JPH08272194A - Charging device and image forming apparatus - Google Patents

Abstract

(57) [Abstract] [Purpose] To eliminate uneven charging due to application of an oscillating voltage during charging in a proximity charging device. [Structure] The surface of the photosensitive drum 101 is in a non-contact state,
A plurality of contact charging members 102 and 103 are arranged, and charging voltages are applied by different power sources 104 and 105, respectively. The frequency and phase of the oscillating voltage applied as these charging voltages are individually adjusted by the controller 106. As a result, good charging can be performed without increasing the voltage and frequency, and the life of the charging members 102 and 103 can be extended.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a charging member, a charging device, and an image forming apparatus which are arranged in the vicinity of a member to be charged and which is applied with an oscillating voltage to charge the member.

[0002]

[Prior art]

1. 2. Related Art Image Forming Apparatus As an image forming apparatus, a so-called copying machine for copying a document has been well known, but in recent years, a computer,
The demand for printers used as output means such as word processors is growing rapidly. Since such printers are used not only for conventional office use but also for personal use, there are demands for further cost efficiency and convenience such as cost reduction and maintenance free.

Further, from the viewpoint of ecology, double-sided copying, resource saving by reducing paper consumption by utilizing recycled paper,
Energy saving by reduction of power consumption and improvement of working environment by reduction of ozone amount are demanded with the same importance as economic efficiency and convenience.

The corona charger, which has been the mainstream of the conventional charging method, has a metal wire of 50 to 100 μm and a thickness of 5 to 10 k.
By applying a high voltage of about V, the atmosphere is ionized and the opposite object (charged body) is charged. In the process, the wire itself also adsorbs dirt, and therefore periodical cleaning and replacement are required. In addition, unnecessary ozone is generated with the corona discharge.

Regarding energy saving, there is also a problem with the photoconductor heater. The surface hardness of electrophotographic photoconductors used in recent years is high in order to increase the number of printable sheets, and due to the corona product derived from ozone generated from the charger by repeated use, the photoconductor surface is exposed to humidity. It becomes sensitive and tends to adsorb moisture, which causes a lateral flow of charges on the surface of the photoconductor, and has a drawback of causing image quality deterioration called image deletion.

In order to prevent such image deletion, heating with a heater as described in Japanese Utility Model Publication No. 1-34205 and a magnet roller as described in Japanese Patent Publication No. 2-38956 are used. A method of removing the corona product by rubbing the surface of the photoconductor with a brush formed of magnetic toner, and a method of removing the corona product by rubbing the surface of the photoconductor with an elastic roller as described in JP-A-61-110080. Etc. have been used.

The method of inspecting the surface of the photosensitive member reduces the number of printable sheets except when the photosensitive member is an amorphous silicon photosensitive member having an extremely high hardness. Further, the constant heating by the heater causes an increase in power consumption as described above. The capacity of such a heater is usually about 15 to 80 W, which does not necessarily give a large electric power impression, but in most cases, it is always energized even at night. 5 of power consumption
It reaches 15%.

Also, in the external heater heating system in a form similar to that of the present invention, that is, in JP-A-59-111179 and JP-A-62-278577, the image density error due to the temperature change of the photoconductor is not detected. There is no disclosure about improvement of stability factors.

Further, the above-mentioned ozone which causes such image deletion is not environmentally preferable, and has been conventionally decomposed and harmless by an ozone removing filter before being discharged. Especially for personal use, the amount of ozone discharged must be reduced as much as possible. Thus, from the economical aspect, there is a demand for a method of significantly reducing the amount of ozone generated during charging.

Under these circumstances, there is a demand for a new image forming apparatus having a reduced amount of ozone. 2. Charging Device Various charging devices have been proposed to solve the above problems.

In the contact charging as described in JP-A-63-208878, a charging member to which a voltage is applied is brought into contact with a member to be charged to charge the surface to be charged to a predetermined potential. First, compared to a corona charging device that is widely used as a device, the applied voltage required to obtain a desired potential on the surface of the body to be charged can be reduced.
In addition, there is no or only a very small amount of ozone generated during the charging process, and the need for an ozone removal filter is eliminated. Therefore, the structure of the exhaust system of the device is simplified, and maintenance-free. The ozone and ozone products generated in the charging process adhere to the surface of the image carrier, which is the surface to be charged, such as the surface of the photoconductor, and the surface of the photoconductor becomes sensitive to humidity due to the influence of corona products, and water is easily absorbed. This eliminates the need for dehumidification with a heating heater, which is performed all day to prevent image deletion due to the low resistance of the surface, and thus can significantly reduce power consumption such as night-time energization. are doing.

Therefore, for example, in an image forming apparatus such as an electrophotographic system (copier, laser beam printer) or electrostatic recording system, an image carrier such as a photoconductor or a dielectric is charged, and other members to be charged are charged. As a means, it has attracted attention as an alternative to the corona discharge device and has been put into practical use.

Conventionally, as the contact charging means, it is well known that a blade or a sheet-shaped fixed charging member is brought into contact with a member to be charged, and a bias is applied to the member to perform charging.

FIG. 9 shows an embodiment thereof. Reference numeral 801 denotes a drum type photoconductor as an image bearing member (hereinafter appropriately referred to as “photosensitive drum”), which is rotationally driven in a clockwise direction indicated by an arrow A at a predetermined peripheral speed (process speed). 802
Is a contact charging member, which is composed of an electrode 802-1 and a resistance layer 802-2 formed on the charging surface thereof.

The electrode 802-1 is usually made of a metal such as aluminum, aluminum alloy, brass, copper, iron or stainless, or an insulating material such as resin or ceramic, which is subjected to a conductive treatment, that is, coated with a metal or a conductive paint. Use what you did.

The resistance layer 802-2 is generally made of a resin such as polypropylene or polyethylene or an elastomer such as silicon rubber or urethane rubber in which a conductive filler such as titanium oxide, carbon powder or metal powder is dispersed. To be

The resistance value of the resistance layer 802-2 is HIOKI.
In measurement of company (manufacturer) manufactured 0.25~1kV the applied voltage MΩ ^{tester, 1 × 10 3 ~1 × 10} 12 Ω ·
It has a resistance of cm.

Reference numeral 803 denotes a voltage application power source for the charging member. The power source 803 supplies an oscillating voltage V _ac and a DC voltage V _dc having a peak-to-peak voltage V _pp which is more than twice the charging start voltage.
A superposed voltage (V _ac + V _dc ) superposed by and is applied to the electrode 802-1 of the charging member, so that the outer peripheral surface of the photosensitive drum 801 which is rotationally driven is uniformly charged.

Furthermore, an electrostatic latent image is formed on the photosensitive drum 801 by scanning the laser beam printer light 805 whose intensity is modulated according to the image signal.

This latent image is transferred onto the transfer material 807 via the transfer roller 808. The transfer residual toner is removed from the photosensitive drum 801 by the cleaning blade 809. On the other hand, the transfer material 807 is a fixing device (not shown).
Thus, the unfixed toner image on the surface is fixed, and then discharged to the outside of the image forming apparatus main body.

However, in this method, since the image carrier and the contact charging member are in direct contact with each other, the influence of friction is large, and the contact charging member is inevitably worn by long-term use, and it is necessary to replace it regularly. Become. Amorphous silicon photoconductors, which have been widely used in image forming apparatuses in recent years, have a semi-permanent life, and replacement of the contact charging member is a maintenance-free rate-determining problem of the apparatus, and improvement is strongly demanded. It was

As a solution to the problem, in addition to the progress such as various improvements of the contact charging member, a method which should be called proximity charging, that is, the contact charging member is in a non-contact state with the image carrier, is applied to the image carrier. A method of applying an electric charge has been proposed.

FIG. 10 shows an embodiment thereof. A photosensitive drum 901 is an image bearing member, and is a drum-type electrophotographic photosensitive member that is rotationally driven in the clockwise direction of arrow A at a predetermined peripheral speed (process speed). A charging member 902 includes an electrode 902-1 and a resistance layer 902-2 formed on the charging surface of the electrode 902-1.

The electrode 902-1 is usually made of a metal such as aluminum, an aluminum alloy, brass, copper, iron or stainless, or an insulating material such as resin or ceramic, which is subjected to a conductive treatment, that is, coated with a metal or a conductive paint. Use the applied one.

The resistance layer 902-2 is generally made of a resin such as polypropylene or polyethylene or an elastomer such as silicon rubber or urethane rubber in which a conductive filler such as titanium oxide, carbon powder or metal powder is dispersed. To be

The resistance value of the resistance layer has a resistance of 1 × 10 ³ to 1 × 10 ¹² Ω · cm measured by an MΩ tester manufactured by HIOKI (manufacturer) at an applied voltage of 0.25 to 1 kV. .

The closest gap between the image carrier 901 and the contact charging member 902 must be stably set to a very short distance of 50 to 500 μm.

Reference numeral 904 denotes a voltage application power source for the charging member. The power source 904 supplies an oscillating voltage V _ac and a DC voltage V _dc having a peak-to-peak voltage V _pp which is more than twice the charging start voltage.
A superposition (V _ac + V _dc ) obtained by superposing and is applied to the electrode 902-1 of the charging member 902, and the outer peripheral surface of the photosensitive drum 901 which is rotationally driven is uniformly charged.

Further, an electrostatic latent image is formed on the photosensitive drum 901 by scanning the laser beam printer light 907 whose intensity is modulated according to the image signal. This latent image is visualized as a toner image by a developing sleeve 908 coated with a developer, and then transferred onto a transfer material 909 via a transfer roller 910. The transfer residual toner is removed from the photosensitive drum 9 by the cleaning blade 911.
01 removed from above. On the other hand, a toner image on the surface of the transfer material 909 is fixed by a fixing device (not shown), and then the transfer material 909 is discharged to the outside of the image forming apparatus main body.

According to the above-mentioned method, the image carrier and the contact charging member are brought into non-contact with each other, and the durability is remarkably improved against deterioration of durability such as mechanical friction. 3. Photoreceptor [Organic Photoconductive Material (OPC)] In recent years, various organic photoconductive materials have been developed as photoconductive materials for electrophotographic photosensitive materials.
In particular, a function-separated type photoreceptor having a charge generation layer and a charge transport layer laminated has already been put to practical use and mounted on a copying machine or a laser beam printer.

However, one of the major drawbacks of these photoconductors has been their low durability. Durability is roughly classified into sensitivity, residual potential, chargeability, durability of electrophotographic physical surface such as image blur, and mechanical durability such as abrasion and scratch on the surface of photoconductor due to rubbing It is a major factor in determining the life span of the body.

Of these, the durability of the electrophotographic physical properties, particularly the blurring of the image, the ozone generated from the corona charger,
It is known that the cause is that the charge transport material contained in the surface layer of the photoconductor is deteriorated by the active material such as NOx.

It is known that the mechanical durability is caused by the physical contact of the paper, the cleaning member such as the blade / roller, the toner and the like with the photosensitive layer and the slidability.

In order to improve the durability of the physical properties of electrophotography, it is important to use a charge transport substance that is not easily deteriorated by active substances such as ozone and NOx, and it is necessary to select a charge transport substance having a high oxidation potential. It has been known. In addition, in order to increase mechanical durability, in order to withstand rubbing by paper or a cleaning member, surface lubricity is increased to reduce friction, and toner filming fusion is prevented. It is important to improve the releasability, and it is known to mix a lubricant such as a fluorine-based resin powder, fluorinated graphite, or a polyolefin-based resin powder in the surface layer. However, when the wear is significantly reduced, ozone,
A hygroscopic substance formed by an active substance such as NOx is deposited on the surface of the photoconductor, and as a result, the surface resistance is lowered and the surface charge is moved laterally, causing so-called image deletion. [Amorphous Silicon-Based Photoreceptor (a-Si)] In electrophotography, as a photoconductive material for forming a photosensitive layer of a photoreceptor, it has a high sensitivity and an SN ratio [photocurrent (I _p ) / dark current (I _d ). ], Having an absorption spectrum adapted to the spectral characteristics of the electromagnetic wave to be irradiated, having a fast photoresponsiveness and having a desired dark resistance value, being harmless to the human body during use, and the like. Required. Particularly, in the case of a photoreceptor for an image forming apparatus incorporated in an image forming apparatus used in an office as an office machine, the pollution-free property at the time of use is an important point.

A photoconductive material exhibiting excellent properties in this respect is hydrogenated amorphous silicon (hereinafter referred to as "a-Si"). For example, Japanese Patent Publication No. 60-35059 discloses a photoconductor for an image forming apparatus. The application as is described.

In such a photoreceptor for an image forming apparatus, generally, a conductive support is heated to 50 to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a heat treatment are applied to the support. CVD method, photo CVD method, plasma CV
A photoconductive layer made of a-Si is formed by a film forming method such as D method. Among them, a plasma CVD method, that is, a method of decomposing a raw material gas by direct current or high frequency or micro method glow discharge to form an a-Si deposited film on a support is put to practical use as a suitable one.

Further, Japanese Patent Application Laid-Open No. 54-83746 proposes a photoreceptor for an image forming apparatus comprising a conductive support and an a-Si photoconductive layer containing a halogen atom as a constituent element. In this publication, by containing 1 to 40 atomic% of halogen atoms in a-Si, the heat resistance is high and good electrical and optical characteristics can be obtained as a photoconductive layer of a photoreceptor for an image forming apparatus. I am going to do it.

Further, in Japanese Patent Laid-Open No. 57-115556, a photoconductive member having a photoconductive layer composed of an a-Si deposited film has an electrical and optical property such as dark resistance, photosensitivity and photoresponsiveness. , Photoconductive properties, and moisture resistance, and other environmental characteristics for use, as well as stability over time, in order to improve the stability over time, silicon atoms and carbon atoms are formed on the photoconductive layer composed of an amorphous material with silicon atoms as the base material. A technique for providing a surface barrier layer composed of a non-photoconductive amorphous material containing is described.

Further, Japanese Patent Application Laid-Open No. 60-67951 discloses a technique relating to a photoconductor in which a translucent insulating overcoat layer containing amorphous silicon, carbon, oxygen and fluorine is laminated. Sho 62-1681
Japanese Patent Laid-Open No. 61-61 discloses a technique of using, as the surface layer, an amorphous material containing silicon atoms, carbon atoms, and 41 to 70 atomic% hydrogen atoms as constituent elements.

[0040] Further, in JP-A-57-158650, hydrogen containing 10 to 40 atomic%, 0.2 absorption coefficient ratio of the absorption peak of 2100 cm ^-1 and 2000 cm ^-1 in the infrared absorption spectrum It is described that a photosensitive material for an image forming apparatus having high sensitivity and high resistance can be obtained by using 1.7 a-Si for a photoconductive layer.

On the other hand, in JP-A-60-95551, in order to improve the image quality of an amorphous silicon photoconductor, charging, exposure, development and transfer are performed while maintaining the temperature in the vicinity of the photoconductor surface at 30 to 40 ° C. By performing the image forming process as described above, there is disclosed a technique for preventing a decrease in surface resistance due to the adsorption of moisture on the surface of the photoconductor and a resulting image deletion.

These techniques have improved the electrical, optical and photoconductive characteristics of the photoconductor for an image forming apparatus and the environmental characteristics of use, and the image quality has been improved accordingly.

[0043]

By the way, the following points can be cited as problems when the above-mentioned voltage application type fixed type proximity charging device is used as a charging means of the image bearing member.

[0044] Typically, the proximity charging member, in order to facilitate the charging of the electrophotographic photosensitive member, and superimposing the oscillating voltage V _ac with 2 times or more the peak voltage V _pp of the charge starting voltage to a DC voltage V _dc However, since the vibration voltage V _ac greatly contributes to the charging, the electrophotographic photosensitive member has a charging unevenness having a cycle corresponding to the frequency of the vibration voltage V _ac. However, there arises a problem that it appears as minute image density unevenness.

For this reason, conventionally, the oscillating voltage V _ac is applied to the extent that the minute image density unevenness is inconspicuous, and a larger direct current voltage V _dc is applied for the insufficient charging voltage. If the DC voltage V _dc is increased too much, another problem that abnormal discharge is likely to occur occurs, and it is difficult to give a sufficient charging voltage to the electrophotographic photosensitive member.

Further, by increasing the frequency of the oscillating voltage V _ac , the periodic pitch of the charging unevenness is made small, and the minute image density unevenness caused by the charging unevenness is made to be less than visible. There is also a method of eliminating it, but if the frequency of the oscillating voltage V _ac is increased, the current flowing through the proximity charging member increases, and it is necessary to increase the capacity of the voltage applying power source accordingly, resulting in an increase in cost and the proximity charging member. There was a problem of shortening the life of the resistance layer.

This problem becomes more serious in the case of the amorphous silicon photosensitive drum (a-Si), which requires a larger vibration voltage V _{ac in} order to obtain a constant charging voltage.

Furthermore, since the resistance layer of the proximity charging member is constantly exposed to discharge and exposed to an atmosphere of high activity such as ozone, the resistance layer gradually deteriorates. As described above, in an image forming apparatus using a photoconductor having an extremely long life, image quality is deteriorated due to deterioration of the resistance layer of the proximity charging member, and maintenance and replacement of the charging member are unavoidable. This leads to an increase in service costs, which hinders maintenance-free operation.

Therefore, in designing the image forming apparatus and the electrophotographic image forming method, the electrophotographic physical properties and mechanical durability of the photoreceptor for the image forming apparatus are comprehensively adjusted so that the above-mentioned problems can be solved. From the point of view of improvement,
It is necessary to further improve the charging member, the charging device, and the image forming apparatus.

By solving the above problems, the present invention provides a charging device having a small amount of ozone generation and excellent durability, and an image having excellent image quality with high image contrast and no minute image density unevenness. It is an object of the present invention to provide an image forming apparatus that can be stably formed.

[0051]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, in which a charging member is arranged in a non-contact state so as to face a movable charged surface of a charged body, In a charging device for charging the surface to be charged by applying a voltage to the charging member, at least two charging members arranged on an upstream side and a downstream side in a moving direction of the surface to be charged, and these charging members. A control device for individually controlling the charging voltage applied to the member is provided.

In this case, the control device may apply the oscillating voltages of different phases to the plurality of charging members.

Further, the control device may apply an oscillating voltage having different amplitudes to the plurality of charging members.

Further, the control device can change the frequency of the oscillating voltage applied to the plurality of charging members according to the change in the moving speed of the surface to be charged.

Next, the control device may change the phase difference of the oscillating voltage applied to the plurality of charging members according to the change in the moving speed of the surface to be charged.

Next, the control device may change the amplitude of the oscillating voltage applied to the plurality of charging members according to the change in the moving speed of the surface to be charged.

The image forming apparatus exposes an electrostatic latent image by exposing an object to be charged having a surface to be charged, the charging device described above, and the surface to be charged charged by the charging device. An exposure unit for forming the electrostatic latent image, a developing device for forming a toner image by adhering a developer to the electrostatic latent image, and a transfer device for transferring the toner image formed on the surface to be charged onto a transfer material. It is characterized by

In the image forming apparatus, the member to be charged is
A photoconductor comprising a conductive support and a photoreceptive layer having a photoconductive layer containing a non-single-crystal material containing at least one of a hydrogen atom and a halogen atom with a silicon atom as a base, and a photoreceptor. The conductive layer contains 10 to 30 atomic% of hydrogen, and the characteristic energy of the exponential tail obtained from the light absorption spectrum at least in the light incident portion is 50.
˜60 meV and the localized density of states is 1 × 10 ¹⁴ ˜
It can be 1 × 10 ¹⁶ cm ^-3 .

In the image forming apparatus, the member to be charged may be an electrophotographic photosensitive member including a conductive support, a high melting point polyester resin and a cured resin.

[0060]

Based on the above configuration, for example, by independently adjusting (controlling) the frequency and phase of the oscillating voltage applied to the plurality of charging members, a cycle corresponding to the frequency of the oscillating voltage generated by each charging member can be obtained. Uneven charging can be averaged to substantially eliminate uneven charging.

By adjusting the phase of the oscillating voltage applied to the plurality of charging members, it becomes possible to easily adjust the uneven charging to be averaged.

Furthermore, by optimizing the amplitude and / or the DC voltage of the oscillating voltage applied to the plurality of charging members individually, more efficient charging can be achieved than with a single charging member, and a higher charging voltage can be obtained. Can be obtained, or a sufficient charging voltage can be obtained by a lower oscillation voltage amplitude and / or a DC voltage.

Further, for example, when the moving speed of the member to be charged is changed to change the magnification of the image, the frequency and / or the phase of the oscillating voltage is changed according to the change in the moving speed, thereby making it uniform. Easy charging.

Furthermore, by changing the amplitude of the oscillating voltage and / or the DC potential in accordance with the change in the moving speed, the charging can be efficiently performed.

[0065]

Embodiments of the present invention will be described below with reference to the drawings. <Embodiment 1> [Image forming apparatus] FIG. 1 shows a schematic configuration of an image forming unit of an image forming apparatus according to the present invention.

Reference numeral 101 is a photosensitive drum which is an image bearing member (charged member), and is a drum type electrophotographic photosensitive member which is rotationally driven in the clockwise direction of arrow A at a predetermined peripheral speed (process speed). . Reference numerals 102 and 103 denote proximity charging members, which are electrodes 102-1 and 103-1 and resistance layers 102-2 and 103-2 formed on their charging surfaces, respectively.
Have and. Image carrier 101 and proximity charging members 102, 1
The closest gap No. 03 should be stably set to an extremely short distance of 50 to 500 μm.

Reference numerals 104 and 105 denote power sources for the proximity charging members 102 and 103, respectively.
Due to 105, the superposition voltage (V _ac + V _dc ) obtained by superposing the oscillating voltage V _ac having the peak-to-peak voltage V _pp that is at least twice the charging start voltage of the photosensitive drum 101 and the DC voltage V _dc causes the proximity charging members to move. Electrodes 102-1, 1 of 102, 103
03-1 is applied to uniformly charge the outer peripheral surface of the photosensitive drum 101 which is rotationally driven.

Reference numeral 106 denotes a controller for controlling the power supplies 104 and 105. The controller 106 controls the DC voltage V _dc output from the power supplies 104 and 105 according to the peripheral speed of the image carrier 101.
The peak-to-peak voltage V _pp , frequency and phase difference of the oscillating voltage V _ac are controlled.

Further, by scanning the laser beam printer light 107 whose intensity is modulated according to the image signal, an electrostatic latent image is formed on the photosensitive drum 101. This latent image is visualized as a toner image by the developing sleeve 108 coated with the developer, and the toner image on the image carrier 101 is transferred onto the transfer material 109 via the transfer roller 110. The transfer residual toner on the photosensitive drum 101 is removed by the cleaning blade 111.
01 removed from above. On the other hand, on the transfer material 109, the transferred toner image is fixed on the surface by a fixing device (not shown), and then discharged to the outside of the image forming apparatus main body. [Resistive Layer Material of Charging Member and Coating Method] The charging member, which is a main component of the charging device of the present invention, will be described.
FIG. 2A is a side view of the charging member and the like.
Similarly, (b) shows a front view.

In these figures, 200 is a proximity charging member, 201 is a support for the proximity charging member, 202 is a resistance layer of the proximity charging member, and 203 is a gap provided between the proximity charging member and the photosensitive member, which is provided as necessary. Regulating spacer, 204
Is an object to be charged such as a photoconductor.

The support 201 of the proximity charging member is usually made of a metal such as aluminum, aluminum alloy, brass, copper, iron, stainless steel, or an insulating material such as resin or ceramic, which is subjected to a conductive treatment, that is, coated with a metal or a conductive material. Use the one that has been coated with a hydrophilic paint.

The resistance layer 202 of the proximity charging member is formed by coating a resin such as polypropylene or polyethylene or an elastomer such as silicon rubber or urethane rubber with a conductive filler such as titanium oxide, carbon powder or metal powder dispersed therein. Furthermore, it is more preferable to coat, film-form or spray a novel inorganic resistance layer described later.

The member 204 to be charged such as a photoconductor may be the same as the conventional one, but if necessary, a new photoconductor described below is used. [Inorganic resistance layer] As the above-mentioned new inorganic resistance layer, a strong and uniform metal oxide film by a sol-gel method, a strong and uniform amorphous thin film by a plasma CVD method, a strong by plasma spraying, and Examples include a dense metal coating or a magnetic metal coating. [Sol-Gel] Examples of the organometallic compound formed by the “sol-gel method” include “metal alkoxide” and “metal chelate”, and as the metal chelate, acetylacetonate is preferable.

The sol-like polymer liquid dispersion containing the metal alkoxide is coated on a support, and the following formula: M (OR) _n + nH ₂ O → M (OH) _n + nROH (M is Si, Al, Ti, Metals such as Zr and Be, R is C
_{H 3, C 2 H 5,} C 3 H 7 and alkyl group, n is hydrolyzed by reaction of the metal number of oxide), further polycondensation as follows _{M (OH) 2n → MO n} + nH 2 O Then, in the solution, oxide fine particles having a skeleton in which —M—O—M—O— bonds are formed are formed and gelled.
The resistance is controlled by dispersing a conductive material such as titanium oxide or metal fine particles in the sol-like polymer dispersion liquid described above.

This is heated to obtain a strong medium resistance metal oxide film.

On the other hand, as a method of using a metal chelate, there is a method of obtaining a metal oxide film from a sol-like polymer dispersion liquid mixture of acetylacetonate, water, alcohol, hydrochloric acid, and a conductive material. Indicated by.

The sol-type polymer dispersion liquid is applied to the charger support by a known coating method such as spray coating or dipping coating. Further, it is preferable to utilize rheological properties such as thixotropy or dilancy in the sol-gel method as an effective method for forming a uniform surface state. For example, in the dipping method, the thixotropy of the former is used to apply evenly in a low viscosity state, and then the solution is pulled up and the viscosity rises when the solution stands still. Use properties that do not exist.

With respect to the film thickness, if the thickness is 0.1 μm or more, the discharge and surface protection functions are poor, and if it is 100 μm or more, cracks are likely to occur. Therefore, the range of 0.1 to 100 μm is preferable, and 1 to 50 μm is more preferable. [CVD] As will be described later, SiC: H, S is applied to the charging member support by the same device and method as the amorphous silicon photoconductor film forming furnace.
iN: H, BN or the like is deposited. [Flaming] Examples of the magnetic material used in the present invention include nickel, cobalt, iron and the like, and a material having excellent oxidation resistance such as nickel is preferable from the viewpoint of ozone corrosion resistance.

Surface coating by a spraying means is more preferable because it is less likely to be restricted by the size and shape of the object to be coated, and the plasma spraying method is more preferable because the porosity is low and the adhesion is good.

The thickness of the spray is not particularly limited, but it is 1 μm in order to increase durability and uniformity and from the viewpoint of manufacturing cost.
m to 10 mm is preferable, and 10 μm to 5 mm is more preferable.

By using a magnetic material for the resistance layer of the proximity charging member, an AC voltage of 100 Hz applied to the charging member is used.
AC resistance becomes large particularly in a high frequency region of up to 1 MHz, and the resistance can be substantially controlled by controlling the frequency of the applied voltage after the image forming apparatus is worn, in addition to adjusting the resistance when forming the resistance layer. Become. By this action,
A proximity charging system that can flexibly respond to changes in the settings of the image forming apparatus such as the process speed and the charging setting of the image holding member has become possible. [Photoreceptor] An organic photoconductor (OPC) and an amorphous silicon-based photoreceptor (a-) are used as an image carrier used in the present invention.
Si). [Organic Photoconductor (OPC)] An OPC photoreceptor, which is one mode of a suitable photoreceptor used in the present invention, will be described below.
FIG. 3 is a schematic configuration diagram for explaining the layer configuration of the photoconductor for an image forming apparatus of the present invention.

OPC photoconductor 3 for image forming apparatus shown in FIG.
In No. 00, a photosensitive layer 302 is provided on a support 301 for a photosensitive body. The photosensitive layer 302 has a charge generation layer 303 and a charge transport layer 304. Further, if necessary, a protective layer or surface layer 306, and a support 301
The intermediate layer 305 is provided between the charge generation layer 303 and the charge generation layer 303.

The resin component used for forming the charge generation layer, charge transport layer, protective layer or surface layer, and intermediate layer of the electrophotographic photoreceptor of the present invention will be described.

The polyester is a binding polymer of an acid component and an alcohol component, and is a polymer obtained by condensation of dicarboxylic acid and glycol or condensation of a compound having a hydroxy group and a carboxy group of hydroxybenzoic acid.

Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid as acid components,
Aliphatic dicarboxylic acids such as succinic acid, adipic acid, and sebacic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, and oxycarboxylic acids such as hydroxyethoxybenzoic acid can be used.

As the glycol component, ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, cyclohexanedimethylol, polyethylene glycol, polypropylene glycol or the like can be used.

Polyfunctional compounds such as pentaerythritol, lolimethylolpropane, pyromellitic acid and their ester-forming derivatives may be copolymerized within the range where the above polyester resin is substantially linear.

As the polyester resin used in the present invention, a high melting point polyester resin is used.

The high melting point polyester resin has an intrinsic viscosity of 0.4 measured at 36 ° C. in orthochlorophenol.
dl / g or more, preferably 0.5 dl / g or more, and more preferably 0.65 dl / g or more are used.

Examples of preferred high melting point polyester resins include polyalkylene terephthalate resins. The polyalkylene terephthalate resin is mainly composed of terephthalic acid as an acid component and alkylene glycol as a glycol component.

Specific examples thereof include polyethylene terephthalate (PET) mainly composed of a terephthalic acid component and an ethylene glycol component, and mainly composed of a terephthalic acid component and a 1,4-tetramethylene glycol (1,4-butylene glycol) component. And polycyclohexyl dimethylene terephthalate (PCT) mainly composed of a terephthalic acid component and a cyclohexane dimethylol component. Examples of other preferable high molecular weight polyester resins include polyalkylene naphthalate resins. The polyalkylene naphthalate-based resin is mainly composed of a naphthalene dicarboxylic acid component as an acid component and an alkylene glycol component as a glycol component, and its specific example is mainly composed of a naphthalene dicarboxylic acid component and an ethylene glycol component. Examples thereof include polyethylene naphthalate (PEN).

The high melting point polyester resin has a melting point of preferably 160 ° C. or higher, particularly preferably 200 ° C.
That is all.

The high melting point polyester resin has high crystallinity due to its high melting point. As a result, the entanglement between the cured resin polymer chain and the high melting point polymer chain becomes uniform and dense, resulting in a highly durable surface. It is believed that layers can be formed. In the case of a low-melting point polyester resin or the like, since the crystallinity is low, there are places where the degree of entanglement with the cured resin polymer chain is large and places where the degree of entanglement is small, resulting in poor durability. [Amorphous Silicon Photoreceptor (a-Si)] An amorphous silicon photoreceptor, which is one mode of a suitable photoreceptor used in the present invention, will be described below.

Focusing on the behavior of carriers in the photoconductive layer of the amorphous silicon photoconductor, as a result of diligent study on the relationship between the localized state distribution in the bandgap and the temperature dependence of the chargeability and the optical memory, the results show that It has been found that the above-mentioned object can be achieved by controlling the localized density of states in a certain range at least in a portion where light is incident. That is, it is composed of a non-single-crystal material having a silicon atom as a base and containing a hydrogen atom and / or a halogen atom (“and / or” is used to mean “both or at least one,” the same below) In the photoconductor having a photoconductive layer, the photoconductor designed and produced so as to specify the layer structure thereof not only exhibits remarkably excellent characteristics in practical use, but also has almost no characteristics when compared with conventional photoconductors. It has been found that it is superior in the point, and particularly has excellent characteristics as a photoreceptor for an image forming apparatus.

The photoconductor for an image forming apparatus of the present invention comprises a conductive support and a photoconductive layer having a photoconductive layer made of a non-single crystal material having silicon atoms as a matrix. It contains 30 atomic% of hydrogen, and the characteristic energy of the inter-exponential tail of the optical absorption spectrum is 50 to 50.
60 meV and a localized density of states of 1 × 10 ¹⁴ to
It is characterized in that it is 1 × 10 ¹⁶ cm ^-3 .

The photoconductor for an image forming apparatus of the present invention designed to have the above-mentioned constitution can solve all of the above-mentioned problems and is extremely excellent in electrical, optical and photoconductive properties. It shows characteristics, image quality, durability and environmental characteristics of use.

Generally, in the band gap of a-Si: H, a tail level due to structural disorder of Si-Si bond and a dangling bond of Si (dangling bond).
There are deep levels due to structural defects such as. It is known that these levels act as traps for electrons and holes, and as recombination centers, and cause deterioration of device characteristics.

As a method of measuring the state of the localized level in the band gap, generally, deep level spectroscopy, isothermal capacitance transient spectroscopy, photothermal deflection spectroscopy, constant photocurrent method, etc. are used. . Among them, the constant photocurrent method [Constant
PhotocurrentMethod: After that, "C
PM ”] is useful as a method for simply measuring a subgap optical absorption spectrum based on the localized level of a-Si: H.

The present applicants have used the characteristic energy (hereinafter referred to as “Eu”) and the localized density of states (hereinafter referred to as “DOS”) of the exponential function tail (Urback tail) obtained from the optical absorption spectrum measured by CPM. As a result of investigating the correlation between the photoconductor characteristics and the photoconductor characteristics under various conditions, Eu and D
We have found that the OS has a close relationship with the temperature characteristics of the a-Si photoconductor and the optical memory, and completed the present invention.

The reason why the charging ability is lowered when the photosensitive member is heated by the drum heater or the like is that the thermally excited carriers are attracted to the electric field at the time of charging and the localized level at the band skirt or the deep local region in the band gap. It is possible that the surface charge is canceled by traveling to the surface while repeatedly capturing and releasing the current level. At this time, the carriers that have reached the surface while passing through the charger have almost no effect on the decrease in chargeability, but the thermally excited carriers trapped in deep levels reach the surface after passing through the charger. Then, it is observed as a temperature characteristic to cancel the surface charge. Further, the carriers that are thermally excited after passing through the charger also cancel the surface charge and cause a decrease in charging ability. Therefore, in order to improve the temperature characteristics, it is necessary to suppress the generation of thermally excited carriers in the operating temperature range of the photoconductor and improve the phototactic property of the carriers.

Further, the optical memory is generated when the photo carriers generated by blank exposure or image exposure are trapped in the localized level in the band gap and the photo carriers remain in the photoconductive layer. That is, among the photocarriers generated in a certain copying process, the photocarriers remaining in the photoconductive layer are swept out by the electric field due to the surface charge at the time of the next charging or thereafter, and the potential of the portion irradiated with light is changed to another. Is lower than that of the image, and as a result, shading occurs on the image. Therefore, the runnability of the photocarriers must be improved so that the photocarriers travel in a single copying step without remaining in the photoconductive layer.

Therefore, as in the present invention, Eu and D
By controlling the OS, the generation of thermally excited carriers can be suppressed, and the rate at which thermally excited carriers and photocarriers are trapped in localized levels can be reduced, so that the mobility of carriers is significantly improved. . As a result, the temperature characteristics of the photosensitive member in the operating temperature range are dramatically improved, and at the same time, the generation of optical memory can be suppressed, so that the stability of the photosensitive member in the operating environment is improved and the halftone becomes clear. It is possible to stably obtain a high-quality image that appears and has a high resolution.

The photoconductive member will be described in detail below with reference to the drawings.

FIGS. 4A to 4D are schematic configuration diagrams for explaining the layer configuration of the photoreceptor for an image forming apparatus of the present invention.

Photoreceptor 4 for image forming apparatus shown in FIG.
In No. 00, a photosensitive layer 402 is provided on a support 401 for a photosensitive body. The photosensitive layer 402 is hydrogen (H)
And / or a photoconductive layer 403 having photoconductivity made of amorphous silicon containing halogen atoms (X) (hereinafter referred to as “a-Si (H, X)”).

FIG. 4B is a schematic structural view for explaining another layer structure of the photoconductor for an image forming apparatus of the present invention. The image forming apparatus photoconductor 400 shown in FIG.
A photosensitive layer 402 is provided on a support 401 for a photoreceptor. The photosensitive layer 402 is a-Si (H, X)
And a photoconductive layer 403 having photoconductivity and an amorphous silicon-based surface layer 404.

FIG. 4C is a schematic structural view for explaining another layer structure of the photoconductor for an image forming apparatus of the present invention. The image forming apparatus photoconductor 400 shown in FIG.
A photosensitive layer 402 is provided on a support 401 for a photoreceptor. The photosensitive layer 402 is a-Si (H, X)
And a photoconductive layer 403 having photoconductivity, an amorphous silicon-based surface layer 404, and an amorphous silicon-based charge injection blocking layer 405.

FIG. 4D is a schematic structural view for explaining still another layer structure of the photoconductor for an image forming apparatus of the present invention. Image forming apparatus photoconductor 400 shown in FIG.
Is the photosensitive layer 40 on the support 401 for the photoreceptor.
2 are provided. The photosensitive layer 402 is a photoconductive layer 403.
Of the charge generation layer 40 made of a-Si (H, X)
6 and charge transport layer 407, and an amorphous silicon-based surface layer 404. [Support] As the support used in the present invention,
It may be electrically conductive or electrically insulating. As the conductive support, Al, Cr, Mo, Au, In, Nb, Te,
Examples thereof include metals such as V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. Further, at least the surface of the electrically insulating support made of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, etc. on the side where the photosensitive layer is formed is formed. A conductively treated support can also be used.

The shape of the support 401 used in the present invention may be a cylindrical or plate-like endless belt having a smooth surface or an uneven surface, and the thickness of the support 401 is as desired. However, when flexibility as the photoreceptor 400 for the image forming apparatus is required, it should be as thin as possible within the range in which the function of the support 401 can be sufficiently exerted. You can However, the support 401 is usually 10 μm or more in terms of manufacturing and handling, mechanical strength and the like.

In particular, when image recording is performed by using coherent light such as laser light, in order to more effectively eliminate image defects due to so-called interference fringe patterns that appear in a visible image, the surface of the support 401 is You may provide unevenness in. The unevenness provided on the surface of the support 401 is disclosed in JP-A-60-1.
68156, 60-178457, and 6
It is produced by a known method described in, for example, 0-225854.

As another method for more effectively eliminating the image defect due to the interference fringe pattern when the coherent light such as the laser light is used, the surface of the support 401 is formed with a concavo-convex shape by a plurality of spherical trace dents. It may be provided. That is, the surface of the support 401 has unevenness smaller than the resolving power required for the photoreceptor 400 for an image forming apparatus, and the unevenness is due to a plurality of spherical dents. The unevenness due to the plurality of spherical trace depressions provided on the surface of the support 401 is produced by the known method described in JP-A-61-235661. [Photoconductive Layer] In the present invention, the photoconductive layer 403, which is formed on the support 401 and constitutes a part of the photosensitive layer 402 in order to effectively achieve the object, has a desired characteristic by a vacuum deposition film forming method. The numerical conditions of the film forming parameters are appropriately set so as to obtain Specifically, for example, glow discharge method (low-frequency CVD method, high-frequency CVD method, alternating-current discharge CVD method such as microwave CVD method, or direct-current discharge CVD method), sputtering method, vacuum deposition method, ion plating method, It can be formed by various thin film deposition methods such as 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, load level under capital investment, manufacturing scale, and characteristics desired for a photoreceptor for an image forming apparatus to be manufactured. The glow discharge method, particularly the high-frequency glow discharge method using a power supply frequency in the RF band or the VHF band, is preferable because it is relatively easy to control the conditions for manufacturing the photoconductor for an image forming apparatus having characteristics. is there.

To form the photoconductive layer 403 by the glow discharge method, basically, a source gas for supplying Si, which can supply silicon atoms (Si), and a source gas for supplying H, which can supply hydrogen atoms (H). The raw material gas of (1) and / or the raw material gas for supplying X, which can supply the halogen atom (X), is introduced in a desired gas state into a reaction vessel whose inside can be decompressed to cause glow discharge in the reaction vessel. A-Si on a predetermined support 401 which is set in advance at a predetermined position.
A layer made of (H, X) may be formed.

In the present invention, it is necessary for the photoconductive layer 403 to contain hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms and improves the layer quality, particularly This is because it is essential for improving photoconductivity and charge retention characteristics. Therefore, the content of hydrogen atoms or halogen atoms, or the amount of the sum of hydrogen atoms and halogen atoms is 10 to 30 atom%, more preferably 15 to 25 atom% with respect to the sum of silicon atoms and hydrogen atoms and / or halogen atoms. It is desirable that

Materials that can be used as the Si supply gas in the present invention include SiH ₄ , Si ₂ H ₆ , and Si _3.
Silicon hydrides (silanes) in a gas state such as H ₈ and Si ₄ H ₁₀ or that can be gasified are mentioned as being effectively used. Further, they are easy to handle during layer formation and have good Si supply efficiency. In this respect, SiH ₄ and Si ₂ H ₆ are preferable.

Then, hydrogen atoms are structurally introduced into the photoconductive layer 403 to be formed so that the introduction ratio of hydrogen atoms can be controlled more easily to obtain film characteristics that achieve the object of the present invention. In order to further add H ₂ and / or
Alternatively, it is necessary to mix a desired amount of He or a silicon compound gas containing hydrogen atoms to form a layer. Further, each gas may be mixed not only with one kind but also with plural kinds at a predetermined mixing ratio.

Further, as a raw material gas for supplying halogen atoms used in the present invention, a gas or gas such as a halogen gas, a halide, an interhalogen compound containing halogen, or a silane derivative substituted with halogen is effective. Preferred examples thereof include halogen compounds that can be converted. Further, a gaseous or gasifiable hydrogen silicon compound containing a halogen atom, which contains silicon atoms and a halogen atom as constituent elements, can also be cited as an effective one. Specific examples of the halogen compound preferably used in the present invention include fluorine gas (F ₂ ), Br
F, ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ ,
Interhalogen compounds such as IF ₇ can be mentioned. As a silicon compound containing a halogen atom, that is, a so-called silane derivative substituted with a halogen atom, silicon fluorides such as SiF ₄ and Si ₂ F ₆ can be specifically mentioned as preferable examples.

The amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer 403 can be controlled by, for example, the temperature of the support 401, the raw material used for containing hydrogen atoms and / or halogen atoms. The amount of the substance introduced into the reaction container, the discharge power, etc. may be controlled.

In the present invention, it is preferable that the photoconductive layer 403 contains atoms for controlling the conductivity, if necessary. Atoms for controlling conductivity may be contained in the photoconductive layer 403 in a uniformly distributed state, or there may be a part in which they are contained in a nonuniformly distributed state in the layer thickness direction. Good.

Examples of the above-mentioned atoms that control conductivity include so-called impurities in the field of semiconductors, and atoms that belong to Group 3b of the periodic table that give p-type conductivity (hereinafter referred to as "Group 3b atoms"). Alternatively, an atom belonging to group 5b of the periodic table (hereinafter referred to as “group 5b atom”) which imparts n-type conductivity can be used.

Specific examples of the Group 3b atom include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). Particularly, B, Al, and Ga are included. It is suitable. As the group 5b atom,
Specifically, phosphorus (P), arsenic (As), antimony (S)
b), bismuth (Bi), etc., and P and As are particularly preferable.

The content of the atoms contained in the photoconductive layer 403 for controlling the conductivity is preferably 1 × 10 ^-2 to 1
× 10 ⁴ atomic ppm, more preferably 5 × 10 ^{-2 to} 5 ×
It is desirable that the concentration is 10 ³ atomic ppm, optimally 1 × 10 ⁻¹ to 1 × 10 ³ atomic ppm.

Atoms controlling conductivity, eg 3b
To introduce a group atom or a group 5b atom structurally,
If a raw material for introducing a Group 3b atom or a raw material for introducing a Group 5b atom is introduced into the reaction vessel in a gas state together with another gas for forming the photoconductive layer 403 during layer formation. Good. As a raw material for introducing a Group 3b atom or a raw material for introducing a Group 5b atom, a substance which is gaseous at room temperature and normal pressure or which can be easily gasified under at least the layer forming condition is adopted. Is desirable.

As a raw material for introducing such a Group 3b atom, specifically, for introducing a boron atom, B ₂ H
_{6, B 4 H 10, B} 5 H 9, B 5 H 11, B 6 H 10, B 6 H
₁₂ , borohydride such as B ₆ H ₁₄ , BF ₃ , BCl ₃ , BB
Examples thereof include boron halides such as r ₃ . Besides this, Al
Cl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ ,
TlCl _{3 and the} like can also be mentioned.

As a raw material for introducing a Group 5b atom, PH ₃ and P are effectively used for introducing a phosphorus atom.
₂ H ₄ , etc., phosphorus hydride, PH ₄ 1, PF ₃ , PF ₅ , P
Examples thereof include phosphorus halides such as Cl ₃ , PCl ₅ , PBr ₃ , PBr ₅ , and Pl ₃ . In addition, AsH ₃ and AsF
₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , SbH ₃ , S
bF ₃ , SbF ₅ , SbCl ₃ , SbCl ₅ , BiH
It can be cited as an effective starting material for introducing a Group 5b atom such as ₃ , BiCl ₃ and BiBr ₃ .

Further, these raw material substances for atom introduction for controlling the conductivity may be diluted with H ₂ and / or He as necessary and used.

Further, in the present invention, the photoconductive layer 403.
It is also effective to contain carbon atoms and / or oxygen atoms and / or nitrogen atoms. Carbon atom and /
The content of oxygen atoms and / or nitrogen atoms is preferably 1 × 10 ⁻⁵ to 10 atom%, more preferably 1 × 10 ⁻⁴ to 8 with respect to the sum of silicon atoms, carbon atoms, oxygen atoms and nitrogen atoms. Atomic%, optimally 1 × 10 ^{−3 to} 5 atomic% is desirable. The carbon atom and / or the oxygen atom and / or the nitrogen atom may be uniformly contained in the photoconductive layer, or may be non-uniformly distributed such that the content varies in the thickness direction of the photoconductive layer. There may be a part that has.

In the present invention, the layer thickness of the photoconductive layer 403 is appropriately determined as desired in view of obtaining desired electrophotographic characteristics and economical effects, and is preferably 2
The thickness is preferably 0 to 50 μm, more preferably 23 to 45 μm, and most preferably 25 to 40 μm.

In order to achieve the object of the present invention and form the photoconductive layer 403 having desired film characteristics, the mixing ratio of the gas for supplying Si and the diluting gas, the gas pressure in the reaction vessel, the discharge power and It is necessary to set the support temperature appropriately.

The flow rate of H ₂ and / or He used as a diluent gas is appropriately selected in accordance with the layer design, but H ₂ and / or He is usually added to the Si supply gas in the range of 3 to 3. 20 times, preferably 4 to 15
It is desirable to control in the range of double, optimally 5 to 10 times.

Similarly, the gas pressure in the reaction vessel is appropriately selected in accordance with the layer design, and an optimum range is selected.
It is preferably 1000 Pa, preferably 0.1 to 500 Pa, and most preferably 0.5 to 100 Pa.

Similarly, the discharge power is appropriately selected in accordance with the layer design, but the discharge power with respect to the flow rate of the gas for supplying Si is usually 1 to 7 times, preferably 2 to 6 times. It is desirable to set the range of 3 to 5 times.

Further, the temperature of the support 401 is appropriately selected in accordance with the layer design, but in the usual case,
Preferably from 200 to 350 ° C, more preferably from 230 to
It is desirable that the temperature is 330 ° C., optimally 250 to 310 ° C.

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the temperature and gas pressure of the support for forming the photoconductive layer, but the conditions are not usually independently determined separately. It is desirable to determine the optimum value based on mutual and organic relationships to form a photoreceptor having desired characteristics. [Surface Layer] In the present invention, it is preferable to further form an amorphous silicon-based surface layer 404 on the photoconductive layer 403 formed on the support 401 as described above. This surface layer 404 is a free surface 404a (see FIG.
(See (b)), and is provided to achieve the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability.

Further, in the present invention, since each of the amorphous materials forming the photoconductive layer 403 and the surface layer 404 forming the photosensitive layer 402 has a common constituent element of silicon atom, they are laminated. The chemical stability is sufficiently ensured at the interface.

The surface layer 404 can be made of any material as long as it is an amorphous silicon type material. For example, a hydrogen atom (H) and / or a halogen atom (X) can be used.
Containing amorphous carbon (hereinafter referred to as “a-SiC (H, X)”), a hydrogen atom (H) and / or a halogen atom (X),
Further, amorphous silicon containing oxygen atoms (hereinafter referred to as "a-SiO ((H, X)"), hydrogen atoms (H)
Amorphous silicon containing a halogen atom (X) and / or a nitrogen atom (hereinafter “a-S”).
iN (H, X) "), a hydrogen atom (H) and / or a halogen atom (X), and further at least one of a carbon atom, an oxygen atom and a nitrogen atom (hereinafter referred to as" a- "). Si (C, O, N) (H,
X) ”)) and the like are preferably used.

In the present invention, in order to effectively achieve the object, the surface layer 404 is produced by a vacuum deposition film forming method with appropriate numerical conditions of film forming parameters set so that desired characteristics can be obtained. . Specifically, for example, glow discharge method (low-frequency CVD method, high-frequency CVD method, alternating-current discharge CVD method such as microwave CVD method, or direct-current discharge CVD method), sputtering method, vacuum deposition method, ion plating method, It can be formed by various thin film deposition methods such as 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, a load level under capital investment, manufacturing scale, and characteristics desired for a photoreceptor for an image forming apparatus to be manufactured. From the viewpoint of productivity, it is preferable to use the same deposition method as for the photoconductive layer.

For example, a-SiC is formed by the glow discharge method.
In order to form the surface layer 404 composed of (H, X), basically, a source gas for supplying Si that can supply silicon atoms (Si) and a source gas for supplying C that can supply carbon atoms (C). Source gas, and source gas for supplying H that can supply hydrogen atoms (H) and / or X that can supply halogen atoms (X)
A raw material gas for supply is introduced in a desired gas state into a reaction vessel capable of reducing the pressure inside to cause glow discharge in the reaction vessel to form a photoconductive layer 403 installed at a predetermined position in advance. A-SiC (H,
X) may be formed.

The material of the surface layer used in the present invention may be any amorphous material containing silicon, but a compound with a silicon atom containing at least one element selected from carbon, nitrogen and oxygen is preferable, and particularly, Those containing a-SiC as a main component are preferable.

When the surface layer is composed mainly of a-SiC, the amount of carbon is preferably in the range of 30 to 90% with respect to the sum of silicon atoms and carbon atoms.

Further, in the present invention, it is necessary that the surface layer 404 contains hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms and improves the layer quality, especially light. It is indispensable for improving the conductivity and charge retention characteristics. The hydrogen content is usually 30 to 70 atom%, preferably 35 to 65 atom%, and optimally 40 to 60 atom% with respect to the total amount of the constituent atoms. In addition, the content of fluorine atoms is usually 0.01 to 15 atom%, preferably 0.
1 to 10 atomic% Optimally, it is desired to be 0.6 to 4 atomic%.

The photoconductor formed within the range of the hydrogen and / or fluorine content can be sufficiently applied as a remarkably excellent one which has not been hitherto available. That is, it is known that defects existing in the surface layer (mainly dangling bonds of silicon atoms and carbon atoms) adversely affect the characteristics as a photoreceptor for an image forming apparatus. For example, deterioration of charging characteristics due to injection of electric charges from the free surface, fluctuation of charging characteristics due to change of surface structure in use environment, for example, high humidity, and further charge on surface layer due to photoconductive layer during corona charging or light irradiation. This is adversely affected by, for example, the occurrence of an afterimage phenomenon during repeated use due to the injection of charges and the trapping of charges in the above-mentioned defects in the surface layer.

However, by controlling the hydrogen content in the surface layer to 30 atomic% or more, the defects in the surface layer are significantly reduced, and as a result, electrical characteristics and high-speed continuous usability are improved as compared with the conventional one. It is possible to achieve a dramatic improvement in.

On the other hand, when the hydrogen content in the surface layer is 71 atomic% or more, the hardness of the surface layer is lowered, and it 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 the desired electrophotographic characteristics that are remarkably excellent. The hydrogen content in the surface layer depends on the flow rate of H ₂ gas,
It can be controlled by the support temperature, discharge power, gas pressure and the like.

The fluorine content in the surface layer is 0.01
By controlling the content to be in the range of atomic% or more, it becomes possible to more effectively achieve the bond between silicon atoms and carbon atoms in the surface layer. Further, as a function of the fluorine atom in the surface layer, the breaking of the bond between the silicon atom and the carbon atom due to damage such as corona can be effectively prevented.

On the other hand, when the fluorine content in the surface layer exceeds 15 atomic%, the effect of generating the bond between the silicon atom and the carbon atom in the surface layer and the effect of preventing the breaking of the bond between the silicon atom and the carbon atom are almost obtained. Will not be recognized. Furthermore, since excess fluorine atoms impede the mobility of carriers in the surface layer, the residual potential and image memory are noticeable. Therefore, controlling the fluorine content in the surface layer within the above range is one of the important factors in obtaining the desired electrophotographic characteristics. Like the hydrogen content, the fluorine content in the surface layer can be controlled by the flow rate of the raw material gas for supplying halogen atoms, the support temperature, the discharge power, the gas pressure and the like.

As the substance which can be used as a gas for supplying silicon (Si) used in the formation of the surface layer of the present invention,
_{SiH 4, Si 2 H 6,} Si 3 H 8, Si 4 H , etc. of the gas states of ₁₀ or silicon hydride can be gasified, (silanes)
Is effectively used, and SiH is more advantageous in terms of easiness of handling at the time of layer preparation and good Si supply efficiency.
₄ , and Si ₂ H ₆ are preferred. In addition, if necessary, the source gas for supplying Si may be H
_It may be diluted with a gas such as ₂ , He, Ar, or Ne before use.

As a substance that can be a gas for supplying carbon,
Carbon hydrogen in a gas state such as CH ₄ , C ₂ H ₆ , C ₃ H ₈ , C ₄ H ₁₀ or the like which can be gasified is mentioned as being effectively used, and further, it is easy to handle during layer formation and carbon. CH ₄ and C ₂ H ₆ are preferable as they are preferable in terms of supply efficiency. In addition, these raw material gases for supplying C may be diluted with a gas such as H ₂ , He, Ar, or Ne as needed before use.

Examples of substances that can serve as nitrogen or oxygen supply gas include NH ₃ , NO, N ₂ O, NO ₂ , H ₂ O and O.
_The compounds in the gas state such as ₂ , CO, CO ₂ , N ₂ or the like, which can be gasified, are mentioned as being effectively used. In addition, these raw material gases for supplying nitrogen and oxygen may be diluted with a gas such as H ₂ , He, Ar, and Ne as needed before use.

Further, in order to more easily control the introduction ratio of hydrogen atoms introduced into the surface layer 404 to be formed, hydrogen gas or a silicon compound gas containing hydrogen atoms is added to these gases. It is also preferable to mix a desired amount to form a layer. Further, each gas may be mixed not only with one kind but also with plural kinds at a predetermined mixing ratio.

As a raw material gas for supplying halogen atoms, for example, a halogen gas, a halide, an interhalogen compound containing halogen, a halogenated compound such as a silane derivative substituted with halogen, or a halogenated compound which can be gasified is preferable. . Further, a gaseous or gasifiable silicon hydride compound containing a halogen atom, which contains silicon atoms and a halogen atom as constituent elements, can also be cited as an effective one.

Specific examples of the halogen compound preferably used in the present invention include fluorine gas (F ₂ ) and Br.
F, ClF, ClF ₃ , BrF ₃ , BrF ₅ , IF ₃ ,
Interhalogen compounds such as IF ₇ can be mentioned. As a silicon compound containing a halogen atom, that is, a so-called silane derivative substituted with a halogen atom, silicon fluorides such as SiF ₄ and Si ₂ F ₆ can be specifically mentioned as preferable examples.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the surface layer 404, for example, the temperature of the support 401, the raw material used for containing hydrogen atoms and / or halogen atoms. The amount to be introduced into the reaction container, the discharge power, and the like may be controlled.

Carbon atom and / or oxygen atom and /
Alternatively, the nitrogen atoms may be evenly and uniformly contained in the surface layer, or the surface layer may have a portion having an uneven distribution such that the content changes in the layer thickness direction.

Further, in the present invention, it is preferable that the surface layer 404 contains an atom for controlling conductivity, if necessary. Atoms that control conductivity may be contained in the surface layer 404 in a state where they are evenly distributed.
Alternatively, there may be a portion containing a non-uniform distribution in the layer thickness direction.

Examples of the above-mentioned atoms that control conductivity include so-called impurities in the field of semiconductors, and atoms that belong to Group 3b of the periodic table that give p-type conductivity (hereinafter referred to as "Group 3b atoms"). Alternatively, an atom belonging to group 5b of the periodic table (hereinafter referred to as “group 5b atom”) which imparts n-type conductivity can be used.

Specific examples of the Group 3b atom include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl), and B, Al, and Ga are particularly preferable. It is suitable. As the group 5b atom,
Specifically, phosphorus (P), arsenic (As), antimony (S)
b), bismuth (Bi), etc., and P and As are particularly preferable.

The content of atoms controlling the conductivity contained in the surface layer 404 is preferably 1 × 10 ⁻³ to 1 ×.
10 ³ atom ppm, more preferably 1 × 10 ^{-2 to} 5 ×
It is desirable that the concentration be 10 ² atomic ppm, optimally 1 × 10 ^-1 to 1 × 10 ² atomic ppm. To structurally introduce a conductivity controlling atom, for example, a Group 3b atom or a Group 5b atom, a raw material for introducing a Group 3b atom or a raw material for introducing a Group 5b atom during layer formation. The substance may be introduced into the reaction container in a gas state together with another gas for forming the surface layer 404. As a raw material for introducing a Group 3b atom or a raw material for introducing a Group 5b atom, a gaseous substance at room temperature and normal pressure, or at least a substance that can be easily gasified under a layer forming condition is adopted. Is desirable.

As a raw material for introducing such a Group 3b atom, specifically, for introducing a boron atom, B ₂ H
_{6, B 4 H 10, B} 5 H 9, B 5 H 11, B 6 H 10, B 6 H
₁₂ , borohydride such as B ₆ H ₁₄ , BF ₃ , BCl ₃ , BB
Examples thereof include boron halides such as r ₃ and the like. Besides this, A
lCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InC
Other examples include l ₃ and TlCl ₃ .

As a raw material for introducing a Group 5b, PH ₃ and P ₂ are effectively used for introducing a phosphorus atom.
H ₄ hydrogen such as phosphorus _{halides, PH 4 l, PF 3,} PF 5, PCl
Examples thereof include phosphorus halides such as ₃ , PCl ₅ , PBr ₅ , and Pl ₃ . In addition, AsH ₃ , AsF ₃ , AsCl ₃ ,
AsBr ₃ , AsF ₅ , SbH ₃ , SbF ₃ , SbF
₅ , SbCl ₃ , SbCl ₅ , BiH ₃ , BiCl ₃ ,
BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing the Group 5b.

Further, these raw material substances for introducing atoms for controlling the conductivity may be diluted with a gas such as H ₂ , He, Ar, Ne or the like, if necessary.

The thickness of the surface layer 404 in the present invention is usually 0.01 to 3 μm, preferably 0.05 to 2 μm.
m, most preferably 0.1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer will be lost due to wear or the like during use of the photoconductor, and the surface layer will be 3 μm.
When it exceeds m, electrophotographic characteristics such as increase in residual potential are deteriorated.

The surface layer 404 according to the present invention is carefully formed to provide its desired properties as desired. That is, a substance having Si, C and / or N and / or O, H and / or X as a structural element structurally takes a form from crystalline to amorphous silicon and is electrically conductive in terms of electrical properties. In the present invention, it has a desired property depending on the purpose because it exhibits properties ranging from photoconductive property to semiconducting property and insulating property and from photoconductive property to non-photoconductive property. The choice of formation conditions is made strictly as desired so that the compound is formed.

For example, in order to provide the surface layer 404 mainly for the purpose of improving the pressure resistance, the surface layer 404 is formed as a non-single-crystal material having a remarkable electric insulating behavior in the use environment.

When the surface layer 404 is provided mainly for the purpose of improving continuous repeated use characteristics and use environment characteristics, the above-mentioned degree of electrical insulation is relaxed to some extent, and to some extent to the irradiated light. It is formed as a non-single crystal material with sensitivity.

In order to form the surface layer 404 having the characteristics that can achieve the object of the present invention, it is necessary to appropriately set the temperature of the support 401 and the gas pressure in the reaction vessel as desired.

The temperature (Ts) of the support 401 is appropriately selected in accordance with the layer design, but in the usual case, it is preferably 200 to 350 ° C., more preferably 230 to 33.
It is desirable that the temperature is 0 ° C., optimally 250 to 300 ° C.

Similarly, the gas pressure in the reaction vessel is appropriately selected according to the layer design, but in the usual case, it is preferably 0.05 to 1000 Pa, more preferably 0.1.
˜500 Pa, and most preferably 0.5 to 100 Pa.

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges of the temperature of the support and the gas pressure for forming the surface layer 404, but the conditions are not usually independently determined separately. It is desirable to determine the optimum value based on mutual and organic relationships to form a photoreceptor having desired characteristics.

Further, in the present invention, the photoconductive layer 403.
In order to further improve characteristics such as charging ability, it is also possible to provide a blacking layer (lower surface layer) in which the content of carbon atoms, oxygen atoms, and nitrogen atoms is smaller than that of the surface layer between the surface layer 404 and the surface layer 404. It is valid.

Further, a region where the content of carbon atoms and / or oxygen atoms and / or nitrogen atoms changes so as to decrease toward the photoconductive layer 403 is provided between the surface layer 404 and the photoconductive layer 403. Good. This can improve the adhesion between the surface layer and the photoconductive layer, and further reduce the influence of interference due to the reflection of light at the interface. [Charge Injection Blocking Layer] In the photoconductor for an image forming apparatus of the present invention, the charge injection having a function of blocking injection of charges from the conductive support side between the conductive support 401 and the photoconductive layer 403. It is even more effective to provide the blocking layer 405. That is, the charge injection blocking layer 405 has a function of blocking the injection of charges from the support side to the photoconductive layer side when the photosensitive layer undergoes a charging treatment of a constant polarity on its free surface, and the reverse polarity. Such a function is not exhibited when it is subjected to the charging treatment of 1. In order to impart such a function, the charge injection blocking layer 405
Contains a relatively large number of atoms whose conductivity is controlled as compared with the photoconductive layer 403.

The conductivity-controlling atoms contained in the layer may be evenly distributed in the layer, or they may be distributed in the layer thickness direction evenly. There may be a portion that contains it in a uniformly distributed state. When the distribution concentration is non-uniform, it is preferable that the content is so distributed as to be distributed more on the support side.

However, in any case, the support 4
In the in-plane direction parallel to the surface of No. 01, it is necessary that the particles are evenly distributed in a uniform distribution from the viewpoint of uniformizing the characteristics in the in-plane direction.

The atoms contained in the charge injection blocking layer 405 for controlling the conductivity include so-called impurities in the field of semiconductors, and the atoms belonging to Group 3b of the Periodic Table (hereinafter, referred to as “p-type conduction characteristics”). Group 3b atom) or an atom belonging to group 5b of the periodic table (hereinafter referred to as “group 5b atom”) that imparts n-type conductivity.

As the group 3b atom, specifically, B
There are (boron), Al (aluminum), Ga (gallium), In (indium), Ta (thallium), etc., and B, Al, and Ga are particularly preferable. Specific examples of the Group 5b atom include P (phosphorus), As (arsenic), and Sb.
(Antimony), Bi (bismuth), etc., especially P,
As is preferred.

In the present invention, the content of atoms for controlling the conductivity contained in the charge injection blocking layer 405 is appropriately determined according to the desire so that the object of the present invention can be effectively achieved, but is preferable. Is 10 to 1 × 10 ⁴ atomic ppm, more preferably 50 to 5 × 10 ³ atomic ppm,
Optimally, the concentration is preferably set to 1 × 10 ² to 1 × 10 ³ atomic ppm.

Further, the charge injection blocking layer 405 contains at least one kind of carbon atom, nitrogen atom and oxygen atom so that the charge injection blocking layer 405 is provided between the charge injection blocking layer 405 and another layer provided in direct contact therewith. It is possible to further improve the adhesion.

The carbon atoms, nitrogen atoms or oxygen atoms contained in the layer may be evenly distributed in the layer, or may be contained evenly in the layer thickness direction. There may be a portion containing the non-uniformly distributed state. However, in any case, it is necessary that the content be evenly distributed in the in-plane direction parallel to the surface of the support in order to obtain uniform properties in the in-plane direction.

The content of carbon atoms and / or nitrogen atoms and / or oxygen atoms contained in the entire region of the charge injection blocking layer 405 in the present invention is appropriately selected so that the object of the present invention can be effectively achieved. It is determined, but in the case of one kind, as the amount thereof, in the case of two or more kinds, as the sum thereof, preferably 1 × 10 ⁻³ to 50 atom%, more preferably 5 × 10 5.
^-3 to 30 atom%, optimally 1 × 10 ^-2 to 10 atom% is desirable.

In addition, the charge injection blocking layer 40 in the present invention.
Hydrogen atoms and / or halogen atoms contained in 5 compensate for dangling bonds existing in the layer and are effective in improving the film quality. The content of hydrogen atoms or halogen atoms or the sum of hydrogen atoms and halogen atoms of 405 in the charge injection blocking layer is preferably 1 to 50 atom%, more preferably 5 to 40 atom%, and most preferably 10 to 30 atom%. It is desirable to set it as%.

In the present invention, the thickness of the charge injection blocking layer 405 is preferably 0.1 to 5 μm, more preferably 0.3 to 4 μm from the viewpoint of obtaining desired electrophotographic characteristics and economical effects. The optimum value is 0.5 to 3 μm.

To form the charge injection blocking layer 405 in the present invention, a vacuum deposition method similar to the method for forming the photoconductive layer described above is adopted.

In order to form the charge injection blocking layer 405 having the characteristics capable of achieving the object of the present invention, as in the photoconductive layer 403, the mixing ratio of the gas for supplying Si and the diluent gas, the gas in the reaction vessel, and the like. It is necessary to appropriately set the pressure, the discharge power, and the support 401.

The flow rate of the diluting gas H ₂ and / or He is appropriately selected in accordance with the layer design, but H ₂ and / or He may be added to the Si supply gas.
In the usual case, it is desirable to control in the range of 1 to 20 times, preferably 3 to 15 times, and optimally 5 to 10 times.

Similarly, the gas pressure in the reaction vessel is appropriately selected according to the layer design, but is usually 0.05 to 10
The pressure is preferably 00 Pa, preferably 0.1 to 500 Pa, and most preferably 0.5 to 100 Pa.

Similarly, the discharge power is appropriately selected in the optimum range according to the layer design, but the discharge power with respect to the gas flow rate for supplying Si is usually 1 to 7 times, preferably 2 times.
It is desirable to set the range of up to 6 times, optimally 3 to 5 times.

Further, the temperature of the support 401 is appropriately selected according to the layer design, but in the normal case,
Preferably from 200 to 350 ° C, more preferably from 230 to
It is desirable to set the temperature to 330 ° C., optimally 250 to 300 ° C.

In the present invention, the charge injection blocking layer 405.
The above-mentioned ranges are mentioned as desirable numerical ranges of the mixing ratio of the dilution gas for forming the, the gas pressure, the discharge power, and the temperature of the support, but these layer preparation factors are not usually independently determined separately. Instead, it is desirable to determine the optimum value for each layer making factor based on mutual and organic relevance to form a surface layer having the desired properties.

In addition, in the image forming apparatus photoreceptor of the present invention, at least aluminum atoms, silicon atoms, hydrogen atoms and / or halogen atoms are provided in the layer thickness direction on the side of the support 401 of the photosensitive layer 402. It is desirable to have the layer regions contained in a non-uniform distribution.

In the photoconductor for an image forming apparatus of the present invention, for the purpose of further improving the adhesion between the support 401 and the photoconductive layer 403 or the charge injection blocking layer 405, for example, Si ₃ N ₄ , SiO ₂ , SiO, or a silicon atom as a host, a hydrogen atom and / or a halogen atom, a carbon atom and / or an oxygen atom, and / or
Alternatively, an adhesion layer formed of an amorphous material containing a nitrogen atom or the like may be provided. Further, a light absorption layer may be provided to prevent the occurrence of an interference pattern due to the reflected light from the support.

Next, the apparatus and film forming method for forming the photosensitive layer will be described in detail.

FIG. 5 is a schematic configuration diagram showing an example of a photoconductor manufacturing apparatus for an image forming apparatus by a high frequency plasma CVD method (hereinafter referred to as "RF-PCVD") using an RF band as a power supply frequency. The structure of the manufacturing apparatus shown in FIG. 5 is as follows.

This apparatus is roughly classified into a deposition apparatus 510.
0, a source gas supply device 5200, and an exhaust device (not shown) for reducing the pressure inside the reaction vessel 5111. A cylindrical support 5112, a heater 5113 for heating the support, a source gas introduction pipe 5114 are installed in a reaction vessel 5111 in the deposition apparatus 5100, and a high frequency matching box 5115 is further connected.

The source gas supply device 5200 is made of SiH ₄ ,
Cylinders 5221 to 5226 for raw material gases such as GeH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , and PH ₃ and valves 5231 to 52
36, inflow valves 5241 to 5246, outflow valve 52
51-5256 and mass flow controller 5211
˜5216, and each source gas cylinder is connected to a gas introduction pipe 5114 in a reaction vessel 5111 via an auxiliary valve 5260.

The deposited film can be formed using this apparatus, for example, as follows.

First, a cylindrical support 5112 is installed in the reaction container 5111, and the reaction container 5111 is evacuated by an exhaust device (not shown) (for example, a vacuum pump). Continuing,
The cylindrical support 511 is heated by the heater 5113 for heating the support.
The temperature of 2 is controlled to a predetermined temperature of 200 to 350 ° C.

The source gas for forming the deposited film is supplied to the reaction vessel 511.
In order to make it flow into 1, the gas cylinder valves 5231-5
236, make sure that the leak valve 5117 of the reaction vessel is closed, and check the inflow valves 5241 to 524.
6, outflow valves 5251 to 5256, auxiliary valve 526
Make sure 0 is open, then first open main valve 5
118 is opened and the reaction vessel 5111 and the gas pipe 511 are opened.
The inside of 6 is exhausted.

Next, the reading of the vacuum gauge 5119 is about 1 × 10.
^{When the} pressure reaches ⁻³ Pa, the auxiliary valve 5260 and the outflow valves 5251 to 5256 are closed.

After that, each gas is introduced from the gas cylinders 5221 to 5226 by opening the valves 5231 to 5236, and each gas pressure is adjusted to 2 by the pressure regulators 5261 to 5266.
Adjust to kg / cm ² . Next, inflow valves 5241-5
246 is gradually opened to introduce each gas into the mass flow controllers 5211 to 5216.

After the preparation for film formation is completed as described above, each layer is formed by the following procedure.

When the cylindrical support 5112 reaches a predetermined temperature, the necessary ones of the outflow valves 5251 to 5256 and the auxiliary valve 5260 are gradually opened, and a predetermined gas is supplied from the gas cylinders 5221 to 5226.
It is introduced into the reaction vessel 5111 via 114. Next, the mass flow controllers 5211 to 5216 are adjusted so that each raw material gas has a predetermined flow rate. that time,
The opening of the main valve 5118 is adjusted while observing the vacuum gauge 5119 so that the pressure in the reaction vessel 5111 becomes a predetermined pressure of 1000 Pa or less. When the internal pressure is stable, the RF power supply (not shown) having a frequency of 13.56 MHz is set to a desired power, and the high frequency matching box 511 is set.
RF power is introduced into the reaction vessel 5111 through 5 to cause glow discharge. The source energy introduced into the reaction vessel 5111 is decomposed by this discharge energy, and a predetermined deposited film containing silicon as a main component is formed on the cylindrical support 5112. After the desired film thickness is formed, the supply of RF power is stopped and the outflow valve 525
1 to 5256 are closed to stop the gas from flowing into the reaction container 5111, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, a photosensitive layer having a desired multilayer structure is formed.

Needless to say, all the outflow valves other than the necessary gas are closed when forming each layer, and each gas is used in the reaction vessel 5111.
Inside, outflow valves 5251 to 5256 to reaction vessel 511
In order to avoid remaining in the pipe leading to 1, it is necessary to close the outflow valves 5251 to 5256, open the auxiliary valve 5260, and fully open the main valve 5118 to once exhaust the system to a high vacuum. Do accordingly.

Further, in order to make the film formation uniform, it is also effective to rotate the support 5112 at a predetermined speed by a driving device (not shown) while the layers are being formed.

Needless to say, the above-mentioned gas species and valve operation may be changed according to the production conditions of each layer.

Next, a method of manufacturing a photoconductor for an image forming apparatus, which is formed by a high frequency plasma CVD (hereinafter referred to as “VHF-PCVD”) method using a VHF band frequency as a power source, will be described.

RF-PC in the manufacturing apparatus shown in FIG.
A deposition apparatus 5100 according to the VD method is shown in FIG.
By replacing with 100 and connecting to the source gas supply device 5200, the photoconductor manufacturing apparatus for an image forming apparatus having the following configuration by the VHF-PCVD method shown in FIG. 6 can be obtained.

This apparatus is roughly divided into a reaction vessel 6111 having a vacuum-tightened structure and capable of reducing the pressure, a source gas supply apparatus 5200, and an exhaust apparatus (not shown) for reducing the pressure inside the reaction vessel. There is. A cylindrical support 6112 and a heater 611 for heating the support are provided in the reaction vessel 6111.
3, a source gas introduction pipe 6114 and an electrode 6115 are installed, and a high frequency matching back 6116 is further connected to the electrode 6115. Further, the inside of the reaction vessel 6111 is connected to a diffusion pump (not shown) through an exhaust pipe 6121.

The source gas supply device 5200 is made of SiH ₄ ,
Cylinders 5221 to 5226 for raw material gases such as GeH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , and PH ₃ and valves 5231 to 52
36, inflow valves 5241 to 5246, outflow valve 52
51-5256 and mass flow controller 5211
˜5216, and each source gas cylinder is connected to the gas introduction pipe 6114 in the reaction vessel 6111 via the auxiliary valve 5260. In addition, the cylindrical support 611
A space 6130 surrounded by 2 forms a discharge space.

The formation of the deposited film by this apparatus by the VHF-PCVD method can be performed as follows.

First, the cylindrical support 6112 is set in the reaction vessel 6111, and the support 6 is driven by the drive unit 6120.
112 is rotated and the inside of the reaction vessel 6111 is exhausted through an exhaust pipe 6121 by an exhaust device (not shown) (for example, a vacuum pump), and the pressure inside the reaction vessel 6111 is 1 × 10 ⁻³ Pa.
Adjust as follows. Next, the heater 611 for heating the support.
3, the temperature of the cylindrical support 6112 is set to 200 to 350.
Hold at a predetermined temperature of ° C.

A source gas for forming a deposited film is supplied to the reaction vessel 611.
In order to make it flow into 1, the gas cylinder valves 5231-5
236, make sure that the leak valve (not shown) of the reaction vessel 6111 is closed, and check the inflow valve 524.
After confirming that 1 to 5246, the outflow valves 5251 to 5256, and the auxiliary valve 5260 are opened, first, the main valve (not shown) is opened to evacuate the reaction vessel 6111 and the gas pipe (not shown).

Next, the reading of the vacuum gauge (not shown) is about 1 × 10.
^{When the} pressure reaches ⁻³ Pa, the auxiliary valve 5260 and the outflow valves 5251 to 5256 are closed.

Then, each gas is introduced from the gas cylinders 5221 to 5226 by opening the valves 5231 to 5236,
2 kg of each gas pressure by pressure regulators 5261-5266
Adjust to / cm ² . Next, inflow valves 5241 to 524
6 is opened gradually to let each gas flow through the mass flow controller 5
211 to 5216.

After the preparation for film formation is completed as described above, each layer is formed on the cylindrical support 6112 as follows.

When the cylindrical support body 6112 reaches a predetermined temperature, the necessary ones of the outflow valves 5251 to 5256 and the auxiliary valve 5260 are gradually opened, and a predetermined gas is supplied from the gas cylinders 5221 to 5226.
Discharge space 6130 in reaction vessel 6111 via 114
To be introduced. Next, mass flow controllers 5211-5
216 adjusts each source gas so that it has a predetermined flow rate. At that time, the pressure in the discharge space 6130 is 1000
The opening of the main valve (not shown) is adjusted while observing the vacuum gauge (not shown) so that a predetermined pressure of Pa or less is obtained.

When the pressure is stable, the frequency is 105M.
Set the VHF power source (not shown) of Hz to the desired power,
Discharge space 6130 through matching box 6116
VHF electric power is introduced to generate a glow discharge. The discharge space 613 thus surrounded by the support 6112
At 0, the introduced source gas is excited by discharge energy and dissociates, and a predetermined deposited film is formed on the cylindrical support 6112. At this time, in order to make the layer formation uniform, the support rotation motor 6120 rotates the support at a desired rotation speed.

After the desired film thickness is formed, the supply of VHF power is stopped, the outflow valves 5251 to 5256 are closed to stop the gas flow into the reaction vessel 6111, and the formation of the deposited film is completed.

By repeating the same operation a plurality of times, a photosensitive layer having a desired multilayer structure is formed.

Needless to say, all the outflow valves other than the necessary gas were closed when forming each layer, and each gas was stored in the reaction vessel 6111.
In order to avoid remaining in the pipe from the outflow valves 5251 to 5256 to the reaction vessel 6111, the outflow valves 5251 to 5256 are closed, the auxiliary valve 5260 is opened, and the main valve (not shown) is fully opened to open the system. If necessary, the operation of once evacuating to high vacuum is performed.

Needless to say, the above-mentioned gas species and valve operation may be changed according to the production conditions of each layer.

In either method, the temperature of the support during the formation of the deposited film is particularly 200 to 350 ° C., preferably 23.
The temperature is preferably 0 to 330 ° C, more preferably 250 to 300 ° C.

The heating method of the support may be any heating element having a vacuum specification, and more specifically, an electric resistance heating element such as a wound heater of a sheath heater, a plate heater, a ceramic heater, a halogen lamp, an infrared ray. Examples thereof include a heat-radiating lamp heating element such as a lamp, and a heating element by a heat exchange means using liquid, gas or the like as a heating medium. As the surface material of the heating means, metals such as stainless steel, nickel, aluminum and copper, ceramics, heat resistant polymer resin and the like can be used.

In addition to the above, a method in which a container dedicated to heating is provided in addition to the reaction container, and after heating, the support is conveyed into the reaction container in vacuum is used.

Further, particularly in the VHF-PCVD method,
The pressure of the discharge space is preferably 0.1 Pa or more 10
It is desirable to set 0 Pa or less, more preferably 0.5 Pa or more and 50 Pa or less, and most preferably 1 Pa or more and 10 Pa or less.

In the VHF-PCVD method, the size and shape of the electrode provided in the discharge space may be any as long as they do not disturb the discharge, but in practice a cylindrical shape having a diameter of 1 mm or more and 10 cm or less is preferable. At this time, the length of the electrode can be arbitrarily set as long as the electric field is uniformly applied to the support.

Any material may be used as the material of the electrode as long as it has a conductive surface. For example, stainless steel, Al, Cr, Mo, Au, In, Nb, Te, V,
Metals such as Ti, Pt, Pb, and Fe, alloys of these, or glass, ceramics, plastics whose surface is treated to be conductive, etc. are usually used. Furthermore, the electrode surface may be covered with a dielectric such as ceramics, if necessary.

Hereinafter, the charging device and the image forming apparatus according to the present invention will be described in more detail by giving numerical values. The present invention is not limited to these examples.

Two proximity charging members each having an inorganic resistance layer provided on an aluminum electrode were prepared as the charging members of the contact charging device.

The inorganic resistance layer was applied by spray coating with a mixed solution of tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , water, alcohol, hydrochloric acid, and titanium oxide conductive material, and then heated to 40 to 90 ° C. It was dried to obtain a dried gel body. Furthermore, it heated at 300 degreeC and formed the Si-O inorganic resistance layer of 3 micrometers.

Using the apparatus for producing a photoreceptor for an image forming apparatus by the RF-PCVD method shown in FIG. 5, a charge injection blocking layer, a photoconductive layer, and a surface were formed on a mirror-finished aluminum cylinder under the conditions shown in FIG. A photoreceptor consisting of layers was prepared.

The produced proximity charging member and the photoconductor were set in an image forming apparatus using two proximity charging members as shown in FIG. 1 (Canon NP6060 was modified for testing). <Comparative Example 1> 1 manufactured under the same conditions as in Example 1 above
FIG. 10 shows one proximity charging member and a photosensitive member, and a conventional image forming apparatus using one proximity charging member (N Canon
P6150 was modified for testing).

Using the image forming apparatus of Example 1 and Comparative Example 1, the charging ability, the durability of the proximity charging member, and the image quality were evaluated.

Proximity charging members 102, 103 and 902
The voltage applied to the DC voltage is 1.0 kV _dc , the oscillating voltage V _ac is 1005 Hz, and the proximity charging member 10 is used.
Oscillation voltage V _ac supplied to 2, 103 has the same phase and the same peak-to-peak voltage V _pp , and the process speed is 300 mm.
/ Sec. In addition, the proximity charging member 10 of the first embodiment
The distance between 2 and 103 was 30.0 mm.

The charging ability is determined by the proximity charging members 102 and 103.
And the developing device position 108 when the peak-to-peak voltage V _pp of the vibration voltage V _ac applied to the proximity charging member 902 is changed,
908 (refers to the position where the photosensitive drums 101 and 901 face the developing sleeves 108 and 908, respectively, the same applies hereinafter)
The dark area potential was measured and evaluated. As a result, in order to obtain the same dark part potential at the developing device positions 108 and 908, the first embodiment is used.
In the image forming apparatus of No. 3, the peak-to-peak voltage was applied at 3 kV _pp, whereas in the image-forming apparatus of Comparative Example 1, it was necessary to apply the peak-to-peak voltage of about 1.3 times 4 kV _pp .

Regarding the image quality, the peak-to-peak voltage V _pp is adjusted so that the same dark part potential is obtained at the developing device positions 108 and 908 under the same conditions as the above-mentioned evaluation of the charging ability, and an image is displayed and visually observed. The image quality such as minute image density unevenness was evaluated. As a result, in the image forming apparatus of Example 1, as compared with the image forming apparatus of Comparative Example 1, it was possible to obtain an image with good image quality without minute image density unevenness.

With respect to the durability of the proximity charging member, the peak-to-peak voltage is adjusted so that the same dark part potential can be obtained at the developing device positions 108 and 908 under the same conditions as the above-mentioned evaluation of the charging ability, and the durability of 100,000 sheets is obtained. A printing test was conducted and the image quality was visually evaluated. As a result, in the image forming apparatus of Comparative Example 1, the above-mentioned minute image density unevenness became more conspicuous after printing 100,000 sheets, and deterioration of the image quality was recognized, whereas the image forming of Example 1 was performed. The apparatus showed almost no change in the image quality before and after the printing durability test of 100,000 sheets.

As described above, according to the present invention, it was found that an image forming apparatus excellent in charging ability, durability and image quality can be obtained. Example 2 Various photoconductors were prepared under the same conditions as in Example 1 except that the mixing ratio of SiH ₄ and H _{2 in the} photoconductive layer and the discharge power were changed.

On the other hand, on a glass substrate (Corning 7059) set on a cylindrical sample holder and a Si wafer, an a- film having a film pressure of about 1 μm was formed under the conditions for forming the photoconductive layer.
A Si film was deposited. A comb-shaped electrode of Cr is vapor-deposited on the volume film on the glass substrate, and the characteristic energy (Eu) and the localized level density (DOS) of the exponential tail are measured by CPM to obtain Si.
The amount of hydrogen contained in the deposited film on the wafer was measured by FTIR.

Using the image forming apparatus similar to that of Example 1, the image quality of each of the various photoconductors thus produced was examined under the same conditions as in Example 1 and after the endurance. <Comparative Example 2> Using various image bearing members produced under the same conditions as in Example 2 and using the same image forming apparatus as in Comparative Example 1, the image quality at the initial stage and after durability was examined under the same conditions as in Comparative Example 1. did.

FIG. 7 shows the image quality evaluation results of Eu, DOS, and initial and endurance of each photoconductor in Example 2 and Comparative Example 2.
8A and 8B, and FIGS. 8A and 8B. The image quality rank was evaluated by classifying it into four grades of 1: very good, 2: good, 3: practically no problem, and 4: practically difficult.

The hydrogen content of each sample was 1
It was between 0 and 30 atom%.

As is clear from these figures, the characteristic energy of the exponential tail obtained from the sub-bandgap optical absorption spectrum is 50 to 60 meV, and the density of localized states is 1 × 10 ¹⁴ to 1 × 10 ¹⁶ cm ^−3. It was found that excellent image quality can be obtained both at the initial stage and after the endurance by using the image forming apparatus of the present invention with the photoconductor of No. 1. Example 3 Using the manufacturing apparatus shown in FIG. 5, a photoconductor for an image forming apparatus was manufactured under the manufacturing conditions shown in FIG. At this time, Eu and DOS of the photoconductive layer are 55 meV and 2 respectively.
It was × 10 ¹⁵ cm ^-3 .

Using this photoconductor, the applied voltage conditions of the oscillating voltage V _ac are a frequency of 2000 Hz and the peak-to-peak voltage of 3 kV _pp, and the phase of the oscillating voltage V _ac supplied to each of the proximity chargers 102 and 103 is shifted by 180 degrees. Except for the above, except that the image quality was examined under the same conditions as in Example 1 after the initial stage and after durability, an image with good image quality similar to that in Example 1 was obtained. Example 4 Using the manufacturing apparatus shown in FIG. 5, a photoconductor for an image forming apparatus was manufactured under the manufacturing conditions shown in FIG. At this time, Eu and DOS of the photoconductive layer are 50 meV and 8 ×, respectively.
It was 10 ¹⁴ cm ^-3 .

Using this photoconductor, each proximity charger 10
The phase of the oscillating voltage V _ac supplied to 2 and 103 is shifted 180 degrees, and the distance between the proximity chargers 102 and 103 is set to 40.0.
When the image quality at the initial stage and after the durability test were examined under the same conditions as in Example 1 except that the thickness was set to mm, an image with good image quality similar to that in Example 1 was obtained. Example 5 A photoconductor for an image forming apparatus was produced under the production conditions shown in FIG. 15 using the apparatus for producing a photoconductor for an image forming apparatus shown in FIG. Eu and DOS of the photoconductive layer at this time are
They were 60 meV and 5 × 10 ¹⁵ cm ⁻³ , respectively.

Using this photoconductor, each proximity charger 10
The peak-to-peak voltage of the oscillating voltage V _ac to the second charger is 3.5 kV _pp , and the peak-to-peak voltage of the oscillating voltage V _ac to the proximity charger 103 is 2.
When the image quality at the initial stage and after the durability test were examined under the same conditions as in Example 1 except that 7 kV _pp was set, an image with good image quality similar to that in Example 1 was obtained. <Sixth Embodiment> In the first embodiment, the process speed is set to 2
30 mm / sec, the applied voltage conditions of the oscillating voltage V _ac were set to a peak-to-peak voltage of 3 kV _pp , and a frequency of 1008 Hz, except that
When the image quality at the initial stage and after the durability test were examined under the same conditions as in Example 1, an image with good image quality similar to that in Example 1 was obtained. <Embodiment 7> In Embodiment 1, the process speed is set to 2
The same as Example 1 except that the applied voltage condition of the vibration voltage V _ac is 30 mm / sec, the peak-to-peak voltage is 3 kV _pp , and the phase of the vibration voltage V _ac supplied to each of the proximity chargers 102 and 103 is shifted by 150 degrees. When the image quality at the initial stage and after the durability test were examined under various conditions, an image with good image quality similar to that of Example 1 was obtained. <Embodiment 8> In Embodiment 1, the process speed is set to 2
The image quality was examined under the same conditions as in Example 1 except that the applied voltage condition of the vibration voltage V _{ac was} 30 mm / sec, the peak-to-peak voltage was 2.5 kV _pp , and the frequency was 1008 Hz. An image of good quality similar to that of No. 1 was obtained. <Embodiment 9> Using the apparatus for manufacturing a photoreceptor for an image forming apparatus by the VHF-PCVD method shown in FIG. 6, an aluminum cylinder having a diameter of 108 mm and having a mirror-finished surface was used under the conditions shown in FIG. A photoconductor comprising a charge injection blocking layer, a photoconductive layer and a surface layer was prepared. At this time, Eu and DOS of the photoconductive layer were 52 meV and 7 × 10, respectively.
It was ¹⁴ cm ^-3 .

Using this photoreceptor, the image quality at the initial stage and after the durability test was examined under the same conditions as in Example 1. As a result, an image with good image quality as in Example 1 was obtained. <Example 10> Using the apparatus for manufacturing a photoreceptor for an image forming apparatus shown in FIG. 6, a photoreceptor for an image forming apparatus was manufactured under the manufacturing conditions shown in FIG. Eu and DOS of the photoconductive layer at this time
Were 55 meV and 3 × 10 ¹⁵ cm ⁻³ , respectively.

Using this photoreceptor, the image quality at the initial stage and after the durability test was examined under the same conditions as in Example 3. As a result, an image with good image quality as in Example 1 was obtained. Example 11 A photoconductor for an image forming apparatus was produced under the production conditions shown in FIG. 18 using the apparatus for producing a photoconductor for an image forming apparatus shown in FIG. Eu and DOS of the photoconductive layer at this time
Were 56 meV and 1.3 × 10 ¹⁵ cm ⁻³ , respectively.

Using this photoreceptor, the image quality at the initial stage and after the durability test was examined under the same conditions as in Example 4. As a result, an image with good image quality as in Example 1 was obtained. Example 12 A photoconductor for an image forming apparatus was produced under the production conditions shown in FIG. 19 using the apparatus for producing a photoconductor for an image forming apparatus shown in FIG. Eu and DOS of the photoconductive layer at this time
Were 55 meV and 5 × 10 ¹⁵ cm ⁻³ , respectively.

Using this photoreceptor, the image quality at the initial stage and after the durability test was examined under the same conditions as in Example 5. As a result, an image with good image quality as in Example 1 was obtained. <Example 13> An aluminum cylinder was used as a substrate, and a 5% methanol solution of alkoxymethylated nylon was applied thereto by a dipping method to form an undercoat layer (intermediate layer) having a film thickness of 1 µm.

Then, 10 parts of titanyl phthalocyanine pigment (parts by weight, the same applies hereinafter), 8 parts of polyvinyl butyral and 50 parts of cyclohexanone were mixed and dispersed for 20 hours in a sand mill using 100 parts of glass beads having a diameter of 1 mm. Methyl ethyl kent 70-120 was added to this dispersion.
(Appropriately) parts are added and coated on the undercoat layer, and the mixture is applied at
It was dried for a minute to form a 0.2 μm charge generation layer.

Next, on this charge generation layer, styryl compound 10 having the structural formula shown in FIG. 20 and 10 parts of bisphenol Z type polycarbonate were dissolved in 65 parts of monochlorobenzene. This solution was applied onto a substrate by a dipping method and dried with hot air at 120 ° C. for 60 minutes to form a 20 μm thick charge transport layer.

Next, a surface layer having a thickness of 1.0 μm was provided on the charge transport layer by the following method.

High melting point polyethylene terephthalate (A) obtained by using terephthalic acid as an acid component and ethylene glycol as a glycol component [intrinsic viscosity of 0.
70 dl / g, melting point 258 ° C (1 using a differential calorimeter)
The measurement was performed at a heating rate of 0 ° C./min. Also, the measurement sample is 5 mg, and the polyester resin to be measured is 2
After melting at 80 ° C., it was rapidly cooled with ice water at 0 ° C. to prepare. The same applies to the following examples), glass point transfer temperature 70 ° C.] 1
Dissolve 00 parts and 30 parts of epoxy resin (B) [epoxy equivalent 160: aromatic ester type: trade name: Epicoat 190P (produced by Yuka Shell Epoxy Co., Ltd.)] in 100 ml of a mixture of phenol and tetrachloroethane (1: 1). Let Then, 3 parts of triphenylsulfonium hexafluoroantimonate (C) was added as a photopolymerization initiator to prepare a resin composition solution.

As the light irradiation conditions, a 2 kW high-pressure mercury lamp (30 W / cm) was irradiated at 130 ° C. for 8 seconds from a position 20 cm away to cure the light. Comparative Example 3 A photoconductor similar to that of Example 13 was prepared except that the protective layer of the photoconductor used in Example 13 was not used. Comparative Example 4 Instead of the protective layer used in Example 13, the same binder as used in the charge transport layer was used, and 4 parts of bisfail Z-type polycarbonate, 70 parts of monochlorobenzene, and 1 part of PTFE fine powder were sand-milled. A coating liquid was prepared by mixing and dispersing for 10 hours. A photoreceptor was prepared in the same manner as in Example 13 except that this coating solution was applied onto the charge transport layer by a spray method so as to have a film thickness of 1.0 μm to form a photoreceptor protective layer.

Using the photoconductors produced in Example 13 and Comparative Examples 3 and 4, the image quality after the initial stage and after the durability test was examined in the same manner as in Example 1. As a result, it was confirmed that the image quality after the durability test was particularly good. In comparison, the photoreceptors of Comparative Examples 3 and 4 were found to be deteriorated,
It was found that excellent image quality can be obtained both in the initial stage and after the endurance by using the image forming apparatus of the present invention, in which the charged body is the photoreceptor containing the high melting point polyester resin and the cured resin. .

[0256]

As described above, according to the present invention,
By providing a plurality of proximity charging members and adjusting the frequency and / or phase of the oscillating voltage applied to each proximity charging member, it has become possible to stably obtain a high-quality image.

In particular, it is possible to prevent minute image density unevenness caused by an oscillating voltage applied to the proximity charging member, and it is possible to easily obtain a high-contrast image, and durability of the proximity charging member. Was able to improve.

[Brief description of drawings]

FIG. 1 is a schematic diagram illustrating configurations of a charging device and an image forming apparatus according to a first exemplary embodiment.

FIG. 2A is a side view schematically showing the configuration of a charging member. FIG. 3B is a front view schematically showing the configuration of the charging member.

FIG. 3 is a schematic diagram showing a layer structure of a photoconductor.

FIG. 4A to FIG. 4D are schematic diagrams showing layer configurations of different photoconductors.

FIG. 5 is a schematic explanatory view of an example of an apparatus for forming a light receiving layer of a photoconductor, which is a manufacturing apparatus by a glow discharge method using a high frequency of RF band.

FIG. 6 is a schematic explanatory view of an example of an apparatus for forming a photoconductive layer of a photoconductor, which is a manufacturing apparatus by a glow discharge method using a VHF band high frequency.

FIG. 7A is a diagram showing the relationship between the image quality and the characteristic energy (Eu) of the back end of the photoconductive layer before endurance.
FIG. 3B is a diagram showing the relationship between the image quality and the characteristic energy (Eu) of the back end of the photoconductive layer after the endurance.

FIG. 8A is a localized density of states (D) of the photoconductive layer before endurance.
FIG. 6 is a diagram showing a relationship between OS) and image quality. FIG. 6B is a diagram showing the relationship between the localized density of states (DOS) of the photoconductive layer after durability and the image quality.

FIG. 9 is a schematic diagram showing a configuration of a conventional contact charging device and an image forming apparatus.

FIG. 10 is a schematic diagram showing configurations of a conventional proximity charging device and an image forming apparatus.

FIG. 11 is a diagram showing a method for obtaining a metal oxide film free time.

FIG. 12 is a view showing the manufacturing conditions of the photoconductor in Example 1.

FIG. 13 is a view showing the manufacturing conditions of the photoconductor in Example 3.

FIG. 14 is a view showing the manufacturing conditions of the photoconductor in Example 4.

FIG. 15 is a view showing the manufacturing conditions of the photoconductor in Example 5.

FIG. 16 is a diagram showing conditions for producing a photoconductor in Example 9.

FIG. 17 is a view showing the manufacturing conditions of the photoconductor in Example 10.

FIG. 18 is a view showing the manufacturing conditions of the photoconductor in Example 11.

FIG. 19 is a view showing the manufacturing conditions of the photoconductor in Example 12.

20 is a diagram showing the structural formula of a styryl compound that constitutes the charged oil tank layer in Example 13. FIG.

[Explanation of symbols]

101 Charged Member (Image Bearing Member, Photosensitive Member, Photosensitive Drum) 102, 103 Proximity Charging Member 102-1, 103-1 Electrode 102-2, 103-2 Resistive Layer 104, 105 Power Supply 106 Bookbinding Device (Controller) 107 Laser Beam printer Light 108 Development sleeve 109 Transfer material 110 Transfer roller 111 Cleaning blade 200 Proximity charging member 201 Support 202 Low resistance layer 203 Spacer 204 Charged member 300 OPC photoconductor 301 Support 302 Photosensitive layer 303 Charge generation layer 304 Charge transport layer 305 Intermediate Layer 306 Protective Layer or Surface Layer 400 a-Si Photoreceptor 401 Support 402 Photosensitive Layer 403 Photoconductive Layer 404 Surface Layer 404a Free Surface 405 Charge Injection Blocking Layer 406 Charge Generation Layer 407 Charge Transport Layer

Claims (9)

[Claims] 1. A charging device in which a charging member is disposed so as to face a movable charged surface of a charged body in a non-contact state, and a voltage is applied to the charging member to charge the charged surface. At least two charging members arranged on the upstream side and the downstream side in the moving direction of the surface to be charged, and a control device for individually controlling the charging voltage applied to these charging members, respectively. Charging device characterized by. 2. The charging device according to claim 1, wherein the control device applies oscillating voltages of different phases to the plurality of charging members. 3. The charging device according to claim 1, wherein the control device applies an oscillating voltage having a different amplitude to each of the plurality of charging members. 4. The control device changes a frequency of an oscillating voltage applied to the plurality of charging members according to a change in a moving speed of the surface to be charged, wherein the control device changes the frequency of the oscillating voltage. The charging device according to any one of 3 above. 5. The control device changes the phase difference of the oscillating voltage applied to the plurality of charging members according to a change in the moving speed of the surface to be charged, wherein the control device changes the phase difference. Item 5. The charging device according to any one of Items 4. 6. The control device changes the amplitude of an oscillating voltage applied to the plurality of charging members according to a change in the moving speed of the surface to be charged, according to any one of claims 3 to 3. The charging device according to any one of 5 above. 7. A charged body having a surface to be charged on its surface, the charging device according to claim 1, and the surface to be charged charged by the charging device exposed to electrostatic. An exposure device for forming a latent image; a developing device for forming a toner image by attaching a developer to the electrostatic latent image; and a transfer device for transferring the toner image formed on the surface to be charged onto a transfer material. An image forming apparatus comprising: 8. A photoreceptive layer in which the member to be charged has a conductive support and a photoconductive layer containing a non-single-crystal material containing a silicon atom as a matrix and at least one of a hydrogen atom and a halogen atom. And a photoconductive layer containing 10 to 30 atomic% of hydrogen, and a characteristic energy of an exponential skirt obtained from a light absorption spectrum at least in a portion where light is incident is 50 to 60 meV.
And the localized density of states is 1 × 10 ¹⁴ to 1 × 10 ¹⁶ cm
The image forming apparatus according to claim 7, wherein the image forming apparatus is ^-3 . 9. The image forming apparatus according to claim 7, wherein the member to be charged is an electrophotographic photosensitive member including a conductive support, a high melting point polyester resin and a cured resin.