem]

In order to solve the above problems, according to the present invention, to 5-
Distillation and melting in the Se alloy raw material refining process (a) 10
-'Torr to 10 Torr in an atmosphere of acid sx) Temperature 550°C to 600°C (c) Holding time 15 hours or more.
The As-Se alloy obtained by this manufacturing method is stably doped with oxygen in an amount of ppm or more by weight, and is vacuum-deposited on a conductive substrate under predetermined conditions to form a photosensitive layer. 130 weight ρpm or more 500 weight p in the layer
The photoreceptor contains oxygen within a range of pm or less.

[Effect]

Conventionally, distillation and melting of As-Se alloy was carried out at 1O-2 Torr.
It was carried out in a vacuum. By performing this distillation and melting in an oxygen-introduced atmosphere, the amount of oxygen doped into the As-Se alloy is more than twice the conventional amount, and the distillation and melting temperature is increased from the conventional 600°C to 650°C. By lowering the temperature by 50° C. to 100° C., the amount of oxygen doped is further increased by 50% to 100%. However, the amount of oxygen introduced into the atmosphere is several tens of Torr.
If the temperature is increased or the distillation/melting temperature is lowered to around 500°C, the original purpose of removing impurities from the 5-Se alloy will become insufficient, which is not preferable.

Furthermore, it is possible to increase the amount of oxygen doped into the 5-Se alloy by increasing the holding time;
It takes more than 24 hours to contain 100 ppm or more of oxygen at a high temperature exceeding 100 for retention time of 15 hours or more
An As-Se alloy containing oxygen in an amount of ppm or more by weight can be efficiently and stably obtained.

Using the As-Se alloy thus obtained, a photosensitive layer is formed under predetermined vacuum deposition conditions to form a photoreceptor.
It contains oxygen in a range of pm or more and 500 pm or less by weight, making it possible to obtain a photoreceptor with excellent charging and holding ability.

〔Example〕

Using an As-Se alloy containing 100 weight ppm of AS203 as a raw material, purification was performed by varying distillation and melting conditions, and the oxygen concentration in the obtained As2Se3 was measured by FT-IR. The results are shown in Table 1. Note that the atmospheric pressure is l
The pressure after introducing varying amounts of oxygen into a vacuum of 10-2 Torr is shown.

/ / As seen in Table 1, there is a large difference in the amount of oxygen doped into ^s, Se = when oxygen is introduced into the atmosphere and when it is not introduced, and the amount of oxygen doped into the atmosphere is The larger the amount introduced, the larger the amount of oxygen doped into S, Se, and Se. However, when the atmospheric pressure is tens of To
It is known that if the temperature exceeds rr, the removal of impurities in Se3 becomes insufficient, and the amount of oxygen introduced into the atmosphere is limited to about 10 orr.

Furthermore, the lower the distillation/melting temperature, the greater the amount of oxygen doped into As2Ses. This is ^S,
0. melting point (275°C for cubic system, 315°C for monoclinic system)
), for example, JP-A-58-12
The temperature of 650°C known in Publication No. 3543 is As20
It is considerably higher than the melting point of 3, ^S20. It is thought that this is because the doping is not stably performed, and it becomes easier to be doped stably at a lower temperature. However, if the temperature is lowered to around 500°C, a problem arises in that impurity removal is insufficient, so 500°C is considered to be the lower limit.

In addition, by increasing the holding time, the oxygen content of ^s, Se increases, but if oxygen is not introduced into the atmosphere and the distillation/melting temperature remains at 650°C, the oxygen content is 100 ppm by weight.
It is estimated that it would take more than 24 hours to contain more than 10% of oxygen, whereas under the conditions according to this invention, 15
It can be seen that more than 100 weight ρpm of oxygen can be contained in about an hour.

Using As2Se purified in this way, I
In a vacuum of X 1O-sTorr, the evaporation source temperature was set to 400
℃, and the glass transition point (Tg
) A photosensitive layer was formed by vapor deposition on an M alloy drum maintained at a temperature of about 180° C. to produce a photoreceptor. As2 using the characteristics of the obtained photoreceptor and the oxygen content in the photosensitive layer
Table 2 shows the Se and oxygen concentrations in the raw materials.

In Table 1, the thickness of the photosensitive layer was 60 μm, and the current flowing into the substrate at the time of measuring the charged potential was 110 μm. Further, the repeated residual potential is the value after 200 charging/discharging cycles.

As seen in Table 2, the charging and holding abilities of photoreceptors 2, 3 and 4 are clearly superior to photoreceptor Nα1,
The effects of this invention are obvious. The repeated residual potential is
It tends to increase as the oxygen concentration in the photosensitive layer increases, but it is not at a level that poses a practical problem at an acid SA seismic intensity of 50 ppm by weight or less).

Further, this problem of repeated increase in residual potential can be easily solved by adding a small amount of a halogen element such as iodine to the photosensitive layer.

〔Effect of the invention〕

Claims (1)

[Claims] 1) Distillation and melting in the As-Se alloy raw material refining process,
(a) In an oxygen atmosphere within the range of 10^-^1 Torr or more and 10 Torr or less (b) At a temperature of 550°C or more and 600°C or less (c) For a holding time of 15 hours or more. 100
A characterized by containing oxygen in an amount of ppm or more by weight
Manufacturing method of s-Se alloy. 2) Electrophotography characterized by forming a photosensitive layer on a conductive substrate by vacuum-depositing an As-Se alloy containing 100 ppm or more of oxygen by the method according to claim 1 under predetermined conditions. Manufacturing method of photoreceptor. 3) Vapor deposition is carried out in a vacuum of 1×10^-^4 Torr or less at an evaporation source temperature of 400°C on a conductive substrate maintained at a temperature of the glass transition point of the As-Se alloy used as the evaporation material. The method for producing an electrophotographic photoreceptor according to claim 2. 4) As-S produced by the production method according to claim 2 or 3
130 ppm or more by weight in the photosensitive layer made of e-alloy 500
An electrophotographic photoreceptor characterized by containing oxygen within a range of ppm by weight or less.