JPH1073941A - Image forming device, image forming method, and electrophotographic photoreceptive member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the charging efficiency and charging stability to a charging device using a magnetic powder as brush, and reduce the change of image density by the drifting of an electric charge in charging on the outermost surface by providing a design so that the surface directional resistance value may be larger than the thickness directional resistance value. SOLUTION: A charging device is formed of a contact type charging member 100, a spacer 102A for regulating the distance between the contact type charging member and a photoreceptive member, and a photographic photoreceptive member 103 such as the photoreceptive member. The contact type charging member 100 is formed of a magnetic brush layer 101-1 formed of a charging carrier on the contact charging member 100, and a roller-like multipolar magnetic body 101-2 of the contact type charging member 100. The electrophotographic photoreceptive member 103 has a light conductive layer formed of a non- monocyrstal silicon material, and a surface layer having one of silicon atom and carbon atom as a base body, and it is formed so that the surface directional resistance value on the outermost surface is larger than the thickness directional resistance value of the surface layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for applying a voltage to a charging member, bringing the charged surface of the charging member into contact with a light receiving member for electrophotography, and charging the charged surface. The present invention relates to an image forming method of writing image information by light to execute image formation and an apparatus used for the method.

Further, the present invention relates to a photoreceptor for electrophotography which is sensitive to electromagnetic waves such as light (here, light in a broad sense and means ultraviolet light, visible light, infrared light, x-rays, γ-rays, etc.). Regarding members.

[0003]

[Prior art]

1. 2. Description of the Related Art Image forming apparatuses are widely used in addition to so-called copiers for copying originals, as well as computers, which have been growing in demand in recent years, and printers as output means of word processors. Since such printers have been used not only for conventional office use but also for personal use, economics such as low cost and maintenance free are emphasized.

Furthermore, from the viewpoint of ecology, measures to reduce the consumption of paper such as double-sided copying and recycled paper, to save energy by reducing the power consumption during image formation, and to reduce the amount of ozone, etc., are the same as economical measures. Required by importance.

[0005] Corona chargers, which have been the mainstream of the conventional charging system, use a metal wire having a diameter of about 50 to 100 µm to have a diameter of 5 to 1 m.
A high voltage of about 0 kV is applied to ionize the atmosphere in the charger to apply charges to the opposing object. In the process, the wire itself also absorbs dirt, and requires periodic cleaning and replacement. In addition, a large amount of ozone is also a problem with corona discharge.

As for energy saving, there is also a problem of a heating means for the light receiving member.

A light-receiving member for electrophotography used in recent years is
Used continuously for high-speed mass copying. for that reason,
The adhesion of the corona product derived from ozone makes it easier for the surface of the light receiving member to adsorb moisture, which causes a lateral flow of charges on the surface of the light receiving member, thereby causing a deterioration in image quality called image deletion. There is.

In order to prevent such image deletion, heating by a heater as described in JP-B-1-34205 and formation from a magnet roller and magnetic toner as described in JP-B-2-38956 are described. A method for removing corona products by rubbing the surface of the light receiving member with a brush, and a method for removing corona products by rubbing the surface of the light receiving member with an elastic roller as described in JP-A-61-100780 Has been used.

Japanese Patent Application Laid-Open No. 60-95551 discloses that in order to improve the image quality of an amorphous silicon photoreceptor member, the temperature near the surface of the photoreceptor member is maintained at 30 to 40.degree. A technique is disclosed in which an image forming process such as transfer is performed to prevent a reduction in surface resistance due to the adsorption of moisture on the surface of the light receiving member and an image deletion caused by the reduction.

[0010] However, the method of rubbing the surface of the light receiving member is used for an amorphous silicon light receiving member having extremely high hardness, but this is one of the difficult factors for reducing the size and cost of the device.

[0011] Further, the constant heating by the heater causes an increase in power consumption as described above. Such heaters usually have a capacity of about 15 W to 800 W, which does not always give the impression of a large amount of power. However, in most cases, the heater is always energized even at night, and the power consumption per day is the consumption of the entire image forming apparatus. As much as 5-15% of the electricity.

Also, in an external heater heating method in a form similar to the present invention, that is, in JP-A-59-111179 and JP-A-62-278577, an image density unstable element caused by temperature fluctuation of a light receiving member is also disclosed. There is no disclosure of improvement.

Further, the above-mentioned ozone, which is a cause of such image deletion, has a risk of harm to humans and organisms around the image forming apparatus. Especially for personal use,
The amount of discharged ozone must be reduced as much as possible. As described above, a method for greatly reducing the amount of ozone generated at the time of charging is demanded from the viewpoint of economy and environmental hygiene.

Under these circumstances, there is a demand for a new charging member, a charging device, and a charging device with no or reduced ozone generation as an image forming apparatus.

2. Charging Device Various charging devices have been proposed to solve the above-mentioned problems.

In the contact charging method described in JP-A-63-208878, a charged member to which a voltage is applied is brought into contact with an electrophotographic light receiving member to charge a charged surface to a required potential. Compared with the corona charging device widely used as a charging device, the applied voltage required to obtain a desired potential on the electrophotographic light receiving member surface can be reduced. The amount of ozone generated in the charging process Is negligible or very small,
Eliminates the need for an ozone removal filter, simplifies the configuration of the exhaust system of the device, and generates no or very little ozone during the charging process so that ozone products adhere to the surface of the electrophotographic light-receiving member It does not absorb moisture and eliminates the necessity of dehumidification by a heater that is performed all day, thereby greatly reducing electric power consumption such as energization at night.

Therefore, for example, in an image forming apparatus such as an image forming apparatus (copier, laser beam printer) and an electrostatic recording apparatus, a light receiving member, an image carrier such as a dielectric, and other light receiving members for electrophotography are used. Attention has been paid as an alternative to the corona discharge device as a means for performing the charging treatment.

In various attempts to improve the contact charging member, a magnetic brush-like contact charging member composed of a magnetic material and magnetic powder (or particles) has been developed as disclosed in Japanese Patent Application Laid-Open No. S59-133569. A new system of a mechanism for applying contact and charging to a carrier has been proposed.

FIG. 2 shows one embodiment. Reference numeral 102 denotes a photosensitive drum as an image carrier, which is a drum-type electrophotographic light receiving member that is driven to rotate at a predetermined peripheral speed (process speed) in a clockwise direction of an arrow A. Reference numeral 101 denotes a charging member, which is composed of a multipolar magnetic body and a magnetic brush layer formed on the charged surface thereof with magnetic powder.

The multipolar magnetic material is constituted like a cylindrical, so-called magnet roller, and is usually a ferrite magnet,
A magnetic material such as a rubber magnet is used.

The magnetic brush layer is made of a magnetic iron oxide (ferrite) powder such as a Cu-Zn-Fe-O system, a magnetite powder, a material in which a magnetic material such as ferrite or magnetite is dispersed in a resin, a known magnetic toner material. Are generally used.

It is desirable that the resistance value of the charging member is appropriately selected according to the environment in which the charging member is used, high charging efficiency, pressure resistance characteristics of the surface layer of the light receiving member, and the like. Normal,
In order to obtain good charging, the resistance of the charging member must be 1 ×
It is necessary to have a resistance of 10 ³ to 1 × 10 ¹² Ωcm. More preferably, when the resistance is 1 × 10 ⁴ to 1 × 10 ⁹ Ωcm, good charging characteristics and improvement in environmental characteristics such as image deletion are obtained.

If the resistance of the charging member is less than 1 × 10 ³ Ωcm, there is a risk that abnormal discharge and pinholes will occur and the light receiving member will be damaged. On the other hand, if it is 1 × 10 ¹² Ωcm or more, the charging efficiency is reduced, and the charging property due to injection is reduced.

The voltage applied to the charging member is a DC voltage Vdc alone, or an AC voltage (Vac) superimposed on the DC voltage Vdc and applied to the multipolar magnetic body and the magnetic brush layer of the charging member to rotate and drive the photosensitive drum. The outer peripheral surface of 102 is uniformly charged.

Further, an electrostatic latent image is formed on the photosensitive drum by scanning with a laser beam printer light whose intensity is modulated according to an image signal. This latent image is
After being visualized by a developing sleeve coated with a developing material, the image is transferred onto a transfer material via a transfer roller. The transfer residual toner is removed from the photosensitive drum by a cleaning blade, and the transferred image is output after being fixed by a fixing device (not shown). By the above method,
The characteristics such as the contact property between the image carrier and the contact charging member were improved.

3. Light-receiving member 1) Amorphous silicon-based light-receiving member (a-Si) In electrophotography, as a photoconductive material for forming a photosensitive layer in the light-receiving member, a high sensitivity and an SN ratio (photocurrent (I
p) / dark current (Id)), having an absorption spectrum suitable for the spectral characteristics of the irradiating electromagnetic wave, fast photoresponse, having a desired dark resistance value, and harmless to the human body during use. Characteristics are required.

In particular, in the case of a light receiving member for an image forming apparatus which is incorporated in an image forming apparatus used in an office as an office machine, the image quality and the image density are considered in view of copying in a large amount and for a long time. Is also important.

Hydrogenated amorphous silicon (hereinafter referred to as “a-Si:
H :), for example, Japanese Patent Publication No. 60-350
No. 59 describes an application as a light receiving member for an image forming apparatus.

[0029] Such a light receiving member for an image forming apparatus includes:
Generally, a conductive support is heated to 50 ° C. to 400 ° C. and formed on the support by a vacuum evaporation method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method, or the like. A photoconductive layer made of a-Si is formed by a film method. Among them, a plasma CVD method, that is, a method in which a raw material gas is decomposed by direct current, high frequency, or microwave glow discharge to form an a-Si deposited film on a support has been put to practical use. Also,
JP-A-54-83746 discloses an image forming apparatus comprising a conductive support and an a-Si (hereinafter referred to as "a-Si: X") photoconductive layer containing a halogen atom as a constituent element. Light receiving members have been proposed. In this publication, 1 to 40 atomic% of halogen atoms are contained in a-Si.
It is said that by containing the compound, it has high heat resistance and can obtain good electrical and optical characteristics as a photoconductive layer of a light receiving member for an image forming apparatus.

Japanese Patent Application Laid-Open No. S57-115556 discloses a photoconductive member having a photoconductive layer composed of an a-Si deposited film, and the electrical and optical characteristics such as dark resistance, light sensitivity, and light responsiveness. Silicon and carbon atoms on a photoconductive layer composed of an amorphous material based on silicon atoms in order to improve the use environment characteristics such as physical, photoconductive and moisture resistance, and the stability over time. A technique for providing a surface barrier layer made of a non-photoconductive amorphous material containing is described.

Further, Japanese Patent Application Laid-Open No. 60-67951 describes a technique for a light receiving member in which a light transmitting insulating overcoat layer containing amorphous silicon, carbon, oxygen and fluorine is laminated. 62-168
Japanese Patent No. 161 describes a technique of using an amorphous material containing silicon atoms, carbon atoms, and 41 to 70 atomic% of hydrogen atoms as constituent elements as a surface layer.

Furthermore, Japanese Patent Application Laid-Open No. 57-158650 discloses that an infrared absorption spectrum contains 10 to 40 atomic% of hydrogen and has an absorption peak coefficient of 2000 cm ^-1 of 2000 cm ^-1.
The ratio of the absorption peak at ^-1 to the absorption coefficient is 0.2 to 1.7.
It is described that a high-sensitivity and high-resistance light-receiving member for an image forming apparatus can be obtained by using a-Si: H which is a photoconductive layer.

[0033] These techniques have improved the electrical, optical, photoconductive and operating environment characteristics of the light receiving member for an image forming apparatus, and the image quality has been improved accordingly.

4. It is well known to provide a heat source on the inner surface of the light receiving member in order to prevent and remove the high-humidity image flow of the light receiving member.
Most commonly, a planar or rod-shaped electric heater is disposed on the inner surface of the cylindrical light receiving member.

[0035]

Problems to be solved by the image forming apparatus using the above amorphous silicon light receiving member include the following.

[0036] What is required from the recent office situation,
By using a charging device that uses a magnetic powder of a voltage application type as a brush as described above to reduce the size of the device, the size can be reduced as compared with a conventional corona charging device. By adopting a charging device using a magnetic powder as a brush, which generates almost no ozone, it is possible to maintain a state in which there is no image bleeding even if rubbing by a cleaner used by a magnetic brush or the like is eliminated. It becomes possible.

However, even when a voltage applying type magnetic powder is charged by a charging device using a brush, there is a new problem that an image density is thin and blurred. When an electrophotographic light-receiving member having such a region is used, there is a problem that image deletion easily occurs in a high-humidity environment.

Further, even if the problem of image deletion can be solved as described above, if the temperature dependence (temperature characteristic) of the electrophotographic characteristic is large due to a change in environmental temperature, it is necessary to consider that the actual image is 1-3.
Precise temperature control by a heater as described in 4205 must be performed. Therefore, in order to remove the heater, it is necessary to reduce the temperature characteristics. In addition, it is necessary to remove the heater in order to reduce the size of the image forming apparatus. In this sense, reducing the temperature characteristics is an important problem.

Further, as an indispensable tool for producing presentation materials, various copying media including resin sheets such as transparency for OHP and thick paper such as postcards have been used in electrophotographic apparatuses.

In particular, frequent copying to a copy medium which is harder than plain paper tends to cause scratches on the surface of the light receiving member for electrophotography. If the scratch is severe, problems such as streaks appearing on the image, or the image is not copied at all without being charged.

In order to prevent this damage, it is desired to improve the durability by increasing the hardness of the surface layer of the electrophotographic light-receiving member. Hardness has been maintained by doing more.
In addition, by laminating a diamond-like amorphous carbon film, it is becoming possible to obtain a surface layer having more excellent overall hardness and the like.

In particular, the present invention solves a new problem that an image density becomes thin and blurred when a voltage applying type magnetic powder is charged by a charging device using a brush. It is a first object of the present invention to solve the problem that an image is likely to flow under a high humidity environment when an electrophotographic light receiving member is used.

Further, in order to solve the above-mentioned problems, an image forming apparatus and an image forming method having a charging device using a magnetic powder of a voltage application type as a brush, and a light receiving member for electrophotography are comprehensively provided. There is a need for further improvement from a different viewpoint.

Therefore, in order to solve the above problems, an image forming apparatus having a charging device using a magnetic powder of a voltage application type as a brush, an image forming method, and a light receiving member for electrophotography are comprehensively provided. There is a need for further improvement from a different viewpoint.

[0045]

The present invention can solve the above-mentioned problems by the following means.

That is, in the present invention, a voltage is applied to a cylindrical charging member having at least a multipolar magnetic material and a magnetic powder, and the magnetic powder is applied to an electrophotographic light receiving member which is an image carrier. In an image forming apparatus which is contacted and charged to form an electrostatic latent image on the electrophotographic light receiving member and visualize the electrostatic latent image with toner, the electrophotographic light receiving member is at least a non-single-crystal silicon type. A photoconductive layer composed of the following materials, and a surface layer having at least one of silicon atoms and carbon atoms as a host, and having a surface direction of the outermost surface as compared with the resistance value in the layer thickness direction of the surface layer. An object of the present invention is to provide an image forming apparatus characterized by having a large resistance value.

Further, in the present invention, the ratio of the resistance value in the surface direction of the outermost surface to the resistance value in the layer thickness direction of the surface layer is 10 to 10.
00 is provided.

Another object of the present invention is to provide an image forming apparatus characterized in that the surface layer has a resistance in the thickness direction of 1 × 10 ^{10 to} 5 × 10 ¹³ Ωcm.

The present invention also relates to the present invention,
Direction resistance value is 1 × 10¹²~ 2 × 10 ^FifteenΩcm
An object of the present invention is to provide an image forming apparatus characterized by the following.

The present invention further provides a photoconductive layer made of at least a non-single-crystal silicon-based material,
In a light receiving member for electrophotography having a surface layer having at least one of carbon atoms as a host, the resistance in the surface direction of the outermost surface of the surface layer is larger than the resistance in the thickness direction of the surface layer. An object of the present invention is to provide a light receiving member for electrophotography.

Further, in the present invention, the ratio of the resistance in the surface direction of the outermost surface of the surface layer to the resistance in the thickness direction of the surface layer of the surface layer is 10 to 1000. It is to provide a light receiving member.

The present invention further provides the electrophotographic light-receiving member, wherein the surface layer has a resistance in the thickness direction of 1 × 10 ^{10 to} 5 × 10 ¹³ Ωcm.

Further, the present invention provides the electrophotographic light-receiving member, wherein the outermost surface of the surface layer has a resistance value in the surface direction of 1 × 10 ¹² to 2 × 10 ¹⁵ Ωcm. is there.

Further, in the present invention, the photoconductive layer preferably has a thickness of 10 to 30.
Atomic hydrogen atoms, and the characteristic energy of the exponential function tail obtained from the light absorption spectrum at least in the light incident portion of the photoconductive layer is 50 meV or more and 60 me
V or less, and an object of the present invention is to provide the electrophotographic light-receiving member according to claim 5.

Further, the present invention provides the photoreceptor for electrophotography, wherein the photoconductive layer contains at least one element belonging to Group IIIb or Group Vb of the periodic table. It is in.

The present invention also provides the light receiving member for electrophotography, wherein the photoconductive layer contains at least one of carbon, oxygen and nitrogen.

The present invention further provides a photoconductive layer in which the photoreceptive layer is made of a non-single-crystal material containing silicon atoms as a base, and at least one of carbon, oxygen and nitrogen provided on the surface of the photoconductive layer. And a surface layer made of a silicon-based non-single-crystal material containing: a light-receiving member for electrophotography.

Further, in the present invention, the photoreceptive layer contains a silicon atom as a base material, and contains at least one of carbon, oxygen and nitrogen and at least one element selected from Group IIIb or Vb of the periodic table. A charge injection blocking layer made of a non-single-crystal material, a photoconductive layer provided on the surface of the charge injection blocking layer, made of a non-single-crystal material containing silicon atoms as a base, and provided on the surface of the photoconductive layer A surface layer made of a silicon-based non-single-crystal material containing at least one of carbon, oxygen and nitrogen.

In the present invention, the photoconductive layer preferably has a thickness of 20
The object of the present invention is to provide the electrophotographic light-receiving member having a thickness of about 50 μm.

Further, in the present invention, a voltage is applied to a cylindrical charging member having at least a multipolar magnetic material and a magnetic powder, and the magnetic powder is brought into contact with an electrophotographic light receiving member as an image carrier. And charging, forming an electrostatic latent image on the electrophotographic light-receiving member, and visualizing the electrostatic latent image with toner, wherein the electrophotographic light-receiving member is at least a non-single-crystal silicon-based. A photoconductive layer made of a material, having a surface layer having at least one of silicon atoms and carbon atoms as a host, and having a resistance in the thickness direction of the surface layer in the surface direction of the outermost surface. An object of the present invention is to provide an image forming method characterized by having a large resistance value.

Further, in the present invention, the ratio of the resistance value in the surface direction of the outermost surface to the resistance value in the thickness direction of the surface layer is 10 to 10.
00 is provided.

The present invention further provides the above-described image forming method, wherein the resistance of the surface layer in the thickness direction is 1 × 10 ^{10 to} 5 × 10 ¹³ Ωcm.

The present invention further provides the above-described image forming method, wherein the outermost surface of the surface layer has a resistance value in the surface direction of 1 × 10 ¹² to 2 × 10 ¹⁵ Ωcm.

[0064]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS When a voltage-applied magnetic powder is charged by a charging device using a brush, the cause of the occurrence of a thin and blurred image density is that the charge at the time of charging drifts on the outermost surface. As a result of careful studies focusing on the resistance value in the surface direction of the outermost surface of the electrophotographic light-receiving member, the resistance value in the layer thickness direction,
By designing the surface layer so that the resistance value in the surface direction becomes large, the charging efficiency and charging stability for the charging device using the magnetic powder as a brush are greatly improved, and the image as described above is obtained. It was found that the change in concentration could be reduced.

By setting the resistance in the surface direction of the outermost surface to be about 10 to 1000 times the resistance in the thickness direction of the surface layer, almost no blurred region with a low image density is generated, It was found that the problem of image deletion in a humid environment can be improved.

In order to solve the problem of reducing the temperature characteristics, the present inventors focused on the behavior of carriers in the photoconductive layer, and focused on the distribution of localized states in the band gap of a-Si and the temperature of the chargeability. As a result of earnestly examining the dependence and the relationship with the optical memory, it has been found that the above object can be achieved by controlling the localized state distribution at least in the light incident portion of the photoconductive layer.

That is, in a light receiving member having a photoconductive layer composed of a non-single-crystal material containing silicon atoms as a base and containing hydrogen atoms and / or halogen atoms,
A light-receiving member designed and made to specify its layer structure not only exhibits remarkably excellent properties in practical use, but also outperforms all other conventional light-receiving members. In particular, they have been found to have excellent properties as a light receiving member for electrophotography.

By the way, the "exponential function tail" used hereinafter refers to an absorption spectrum obtained by subtracting the tail toward the lower energy side from the absorption of the light absorption spectrum. The “characteristic energy” is the slope of the exponential function tail.

The light-receiving member for electrophotography of the present invention comprises a conductive support and a non-single-crystal material containing a hydrogen atom and / or a halogen atom on a surface of the conductive support. A photoreceptive member having at least a photoreceptive layer having a photoconductive layer exhibiting photoconductivity, wherein the photoconductive layer contains 10 to 30 atomic% of hydrogen, and The characteristic energy of the exponential function tail (Urbak tail) obtained from the light absorption spectrum at the incident portion is 50 to 60 meV.

Further, the light-receiving member for electrophotography of the present invention comprises:
A photoreceptive layer having a conductive support and a photoconductive layer on the surface of the conductive support and made of a non-single-crystal material containing silicon atoms as a base and containing hydrogen atoms and / or halogen atoms and exhibiting photoconductivity. Wherein the photoconductive layer contains 10 to 30 atomic% of water, and the absorption peak coefficient of the Si—H ₂ bond obtained from the infrared absorption spectrum of the photoconductive layer. The intensity ratio of the absorption peak of the Si—H bond to the absorption coefficient is 0.1 to 0.5, and an exponential tail (Urbak tail) obtained from a light absorption spectrum of at least a portion of the photoconductive layer where light enters. ) Is 50 to 60 meV and the density of localized states in the photoconductive layer is 1 × 10 ¹⁴
cm ^-3 or more and less than 1 × 10 ¹⁶ cm ^-3 .

Generally, in the band gap of a-Si: H, a tail (tail) level based on a structural disorder of a Si-Si bond and a dangling bond of Si are formed.
And other deep levels due to structural defects. It is known that these levels function as trapping and recombination centers for electrons and holes, and cause deterioration of device characteristics.

As a method for measuring the state of the localized level in such a band gap, generally, deep level spectroscopy, isothermal capacity transient spectroscopy, photothermal deflection spectroscopy, photoacoustic spectroscopy, constant photocurrent method, etc. Is used. Above all, the constant photocurrent method (hereinafter abbreviated as “CPM”) is useful as a method for easily measuring the subgap light absorption spectrum based on the localized level of a-Si: H.

The present inventors have proposed a characteristic energy (hereinafter abbreviated as “Eu”) of an exponential function tail (Urbuck tail) obtained from a sub-bandgap optical absorption spectrum measured by CPM and a localized state density (hereinafter referred to as “Eu”). Hereinafter, "D
As a result of examining the correlation between the photoconductor characteristics and the photoconductor characteristics under various conditions, it was found that Eu and DOS were closely related to the temperature characteristics of the a-Si photoconductor and the optical memory. It was completed.

The reason why the charging ability is reduced when the photosensitive member is heated by a drum heater or the like is that the thermally excited carrier is attracted by the electric field at the time of charging, and the localized level at the band base or the deep level within the band gap. It travels to the surface while repeating capture and emission to a state, and cancels the surface charge. At this time, the carrier that has reached the surface while passing through the charger has little effect on the reduction of the charging ability, but the carrier captured at a deep level reaches the surface after passing through the charger. It is observed as a temperature characteristic to cancel the surface charge. Carriers that are thermally excited after passing through the charger also cancel the surface charge and cause a reduction in charging ability. Therefore, it is necessary to suppress the generation of thermally excited carriers in the operating temperature range of the photoconductor and to improve the traveling properties of the carriers in order to improve the temperature characteristics.

Therefore, as in the present invention, Eu and D
By controlling the OS, the generation of thermally excited carriers is suppressed, and the rate at which the thermally excited carriers and optical carriers are trapped in the localized levels can be reduced, so that the traveling properties of the carriers are significantly improved. .

As a result, the temperature characteristics of the photoreceptor in the operating temperature range are remarkably improved, the stability of the photoreceptor in the use environment is improved, and a high quality image with a clear halftone and high resolution is obtained. Can be obtained stably.

Further, by specifying the absorption intensity ratio of the absorption peak caused by the Si—H ₂ bond and the Si—H bond,
The traveling property of the carrier in the plane of the light receiving member is made uniform,
As a result, it is possible to reduce a minute difference in density in a halftone image, that is, so-called roughness.

Therefore, the electrophotographic light-receiving member of the present invention designed to have the above-described structure can solve all of the above-mentioned problems, and has excellent electrical, optical, and photoconductive properties. It shows the characteristics, image quality, durability and environment of use.

Further, since the adsorption of water is smaller than that of the conventional surface layer, and no ozone product is generated by corona charging as in the conventional charging system, a countermeasure against “high humidity flow” by the ozone product is taken. It became unnecessary, and the temperature characteristics were made smaller than before, so the drum heater was also removed,
This makes it possible to reduce the size of the apparatus, and at the same time, reduces power consumption and power consumption at night, which is effective in terms of ecology.

The operation will be described in more detail below.

[Charging Member] FIG. 1 schematically illustrates a charging member and a light receiving member for electrophotography according to the present invention. In FIG. 1, 100 is a contact-type charging member according to the present invention, 101-1 is a magnetic brush layer made of the above-described charge carrier of the contact-type charging member, 101
Reference numeral -2 denotes a roller-type multi-pole magnetic material of a contact-type charging member (hereinafter, referred to as a mag roller) depending on the shape. It is a light receiving member for electrophotography such as a member.

Mag Roller 101-2 of Contact Type Charging Member
Usually, a metal such as a ferrite magnet, a magnetic material such as a plastic magnet, and the like, which can have a multipolar configuration, are used.
The magnetic line density varies depending on many factors such as the process speed used, the electric field due to the applied voltage and the potential difference between the uncharged portions, the permittivity and surface properties of the electrophotographic light-receiving member, and is appropriately selected according to those conditions. However, the magnetic field line density at the magnetic pole position, measured at a distance of 1 mm from the surface of the mag roller 101-2, is preferably 500 gauss (G) or more. More preferably, it is 1000 G or more.

The closest gap between the image bearing member and the mag roller 100-2 is provided with a roller 102 for stably controlling the contact width (hereinafter referred to as a nip) of the magnetic brush layer 101-1 in the rotation direction of the light receiving member. It is necessary to set an appropriate distance by an appropriate method such as a spacer or a spacer. The distance is 50
To 2000 μm, more preferably 10 μm.
0 to 1000 μm. In addition, a mechanism for adjusting the nip may be provided.

The magnetic brush layer 102 of the charging member made of the above-mentioned charged carrier is generally made of a magnetic powder such as ferrite or magnetite, a well-known toner carrier, or a toner made of a magnetic material and a resin.

The particle size of the magnetic powder is generally 1 to 100 μm.
m or less, but a powder having a larger particle size may be used as long as the image quality is not affected. In addition, a charge carrier having a uniform particle size may be used, or charge carriers having different particle sizes may be mixed and used for improving fluidity.

As shown in FIG. 4, the resistance of the magnetic brush layer keeps the charging efficiency good, while the potential decreases in the major axis direction of the charging member due to leak spots and minute defects on the surface of the light receiving member. 1 × 10 to prevent
It is preferable to have a resistance of ³ to 1 × 10 ¹² Ωcm. More preferably, it is 1 × 10 ⁴ to 1 × 10 ⁹ Ωcm.

Although the mag roller has been described above, a sleeve having a built-in magnetic material (hereinafter referred to as a charging sleeve) may be used as the charging member.

The resistance value was measured using an MΩ manufactured by HIOKI.
The measurement was performed with a tester at an applied voltage of 250 to 1 kV. The light receiving member 102 for electrophotography such as a light receiving member may be the same as a conventional one, but a new light receiving member described later is used as necessary.

[Light Receiving Member] In order to solve the above-mentioned problem, the present inventors have a surface layer having small temperature dependency and excellent surface durability, and have a resistance value in the thickness direction of the surface layer. Using an electrophotographic light-receiving member having a large resistance in the surface direction of the outermost surface of the surface layer, it has been found that extremely suitable image stabilization can be achieved over a long period of time.

[Amorphous silicon-based light receiving member (a
-Si)] Amorphous silicon-based light receiving member (hereinafter referred to as “a-S”), which is an embodiment of a preferable light receiving member used in the present invention.
The "i-light receiving member" will be described below.

The a-Si-based light receiving member according to the present invention includes a well-known conductive support, a photosensitive layer having a photoconductive layer made of a non-single-crystal material having silicon atoms as a base, silicon atoms and carbon atoms. And a surface layer having at least one of them as a base material and having improved characteristics as necessary.

The electrophotographic light-receiving member having the a-Si-based light-receiving member used in the present invention has extremely excellent electrical, optical and photoconductive properties and image quality, including temperature dependency of charging ability. , Durability and use environment characteristics.

Hereinafter, the photoconductive member of the present invention will be described in detail with reference to the drawings.

FIG. 5 is a schematic configuration diagram for explaining the layer configuration of the light receiving member for an image forming apparatus according to the present invention.

A light receiving member 600 for an image forming apparatus shown in FIG. 5A has a photosensitive layer 602 and a surface layer 604 provided on a support 601 for a light receiving member. The photosensitive layer 602 is composed of a photoconductive layer 603 made of a-Si: H, X and having photoconductivity.

FIG. 5B is a schematic configuration diagram for explaining another layer configuration of the light receiving member for an image forming apparatus of the present invention. The light receiving member 60 for an image forming apparatus shown in FIG.
In No. 0, a photosensitive layer 602 is provided on a support 601 for a light receiving member. The photosensitive layer 602 is a-S
i: Photoconductive layer 603 made of H and X and having a photoconductive layer
And a surface layer 604 having at least one of silicon atoms and carbon atoms as a host, and an intermediate layer 605 laminated between the surface layer 604 and the photoconductive layer 603.

There are various functions of the intermediate layer. For example, 1) adhesion between layers having different compositions and structures of the surface layer (604) and the photoconductive layer (603) is determined. Play a role to improve. 2) The function is almost the same as 1 but has a structure of a buffer layer having a structure and smoothly connects from 603 to 604. 3) A layer for preventing charge injection from the surface side. 4) A sensitizing layer for positively generating photocarriers. It is necessary to appropriately select the structure, composition, configuration, and the like according to the role.

FIG. 5C is a schematic configuration diagram for explaining another layer configuration of the light receiving member for an image forming apparatus of the present invention. The light receiving member 60 for an image forming apparatus shown in FIG.
In No. 0, a photosensitive layer 602 is provided on a support 601 for a light receiving member. The photosensitive layer 602 is a-S
i: Photoconductive layer 603 made of H and X and having photoconductivity
, A surface layer 604 having at least one of silicon atoms and carbon atoms as a host, and an amorphous silicon-based charge injection blocking layer 606.

FIG. 5D is a schematic structural view for explaining still another layer constitution of the light receiving member for an image forming apparatus of the present invention. A light receiving member 600 for an image forming apparatus shown in FIG. 5D is provided on a support 601 for a light receiving member.
A photosensitive layer 602 is provided. The photosensitive layer 602 includes a charge generation layer 607 and a charge transport layer 608 made of a-Si: H, X constituting the photoconductive layer 603 and a surface layer 60 having at least one of silicon atoms and carbon atoms as a host.
And 4.

[Photoconductive Layer] In the present invention, a part of the photosensitive layer 602 is formed on a support 601 and, if necessary, on an undercoat layer (not shown) in order to effectively achieve the object. The photoconductive layer 603 constituting is formed by a vacuum deposition film formation method with appropriately setting numerical conditions of film formation parameters so as to obtain desired characteristics. Specifically, for example, a glow discharge method (an AC discharge CVD method such as a low-frequency CVD method, a high-frequency CVD method or a microwave CVD method, or a DC discharge CVD method), a sputtering method, a vacuum deposition method,
It can be formed by various thin film deposition methods such as an ion plating method, a photo CVD method, and a thermal CVD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, the degree of load under capital investment, the manufacturing scale, and the characteristics desired for the light receiving member for an image forming apparatus to be manufactured. The glow discharge method, especially the high frequency glow using the power frequency in the RF band, the μW band or the VHF band, is relatively easy to control the conditions for manufacturing the light receiving member for an image forming apparatus having the characteristics described above. The discharge method is preferred.

In order to form the photoconductive layer 603 by the glow discharge method, it is basically known that silicon atoms (S
a source gas for supplying Si that can supply i), a source gas for supplying H that can supply hydrogen atoms (H), and / or a source gas for supplying X that can supply halogen atoms (X), Is introduced in a desired gas state into a reaction vessel which can be decompressed to generate a glow discharge in the reaction vessel, and a is placed on a predetermined support 601 previously set at a predetermined position.
A layer made of -Si: H, X may be formed.

Further, the dangling bonds of silicon atoms are compensated,
In order to improve the layer quality, in particular, the photoconductivity and the charge retention characteristics, it is necessary that the photoconductive layer 603 contain hydrogen atoms and / or halogen atoms. The amount, or the content of the sum of hydrogen atoms and halogen atoms, is preferably 10 to 30 atom%, more preferably 15 to 25 atom%, based on the sum of silicon atoms and hydrogen atoms and / or halogen atoms.

Then, hydrogen atoms are structurally introduced into the formed photoconductive layer 603 so that the introduction ratio of hydrogen atoms can be more easily controlled, and a film characteristic which achieves the object of the present invention is obtained. For this reason, these gases additionally contain H ₂ and / or
Alternatively, it is necessary to form a layer by mixing a desired amount of He or a silicon compound gas containing a hydrogen atom. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

The source gas for supplying a halogen atom used in the present invention is, for example, a gaseous or gaseous gas such as a halogen gas, a halide, an interhalogen compound containing a halogen, or a silane derivative substituted with a halogen. The obtained halogen compounds are preferred. Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains a silicon atom and a halogen atom as constituent elements, can also be mentioned as an effective compound.

Examples of the halogen compound that can be suitably used in the present invention include fluorine gas (F ₂ ), Br
F, ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ ,
And a halogen or interhalogen compound of the IF ₇ or the like. As a silicon compound containing a halogen atom, that is, a silane derivative substituted with a so-called halogen atom, specifically, for example, silicon fluoride such as SiF ₄ or Si ₂ F ₆ can be preferably mentioned.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer 603, for example, the temperature of the support 601 and the raw material used for containing hydrogen atoms and / or halogen atoms are used. What is necessary is just to control the amount of the substance introduced into the reaction vessel, the discharge power and the like.

In the present invention, it is preferable that the photoconductive layer 603 contain atoms for controlling conductivity as necessary. The atoms that control the conductivity may be contained in the photoconductive layer 603 in a state of being distributed uniformly and evenly, or there may be a part that is contained in the layer thickness direction in a non-uniform distribution state. Is also good.

Examples of the atoms for controlling the conductivity include so-called impurities in the semiconductor field.
An atom belonging to Group IIIb of the periodic table giving p-type conduction properties (hereinafter abbreviated as "IIIb group atom") or an atom belonging to Group Vb of the periodic table giving n-type conduction properties (hereinafter "V
abbreviated as “group b atom”). III
As the group b atom, specifically, boron (B), aluminum (Al), gallium (Ga), indium (In),
There are thallium (Tl) and the like, and B, Al and Ga are particularly preferable. Particularly, the group Vb atom specifically includes phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi) and the like, and P and As are particularly preferable.

Controlling the conductivity contained in photoconductive layer 103
The content of the atoms to be^-2~ 1
× 10^Three Atomic ppm, more preferably 5 × 10^-2~ 5x
10 ^Two Atomic ppm, optimally 1 × 10^-1~ 1 × 10^Two original
Desirably, it is ppm.

In order to structurally introduce an atom for controlling conductivity, for example, a group IIIb atom or a group Vb atom, a source material for introducing a group IIIb atom or a group Vb atom should be used during layer formation. A raw material for introducing atoms may be introduced in a gaseous state into the reaction vessel together with another gas for forming the photoconductive layer 103. As a raw material for introducing a Group IIIb atom or a raw material for introducing a Group Vb atom, a gaseous substance at room temperature and normal pressure or a substance which can be easily gasified at least under layer forming conditions is employed. It is desirable. Being able to gasify is broader than just being gaseous, for example, sublimation like aluminum chloride,
The method of sublimation and introduction into the apparatus with a carrier gas such as hydrogen gas or helium gas is also included in the concept of gasification.

As the raw material for introducing a Group IIIb atom, specifically, for introducing a boron atom, B _{2
H 6, B 4 H 10,} B 5 H 11, B 6 H 10, B 6 H 12, B 10
Borohydride such as _{H 14, BF 3, BCl 3} , BBr boron halides such as _3. In addition, AlCl ₃ ,
GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ , TlCl
₃ etc. can also be mentioned.

Effective as a starting material for introducing group Vb atoms
Used for introducing phosphorus atoms is OH_Three , P_Two 
H_Four Phosphorus hydride, PH_Four I, PF_Three , PF_Five , PCl
_Three , PCl_Five , PBr_Three , PBr_Five , PI_Three Such as haloge
Phosphorus nitride. In addition, AsH_Three , AsF_Three , A
sCl_Three , AsBr_Three , AsF_Five , SbH_Three , SbF
_Three , SbF_Five , SbCl_Three , SbCl_Five , BiH_Three , B
iCl_Three , BiBr_Three Are also starting materials for introducing group Vb atoms
It can be cited as an effective one of quality.

Further, these raw materials for introducing atoms for controlling conductivity may be diluted with H ₂ and / or He if necessary.

Further, in the present invention, the photoconductive layer 60
It is also effective that 3 contains a carbon atom and / or an oxygen atom and / or a nitrogen atom. The content of the carbon atom and / or the oxygen atom and / or the nitrogen atom is preferably 1 × 10 ⁻⁵ to 10 atom%, more preferably 1 ×, based on the sum of the silicon atom, the carbon atom, the oxygen atom and the nitrogen atom. 10 ^-4 to 8 atomic%, optimally 1 × 10 ^{-3 to} 5
Atomic% is preferred.

A carbon atom and / or an oxygen atom and / or
Alternatively, the nitrogen atom may be uniformly contained in the photoconductive layer, or may be a portion having a non-uniform distribution such that the content changes in the thickness direction of the photoconductive layer. .

In the present invention, the layer thickness of the photoconductive layer 603 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
It is desirable that the thickness be 0 to 50 μm, more preferably 23 to 45 μm, and most preferably 25 to 40 μm.

Further, the optimum temperature of the support 601 is appropriately selected according to the layer design.
Preferably from 200 to 350 ° C, more preferably from 230 to
It is desirable that the temperature be 330 ° C., optimally 250 to 310 ° C.

The conditions for forming the photoconductive layer, such as the temperature of the support and the gas pressure, are not usually determined independently and separately, but are mutually or organically determined to form a photoreceptor having desired characteristics. It is desirable to determine the optimal value based on the relevance.

[Surface Layer] In the present invention, a surface layer 604 is formed on the photoconductive layer 603 formed on the support 601 as described above. After forming the photoconductive layer 603, similarly to the photoconductive layer 603, for example, a glow discharge method (an AC discharge CVD method such as a low-frequency CVD method, a high-frequency CVD method or a microwave CVD method, or a DC CV method).
D method, etc.) sputtering method, ion plating method,
The surface layer can be formed by various thin film deposition methods such as a vacuum evaporation method. These thin film deposition methods depend on manufacturing conditions,
It is appropriately selected and adopted depending on factors such as the load under capital investment, the production scale, and the characteristics desired for the electrophotographic light-receiving member to be produced. The discharge method is preferred.

At this time, the temperature of the support is gradually increased with the progress of film formation, and the ratio of the C-atom-containing source gas to the Si-atom-containing source gas is increased. In addition, the surface layer of the present invention can be obtained by reducing the applied power.

The surface layer 604 has a free surface 609, has a large resistance in the surface direction of the outermost surface with respect to the resistance in the layer thickness direction, reduces unevenness in the surface direction, and improves hardness. Suitable for a type in which a voltage is applied to a cylindrical charging member having a multipolar magnetic material and a magnetic powder, and the magnetic powder is charged by contacting the magnetic powder with an electrophotographic light receiving member as an image carrier. To improve the sensitivity and the characteristics of moisture resistance, continuous repeated use, electrical pressure resistance, and use environment.

The surface layer 604 is a layer composed of a hydrogenated amorphous material having at least one of silicon atoms and carbon atoms as a base.

Examples of the substance that can be a gas for supplying silicon atoms (Si) used in forming the surface layer of the present invention include those in a gas state such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , and Si ₄ H _10. Or silicon hydrides (silanes) which can be gasified can be used effectively. Further, in terms of ease of handling at the time of forming a layer, high supply efficiency of Si, etc.
iH ₄ and Si ₂ H ₆ are preferred.
Further, if necessary, these source gases for supplying Si may be converted to H
_It may be used after being diluted with a gas such as ₂ , He, Ar, or Ne.

Examples of the substance that can serve as a carbon supply gas include:
The gaseous hydrocarbons such as CH ₄ , C ₂ H ₂ , C ₂ H ₆ , C ₃ H ₈ , and C ₄ H ₁₀ , or gasifiable hydrocarbons can be used effectively. CH ₄ , C ₂ H ₂ ,
C ₂ H ₆ is preferred. Further, these raw material gases for supplying C may be replaced with H ₂ , He,
It may be diluted with a gas such as r or Ne before use. Further, in the present invention, when a diluent gas is used when forming the surface layer 604, argon (A) is used as the diluent gas.
r), helium (He) and the like.

The surface layer 604 according to the present invention is carefully formed so that its required properties are provided as desired. In other words, a material containing Si, C, and H as components is structurally from crystalline to amorphous depending on the formation conditions, and has electrical properties ranging from conductive to semiconductive and insulating. In addition, since each property between photoconductive property and non-photoconductive property is shown, in the present invention, a- (S
ixCyHz) is strictly selected for its formation conditions as desired.

In the present invention, the surface a- (S
When the surface layer 604 made of (ixCyHz) is formed, it is important that the temperature of the support during layer formation be gradually increased as the film formation proceeds.

As the temperature of the support for forming the surface layer 604 for effectively achieving the object of the present invention, an optimal range is appropriately selected according to the method of forming the surface layer 604. Although the formation is performed, it is desirable that the temperature is 200 to 270 ° C. when the initial temperature of the film formation is normal. To form the surface layer 604, it is necessary to raise the temperature of the support at least in accordance with the film formation. However, the rate of temperature rise must not exceed 2.0 ° C./min. Further, it is desirable that the rate of temperature increase be appropriately adjusted in association with the film formation rate so that the temperature of the support is in the range of 270 to 400 ° C. at the end of the film formation.

When the rate of temperature rise is less than 0 ° C./min, the structural relaxation on the outermost surface is small, the structure of the layer portion of several atoms from the surface tends to be dense, and the disorder of the structure in the plane direction increases. I do. As a result, a region in which the resistance in the surface direction of the outermost surface of the surface layer is smaller than the resistance in the thickness direction of the surface layer is generated. On the other hand, if the temperature rise rate is higher than 2.0 ° C./min, the temperature change becomes too large with respect to the film growth, so that the film tends to be distorted. Initial characteristics such as peeling are deteriorated.

When the initial film forming temperature is lower than 200 ° C.,
It is difficult for silicon atoms and / or carbon atoms and hydrogen atoms to be optimally bonded during the growth process on the surface of the photoconductive layer, and many dangling bonds are formed near the interface of the surface photoconductive layer. It is unsuitable for the purpose of the invention to achieve both higher transparency and higher hardness.
When the initial film forming temperature is higher than 270 ° C., the residual potential tends to increase. When the initial temperature is higher than 290 ° C., the tendency is further increased.

In addition, the effect of the present invention in which the film formation final temperature is lower than 270 ° C. cannot be obtained because silicon atoms and / or carbon atoms are effectively bonded to dangling bonds on the surface layer formation surface. However, it is considered that no improvement in hardness is observed because uncombined hands remain or compensation due to hydrogen and the incorporation of hydrogen increase to easily generate a portion containing a large amount of hydrogen. If the final temperature of the film formation is higher than 400 ° C., the hardness tends to decrease slightly, and the surface of the drum after the endurance becomes noticeable. This is considered to be due to the fact that the proportion of hydrogen termination in the growth surface atoms is reduced, and the hardness is reduced due to the presence of extremely fine holes in the film.

The employment of the glow discharge method or the sputtering method is advantageous because the delicate control of the composition ratio of the atoms constituting the layer and the control of the layer thickness are relatively easy as compared with other methods. When the surface layer 604 is formed by these layer forming methods, the discharge power and the gas pressure at the time of forming the layer are important in determining the characteristics of a- (SixCyHz) to be formed in the same manner as the temperature of the support. Is one of the important factors.

The discharge power condition for effectively producing a- (SixCyHz) having the characteristics for achieving the object of the present invention is usually 10 to 10 per support in the glow discharge method. It is preferably 800 W, preferably 20-500 W. It is desirable that the power is set to 50 to 500 W at the beginning of the surface layer film formation. It is necessary to continuously reduce the discharge power during film formation, but the discharge power is 10 to 10 at the end of film formation.
It is desirable to appropriately adjust the reduction of the discharge power so as to fall within 400 W.

The frequency of the applied voltage is usually DC to
10 GHz, preferably 1 MHz to 5 GHz, optimally 1
It is desirable that the frequency be 0 MHz to 3 GHz. Further, it is also effective to simultaneously apply a plurality of frequencies in this range.

The gas pressure in the deposition chamber is usually 0.001 to 3 T
orr, preferably about 0.005 to 2 Torr, and most preferably about 0.01 to 1 Torr.

In the present invention, the desirable numerical ranges of the temperature of the support, the gas pressure, and the discharge power for forming the surface layer 604 include the values in the above-described ranges. Rather than being determined separately, it is desirable that the optimum value of each layer forming factor be determined based on the mutual organic relationship so that the surface layer 604 made of a- (SixCyHz) having desired characteristics is formed.

The amounts of silicon atoms, carbon atoms, and hydrogen atoms contained in the surface layer 604 in the member for electrophotographic light bath of the present invention are determined in the same manner as the conditions for forming the surface layer 604, so as to achieve the object of the present invention. This is an important factor in forming the surface layer 604 where characteristics can be obtained.

That is, if the display is performed with the display of a- (SixCyHz), x is 0 to obtain the effect of the present invention.
-0.5, preferably 0-0.45, optimally 0-0.
4, y is 0.3 to 1.0, preferably 0.35 to 0.8
5, optimally 0.4-0.8, z is 0.20-0.7,
Preferably, it is 0.25 to 0.6.

In the light receiving member for electrophotography of the present invention, the amount of hydrogen atoms contained in the surface layer 604 is usually 40 to 70 atomic%, preferably 40 to 70 atomic%, based on the total amount of the constituent atoms.
Desirably, it is about 60 atomic%. The light-receiving member formed within the above range of the hydrogen content can be sufficiently applied as an unprecedentedly excellent one in practical terms.

That is, defects (mainly dangling bonds of silicon atoms and carbon atoms) existing in the surface layer composed of a- (SixCyHz) may adversely affect the characteristics as a light receiving member for electrophotography. Are known. For example, deterioration of charging characteristics due to injection of charge from the free surface 609, fluctuation of charging characteristics due to a change in the surface structure under a use environment, for example, high humidity, and a surface caused by the photoconductive layer during corona charging or light irradiation. Charge is injected into the layer,
The adverse effect is, for example, the occurrence of an afterimage phenomenon at the time of repeated use due to the trapping of charges by defects in the surface layer.

However, when the hydrogen content in the surface layer is 40
By controlling the atomic percentage or more, the defects in the surface layer are greatly reduced, and as a result, all of the above-mentioned problems are solved, and the electrical characteristics and high-speed continuous usability can be dramatically improved as compared with the related art. be able to.

On the other hand, when the hydrogen content in the surface layer is 71 atomic% or more, the hardness of the surface layer is reduced, so that the surface layer cannot withstand repeated use. Therefore, controlling the hydrogen content in the surface layer within the above-mentioned range is one of the very important factors in obtaining a very excellent desired electrophotographic property. The hydrogen content in the surface layer can be controlled by the flow rate of the H ₂ gas, the temperature of the support, the discharge power, the gas pressure, and the like.

Further, the inclusion of a very small amount of fluorine atoms in the surface layer of the present invention also has an effect on environmental resistance and durability, and is particularly effective in preventing moisture adsorption. By controlling the fluorine content in the surface layer to a range of 1 atomic% or more, it becomes possible to more effectively achieve the generation of the bond between silicon atoms and carbon atoms in the surface layer. Further, as a function of the fluorine atoms in the film, it is possible to effectively prevent the bond between the silicon atom and the carbon atom from being broken due to damage such as corona.

On the other hand, the fluorine content in the surface layer was 70 atomic%.
Is exceeded, the constituent atoms in the surface layer (ex. Si and Si
And the effect of preventing the breaking of the bond between Si, C and C) is hardly recognized. Furthermore, since excess fluorine atoms hinder the mobility of carriers in the surface layer, remnant potential and image memory are remarkably observed. Therefore, controlling the fluorine content in the surface layer within the range of 1 atomic% to 70 atomic% is one of the very important factors in obtaining a much better desired electrophotographic characteristic. The fluorine content in the surface layer can be controlled by the flow rate of a fluorine atom-containing gas such as silicon tetrafluoride or carbon tetrafluoride, the temperature of the support, the discharge power, the gas pressure, and the like.

In the present invention, the surface layer 604 may contain any other atom in addition to the above-mentioned atoms in a trace amount (1 at% or less).

In the present invention, the bonding state of carbon atoms in the surface layer is a very important component. In order to obtain the effect of the present invention, it is more effective that the total number of carbon atoms is 20% or more and 100% or less when the number of carbon atoms is SP3.

When the composition and bonding state in the surface layer deviate from the above ranges, the strength, transparency, durability,
At the same time, any adverse effect occurs in terms of weather resistance and the like, and the effect of the present invention is significantly reduced.

In the present invention, when a silicon atom is contained,
It is desirable that the number of silicon atoms having at least one bond to a carbon atom is 50% or more and 100% or less, preferably 60% or more and 100% or less of the silicon atoms in the surface layer. The present invention is most effective in distributing in the surface layer so as to be 70% or more and 100% or less on the outermost surface and when designing so that the content of carbon atoms increases toward the outermost surface. The effect of (1) is remarkably exhibited.

The numerical range of the film thickness of the surface layer 604 in the present invention is appropriately determined according to the intended purpose so as to effectively achieve the object of the present invention.

The thickness of the surface layer 604 depends on the thickness of the photoconductive layer 60.
The relationship with the layer thickness of 3 also needs to be appropriately determined as desired based on organic relevance according to the characteristics required for each layer region. In addition, it is desirable that consideration be given to the economic efficiency in consideration of productivity and mass productivity.

The layer thickness of the surface layer 604 in the present invention is usually 500 Å to 10 μm, preferably 800 Å to 5 μm, and most preferably 1000 Å to 2 μm. That is, if the thickness is less than 500 angstroms, the effect of the present invention cannot be sufficiently obtained, and the surface layer may be lost due to abrasion or the like during use of the light receiving member. On the other hand, when the layer thickness exceeds 10 μm, a decrease in electrophotographic characteristics such as an increase in residual potential is observed.

The electrophotographic light receiving member 60 of the present invention
The layer thickness of the photoconductive layer of 0 is appropriately determined as desired according to the purpose.

In the present invention, the sum of the thicknesses of the photoconductive layer 603 and the surface layer 604 is determined by the sum of the photoconductive layer 603 and the surface layer 604.
The photoconductive layer 603 and the surface layer 604 are used so that the properties imparted to the photoconductive layer are effectively utilized and the object of the present invention is effectively achieved.
The thickness of the photoconductive layer 603 is preferably several to several thousand times the thickness of the surface layer 604, preferably several tens to several hundreds. Preferably, it is doubled.

The surface layer 604 of the present invention and the photoconductive layer 6
A region in which the carbon atom content changes so as to greatly decrease toward the photoconductive layer 603 may be provided between the first region and the third region.
Thereby, the influence of interference due to reflected light at the interface between the surface layer and the photoconductive layer can be further reduced.

[Charge Injection Blocking Layer] In the photoreceptor member for an image forming apparatus of the present invention, a function is provided between the conductive support and the photoconductive layer to prevent charge injection from the conductive support side. Providing a charge injection blocking layer is more effective. That is, the charge injection blocking layer has a function of preventing charge from being injected from the support side to the photoconductive layer side when the photosensitive layer is subjected to a charging treatment of a fixed polarity on its free surface. Such a function is not exhibited when it is subjected to a charging treatment, that is, it has a polarity dependency.

In order to provide such a function, the charge injection blocking layer contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer. The atoms controlling the conductivity contained in the layer may be uniformly distributed in the layer, or may be uniformly distributed in the thickness direction of the layer but not uniformly distributed. There may be a part contained in the state where it does. When the distribution concentration is non-uniform, it is preferable that the compound be contained so as to be distributed more on the support side. In any case, in the direction parallel to the surface of the support, it is necessary to be uniformly contained in a uniform distribution in order to make the characteristics in the plane direction uniform.

As the atoms for controlling the conductivity contained in the charge injection blocking layer, there may be mentioned so-called impurities in the field of semiconductors.
Group atom "can be used.

In the present invention, the thickness of the charge injection blocking layer is preferably from 0.1 to 5 μm, more preferably from 0.3 to 4 μm, from the viewpoints of obtaining desired electrophotographic characteristics and economic effects. Most preferably, it is 0.5 to 3 μm.

In the present invention, the desirable ranges of the mixing ratio of the diluent gas, the gas pressure, the discharge power, and the temperature of the support for forming the charge injection blocking layer include the above-mentioned ranges. Is usually not independently determined separately, but it is desirable to determine an optimum value of each layer forming factor based on mutual and organic relations to form a surface layer having desired properties.

In the light receiving member for an image forming apparatus of the present invention, for the purpose of further improving the adhesiveness between the support 601 and the photoconductive layer 603 or the charge injection blocking layer 105, for example, Si is used. ₃ N ₄ , SiO ₂ , SiO, or a close contact composed of an amorphous material or the like containing a silicon atom as a base and a hydrogen atom and / or a halogen atom, and a carbon atom and / or an oxygen atom and / or a nitrogen atom. A layer may be provided. Further, as described above, a light absorbing layer may be provided in order to prevent the occurrence of an interference pattern due to light reflected from the support.

By using the means and actions for solving the problems described above singly or in combination,
It is possible to bring out an excellent effect.

FIGS. 5A to 5D show examples. FIG.
Reference numeral 102 denotes a photosensitive drum serving as an image carrier, and an arrow X
Is a drum type electrophotographic light receiving member that is driven to rotate clockwise at a predetermined peripheral speed (process speed).

The resistance of the surface layer of the light receiving member in the thickness direction has good electric characteristics such as charge retention ability and charging efficiency, and a so-called pinhole leak, which damages the surface layer by voltage. 1 × 10 ^{10 to} 5 × 10 ¹³ Ω to prevent
cm. More preferably, it is 1 × 10 ^{12 to} 5 × 10 ¹³ Ωcm. The measurement of the resistance value was performed by measuring at an applied voltage of 250 to 1 kV, an MΩ tester manufactured by HIOKI.

Reference numeral 101 denotes a contact-type charging member using the above-described charged carrier, which comprises a multipolar magnetic material and a brush layer formed on the surface thereof and made of the charged carrier. The brush layer is made of Cu—Zn based ferrite or Mn—Z as described above.
Magnetic powder dispersed in a resin such as magnetic ferrite, magnetic magnetite, pyrrole such as n-type ferrite,
It is composed of a charged carrier containing magnetic particles such as a carrier of a magnetic toner.

The resistance value of the brush layer of the charging member 101 is as follows:
As shown in FIG. 4, to maintain good charging efficiency,
Further in measurement at HIOKI Co. (Manufacturers) made 250~1kV the applied voltage MΩ tester for pinhole prevention, it is preferable to have a ^{1 × 10 3 ~1 × 10 12} Ωm becomes resistance. More preferably, 1 × 10 ⁴ to 1
× 10 ⁹ Ωm.

The charging member 101 is provided with voltage applying means (not shown). The voltage applying means applies a DC voltage Vdc or a voltage Vdc + Vac on which an AC is superimposed to a brush layer made of a charging carrier of the charging member. The outer peripheral surface of the light receiving member 102 is uniformly charged.

Light receiving member 102 which is an image carrier
It is preferable that the nearest gap between the contact charging member 101 and the contact charging member 101 is set stably such as a spacer (not shown) in the range of 50 to 2000 μm for the nip control, and more preferably 100 to 1000 μm. In addition, a mechanism for adjusting the nip may be provided.

Further, an image signal providing means 1 such as a laser beam printer light intensity-modulated according to the image signal.
By scanning 03, an electrostatic latent image is formed on the photosensitive drum. This latent image is visualized by a developing sleeve 104 coated with a developer such as toner,
The untransferred toner transferred onto the transfer material P via the transfer device 106 (a) is removed from the photosensitive drum by the cleaning blade 120, and the transferred image is fixed by a fixing device (not shown). Is output.

Experimental Example 1 A glass substrate (Corning Co., Ltd. 7059) was set on a sample holder having a diameter of 108 mm using the apparatus for manufacturing a light receiving member for an image forming apparatus by the RF-PCVD method shown in FIG. Various surface layers were produced under the conditions. A comb-shaped electrode of Cr was deposited on the sample, and the surface resistance was measured.

[0169]

[Table 1]

[0170]

[Table 2] Experimental Example 2 A glass substrate (Corning Co., Ltd. 7059) was set on a sample holder having a diameter of 108 mm using the apparatus for manufacturing a light receiving member for an image forming apparatus by the RF-PCVD method shown in FIG. Was produced. A Cr comb electrode was deposited on the sample, and the surface resistance was measured.

[0171]

[Table 3]

[0172]

[Table 4] From the results of Experimental Examples 1 and 2 above, the resistance decreases when the temperature of the support exceeds 300 ° C., and the resistance tends to increase due to the increase in the ratio of the C atom-containing source gas to the Si atom-containing source gas. I have. It was also found that the smaller the applied power, the higher the resistance.

[Experimental Example 3] Using the apparatus for manufacturing a light receiving member for an image forming apparatus by the RF-PCVD method shown in FIG. Was formed. Changes in gas flow rate, support temperature and discharge power were smoothly and continuously changed from the start of film formation to the end of film formation. Thereafter, Cr was deposited on the surface layer, and the resistance in the layer thickness direction was measured.

On a mirror-finished aluminum cylinder having a diameter of 108 mm, a charge injection blocking layer and a photoconductive layer were prepared under the conditions shown in Table 7, and a light receiving member comprising the surface layer shown in Table 5 was prepared. .

[0175]

[Table 5]

[0176]

[Table 6] From the above results, in order to increase the resistance value in the plane direction with respect to the resistance value in the layer thickness direction, it is necessary to raise the support temperature at least gradually as the film formation proceeds,
It has been found that this can be achieved by increasing the ratio of the C-atom-containing source gas to the i-atom-containing source gas and, at the same time, reducing the applied power.

[0177]

[Table 7] The prepared photoreceptor was set in a conventional corona charging type image forming apparatus (NP6060 manufactured by Canon Inc. was modified for testing), and the temperature dependency (temperature characteristics) of charging ability, memory and image defects were evaluated.

The temperature characteristic is such that the temperature of the photoreceptor is changed from room temperature to about 4 degrees.
The charging ability was measured by changing the temperature to 5 ° C., and the change in the charging ability per 1 ° C. of the temperature was measured, and 2 V / deg or less was determined to be acceptable.

Regarding the memory, image defect and image deletion, the image was judged by visual observation. 1: Very good, 2: Good, 3: No problem in practical use, 4: Fair in practical use Ranked.

The residual potential was measured, and the electrical properties of the surface layer were evaluated. 15V or less was rated as 1: very good, 25V or less as 2: good, less than 50V as 3: no practical problem, and 50V or more as 4: practically somewhat difficult.

Table 8 shows the evaluation results.

[0182]

[Table 8] The conventional corona charging method showed good characteristics in all evaluations.

Regarding image defects, those having a small SiH ₄ / CH ₄ ratio tended to cause image defects more easily than others.

Further, a photoreceptor member for electrophotography having a 3-C surface layer laminated by varying the gas flow rate of SiH ₄ , H _2, etc., RF power, internal pressure, and support temperature of the photoconductive layer. Was prepared, and the temperature characteristics and the memory were evaluated. Separately from the drum, the film was deposited on a glass substrate (7059, manufactured by Corning Incorporated) with the same prescription as that of the photoconductive layer, and the characteristic energy localized state density at the exponential function tail was measured.

Then, the relationship between the temperature characteristic rank and the characteristic energy of the exponential function tail was evaluated. The evaluation results are shown in FIG.

The temperature characteristic is such that the temperature of the photosensitive member is changed from room temperature to about 4 ° C.
The charging ability was measured by changing the temperature up to 5 ° C., and the change in charging ability per 1 ° C. temperature was measured. Rank 1 for 1 V / deg or less, Rank 2 for 2 V / deg or less, Rank 3 for 5 V / deg or less. , 5 V / deg or more was evaluated as rank 4.

Next, the light receiving member and the charging member thus manufactured are shown in FIG.
Was set in the image forming apparatus as shown in FIG. 1 and the environmental measure heater 122 was turned off to evaluate the temperature dependency (temperature characteristic) of the charging ability, the memory and the image defect.

The condition of the voltage applied to the charging member 100 is 60
0 Vdc. The process speed was 250 mm / sec. Further, the magnetic brush, that is, the charging member was rotated at a rotation speed of 60 rpm so as to proceed in the same direction as the light receiving member, that is, in the opposite direction at the contact surface with the light receiving member (the contact surfaces respectively proceed in opposite directions). doing).

In order to separate the influence on the image quality due to the change in the amount of the charged carrier in the charging member, the charged carrier was appropriately replenished during the running so as to keep the charging member conditions such as the nip width constant.

The temperature characteristic was measured by changing the temperature of the light receiving member from room temperature to about 45 ° C. and measuring the charging ability.
The change in charging ability per ° C was measured, and a value of 2 V / deg or less was determined to be acceptable.

Regarding the memory, image defect and image deletion, the image was visually judged. 1: Very good, 2: Good, 3: Practically no problem, 4: Practically somewhat difficult Ranked.

Further, in order to examine the ratio of the region where the image density was thin and blurred, the area where image deletion occurred in a high humidity environment was measured, and the ratio to the area of the light receiving member was evaluated. 1: always good (less than 5%) 2: good (5% to
(Less than 10%), 3: practically no problem (10% to less than 20%), 4: practically difficult (20% or more).

The residual potential was measured, and the electrical properties of the surface layer were evaluated. 15V or less was rated as 1: very good, 25V or less was 2: good, less than 50V was 3: no practical problem, and 50V or more was 4: good practically.

Further, the charging efficiency was evaluated by the ratio of the charging potential of the light receiving member 0.3 seconds after charging to the voltage applied to the magnetic brush. 1: 90% or more, 2: 80% or more,
3: Three ranks of 70% or more. Table 9 shows the evaluation results.

[0195]

[Table 9] From this experiment, it was found that setting the ratio of the resistance value in the surface direction of the outermost surface of the surface layer to the resistance value in the thickness direction of the surface layer to 10 to 1000 is more effective for obtaining the effects of the present invention. . If it is less than 10, the effect of the present invention does not appear.
On the other hand, when it exceeds 1,000, the residual potential in the surface layer portion increases.

The conditions of the contact-type charging member 101 used are shown below.

The multipolar magnetic material was formed into a roller shape having a diameter of 22 mm with the charged carrier adhered to the roller-shaped multipolar magnetic material. The magnetic line density is controlled as described above. In this embodiment, the number of magnetic poles is 12, and the magnetic field line density on the local surface is 1000 to 30 by the measurement as described above.
00 Gauss was manufactured.

As the brush layer, a mixture of magnetic iron such as magnetic iron oxide of 5 to 25 μm and magnetic powder of small particle size of 1 to 5 μm in a predetermined ratio was used as a charge carrier. As described above, the charged carrier may have the same component as a known carrier generally used for toner, or may be used by mixing a plurality of components. Further, the particle diameter may be uniform, or a mixture of different particle diameters may be used.

In this embodiment, the nip width is set to 6 to 7 m.
m.

Experimental Example 4 Using the apparatus for manufacturing a light receiving member for an image forming apparatus by the RF-PCVD method shown in FIG. 3, charge injection was prevented under the conditions shown in Table 10 on a mirror-finished aluminum cylinder having a diameter of 108 mm. A light receiving member comprising a layer, a photoconductive layer and a surface layer was prepared. In the formation of the surface layer, changes in the gas flow rate, the support temperature, and the discharge power were smoothly and continuously changed from the start of the film formation to the end of the film formation.

Further, various light receiving members were manufactured by changing the mixing ratio of SiH ₄ and H ₂ and the discharge power of the photoconductive layer.

Further, only the surface layer was formed on a mirror-finished aluminum cylinder having a diameter of 108 mm, and then Cr was deposited on the surface.

A film of the outermost layer was formed on a glass substrate (Corning Co., Ltd. 7059) set in a cylindrical sample holder, and a comb electrode of Cr was deposited.

The produced light receiving member was set in the image forming apparatus used in Experimental Example 3 and evaluated in the same manner as in Experimental Example 3.
In order to confirm the durability, evaluation was performed again after passing 10,000 sheets. The charging stability was evaluated from the change in charging efficiency after running. 1: good stability, 2: practically no problem, 3: practically somewhat difficult. Table 1 shows the evaluation results.
It is shown in FIG.

[0205]

[Table 10] As a result of measuring the resistance value of the surface layer in the layer thickness direction and the plane direction, the resistance value in the layer thickness direction was 7.56 × 10 ¹² Ωcm, and the resistance value in the plane direction was 1.27 × 10 ¹⁵ Ωcm.

The ratio of the resistance value in the surface direction of the outermost surface of the surface layer to the resistance value in the thickness direction of the surface layer of the surface layer was 168.

The following is a method for examining the film characteristics of the photoconductive layer.

On the other hand, an a-Si film having a thickness of about 1 μm was deposited on a glass substrate (Corning Co., Ltd. 7059) and a Si wafer placed in a cylindrical sample holder under the conditions for forming a photoconductive layer. An Al comb electrode was deposited on the deposited film on the glass substrate, and the characteristic energy (Eu) of the exponential function was measured by CPM. The deposited film on the Si wafer was FTIR.
Was used to measure the hydrogen content.

Each sample had a hydrogen content of 10 to 3
It was found to be in the range between 0 atomic%.

The conditions of the light receiving member are as follows: a: Eu is 47 meV b: Eu is 50 meV c: Eu is 52 meV d: Eu is 55 meV e: Eu is 58 meV f: Eu is 64 meV.

[0211]

[Table 11] From the results in Table 11, no difference was observed between the characteristic images of the electrophotographic light-receiving member before and after the endurance.

The characteristic energy of the exponential function tail obtained from the sub-bandgap light absorption spectrum is 50 to 6
It turned out that 0 meV is a suitable condition for electrophotographic characteristics.

[0213] Immediately after charging by applying 600 Vdc, TR
When measured with a surface potentiometer manufactured by ek (manufacturer),
There was no difference in dark state potential before and after endurance.

Experimental Example 5 In this example, instead of the surface layer of Experimental Example 4, the flow rate of the SiH ₄ gas was constant and only the flow rate of the CH ₄ gas was changed in the gas flow rate during the formation of the surface layer. Others were the same as in Experimental Example 4. Table 12 shows the conditions for producing the electrophotographic light-receiving member at this time. Others were the same as in Experimental Example 4.

As a result of measuring the resistance value of the surface layer in the layer thickness direction and the plane direction, the resistance value in the layer thickness direction was 5.58 × 10 ¹¹ Ωcm.
The resistance in the plane direction was 3.32 × 10 ¹⁴ Ωcm.

The ratio of the resistance in the surface direction of the outermost surface of the surface layer to the resistance in the thickness direction of the surface layer was 595.

The physical properties of the photoconductive layer were such that the hydrogen content was 26.7 atomic% and Eu was 57.4 meV. The light receiving member and the charging member were set in an image forming apparatus as shown in FIG. 2 in the same manner as in Experimental Example 3, and the environmentally-friendly heater 122 was turned off. Temperature characteristics), memory and image defects were evaluated.

The voltage applied to the charging member 101 is 600
Vdc. The process speed was 250 mm / sec. Further, the magnetic brush, that is, the charging member was rotated at a rotation speed of 60 rpm so as to proceed in the same direction as the light receiving member, that is, in the opposite direction at the contact surface with the light receiving member. In progress).

Further, in order to separate the influence on the image quality due to the change in the amount of the charge carrier in the charging member, the charging carrier was appropriately replenished during the running so as to keep the charging member conditions such as the nip width constant.

The temperature characteristics were measured by changing the temperature of the light receiving member from room temperature to about 45 ° C. and measuring the charging ability.
The change in the charging ability per ° C was measured, and a value of 2 V / deg or less was judged as acceptable.

Regarding the memory, image defect and image deletion, the image was visually judged. 1: Very good, 2: Good, 3: No practical problem, 4: Practical difficulty Ranked.

Further, in order to examine the ratio of the region where the image density was thin and blurred, the area where image deletion occurred in a high humidity environment was measured, and the ratio to the area of the light receiving member was evaluated. 1: always good (less than 5%) 2: good (5% to
(Less than 10%), 3: practically no problem (10% to less than 20%), 4: practically difficult (20% or more).

The residual potential was measured, and the electrical properties of the surface layer were evaluated. 15V or less was rated as 1: very good, 25V or less was 2: good, less than 50V was 3: no practical problem, and 50V or more was 4: good practically.
The charging member is the same as that used in Experimental Example 3.
Table 13 shows the evaluation results.

[0224]

[Table 12]

[0225]

[Table 13] That is, by changing only the CH ₄ gas flow rate of the surface layer,
It was found that even when ₄ / SiH ₄ was changed, the effect of the surface layer of the present invention was obtained, and good electrophotographic characteristics were obtained.

[0226]

EXAMPLES In the following examples, the surface layer of the present invention is effective for photoreceptor members having different layer configurations using various photoconductive layers, charge injection blocking layers, intermediate layers, etc. The present invention is not limited to these examples.

Example 1 In this example, in place of the surface layer of Experimental Example 4, a surface layer was formed.
CH at gas flow rate _Four Gas flow rate is constant and SiH_Four Moth
Only the flow rate was changed. Others are the same as in Experimental Example 5.
Was. Table 14 shows the production of the light receiving member for electrophotography at this time.
Conditions are shown. Others were the same as in Experimental Example 4.

As a result of measuring the resistance value of the surface layer in the layer thickness direction and the plane direction, the resistance value in the layer thickness direction was 6.87 × 10 ¹¹ Ωcm.
The resistance value of the surface method was 3.14 × 10 ¹³ Ωcm.

The ratio of the resistance in the surface direction of the outermost surface of the surface layer to the resistance in the thickness direction of the surface layer was 45.7.

As for the physical properties of the photoconductive layer, the hydrogen content was 25.4 atomic%, and Eu was 56.4 meV.

The produced light-receiving member was evaluated in the same manner as in Experimental Example 5. As a result, good electrophotographic characteristics were obtained as in Experimental Example 5.

That is, even when the CH ₄ / SiH ₄ ratio is changed by changing the flow rate of the SiH ₄ gas in the surface layer, the effect of the surface layer of the present invention can be obtained and good electrophotographic characteristics can be obtained. Was.

[0233]

[Table 14] Example 2 In this example, an intermediate layer was provided between the photoconductive layer and the surface layer, and a light receiving member including the charge injection blocking layer, the photoconductive layer, the intermediate layer, and the surface layer was manufactured. Others were the same as in Experimental Example 4. Table 15 shows the conditions for producing the light receiving member for electrophotography at this time. Others were the same as in Experimental Example 5.

As a result of measuring the resistance value of the surface layer in the layer thickness direction and the surface direction, the resistance value in the layer thickness direction was 5.58 × 10 ¹¹ Ωcm.
The resistance value in the plane direction was 3.32 × 10 ¹³ Ωcm.

The ratio of the resistance value in the surface direction of the outermost surface of the surface layer to the resistance value in the surface layer thickness direction of the surface layer was 59.5.

As for the physical properties of the photoconductive layer, the hydrogen content was 24.8 atomic%, and Eu was 58.2 meV.

The produced light-receiving member was evaluated in the same manner as in Experimental Example 5. As a result, good electrophotographic characteristics were obtained as in Experimental Example 5.

That is, it was found that even when an intermediate layer was provided, the effect of the surface layer of the present invention was obtained, and good electrophotographic characteristics were obtained.

[0239]

[Table 15] Example 3 In this example, the surface layer was provided by changing the gas flow rate of the surface layer, the temperature of the support, and the discharge power in two steps in the thickness direction. Table 16 shows the conditions for producing the electrophotographic light-receiving member at this time. Others were the same as in Experimental Example 5.

As a result of measuring the resistance value of the surface layer in the layer thickness direction and the surface direction, the resistance value in the layer thickness direction was 9.26 × 10 ¹¹ Ωcm.
The resistance value in the plane direction was 3.71 × 10 ¹³ Ωcm.

The ratio of the resistance value in the surface direction of the outermost surface of the surface layer to the resistance value in the surface layer thickness direction of the surface layer was 401.

The physical properties of the photoconductive layer were such that the hydrogen content was 25.4 atomic% and Eu was 59.7 meV.

When the produced light-receiving member was evaluated in the same manner as in Experimental Example 5, good electrophotographic characteristics were obtained as in Experimental Example 5.

That is, even when the gas flow rate of the surface layer, the temperature of the support and the discharge power are changed in two steps in the thickness direction, the effect of the surface layer of the present invention can be obtained, and good electrophotographic characteristics can be obtained. I understand.

[0245]

[Table 16] Example 4 In this example, a surface layer containing fluorine atoms was provided instead of the surface layer of Example 3. Table 17 shows the conditions for producing the electrophotographic light-receiving member at this time. Others are experimental example 5.
Same as. As a result of measuring the resistance value of the surface layer in the layer thickness direction and the plane direction, the resistance value in the layer thickness direction was 7.76 × 10 ¹¹ Ωc.
m, the resistance in the plane direction was 8.52 × 10 ¹³ Ωcm.

The ratio of the resistance value in the surface direction of the outermost surface of the surface layer to the resistance value in the surface layer thickness direction of the surface layer was 110.

Regarding the physical properties of the photoconductive layer, the hydrogen content was 24.4 atomic%, and Eu was 55.4 meV.

When the produced light-receiving member was evaluated in the same manner as in Experimental Example 5, good electrophotographic characteristics were obtained as in Experimental Example 5. That is, it was found that even when a fluorine atom was contained in the surface layer, the effect of the surface layer of the present invention was obtained and good electrophotographic characteristics were obtained.

[0249]

[Table 17] Example 5 In this example, an IR absorption layer was provided between a support and a charge injection blocking layer as a light absorption layer for preventing generation of an interference pattern due to light reflected from the support. Table 18 shows the conditions for producing the electrophotographic light-receiving member at this time. Other points were the same as in Experimental Example 5.

As a result of measuring the resistance value of the surface layer in the layer thickness direction and the surface direction, the resistance value in the layer thickness direction was 4.19 × 10 ¹² Ωcm.
The resistance value in the plane direction was 3.83 × 10 ¹⁴ Ωcm. The ratio of the resistance in the surface direction of the outermost surface of the surface layer to the resistance in the thickness direction of the surface layer of the surface layer was 94.1.

The physical properties of the photoconductive layer were such that the hydrogen content was 24.9 atomic% and Eu was 54.1 meV.

When the produced light-receiving member was evaluated in the same manner as in Experimental Example 5, good electrophotographic characteristics were obtained as in Experimental Example 5.

That is, even when the IR absorption layer was provided, the ratio of obtaining the effect of the surface layer of the present invention was 110.

As for the physical properties of the photoconductive layer, the hydrogen content was 24.4 atomic%, and Eu was 55.4 meV.

When the produced light-receiving member was evaluated in the same manner as in Experimental Example 5, good electrophotographic characteristics were obtained as in Experimental Example 5.

That is, it was found that even when a fluorine atom was contained in the surface layer, the effect of the surface layer of the present invention was obtained, and good electrophotographic characteristics were obtained.

[0257]

[Table 18] Example 5 In this example, an IR absorption layer was provided between a support and a charge injection blocking layer as a light absorption layer for preventing generation of an interference pattern due to light reflected from the support. Table 18 shows the conditions for producing the electrophotographic light-receiving member at this time. Other points were the same as in Experimental Example 5.

As a result of measuring the resistance value of the surface layer in the layer thickness direction and the surface direction, the resistance value in the layer thickness direction was 4.19 × 10 ¹² Ωcm.
The resistance value in the plane direction was 3.83 × 10 ¹⁴ Ωcm.

The ratio of the resistance value in the surface direction of the outermost surface of the surface layer to the resistance value in the thickness direction of the surface layer of the surface layer was 94.1.

The physical properties of the photoconductive layer were such that the hydrogen content was 24.9 atomic% and Eu was 54.1 meV.

When the produced light-receiving member was evaluated in the same manner as in Experimental Example 5, good electrophotographic characteristics were obtained as in Experimental Example 5.

That is, it was found that even when the IR absorption layer was provided, the effect of the surface layer of the present invention was obtained, and good electrophotographic characteristics were obtained.

[0263]

[Table 19] Example 6 In this example, the charge injection blocking layer was omitted, and the first layer region containing carbon atoms in a non-uniform distribution state in the layer thickness direction as the photoconductive layer and the second layer region containing substantially no carbon atoms. Was formed continuously with the layer region of FIG. Table 19 shows the conditions for producing the light receiving member for electrophotography at this time. Other points were the same as in Example 8.

Experimental Example 5
When the same evaluation was made, good electrophotographic characteristics were obtained as in Experimental Example 5.

That is, the charge injection blocking layer is omitted, and the first layer region containing carbon atoms in a non-uniform distribution state in the layer thickness direction as the photoconductive layer and the second layer region containing substantially no carbon atoms are formed.
It was also found that the effect of the surface layer of the present invention was obtained and good electrophotographic characteristics were obtained even when the layer was formed continuously with the layer region.

[0266]

[Table 20] Example 7 In this example, an intermediate layer (lower surface layer) in which the content of carbon atoms was smaller than that of the surface layer was provided between the photoconductive layer and the surface layer. And a charge transport layer and a charge generation layer. Table 20 shows the conditions for producing the light receiving member for electrophotography at this time.

The other points were the same as in Experimental Example 5.

Experimental Example 5
When the same evaluation was made, good electrophotographic characteristics were obtained as in Experimental Example 5.

That is, an intermediate layer (lower surface layer) in which the content of carbon atoms is smaller than that of the surface layer is provided between the photoconductive layer and the surface layer.
It was found that even when the charge transport layer and the charge generation layer were provided in two layers, the effect of the surface layer of the present invention was obtained and good electrophotographic characteristics were obtained.

[0270]

[Table 21]

[0271]

As described above, according to the present invention, the magnetic powder is used as a brush by designing the surface layer so that the resistance in the surface direction is larger than the resistance value in the layer thickness direction. The charging efficiency and the charging stability of the charging device were greatly improved, and the change in image density due to the drift of the charge at the outermost surface during charging could be reduced.

By setting the resistance in the surface direction of the outermost surface to be about 10 to 1000 times the resistance in the thickness direction of the surface layer, almost no blurred area with a low image density is generated, The problem of image deletion in a humid environment was also improved.

Further, by combining a novel light-receiving member having further improved temperature characteristics and electric characteristics with the surface layer of the present invention having improved stability and durability, there is no power supply at night, energy saving, and high image quality retention. As a result, it was possible to remove the high humidity image flow.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram for explaining the arrangement and configuration of a charging device of the present invention. (A) is sectional drawing, (b) is the figure seen from the front.

FIG. 2 is a schematic configuration diagram illustrating a configuration of an example of a preferred embodiment of a charging device and an image forming apparatus of the present invention.

FIG. 3 is an example of an apparatus for forming a light receiving layer of a light receiving member for an image forming apparatus according to the present invention. It is a schematic explanatory view.

FIG. 4 is a diagram showing the relationship between the resistance value and the charging efficiency of the charging member of the present invention.

FIG. 5 is a schematic layer configuration diagram for explaining a layer configuration of a preferred embodiment of the light receiving member for an image forming apparatus of the present invention.

FIG. 6 is a view showing the relationship between the characteristic energy (Eu) of the Urbach tail of the photoconductive layer and the temperature characteristic in the photoreceptor member for electrophotography of the present invention.

[Explanation of symbols]

REFERENCE SIGNS LIST 100 contact type charging member 101-1 magnetic brush layer 101-2 multipolar magnetic body (mag roller) 102A spacer 103A electrophotographic light receiving member 102 electrophotographic light receiving member 103 image signal applying means 104 developing sleeve 105 transfer paper supply System 106 (a) Transfer charger 106 (b) Separation charger 107 Cleaner 108 Transport system 109 Static elimination light source 110 Lamp 111 Platen glass 112 Document 113-116 Mirror 117 Lens unit 118 Lens 119 (Paper) Transfer material guide 120 Cleaning blade Reference Signs List 121 registration roller 122 environmental heater P transfer material (copy paper etc.) 3100 deposition device 3111 reaction vessel 3112 cylindrical support 3113 support heating heater 3114 raw material gas introduction pipe 3115 machin Gas box 3116 raw material gas pipe 3117 reaction vessel leak valve 3118 main exhaust valve 3119 vacuum gauge 3200 raw material gas supply device 3211-216 mass flow controller 3221-226 raw material gas cylinder 3231-236 raw material gas cylinder valve 3241-3246 gas inflow valve 3251-256 gas outflow Valves 3261 to 3266 Pressure regulator 600 Light receiving member 601 Support 602 Photosensitive layer 603 Photoconductive layer 604 Surface layer 605 Intermediate layer 606 Charge injection blocking layer 607 Charge generation layer 608 Charge transport layer 609 Free surface FIG. . FIG. 2 is a schematic view showing an example of an image forming process of a copying machine, in which a main charging device 101 is provided around a photoreceptor 102 which is controlled in temperature by a planar inner surface heater 122 rotating in an arrow X direction. An electrostatic latent image forming portion 103, a developing device 104, a transfer paper supply system 105, a transfer charger 106 (a), a separation charger 106 (b), a cleaner 107, a transport system 108, a static elimination light source 109 and the like are provided. I have. Hereinafter, the image forming process will be described with reference to a specific example. The photoconductor 102 is uniformly charged by the main charger 101 to which a high voltage of +6 to 8 kV is applied. The emitted light is reflected by a document 112 placed on a platen glass 111, and mirrors 113, 114, and 11
5, an image is formed by the lens 118 of the lens unit 117, and the image is guided and projected by the mirror 116 to form an electrostatic latent image. The negative polarity toner is supplied from the developing device 104 to the latent image to form a toner image. On the other hand, the leading end timing is adjusted by the registration roller 121 through the transfer paper supply system 105, and the transfer material P supplied in the direction of the photoconductor is exposed to the transfer charger 106 (a) to which a high voltage of +7 to 8 kV is applied. A positive electric field having a polarity opposite to that of the toner is applied from the back surface in the gap of the body 102, whereby the negative polarity toner image on the surface of the photoconductor is transferred to the transfer material P. The transfer material P reaches the fixing device 124 through the transfer paper transport system 108 by the separation charger 106 (b) to which a high AC voltage of 12 to 14 kVp-p and 300 to 600 Hz is applied, and the toner image is fixed. It is discharged outside. The toner remaining on the photoconductor 101 is transferred to the cleaner unit 107.
The remaining electrostatic latent image scraped off by the cleaning blade 120 is erased by the charge eliminating light source 109.

Claims (12)

[Claims] 1. An electrophotographic light-receiving member having at least a photoconductive layer made of a non-single-crystal silicon-based material and a surface layer containing at least one of silicon atoms and carbon atoms as a host material. A light-receiving member for electrophotography, wherein the resistance value in the surface direction of the outermost surface of the surface layer is larger than the resistance value in the layer thickness direction. 2. A method according to claim 1, wherein the ratio of the resistance in the surface direction of the outermost surface of the surface layer to the resistance in the thickness direction of the surface layer of the surface layer is 10 to 10.
The light receiving member for electrophotography according to claim 1, wherein the number is 1,000. 3. The resistance of the surface layer in the thickness direction is 1 × 1.
2. The light receiving member for electrophotography according to claim 1, wherein the light receiving member has a value of 0 ^{10 to} 5 × 10 ¹³ Ωcm. 4. The electrophotographic light-receiving member according to claim 1, wherein the outermost surface of the surface layer has a surface resistance of 1 × 10 ¹² to 2 × 10 ¹⁵ Ωcm. 5. The photoconductive layer contains 10 to 30 atomic% of hydrogen atoms, and characteristic energy of an exponential function tail obtained from a light absorption spectrum in at least a part of the photoconductive layer where light is incident is 50 meV or more and 60 meV. The electrophotographic light-receiving member according to claim 1, wherein: 6. The light-receiving member for electrophotography according to claim 5, wherein the photoconductive layer contains at least one element belonging to Group IIIb or Vb of the periodic table. 7. The photoconductive layer contains at least one of carbon, oxygen, and nitrogen.
3. The light receiving member for electrophotography according to item 1. 8. A photoconductive layer in which the light receiving layer is made of a non-single-crystal material containing silicon atoms as a base, and silicon containing at least one of carbon, oxygen and nitrogen provided on a surface of the photoconductive layer. The electrophotographic light-receiving member according to any one of claims 5 to 6, comprising a surface layer made of a system non-single-crystal material. 9. The light-receiving layer according to claim 1, wherein the light-receiving layer has a silicon atom as a host and at least one of carbon, oxygen, and nitrogen, and
III A charge injection blocking layer made of a non-single crystal material containing at least one element selected from Group b or Group Vb, and a non-single crystal based on silicon atoms provided on the surface of the charge injection blocking layer A photoconductive layer made of a material, and a surface layer made of a silicon-based non-single-crystal material containing at least one of carbon, oxygen, and nitrogen provided on the surface of the photoconductive layer. The light-receiving member for electrophotography according to claim 5. 10. The photoconductive layer has a thickness of 20 to 50 μm.
The light receiving member for electrophotography according to claim 1, wherein: 11. A voltage is applied to a cylindrical charging member having at least a multipolar magnetic material and a magnetic powder, and the magnetic powder is charged by contacting the magnetic powder with an electrophotographic light receiving member as an image carrier. 11. An image forming apparatus for forming an electrostatic latent image on the electrophotographic light receiving member and visualizing the electrostatic latent image with toner, wherein the electrophotographic light receiving member is any one of claims 1 to 10. An image forming apparatus, comprising the electrophotographic light-receiving member according to claim 1. 12. A voltage is applied to a cylindrical charging member having at least a multipolar magnetic material and a magnetic powder, and the magnetic powder is charged by contacting the magnetic powder with an electrophotographic light receiving member as an image carrier. 11. An image forming method for forming an electrostatic latent image on the light receiving member for electrophotography and visualizing the electrostatic latent image with toner, wherein the light receiving member for electrophotography is any one of claims 1 to 10. 3. The image forming method according to claim 1, wherein the light receiving member is a light receiving member.