JP3128186B2 - Electrophotographic equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electronic device having a process in which a cylindrical photoreceptor is rotated and rotated to continuously perform charging, exposure, development, transfer, and cleaning, and a fixing process in conjunction therewith. The present invention relates to a dehumidifying device as an environmental stabilizing device for a photographic device.

More specifically, environmental stability of a high quality electrophotographic apparatus which can provide good image quality in a high humidity environment and stable cleaning performance by using a directional heating element which is brought close to the outside of an electrophotographic photosensitive member. The present invention relates to a dehumidifying device as a gasifier.

[0003]

[Prior art]

1. 2. Description of the Related Art With the recent increase in the amount of information processing, the use of electrophotographic devices such as copiers and laser beam printers has been diversified.

[0004] Under these circumstances, first of all, these electrophotographic apparatuses are improved in function to withstand use in a field where the environmental fluctuation is large, specifically, dew condensation in a high humidity environment or a rapid temperature fluctuation. In such a case, there is a demand for an improvement in performance in which so-called "high humidity image deletion" is difficult. Second, reduction of power consumption is required from an ecological viewpoint.
Specifically, removal of a dehumidifying heater provided in or near a photoconductor of a conventional electrophotographic apparatus or reduction in power consumption is known. Such heaters usually have a capacity of about 15 W to 80 W, which does not always give the impression of a large amount of electric power. However, in most cases, the heater is always energized even at night, and the amount of power consumed per day is the entire electrophotographic apparatus. Power consumption reaches 5 to 15%. Thirdly, there is a demand for economy, and it is required that the electrophotographic apparatus itself be inexpensive and have high productivity and operation rate while maintaining high quality and reliability. Specifically, it is required that the stop time due to the regular maintenance is short and that it can be used immediately after the power switch is turned on.

The electrophotographic photoreceptor used in recent years has a high surface hardness in order to increase the number of printing presses, and the surface of the photoreceptor is subject to humidity due to the corona product from the charger due to repeated use. It is sensitive and easily adsorbs moisture, which causes a lateral flow of charges on the surface of the photoreceptor, and has a disadvantage of causing a deterioration in image quality called an image flow.

In order to prevent such image deletion, heating by a heater as described in Japanese Utility Model Publication No. 1-32055 or a magnet roller as described in Japanese Patent Publication No. 2-38956 is used. A method in which a corona product is removed by rubbing the surface of a photoreceptor with a brush formed from a magnetic toner, and a method in which a corona product is rubbed by rubbing the surface of a photoreceptor with an elastic roller as described in JP-A-61-100780. And other methods have been used.

However, the method of rubbing the surface of the photoreceptor reduces the number of printings except for the amorphous silicon photoreceptor having extremely high hardness, and the constant heating by the heater causes an increase in power consumption as described above.

As for an external heater heating system similar to the present invention, Japanese Patent Application Laid-Open No. Sho 59-111179 discloses that a heating member is used to locally and instantaneously heat a photosensitive member. Japanese Patent Application Laid-Open No. Sho 62-278577 discloses a heating method in which a cleaning blade is used for heating, a hot air is blown to a photosensitive member between a cleaning step and a charging step, and a corotron is heated in a charging step. However, there is no disclosure about improvement of an image density unstable element caused by a temperature change of the photoconductor.

[0009] Under these circumstances, there is a need for a new dehumidifying device as an environment stabilizing device for an electrophotographic apparatus and an electrophotographic image forming method.

FIG. 1 is a schematic view showing an example of an image forming process of a copying machine, in which a photoreceptor 101 rotates in an arrow X direction. Around the photosensitive member 101 whose temperature is controlled by the planar inner surface heater 123, a main charger 102, an electrostatic latent image forming portion 103, a developing device 104, the transfer paper supply system 10
5. Transfer charger 106 (a), separation charger 106
(B), a cleaner 107, a transfer paper transport system 108, a static elimination light source 109, and the like are provided.

Hereinafter, the image forming process will be described with reference to a specific example. The photosensitive member 101 is uniformly charged by applying a high voltage of +6 to 8 kV by the main charger 102. On the other hand, the light emitted from the light source lamp 110
The document 112 placed on the document 11 is irradiated, reflected by the document 112, reflected by the reflection mirrors 113, 114, 115, converged by the lens 118 of the lens unit 117, and passed through the mirror 116 to form an electrostatic latent image. The laser light guided and projected at the portion 103 forms an electrostatic latent image on the photoconductor 101. Negative polarity toner is supplied from the developing device 104 to the electrostatic latent image to form a toner image.

On the other hand, the leading edge timing is adjusted by the registration roller 122 through the transfer paper supply system 105,
The transfer material P supplied in the direction of the photoconductor 101 is +7 to 8 kV
Transfer charger 106 (a) to which a high voltage of
In the gap 01, a positive electric field having a polarity opposite to that of the toner is applied from the back surface, whereby the negative polarity toner image on the surface of the photoconductor 101 is transferred to the transfer material P. 12-14kVp
The toner is transferred to the transfer material P by the separation charger 106 (b) to which a high AC voltage of 300 to 600 Hz is applied, and the fixing device (not shown) passes through the transfer paper conveyance system 108.
And the toner image is fixed and discharged out of the apparatus.

The toner remaining on the photoreceptor 101 is scraped off by a cleaning blade 121 of a cleaner unit 107, and the remaining electrostatic latent image is removed by a light source 109.
Will be erased by Then, the photoreceptor is charged again with a positive voltage by the main charger 102, and the same process is repeated. In this example, the temperature of the photoreceptor 101 is controlled by the planar inner surface heater 123 and is maintained at a constant temperature, thereby obtaining a dehumidifying effect. (1) Organic Photoconductor (OPC) In recent years, various organic photoconductive materials have been developed as photoconductive materials for electrophotographic photoreceptors. In particular, function-separated photoconductors having a charge generation layer and a charge transport layer laminated thereon have already been developed. It has been put to practical use and installed in copiers and laser beam printers.

However, one of the major drawbacks of these photoconductors is that their durability is generally low. Durability can be broadly classified into durability of electrophotographic properties such as sensitivity, residual potential, charging ability, and image blur, and mechanical durability such as abrasion of the photoreceptor surface due to rubbing and scratching. It is a major factor in determining body life.

Among them, the durability of the electrophotographic physical properties, particularly the image blur, is related to ozone generated from a corona charger,
The active substances such as NO _x, it is known that the charge-transporting material contained in the photosensitive member surface layer is caused to deteriorate.

The mechanical durability is caused by the fact that transfer paper, a cleaning member such as a blade / roller, toner and the like physically contact the photosensitive layer and rub against the photosensitive member. Are known.

[0017] In order to improve the durability of the electrophotographic properties surface, ozone, by the active substances such as NO _x, it is important to use hard to deteriorate the charge transporting material, the oxidation potential in the charge transport layer of the photoreceptor It is known to select charge transport materials with high Also, to increase mechanical durability,
It is important to increase the lubricity of the surface to reduce friction in order to withstand rubbing by paper and cleaning members, and to improve the surface separation and formation in order to prevent toner filming and fusing. It is known that a lubricant such as a fluororesin powder, fluorinated graphite, or a polyolefin resin powder is blended in the surface layer. However, the wear is significantly reduced and the ozone, the hygroscopic material generated by NO _x or the like active substance deposited on the surface of the photoreceptor, the surface resistance of the photosensitive member surface is lowered as a result of moisture, the surface charge is moved laterally ,
There is a problem that so-called image deletion occurs. (2) Amorphous silicon-based photoreceptor (a-Si) In electrophotography, a photoconductive material for forming a photosensitive layer in the photoreceptor has a high sensitivity and an SN ratio [photocurrent (Ip)
/ Dark current (Id)], has an absorption spectrum suitable for the spectral characteristics of the electromagnetic wave to be irradiated, has a fast light response, has a desired dark resistance value, and is harmless to the human body during use. Characteristics are required. In particular, in the case of an electrophotographic photoreceptor incorporated in an electrophotographic apparatus used in an office as an office machine, the above-mentioned non-polluting property at the time of use is important.

Hydrogenated amorphous silicon (hereinafter referred to as “a-Si:
H "). For example, Japanese Patent Publication No. 60-350
No. 59 describes an application as a photoconductor for electrophotography.

Generally, such an electrophotographic photosensitive member is prepared by heating a conductive support to 50 ° C. to 400 ° C. and depositing the conductive support on the support by a vacuum deposition method, a sputtering method, an ion plating method, CVD method, photo CVD method, plasma CVD
A photoconductive layer made of a-Si is formed by a film forming method such as a method. Among them, a plasma CVD method, that is, a method in which a raw material gas is decomposed by direct current, high frequency, or microwave glow discharge to form an a-Si deposited film on a support has been put to practical use as a suitable method.

In JP-A-54-83746, a conductive support and a-Si containing a halogen atom as a constituent element (hereinafter referred to as "a-Si: X").
An electrophotographic photoconductor comprising a photoconductive layer has been proposed.
In this publication, a-Si contains 1 to 4 halogen atoms.
By including 0 atomic%, heat resistance is high, and good electrical and optical characteristics can be obtained as a photoconductive layer of an electrophotographic photoreceptor.

Japanese Patent Application Laid-Open No. 57-11556 discloses that a photoconductive member having a photoconductive layer composed of an a-Si deposited film has an electrical property such as a dark resistance value, a photosensitivity, and a photoresponsive property. In order to improve the use environment characteristics such as optical and photoconductive properties and moisture resistance, as well as the stability over time, silicon atoms and carbon are deposited on a photoconductive layer composed of an amorphous material based on silicon atoms. A technique of providing a surface barrier layer made of a non-photoconductive amorphous material containing atoms is described.

Further, Japanese Patent Application Laid-Open No. 60-67951 describes a technique relating to a photoconductor in which a light-transmitting insulating overcoat layer containing amorphous silicon, carbon, oxygen and fluorine is laminated. 62-168161
Japanese Patent Application Laid-Open Publication No. H11-163,887 describes a technique using an amorphous material containing silicon atoms, carbon atoms, and 41 to 70 atomic% of hydrogen atoms as constituent elements as a surface layer.

Furthermore, 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 by using a-Si: H of 1.7 for the photoconductive layer, a high-sensitivity and high-resistance electrophotographic photoconductor can be obtained.

On the other hand, Japanese Patent Application Laid-Open No. 60-95551 discloses that in order to improve the image quality of an amorphous silicon photoreceptor, the temperature near the photoreceptor surface is maintained at 30 to 40.degree. By performing such an image forming process, there is disclosed a technique for preventing a reduction in surface resistance due to the adsorption of moisture on the surface of a photoreceptor and an image deletion caused thereby.

These techniques have improved the electrical, optical and photoconductive properties of the electrophotographic photoreceptor and the environmental properties of use, and the image quality has been improved accordingly.

[0026]

As described above, in order to extend the life of a photoreceptor using any of the photoconductive materials, it is necessary to heat the photoreceptor in a high humidity environment. is there.

However, there is a social demand for efficient and quick dehumidification of the photoreceptor, because the power required for heating is from the viewpoint of resource protection and energy saving, the energization of the heater at night is strengthened for safety and reliability standards, and the dehumidification of the photoreceptor is performed quickly. Is growing.

Conventionally, the drum heater is energized even during the night when the copying machine is not used so as to prevent the ozone product generated by the corona discharge of the charger from adhering to the surface of the photoreceptor, thereby preventing the image flow from occurring. I was However, if the copying machine is not energized at night as much as possible to save resources and power, continuous copying will gradually increase the temperature around the photoconductor in the copier, and the charging capability of the photoconductor will increase accordingly. Has caused a problem that the chargeability, that is, the surface potential changes, and the image density changes during copying.

Therefore, when designing an electrophotographic apparatus or an electrophotographic image forming method, the electrophotographic photoreceptor has a comprehensive property such as electrophotographic properties and mechanical durability so as to solve the above-mentioned problems. It is necessary to improve the dehumidifying device and the dehumidifying method at the same time as the improvement from the above viewpoints.

[0030]

SUMMARY OF THE INVENTION It is an object of the present invention to efficiently dehumidify a conventional dehumidifier constituted by an inefficient heat source as described above by combining a novel photoreceptor and a novel heat source to give an image quality. The purpose of the present invention is to solve various problems such as image deletion.

That is, the main object of the present invention is to heat and dehumidify very quickly by a heat transfer structure from a novel heating element so that a high-quality image can be obtained even in high humidity or after a long pause. To

[0032] It is a second object, by strictly controlling the heat source to provide a partial heat amount required to only the necessary heating, suppressing heat transfer to did need to be heated portion The second problem is to solve the conventional problems of uneven pitch due to thermal eccentricity of the developing sleeve and poor cleaning due to waste toner blocking in the cleaner.
For the purpose.

A third object of the present invention is to solve the problem of energy saving by heating and dehumidifying only necessary portions by a heat transfer structure from a novel heating element.

As a fourth object, a power supply mechanism such as a slip ring is conventionally required for disposing a heat source on the inner surface of the rotating cylindrical photoconductor, thereby solving the problem of increasing the cost of the electrophotographic apparatus main body. The purpose is to do so.

[0035]

As means for solving the above-mentioned problems, the present inventors have used a heater which rises in temperature from several seconds to several hundred seconds to several hundred degrees Celsius, and has a small temperature dependency. It has been found that by using a photosensitive member having excellent surface heat resistance, dehumidification can be performed under limited conditions, and extremely suitable image stabilization can be achieved. Hereinafter, an important configuration of the present invention will be described. (1) Heating Element and Electrophotographic Apparatus A suitable heater used in the present invention has a high temperature rising speed, a second high output, a third directionality in heat transfer or heat radiation, and a fourth direction. It is required to be small, thin, high in mechanical accuracy, and fifthly, inexpensive.

More specifically, a device in which an electric heating element such as a nichrome wire is provided on the surface of an elongated plate-like substrate made of alumina ceramics, etc. For example, it is preferable to use an electric heating element made of a silver-palladium alloy and having a long terminal formed at both ends of a long and thin heating section, and the surface of the heating section coated with a glassy protective layer.
Hereinafter, this heating element heater is referred to as a ceramic heater.

The heating element will be described more specifically with reference to FIGS. 9 (a), 9 (b), 9 (c) and 9 (d).

FIG. 9A is a top view of a ceramic heating element (hereinafter referred to as an external heater A) as viewed from above, and FIG.
Is a cross-sectional view.

Reference numeral 901 denotes a base, 902 denotes an electric heating element provided on the base 901, and 903 denotes a protective film. The base 901 is made of mullite ceramic and has a length of 36.
It forms an elongated flat plate having a thickness of 0 mm, a width of 8 mm, and a thickness of 1 to 2 mm. The mullite has a chemical composition of Al ₂ O ₃ .2SiO ₂ , has intermediate properties between ceramics and glass, has a thermal conductivity of about half that of alumina ceramics, is easy to process, and has sufficient mechanical strength. is there.

The electric heating element 902 is made of, for example, a silver / palladium alloy powder printed on a substrate 901 and baked. The central heating section 906 has an elongated heating section 906, and terminal sections 904 are formed at both ends of the heating section. Further, a conductive film 90 of silver or the like
5, and a protective film such as glass is formed on the surface of the heat generating portion 906.

FIG. 9C is a view of the nichrome wire heating element (hereinafter referred to as an external heater B) as viewed from above, and FIG. 9D is a cross-sectional view.

Reference numeral 911 denotes a base, and 912 denotes a nichrome electric heating element provided on the base 911. The base 91
1 is made of ceramics, etc., length 360mm, width 8m
m, forming an elongated flat plate having a thickness of 1 to 2 mm.

The electric heating element 912 is formed by embedding about half of the base body 911. Terminal portions 914 are formed at both ends of the heating section, and a protective film such as glass is formed on the surface of the heating section 916 if necessary. I have.

With reference to FIG. 10, the heating rate and output characteristics of the heat source, which are important for the present invention, will be specifically described.

In FIG. 10, the conventional example is a planar heating element (hereinafter referred to as an inner heater) in which a heating element such as a nichrome wire is sandwiched by a polyethylene terephthalate resin or the like. slow. On the other hand, the ceramic heater (external heater A) according to the present invention includes:
The temperature rises to several hundred degrees Celsius in a few seconds, and the rate of increase can be controlled by the input voltage.

FIG. 4 is a schematic view showing an example of an image forming process of a copying machine provided with a heater according to the present invention, in which a photosensitive member 401 rotates in an arrow X direction. Around the photosensitive member 401 whose temperature is controlled by the heater 423, which is a feature of the present invention, a main charger 402, an electrostatic latent image forming portion 403, a developing device 404, a transfer paper supply system 405, and a transfer charger 406 (a ), A separation charger 406 (b), a cleaner 407, a transfer paper transport system 408, a static elimination light source 409, and the like.

The heater 423 has the above-described structure, and is mounted at a mounting position within a range of 0.1 to 10 mm, preferably 0.2 to 1 mm from the surface of the photoreceptor. The laser beam is disposed at a site before the laser beam is irradiated on the photoconductor via the. Most preferably, the surface other than the surface facing the photoreceptor is insulated with glass fiber, ceramics, or the like, and heat is directed only in the direction facing the photoreceptor.

Hereinafter, the image forming process will be described with reference to a specific example. The photosensitive member 401 rotates in the X direction, and
The main charger 402 to which a high voltage of about 8 kV is applied is uniformly charged, and the surface of the photoconductor is rapidly heated by the adjacent heating element 423. Then, the light emitted from the light source lamp 410 is reflected on the original 412 placed on the original platen glass 411, passes through the reflection mirrors 413, 414, and 415, and is imaged by the lens 418 of the lens unit 417. The light is guided to the electrostatic latent image forming portion 403 via the 416 and is projected on the photoconductor 401 to form an electrostatic latent image.
Negative polarity toner is supplied to this latent image from the developing device 404 to form a toner image.

On the other hand, the leading edge timing is adjusted by the registration roller 422 through the transfer paper supply system 405,
The transfer material P supplied in the direction of the photoreceptor is applied with a positive electric field having a polarity opposite to that of the toner from the back surface in a gap between the transfer charger 406 (a) to which a high voltage of +7 to 8 kV is applied and the photoreceptor 401. As a result, the negative polarity toner image on the surface of the photoconductor is transferred to the transfer material P. 12-14 kVp-p, 300
Separation charger 40 to which high-voltage AC voltage of ~ 600 Hz is applied
6 (b), the transfer material P reaches the fixing device (not shown) through the transfer paper transport system 408, and the toner image is fixed and discharged out of the device.

The toner remaining on the photoconductor 401 is scraped off by the cleaning blade 421 of the cleaner unit 407, and the electrostatic latent image remaining on the photoconductor 401 is erased by the charge eliminating light source 409.

By rapidly heating the surface of the photoreceptor in such a configuration, firstly, the surface of the photoreceptor is heated and efficiently dehumidified due to a large relative humidity difference from an external atmosphere in which the temperature has not yet risen, thereby preventing image deletion. it can. Second, while the photoreceptor is dehumidified, the temperature rise inside the electrophotographic apparatus, that is, the most characteristic substrate, and then the temperature near the photoreceptor is smaller than that of the photoreceptor surface. Image unevenness due to thermal eccentricity of the container is prevented.
Third, since only the surface of the photoconductor is mainly heated, energy saving is achieved. Fourth, a power supply mechanism such as a slip ring is conventionally required to dispose a heat source on the inner surface of the rotating cylindrical photoconductor, thereby solving the problem of increasing the cost of the electrophotographic apparatus main body. (2) Photoconductor As another element for solving the above problem, the present inventors use a photoconductor having low temperature dependency and excellent surface heat resistance, and perform rapid dehumidification under limited conditions. It has been found that a very favorable image stabilization is thereby achieved. (A) OPC Photoreceptor The OPC photoreceptor, which is one form of a preferable photoreceptor used in the present invention, will be described below. FIG. 12 is a schematic configuration diagram for explaining the layer configuration of the electrophotographic photoreceptor of the present invention.

The electrophotographic OPC photosensitive member shown in FIG.
A photosensitive layer 120 is provided on a support 1203 for a photosensitive member.
2 are provided. The photosensitive layer 1202 includes a charge generation layer 1205, a charge transport layer 1204, and a protective layer or a surface layer 1201. If necessary, an intermediate layer between the support 1203 and the charge generation layer 1205 is provided. .

The OPC photosensitive member used in the present invention comprises a surface layer, a charge generation layer 1205 and a charge transport layer 1204.
, And an intermediate layer provided as necessary. In particular, the surface layer of the photoconductive layer must withstand the high-temperature radiant heat from the heater and not soften. The present inventors have found that a mixture of a high-melting polyester resin and a cured resin causes the properties of the respective resin components to act synergistically, thereby satisfying these conditions.

The resin components used for forming the photoconductive layer including the surface layer, the charge transport layer and the charge generation layer of the electrophotographic photoreceptor of the present invention will be described.

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

As the acid component, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid;
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, cyclohexane dimethylol, polyethylene glycol, polypropylene glycol and the like can be used.

Incidentally, polyfunctional compounds such as pentaerythritol, lorimethylolpropane, pyromellitic acid and their ester-forming derivatives may be copolymerized as long as the 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 polyester resin has an intrinsic viscosity of 0.4 dl / g or more, preferably 0.5 dl / g or more, more preferably 0.65 dl / g, measured in orthochlorophenol at 36 ° C.
The above is used.

Preferred high melting polyester resins include polyalkylene terephthalate resins. The polyalkylene terephthalate resin mainly comprises terephthalic acid as an acid component and alkylene glycol as a glycol component.

As specific examples, polyethylene terephthalate (PET) mainly composed of a terephthalic acid component and an ethylene glycol component,
Examples include polybutylene terephthalate (PBT) mainly composed of a 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. it can. As another preferable high molecular weight polyester resin, a polyalkylene naphthalate resin can be exemplified. The polyalkylene naphthalate resin is mainly composed of a naphthalenedicarboxylic acid component as an acid component and an alkylene glycol component as a glycol component. Specific examples thereof include polyethylene naphthalenedicarboxylic acid components and an ethylene glycol component. Phthalate (PEN) and the like can be mentioned.

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

The high melting point polyester resin has high crystallinity because of its high melting point. As a result, it is considered that the entanglement between the cured resin polymer chain and the high melting point polymer chain is uniform and dense, and a highly durable surface layer can be formed. In the case of the low melting point polyester resin, since the crystallinity is low, there are portions where the degree of entanglement with the cured resin polymer chain is large and small, and it is considered that the durability is inferior. (B) Amorphous silicon (a-Si) photoreceptor An amorphous silicon photoreceptor which is one form of a preferable photoreceptor used in the present invention will be described below.

Focusing on the behavior of carriers in the photoconductive layer of the amorphous silicon photoreceptor, as a result of intensive studies on the relationship between the localized state distribution in the band gap, the temperature dependence of the charging ability, and the optical memory, It has been found that the above object can be achieved by controlling the local density of states in a specific energy range at least in a portion where light is incident. That is, in a photoreceptor having a photoconductive layer composed of a non-single-crystal material containing a silicon atom as a base and a hydrogen atom and / or a halogen atom, the photoreceptor is designed and manufactured to specify the layer structure. The photoreceptor not only exhibits remarkably excellent properties in practical use, but also surpasses in all respects as compared with conventional photoreceptors, and particularly has excellent properties as a photoreceptor for electrophotography. I found something.

The electrophotographic photoreceptor of the present invention comprises a conductive support and a photosensitive layer having a photoconductive layer made of a non-single-crystal material having silicon atoms as a base.
It contains hydrogen of 0 to 30 atomic% and has a characteristic energy of 50 to 50 exponential tails (Urbuck tail) of the light absorption spectrum.
60 meV, and the density of localized states in the photoconductive layer is 3 × 10 ^{14 to} 3 × 10 ¹⁶ cm ⁻³ .

Further, the electrophotographic photoreceptor of the present invention comprises a conductive support and a photoreceptive layer having a photoconductive layer made of a non-single-crystal material having silicon atoms as a base.水 素 30 atomic% of hydrogen, the absorption peak intensity ratio of the Si—H ₂ bond and the Si—H bond obtained from the infrared absorption spectrum is 0.1 to 0.5, and the sub-band gap light absorption spectrum It is characterized in that the characteristic energy of the exponential function tail (Urbach tail) is 50 to 60 meV and the density of localized states of the photoconductive layer is 3 × 10 ^{14 to} 5 × 10 ¹⁶ cm ⁻³ .

Further, the electrophotographic photoreceptor according to the present invention comprises a conductive support and a photoreceptive layer having a photoconductive layer made of a non-single-crystal material having silicon atoms as a base. comprises 10 to 30 atomic% of hydrogen, the absorption peak intensity ratio of Si-H ₂ bonds and Si-H bonds obtained from the infrared absorption spectrum is a 0.1 to 0.5, sub-bandgap light absorption spectrum The characteristic energy of the exponential function tail (Urbuck tail) is 50 to 60 meV, and the local density of states of the photoconductive layer is 3 × 10 ^{14 to} 5 × 10 ¹⁶ c.
m ^-3 .

The electrophotographic photoreceptor of the present invention designed to have the above-described structure can solve all of the above-mentioned problems and has extremely excellent electrical, optical and photoconductive properties. , Image quality, durability and use environment characteristics.

Generally, in the band gap of a-Si: H, the tail (tail) level based on the structural disorder of the Si-Si bond and the dangling bond of Si, etc. There are deep levels due to structural defects. It is known that these levels work mainly on capture and recombination of electrons and holes, and cause deterioration of device characteristics.

As a method for measuring the state of the localized level in the band gap, deep level spectroscopy, isothermal capacity transient spectroscopy, photothermal deflection spectroscopy, constant photocurrent method, and the like are generally used. . Above all, the constant photocurrent method (Consta
nt Photocurent Method (hereinafter abbreviated as “CPM”) is useful as a simple method for measuring a subgap light absorption spectrum based on the localized level of a-Si: H.

The present inventors have proposed a characteristic energy (hereinafter abbreviated as “Eu”) of an exponential function tail (hereinafter referred to as “Eu”) and a localized density of states (hereinafter referred to as “Eu”) obtained from a light absorption spectrum measured by CPM. Abbreviated as “DOS”) and the characteristics of the photoreceptor over various conditions.
The inventors have found that Eu and DOS are closely related to the temperature characteristics of the a-Si photosensitive member and the optical memory, and have completed the present invention.

The reason why the charging ability is reduced when the photosensitive member is heated by a drum heater or the like is that a thermally excited carrier is attracted by an electric field at the time of charging and a localized level at a band base or a deep station within a band gap. It travels to the surface while repeating capture and emission to a state, and cancels the surface charge. At this time, carriers reaching the surface while passing through the charger have almost no effect on the decrease in charging ability, but carriers captured at a deep level reach the surface after passing through the charger. To cancel the surface charge,
Observed as a change in temperature characteristics. Carriers that are thermally excited after passing through the charger also cancel the surface charge and cause a reduction in charging ability. Therefore, it is necessary to suppress the generation of thermally excited carriers in the operating temperature range of the photoconductor and to improve the traveling properties of the carriers in order to improve the temperature characteristics.

Further, the optical memory is generated when the optical carriers generated by the blank exposure or the image exposure are captured by localized levels in the band gap, and the carriers remain in the photoconductive layer. That is, of the photocarriers generated in a certain copying process, the carriers remaining in the photoconductive layer are swept out by the electric field due to the surface charge at the next charging or thereafter, and the potential of the light-irradiated portion is changed to the other. Lower than the area, resulting in shading on the image. Therefore, it is necessary to improve the traveling properties of the photocarrier so that the photocarrier travels in one copying process without remaining in the photoconductive layer.

Therefore, by controlling Eu and DOS in a specific energy range as in the present invention, the generation of thermally excited carriers is suppressed, and the rate at which the thermally excited carriers and optical carriers are trapped in the localized levels is reduced. Can be reduced, so that the traveling property of the carrier is significantly improved. As a result, the temperature characteristics of the photoconductor in the operating temperature range are dramatically improved, and at the same time, the occurrence of optical memory can be suppressed, so that the stability of the photoconductor in the usage environment is improved and the halftone is sharp. And a high-quality image with high resolution can be stably obtained.

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

FIG. 11 is a schematic diagram for explaining the layer structure of the electrophotographic photosensitive member of the present invention.

The photoconductor 11 for electrophotography shown in FIG.
In No. 00, a photosensitive layer 1102 is provided on a support 1101 for a photosensitive member. The photosensitive layer 1102 is a
-Photoconductive layer 11 made of Si: H, X and having photoconductivity
03.

FIG. 11 (b) is a schematic configuration diagram for explaining another layer configuration of the electrophotographic photosensitive member of the present invention.
An electrophotographic photosensitive member 1100 shown in FIG. 11B has a photosensitive layer 1102 provided on a support 1101 for the photosensitive member. The photosensitive layer 1102 is made of a-Si: H,
It is composed of a photoconductive layer 1103 made of X and having photoconductivity, and an amorphous silicon-based surface layer 1104.

FIG. 11 (c) is a schematic configuration diagram for explaining another layer configuration of the electrophotographic photosensitive member of the present invention.
An electrophotographic photosensitive member 1100 shown in FIG. 11C has a photosensitive layer 1102 provided on a support 1101 for the photosensitive member. The photosensitive layer 1102 is made of a-Si: H,
It is composed of a photoconductive layer 1103 made of X and having photoconductivity, an amorphous silicon-based surface layer 1104, and an amorphous silicon-based charge injection blocking layer 1105.

FIG. 11D is a schematic structural view for explaining still another layer constitution of the electrophotographic photosensitive member of the present invention. An electrophotographic photoreceptor 1100 shown in FIG.
Is a photosensitive layer 1 on a support 1101 for a photosensitive member.
102 are provided. The photosensitive layer 1102 includes a charge generation layer 1106 and a charge transport layer 1107 made of a-Si: H, X constituting a photoconductive layer 1103, and an amorphous silicon-based surface layer 1104. (3) Support The support used in the present invention may be either conductive or electrically insulating. As the conductive support, A
1, Cr, Mo, Au, In, Nb, Te, V, Yi,
Examples include metals such as Pt, Pd, and Fe, and alloys thereof, for example, stainless steel. In addition, polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene,
An electrically insulating support such as a film or sheet of a synthetic resin such as polyamide, glass, ceramic or the like, or a support having at least a surface on the side on which a photosensitive layer is to be formed conductively treated can also be used.

Hereinafter, the electrophotographic photoreceptor 10 comprises a cylindrical support 11 and a charge injection blocking layer 12 deposited on the support 11, a photoconductive layer 13 and a surface layer 14, or a charge generation layer 15. It is assumed that the photosensitive layer 17 includes the charge transport layer 16 and the photosensitive layer 17.

The support 11 used in the present invention may be in the form of a cylindrical or plate-like endless belt having a smooth surface or an uneven surface, and the thickness of the support may be as small as desired. It is appropriately determined so that the electrophotographic photoreceptor 10 can be formed, but when flexibility as the electrophotographic photoreceptor 10 is required, it can be made as thin as possible within a range where the function as the support 11 can be sufficiently exhibited. . However, the thickness of the support 11 is usually 10 μm or more in terms of production, handling, mechanical strength, and the like.

In particular, when performing image recording using coherent light such as laser light, the surface of the support 11 is more effectively eliminated in order to more effectively eliminate image defects due to so-called interference fringe patterns appearing in a visible image. May be provided with irregularities. The unevenness provided on the surface of the support 11 is described in JP-A-60-16.
Nos. 8156, 60-178457 and 60
It is prepared by a known method described in JP-A-225854 and the like.

As another method for more effectively eliminating image defects due to interference fringe patterns when coherent light such as laser light is used, an uneven shape formed by a plurality of spherical trace depressions on the surface of the support 11 is described. It may be provided. That is, the support 11
Has a finer irregularity than the resolution required for the electrophotographic photoreceptor 10, and the irregularity is caused by a plurality of spherical trace depressions. Unevenness due to a plurality of spherical trace depressions provided on the surface of the support 11 is described in JP-A-61-23.
It is prepared by a known method described in No. 1561. (4) Photoconductive layer In the present invention, the photoconductive layer 13 formed on the support 11 and constituting a part of the photoreceptor 10 is formed by a vacuum deposition film forming method in order to effectively achieve the object. It is created by appropriately setting the numerical conditions of the film forming parameters so as to obtain the characteristics. Specifically, for example, a glow discharge method (low-frequency CVD method, high-frequency CVD method, microwave CV
It can be formed by various thin film deposition methods such as an AC discharge CVD method such as a D method or a DC discharge CVD method), a sputtering method, a vacuum evaporation method, an ion plating method, a photo CVD method, and a thermal CVD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, the degree of load under capital investment, the manufacturing scale, and the characteristics desired for the electrophotographic photoreceptor to be produced. The glow discharge method, since it is relatively easy to control the conditions for producing an electrophotographic photosensitive member having
Particularly, a high-frequency glow discharge method using a power supply frequency in the RF band or the VHF band is preferable.

In order to form the photoconductive layer 13 by the glow discharge method, a source gas for supplying Si that can supply silicon atoms (Si) and a gas for supplying H that can supply hydrogen atoms (H) are basically used. Raw material gas and / or halogen atom (X)
Is supplied in a desired gas state into a reaction vessel in which the inside can be reduced in pressure to generate a glow discharge in the reaction vessel, which is previously set at a predetermined position. A-Si: H, X on a predetermined support 11
May be formed.

In the present invention, it is necessary that the photoconductive layer 13 contains a hydrogen atom and / or a halogen atom, which compensates for dangling bonds of silicon atoms,
This is because it is indispensable for improving the layer quality, particularly for improving the photoconductivity and the charge retention characteristics. Therefore, the content of the hydrogen atom or the halogen atom, or the sum of the hydrogen atom and the halogen atom is determined by the relationship between the silicon atom and the hydrogen atom or /
And 30 to 30 atomic%, and more preferably 15 to 25 atomic%, based on the sum of the halogen atoms and the halogen atoms.

The substances that can be used as the Si supply gas used in the present invention include SiH ₄ , Si ₂ H ₆ , Si
Silicon hydrides (silanes) in a gas state such as ₃ H ₈ , Si ₄ H ₁₀ , or the like, which can be gasified, are effectively used, and further, ease of handling at the time of forming a layer, and excellent Si supply efficiency. In view of the above, SiH ₄ and Si ₂ H ₆ are preferred.

Then, hydrogen atoms are structurally introduced into the formed photoconductive layer 13 so that the introduction ratio of hydrogen atoms can be more easily controlled, and the film characteristics which achieve the object of the present invention can be obtained. Therefore, it is necessary to form a layer by mixing a desired amount of H ₂ and / or He or a silicon compound gas containing a hydrogen atom with these gases. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

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

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

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the photoconductive layer 13, for example, the temperature of the support 11, a raw material used to contain hydrogen atoms and / or halogen atoms, What is necessary is just to control the amount of the substance introduced into the reaction vessel, the discharge power and the like.

In the present invention, it is preferable that the photoconductive layer 13 contains atoms for controlling conductivity as necessary. The atoms controlling the conductivity may be contained in the photoconductive layer 13 in a state of being distributed uniformly and evenly, or there may be a part containing the atoms in the layer thickness direction in a non-uniform distribution state. Is also good.

The atoms controlling the conductivity include so-called impurities in the semiconductor field.
An atom belonging to group IIIb of the periodic table giving p-type conduction characteristics (hereinafter abbreviated as "group IIIb atom") or an atom belonging to group Vb of the periodic table giving n-type conduction characteristics (hereinafter "V
abbreviated as “group b atom”).

Specific examples of the group IIIb atoms include boron (B), aluminum (Al), gallium (Ga),
There are indium (In), thallium (Tl) and the like, and B, Al and Ga are particularly preferable. Group Vb atoms include:
Specifically, phosphorus (P), arsenic (As), antimony (S
b), bismuth (Bi) and the like, and P and As are particularly preferable.

The content of the atoms for controlling the conductivity contained in the photoconductive layer 13 is preferably 1 × 10 ^-2 to 1 ×.
10 ⁴ atomic ppm, more preferably 5 × 10 ^{-2 to} 5 × 1
Desirably, the concentration is 0 ³ atomic ppm, most preferably 1 × 10 ^-1 to 1 × 10 ³ atomic ppm.

Atoms for controlling conductivity, for example,
In order to introduce a group b atom or a group Vb atom structurally, a source material for introducing a group IIIb atom,
Alternatively, a raw material for introducing a group Vb atom may be introduced in a gaseous state into the reaction vessel together with another gas for forming the photoconductive layer 13. As a source material for introducing a Group IIIb atom or a source material for introducing a Group Vb atom, a gaseous material at ordinary temperature and normal pressure or a material which can be easily gasified at least under layer forming conditions is employed. It is desirable.

As such a raw material for introducing a Group IIIb atom, specifically, for introducing a boron atom, B ₂ H
_{6, B 4 H 10, B} 5 H 9, B 5 H 11, B 6 H 10, B 6 H
_12, B ₆ H ₁₄ borohydride such as, BF _3, BCl _3, BB
and boron halide such as r ₃ . In addition, Al
Cl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , InCl ₃ ,
TlCl _{3 and the} like can also be mentioned.

[0098] The source material for introducing a group Vb atom is effectively used as a source material for introducing a phosphorus atom.
₃ , hydrogenated phosphorus such as P ₂ H ₄ , PH ₄ I, PF ₃ , P
_{F 5, PCl 3, PCl 5} , PBr 3, PBr 5, PI
_{And the} like. In addition, AsH ₃ ,
AsF ₃ , AsCl ₃ , AsBr ₃ , AsF ₅ , SbH
_{3, SbF 3, SbF 5,} SbCl 3, SbCl 5, B
iH ₃ , BiCl ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing a group Vb atom.

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

Further, in the present invention, it is also effective that the photoconductive layer 13 contains carbon atoms and / or oxygen atoms and / or nitrogen atoms. The content of carbon atom and / or oxygen atom and / or nitrogen atom is silicon atom,
Preferably 1 × 10 ⁻⁵ to 10 atomic%, more preferably 1 × 10 ⁵ %, based on the sum of carbon atoms, oxygen atoms and nitrogen atoms.
^-4 to 8 atomic%, optimally 1 × 10 ^{-3 to} 5 atomic% is desirable. The carbon atoms and / or oxygen atoms and / or nitrogen atoms may be evenly and uniformly contained in the photoconductive layer, or may have an uneven distribution such that the content changes in the thickness direction of the photoconductive layer. May be provided.

In the present invention, the layer thickness of the photoconductive layer 13 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economical effects.
50 μm, more preferably 23-45 μm, optimally 2
Desirably, the thickness is 5 to 40 μm.

In order to achieve the object of the present invention and to form the photoconductive layer 13 having desired film characteristics, the mixing ratio between the gas for supplying Si and the diluent gas, the gas pressure in the reaction vessel, the discharge power, It is necessary to appropriately determine the temperature of the support.

[0103] The flow rate of H ₂ and / or He used as a dilution gas is properly selected within an optimum range in accordance with the layer design, to Si-feeding gas H ₂ and / or He
Is usually controlled in the range of 3 to 20 times, preferably 4 to 15 times, and most preferably 5 to 10 times.

Similarly, the optimum range of the gas pressure in the reaction vessel is appropriately selected according to the layer design.
0 ^{-4 to} 10 Torr, preferably 5 × 10 ^{-4 to} 5 Torr
r, and most preferably, 1 × 10 ^{−3 to} 1 Torr.

Similarly, the optimum range of the discharge power is appropriately selected according to the layer design. The discharge power with respect to the flow rate of the gas for supplying Si is usually 2 to 7 times, preferably 2.5 to 6 times. It is desirable to set it in the range of 2 times, optimally 3 to 5 times.

Further, the temperature of the support 11 is appropriately selected in an optimum range according to the layer design, but is usually preferably 200 to 350 ° C., more preferably 230 to 3 ° C.
It is desirable that the temperature is 30 ° C, optimally 250 to 310 ° C.

In the present invention, the preferable ranges of the temperature and the gas pressure of the support 11 for forming the photoconductive layer 13 include the above-mentioned ranges, but the conditions are usually determined independently and separately. Instead, it is desirable to determine the optimum value based on mutual and organic relevance to form the photoreceptor 10 having desired characteristics. (5) Surface Layer In the present invention, it is preferable to further form an amorphous silicon-based surface layer 14 on the photoconductive layer 13 formed on the support 11 as described above. The surface layer 14 has a free surface and is provided in order to achieve the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, electric pressure resistance, use environment characteristics, and durability.

In the present invention, since each of the amorphous materials forming the photoconductive layer 13 and the surface layer 14 constituting the photosensitive layer 17 has a common component of silicon atoms, Ensuring sufficient chemical stability at the interface.

The surface layer 14 can be made of any material as long as it is an amorphous silicon-based material.
Amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X) and further containing a carbon atom (hereinafter referred to as “a-SiC: H, X”), a hydrogen atom (H) and / or a halogen Amorphous silicon containing an atom (X) and further containing an oxygen atom (hereinafter referred to as “a-
SiO: H, X "), a hydrogen atom (H) and / or
Alternatively, amorphous silicon containing a halogen atom (X) and further containing a nitrogen atom (hereinafter referred to as “a-SiN: H,
X), amorphous silicon containing a hydrogen atom (H) and / or a halogen atom (X) and further containing at least one of a carbon atom, an oxygen atom and a nitrogen atom (hereinafter referred to as “a-SiCON: H , X ") are suitably used.

In the present invention, in order to effectively achieve the object, the surface layer 14 is formed by a vacuum deposition film forming method by appropriately setting numerical conditions of film forming parameters so as to obtain desired characteristics. . Specifically, for example, a glow discharge method (an AC discharge CVD method such as a low-frequency CVD method, a high-frequency CVD method, or a microwave CVD method, or a DC discharge CVD method), a sputtering method, a vacuum deposition method,
It can be formed by various thin film deposition methods such as an ion plating method, a photo CVD method, and a thermal CVD method. These thin film deposition methods are appropriately selected and adopted depending on factors such as manufacturing conditions, the degree of load under capital investment, the manufacturing scale, and the characteristics desired for the electrophotographic photoconductor to be produced. It is preferable to use the same deposition method as that for the photoconductive layer in terms of productivity.

[0111] For example, a-Si
In order to form the surface layer 14 made of C: H, X, 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) are basically used. A raw material gas and a raw material gas for supplying H that can supply hydrogen atoms (H) or / and a raw material gas for X supply that can supply halogen atoms (X) are placed in a reaction vessel capable of reducing the pressure inside a desired reaction vessel. Introduced in a gaseous state, a glow discharge is generated in the reaction vessel, and a layer made of a-SiC: H, X is formed on the support 11 on which the photoconductive layer 13 previously formed at a predetermined position is formed. do it.

The material of the surface layer 14 used in the present invention may be any amorphous material containing silicon, but is preferably a compound with a silicon atom containing at least one element selected from carbon, nitrogen and oxygen. Particularly, those containing a-SiC as a main component are preferable.

When the surface layer 14 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 14 contains hydrogen atoms and / or halogen atoms, which compensates for dangling bonds of silicon atoms and improves the quality of the layer, especially the optical quality. It is indispensable to improve the conductivity characteristics and the charge retention characteristics. In general, the hydrogen content is desirably 30 to 70 atomic%, preferably 35 to 65 atomic%, and most preferably 40 to 60 atomic%, based on the total amount of the constituent atoms. The content of fluorine atoms is usually 0.01 to 15 atomic%, preferably 0.1 to 10 atomic%.
Atomic%, optimally 0.6 to 4 atomic% is desirable.

The photoreceptor formed within the above range of hydrogen and / or fluorine content can be sufficiently applied as a material which is far superior in practice.
That is, it is known that defects (mainly dangling bonds of silicon atoms and carbon atoms) existing in the surface layer 14 adversely affect the characteristics of the electrophotographic photosensitive member. For example, deterioration of charging characteristics due to injection of electric charge from the free surface of the surface layer 14, fluctuation of charging characteristics due to a change in the surface structure under the use environment, for example, high humidity, furthermore, the photoconductive layer during corona charging or light irradiation. As a result, charges are injected into the surface layer, and charges are trapped in defects in the surface layer.

However, by controlling the hydrogen content in the surface layer 14 to 30 atomic% or more, defects in the surface layer 14 are greatly reduced, and as a result, electric characteristics and high-speed continuous In this case, a dramatic improvement can be achieved.

On the other hand, when the hydrogen content in the surface layer 14 is 7
If the content exceeds 1 atomic%, the hardness of the surface layer 14 decreases, so that the surface layer 14 cannot withstand repeated use. Therefore, controlling the hydrogen content in the surface layer 14 to be within the above range,
This is one of the very important factors in obtaining extremely excellent desired electrophotographic properties. The hydrogen content in the surface layer 14 is H
_{2 It} can be controlled by the flow rate of the gas, the temperature of the support, the discharge power, the gas pressure, and the like.

Further, the fluorine content in the surface layer 14 is set to 0.0
By controlling the content to be in the range of 1 atomic% or more, it is possible to more effectively achieve the generation of the bond between silicon atoms and carbon atoms in the surface layer 14. Further, the function of the fluorine atoms in the surface layer 14 can effectively prevent the bond between the silicon atoms and the carbon atoms from being broken due to damage such as corona.

On the other hand, the fluorine content in the surface layer is 15 atomic%.
If it exceeds 300, the effect of generating the bond between the silicon atom and the carbon atom in the surface layer and the effect of preventing the break of the bond between the silicon atom and the carbon atom due to damage such as corona can hardly be recognized. Furthermore, since excess fluorine atoms hinder the mobility of carriers in the surface layer, remnant potential and image memory are remarkably observed.

Therefore, controlling the fluorine content in the surface layer 14 within the above range is one of the important factors for obtaining desired electrophotographic characteristics. The fluorine content in the surface layer is
Like the hydrogen content, it can be controlled by the flow rate of the H ₂ gas, the temperature of the support, the discharge power, the gas pressure, and the like.

The substance which can be a gas for supplying silicon (Si) used in the formation of the surface layer 14 of the present invention includes gaseous substances such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ and Si ₄ H _10. Or silicon hydrides (silanes) that can be gasified are used effectively. Further, Si hydrides are easy to handle at the time of forming a layer and Si supply efficiency is high.
H ₄ and Si ₂ H ₆ are preferred. Further, these Si supply source gases may be diluted with a gas such as H ₂ , He, Ar, Ne or the like as necessary.

Examples of the substance that can serve as a carbon supply gas include:
Hydrocarbons in the gas state, such as CH ₄ , C ₂ H ₆ , C ₃ H ₈ , and C ₄ H ₁₀ , or gasifiable hydrocarbons are effectively used.
CH ₄ and C ₂ H ₆ are preferred in terms of good supply efficiency and the like. Further, the raw material gas for supplying C may be used after being diluted with a gas such as H ₂ , He, Ar, or Ne as necessary.

Substances that can serve as nitrogen or oxygen supply gas include NH ₃ , NO, N ₂ O, NO ₂ , H ₂ O, O ₂
Compounds in the gaseous state or gasifiable compounds such as ₂ , CO, CO ₂ , and N ₂ can be effectively used. Further, these nitrogen and oxygen supply source gases may be diluted with a gas such as H ₂ , He, Ar, Ne or the like as necessary.

In order to make it easier to control the introduction ratio of hydrogen atoms introduced into the surface layer 14 to be formed, these gases may be further mixed with hydrogen gas or silicon compound gas containing hydrogen atoms. Also, it is preferable to form a layer by mixing desired amounts. Further, each gas is not limited to a single species, and a plurality of species may be mixed at a predetermined mixture ratio.

Effective as a source gas for supplying halogen atoms
For example, halogen gas, halide, halogen
Compounds containing halogen, sila substituted with halogen
Gaseous or gasifiable halogenated compounds such as
Thing is mentioned preferably. Also, even silicon atoms
Gas or gas containing nitrogen and halogen atoms
Effective for silicon hydride compounds containing halogen atoms
Can be cited. Suitable in the present invention
Specific examples of the halogen compound that can be used for
Gas (F_Two), BrF, ClF, ClF_Three, BrF_Three,
BrF_Five, IF _Three, IF₇And interhalogen compounds such as
Can be Silicon compounds containing halogen atoms,
As a silane derivative substituted with any halogen atom,
Specifically, for example, SiF_Four, Si_TwoF₆Etc.
Element is preferred.

In order to control the amount of hydrogen atoms and / or halogen atoms contained in the surface layer 14, for example, the temperature of the support 11, a raw material used to contain hydrogen atoms and / or halogen atoms The amount to be introduced into the reaction vessel, the discharge power and the like may be controlled.

The carbon atoms and / or oxygen atoms and / or nitrogen atoms may be evenly and uniformly contained in the surface layer 14, or may be such that the content changes in the thickness direction of the surface layer 14. There may be a portion having a uniform distribution.

Further, in the present invention, it is preferable that the surface layer 14 contains atoms for controlling conductivity as necessary. The atoms for controlling the conductivity may be contained in the surface layer 14 in a state of being uniformly distributed in the surface layer 14, or even if there is a part contained in the layer thickness direction in a non-uniform distribution state. Good.

The above-mentioned atoms for controlling conductivity include so-called impurities in the field of semiconductors, and include atoms belonging to Group IIIb of the Periodic Table giving p-type conduction characteristics (hereinafter abbreviated as “Group IIIb atoms”). Or an atom belonging to Group Vb of the Periodic Table that gives n-type conduction characteristics (hereinafter abbreviated as “Group Vb atom”).

Examples of Group IIIb atoms include boron (B), aluminum (Al), gallium (Ga),
There are indium (In), thallium (Tl) and the like, and B, Al and Ga are particularly preferable. Group Vb atoms include:
Specifically, phosphorus (P), arsenic (As), antimony (S
b), bismuth (Bi) and the like, and P and As are particularly preferable.

The content of atoms controlling conductivity contained in the surface layer 14 is preferably 1 × 10 ⁻³ to 1 × 1.
0 ³ atomic ppm, more preferably 1 × 10 ^{-2 to} 5 × 10
² atomic ppm, optimally 1 × 10 ^-1 × 1 × 10 ² atomic p
pm. In order to structurally introduce an atom for controlling conductivity, for example, a group IIIb atom or a group Vb atom, a source material for introducing a group IIIb atom or a group material for introducing a group Vb atom in forming a layer. The raw material may be introduced in a gaseous state into the reaction vessel together with another gas for forming the surface layer 14. As a raw material for introducing a Group IIIb atom or a raw material for introducing a Group Vb atom, a gaseous substance at ordinary temperature and pressure, or
It is desirable to employ one that can be easily gasified at least under layer forming conditions. As such a raw material for introducing a Group IIIb atom, specifically, for introducing a boron atom, B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H
_{10, B 6 H 12, B} 6 borohydride of H _14, etc., BF _3, BC
l _3, BBr ₃ boron halides, etc., and the like. In addition, AlCl ₃ , GaCl ₃ , Ga (CH ₃ ) ₃ , I
nCl ₃ , TlCl _{3 and the} like can also be mentioned.

[0132] being effectively used as a raw material for the Vb atoms introduced as the for introducing phosphorus atoms, PH _3, P
Phosphorus hydride such as ₂ H ₄ , PH ₄ I, PF ₃ , PF ₅ , PC
and phosphorus halides such as l ₃ , PCl ₅ , PBr ₃ , PBr ₅ and PI 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, B
iCl ₃ , BiBr _{3 and the} like can also be mentioned as effective starting materials for introducing a group Vb atom.

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

In the present invention, the thickness of the surface layer 14 is usually 0.01 to 3 μm, preferably 0.05 to 2 μm.
m, and most preferably 0.1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer is lost due to abrasion during use of the photoreceptor, and the
If it exceeds m, a decrease in electrophotographic characteristics such as an increase in residual potential is observed.

The surface layer 14 according to the present invention is carefully formed so that its required properties are provided as desired. That is, Si, C and / or N and / or O, H
And / or a substance having X as a constituent element structurally takes a form from crystalline to amorphous depending on its forming conditions, and has electrical properties ranging from conductive to semiconductive and insulating properties, and Since the properties between photoconductive properties and non-photoconductive properties are shown, in the present invention, the formation conditions are selected as desired so that a compound having desired properties according to the purpose is formed. Is strictly done.

For example, in order to provide the surface layer 14 mainly for the purpose of improving the pressure resistance, the surface layer 14 is formed as a non-single-crystal material having a remarkable electric insulating behavior in a use environment.

In the case where the surface layer 14 is provided for the purpose of mainly improving the continuous repetitive use characteristics and the use environment characteristics, the degree of the above-mentioned electrical insulation is alleviated to a certain extent, and a certain degree with respect to the irradiated light. Formed as a non-single-crystal material having a sensitivity of

In order to form the surface layer 14 having characteristics capable of achieving the object of the present invention, it is necessary to appropriately set the temperature of the support 11 and the gas pressure in the reaction vessel as desired.

The temperature (Ts) of the support 11 is appropriately selected in an optimum range according to the layer design, but is usually preferably 200 to 350 ° C., more preferably 230 to 3 ° C.
It is desirable that the temperature is 30 ° C, optimally 250 to 300 ° C.

The gas pressure in the reaction vessel was similarly designed in layers.
Therefore, the optimum range is appropriately selected, but in the normal case, it is preferable.
Or 1 × 10^-Four-10 Torr, more preferably 5 ×
10 ^-Four~ 5 Torr, optimally 1 × 10^-3~ 1 Torr
It is preferred that

In the present invention, the preferable ranges of the temperature and the gas pressure of the support 11 for forming the surface layer 14 include the above-mentioned ranges. However, the conditions are not usually determined independently and separately. It is desirable to determine the optimum value based on mutual and organic relevance in order to form the photoreceptor 10 having desired characteristics.

Further, in the present invention, a blocking layer (lower surface layer) having a lower content of carbon atoms, oxygen atoms and nitrogen atoms than the surface layer 14 may be provided between the photoconductive layer 13 and the surface layer 14. It is effective to further improve the characteristics such as charging ability.

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 13 may be provided between the surface layer 14 and the photoconductive layer 13. good. Thereby, the adhesion between the surface layer 14 and the photoconductive layer 13 can be improved, and the influence of interference due to light reflection at the interface can be further reduced. (6) Charge Injection Blocking Layer In the electrophotographic photoreceptor 10 of the present invention, between the conductive support 11 and the photoconductive layer 13, a charge having a function of preventing charge injection from the conductive support side. It is more effective to provide the injection blocking layer 12. That is, the charge injection blocking layer 12 has a function of preventing charges from being injected from the support 11 side to the photoconductive layer 13 side when the photosensitive layer 17 is subjected to a charging treatment of a fixed polarity on its free surface. However, such a function is not exhibited when it is subjected to charging treatment of the opposite polarity, that is, it has a so-called polarity dependency. In order to provide such a function, the charge injection blocking layer 12 contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer 13.

The atoms for controlling the conductivity contained in the charge injection blocking layer 12 may be uniformly distributed in the charge injection blocking layer 12, or may be uniformly distributed in the layer thickness direction. Although it is contained, there may be a portion contained in a state of being unevenly distributed. When the distribution concentration is non-uniform, it is preferable that the compound be contained so as to be distributed more on the support side.

However, in any case, it is necessary that the metal is uniformly contained in a uniform distribution in the in-plane direction parallel to the surface of the support from the viewpoint of making the characteristics in the in-plane direction uniform. .

As the atoms for controlling the conductivity contained in the charge injection blocking layer 12, there can be mentioned so-called impurities in the field of semiconductors, and atoms belonging to the periodic table group which gives p-type conduction characteristics (hereinafter referred to as " (Abbreviated as “Group III atom”) or an atom belonging to the periodic group that gives n-type conduction characteristics (hereinafter abbreviated as “Group V atom”) can be used.

As the Group III atom, specifically, B
(Boron), Al (aluminum), Ga (gallium), In (indium), Ta (thallium), and the like, and B, Al, and Ga are particularly preferable. Specific examples of Group V atoms include P (phosphorus), As (arsenic), Sb (antimony), and Bi (bismuth). In particular, P and As
Is preferred.

In the present invention, the content of atoms controlling the conductivity contained in the charge injection blocking layer 12 is appropriately determined as desired so that the object of the present invention can be effectively achieved. Is 10-1 × 10 ⁴ atoms p
pm, more preferably 50 to 5 × 10 ³ atomic ppm, and most preferably 1 × 10 ² to 1 × 10 ³ atomic ppm.

Further, the charge injection blocking layer 12 contains at least one of carbon atoms, nitrogen atoms and oxygen atoms, thereby allowing the charge injection blocking layer 12 to be in direct contact with the charge injection blocking layer 12. The adhesion can be further improved.

The carbon atoms, nitrogen atoms or oxygen atoms contained in the charge injection blocking layer 12 may be uniformly distributed in the layer, or may be uniformly distributed in the layer thickness direction. However, there may be portions that are contained in a non-uniformly distributed state. However, in any case, it is necessary to uniformly contain the particles in a uniform distribution in a plane parallel to the surface of the support from the viewpoint of making the characteristics uniform in the plane.

In the present invention, carbon atoms and / or nitrogen atoms and / or
Alternatively, the content of the oxygen atom is appropriately determined so that the object of the present invention can be effectively achieved. In the case of one kind, the content is two times or more. ^-3 to 50 atomic%, more preferably 5 × 10 ^{-3 to} 3
It is desirable that the content be 0 atomic%, and optimally 1 × 10 ⁻² to 10 atomic%.

The charge injection blocking layer 12 according to the present invention
The hydrogen atoms and / or halogen atoms contained in the compound 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 in the charge injection blocking layer 12 is preferably 1 to 50 atomic%, more preferably 5 to 40 atomic%,
Most preferably, it is set to 10 to 30 atomic%.

In the present invention, the thickness of the charge injection blocking layer 12 is preferably from 0.1 to 5 μm, more preferably from 0.3 to 4 μm, from the viewpoint of obtaining desired electrophotographic characteristics and economic effects. Optimally, the thickness is desirably 0.5 to 3 μm.

In the present invention, in order to form the charge injection blocking layer 12, a vacuum deposition method similar to the above-described method of forming the photoconductive layer 13 is employed.

In order to form the charge injection blocking layer 12 having characteristics capable of achieving the object of the present invention, similarly to the photoconductive layer 13, the mixing ratio between the gas for supplying Si and the diluent gas, It is necessary to appropriately set the gas pressure, the discharge power, and the temperature of the support 11.

The flow rate of the diluent gas H ₂ and / or He is appropriately selected in accordance with the layer design. The flow rate of H ₂ and / or He is usually 1 to 20 to the Si supply gas. It is desirable to control the pressure within the range of 3 times, preferably 3 to 15 times, and optimally 5 to 10 times.

Similarly, the optimum range of the gas pressure in the reaction vessel is appropriately selected according to the layer design.
10 ^{-4 to} 10 Torr, preferably 5 × 10 ^{-4 to} 5 To
rr, and most preferably, 1 × 10 ^{−3 to} 1 Torr.

Similarly, the optimum range of the discharge power is appropriately selected in accordance with the layer design. However, the discharge power relative to the flow rate of the gas for supplying Si is usually 1 to 7 times, preferably 2 to 6 times. Is preferably set in a range of 3 to 5 times.

Furthermore, the temperature of the support 11 is appropriately selected in an optimum range according to the layer design, but is usually preferably 200 to 350 ° C., more preferably 230 to 3 ° C.
It is desirable that the temperature be 30 ° C, optimally 250 to 300 ° C.

In the present invention, the mixing ratio of the diluent gas, the gas pressure, the discharge power,
Desirable numerical ranges of the support temperature include the above-mentioned ranges. However, these layer forming factors are not usually independently determined separately, but are mutually and organically formed to form a surface layer having desired properties. It is desirable to determine the optimum value of each layer forming factor based on the target relevance.

In addition, in the electrophotographic photoreceptor of the present invention, at least aluminum atom, silicon atom, hydrogen atom and / or
And a layer region in which halogen atoms are contained in a non-uniform distribution state in the layer thickness direction.

Further, in the electrophotographic photoreceptor 10 of the present invention, for the purpose of further improving the adhesion between the support 11 and the photoconductive layer 13 or the charge injection blocking layer 12, for example, Si ₃ An adhesion layer composed of an amorphous material or the like containing N ₄ , SiO ₂ , SiO, or silicon atoms as a base and containing hydrogen atoms and / or halogen atoms, and carbon atoms and / or oxygen atoms and / or nitrogen atoms. May be provided. Further, a light absorbing layer for preventing an interference pattern from being generated by light reflected from the support 11 may be provided.

Next, an apparatus and a film forming method for forming the photosensitive layer 17 will be described in detail.

FIG. 2 is a schematic diagram showing an example of an apparatus for manufacturing an electrophotographic photosensitive member by a high-frequency plasma CVD method (hereinafter abbreviated as “RF-PCVD”) using an RF band as a power supply frequency. The configuration of the manufacturing apparatus shown in FIG. 2 is as follows.

This apparatus is roughly classified into a deposition apparatus (210
0), a source gas supply device (2200), a reaction vessel (2
111) is constituted by an exhaust device (not shown) for reducing the pressure inside. A cylindrical support (2112), a heater for heating the support (2113), a raw material gas introduction pipe (211) are provided in a reaction vessel (2111) in the deposition apparatus (2100).
4) is installed, and a high-frequency matching box (21)
15) is connected.

The source gas supply device (2200) is made of SiH
₄ , cylinders (2221-2226) of raw material gases such as GeH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , PH ₃ and valves (22
31-2236, 2241-2246, 2251-22
56) and a mass flow controller (2211-2)
216), and a cylinder for each source gas is connected to a gas introduction pipe (2114) in the reaction vessel (2111) via a valve (2260).

The formation of a deposited film using this apparatus can be performed, for example, as follows.

First, the cylindrical support (2112) in the reaction vessel (2111) is set, and the inside of the reaction vessel (2111) is evacuated by an exhaust device (not shown) (for example, a vacuum pump). Subsequently, the temperature of the cylindrical support (2112) is increased by 200 ° C. to 350 ° C. by the support heating heater (2113).
Is controlled to a predetermined temperature.

A source gas for forming a deposited film is supplied to a reaction vessel (21).
To flow into 11), use a gas cylinder valve (2231).
To 2237), confirm that the leak valve (2117) of the reaction vessel is closed, and check the inflow valve (224).
1-2246), outflow valve (2251-2256),
After confirming that the auxiliary valve (2260) is open, first, the main valve (2118) is opened to exhaust the reaction vessel (2111) and the inside of the gas pipe (2116).

Next, the reading of the vacuum gauge (2119) was about 5 × 1.
When the ^pressure reaches 0 ^-6 Torr, the auxiliary valve (2260)
Close the outlet valves (2251-2256).

Thereafter, gas cylinders (2221-222)
From 6), each gas is introduced by opening the valves (2231-2236), and each gas pressure is adjusted to ² kg / cm ² by the pressure regulators (2261-2266). Next, the inflow valves (2241 to 2246) are gradually opened to introduce each gas into the mass flow controllers (2211 to 2216).

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

When the temperature of the cylindrical support (2112) reaches a predetermined temperature, necessary ones of the outflow valves (2251 to 2256) and the auxiliary valve (2260) are gradually opened, and a predetermined amount is opened from the gas cylinder (2221 to 2226). Of the reaction vessel (221) via the gas introduction pipe (2114).
Introduce in 1). Next, the mass flow controller (2
211 to 2216), each raw material gas is adjusted to a predetermined flow rate. At this time, the opening of the main valve (2118) is adjusted while watching the vacuum gauge (2119) so that the pressure in the reaction vessel (2111) becomes a predetermined pressure of 1 Torr or less. When the internal pressure becomes stable, frequency 1
A 3.56 MHz RF power source (not shown) is set to a desired power, and RF power is introduced into the reaction vessel (2111) through the high frequency matching box (2115) to generate glow discharge. The raw material gas introduced into the reaction vessel is decomposed by the discharge energy, and a deposited film containing silicon as a main component is formed on the cylindrical support (2112). After the formation of the desired film thickness, the supply of the RF power is stopped, the outflow valve is closed, the flow of gas into the reaction vessel is stopped, and the formation of the deposited film is completed.

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

When forming each layer, it goes without saying that all outflow valves other than the necessary gas are closed, and each gas is supplied to the reaction vessel (211).
1) Close the outflow valves (2251 to 2256), open the auxiliary valve (2260) and open the main valve to avoid remaining in the piping from the outflow valves (2251-2256) to the reaction vessel (2111). Valve (21
The operation of fully opening 18) and once evacuating the system to a high vacuum is performed as necessary.

In order to make the film formation uniform, it is also effective to rotate the support (2112) at a predetermined speed by a driving device (not shown) during the layer formation.

Further, it goes without saying that the above-mentioned gas types and valve operations are changed according to the conditions for forming each layer.

Next, a method for manufacturing an electrophotographic photosensitive member formed by a high-frequency plasma CVD (hereinafter abbreviated as “VHF-PCVD”) method using a VHF band frequency as a power supply will be described.

RF-PC in the manufacturing apparatus shown in FIG.
The deposition apparatus (2100) using the VD method is replaced with a deposition apparatus (3100) shown in FIG.
200), VH shown in FIG.
An electrophotographic photoreceptor manufacturing apparatus having the following configuration by the F-PCVD method can be obtained.

This apparatus is roughly classified into a reaction vessel (3111) having a vacuum-tight structure capable of reducing pressure, a supply device (2200) for raw material gas, and an exhaust device (not shown) for reducing the pressure inside the reaction vessel. ). Inside the reaction vessel (3111), a cylindrical support (3112), a heater for heating the support (3113), and a raw material gas introduction pipe (311)
4), an electrode (3115) is provided, and a high-frequency matching box (3116) is further connected to the electrode.
The inside of the reaction vessel (3111) is connected to a diffusion pump (not shown) through an exhaust pipe (3121).

The source gas supply device (2200) is made of SiH
₄ , cylinders (2221-2226) of raw material gases such as GeH ₄ , H ₂ , CH ₄ , B ₂ H ₆ , PH ₃ and valves (22
31-2236, 2241-2246, 2251-22
56) and a mass flow controller (2211-2)
216), and a cylinder for each source gas is connected to a gas introduction pipe (3114) in the reaction vessel (3111) via a valve (2260). A space (3130) surrounded by the cylindrical support (3112) forms a discharge space.

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

First, a cylindrical support (3112) is set in a reaction vessel (3111), the support (3112) is rotated by a driving device (3120), and the reaction is performed by an exhaust device (not shown) (for example, a vacuum pump). The inside of the vessel (3111) is evacuated through the exhaust pipe (3121), and the reaction vessel (311) is evacuated.
1) Adjust the pressure within 1 × 10 ⁻⁷ Torr or less. Subsequently, the temperature of the cylindrical support (3112) is heated and maintained at a predetermined temperature of 200 ° C. to 350 ° C. by the support heating heater (3116).

A source gas for forming a deposited film is supplied to a reaction vessel (31).
11), the gas cylinder valve (223)
1-2236), confirming that the leak valve (not shown) of the reaction vessel is closed, and checking the inflow valve (224)
1-2246), outflow valve (2251-2256),
After confirming that the auxiliary valve (2260) is open, first open the main valve (not shown) to open the reaction vessel (3).
111) and the inside of the gas pipe (3122).

Next, a vacuum gauge (not shown) reads about 5 × 10
^{When the} pressure reaches ^-6 Torr, the auxiliary valve (2260) and the outflow valves (2251 to 2256) are closed.

Thereafter, gas cylinders (2221-222)
From 6), each gas is introduced by opening the valves (2231-2236), and each gas pressure is adjusted to ² kg / cm ² by the pressure regulators (2261-2266). Next, the inflow valves (2241 to 2246) are gradually opened to introduce each gas into the mass flow controllers (2211 to 2216).

After the preparation for film formation is completed as described above, each layer is formed on the cylindrical support (3112) as follows.

When the temperature of the cylindrical support (3112) reaches a predetermined temperature, necessary ones of the outflow valves (2251 to 2256) and the auxiliary valve (2260) are gradually opened, and a predetermined amount is opened from the gas cylinder (2221 to 2226). Gas from the reaction vessel (311) via the gas introduction pipe (3117).
It is introduced into the discharge space (3130) in 1). Next, each raw material gas is adjusted by a mass flow controller (2211 to 2216) so as to have a predetermined flow rate. that time,
The opening of the main valve (not shown) is adjusted while watching the vacuum gauge (not shown) so that the pressure in the discharge space (3130) becomes a predetermined pressure of 1 Torr or less.

When the pressure becomes stable, the frequency becomes 500M.
Hz VHF power supply (not shown) is set to the desired power,
Discharge space (3) through matching box (3116)
130), VHF power is introduced to generate glow discharge. Thus, in the discharge space (3130) surrounded by the support (3112), the introduced source gas is excited by the discharge energy and dissociated, and a predetermined deposited film is formed on the cylindrical support (3112). You. At this time, the layer is rotated at a desired rotation speed by a support rotation motor (3120) in order to make the layer formation uniform.

After the desired film thickness is formed, the supply of VHF power is stopped, the outflow valve is closed to stop the gas from flowing into the reaction vessel, and the formation of the deposited film is completed.

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

When forming each layer, it goes without saying that all the outflow valves other than the necessary gas are closed, and each gas is supplied to the reaction vessel (311).
1) Close the outflow valves (2251 to 2256), open the auxiliary valve (2260) and open the main valve to avoid remaining in the piping from the outflow valves (2251 to 2256) to the reaction vessel (3111). An operation of fully opening a valve (not shown) and once evacuating the system to a high vacuum is performed as necessary.

It goes without saying that the above-mentioned gas types and valve operations are changed according to the conditions for forming each layer.

In any of the methods, the temperature of the support during the formation of the deposited film is particularly 200 ° C. to 350 ° C., preferably 230 ° C. to 330 ° C., more preferably 250 ° C.
The temperature is preferably from 300C to 300C.

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

In addition to the above, a method other than providing a reaction vessel other than the reaction vessel, heating the vessel, and then transporting the support in the reaction vessel in a vacuum may be used.

In particular, in the VHF-PCVD method,
The discharge space pressure is preferably 1 mTorr or more and 5 mTorr or more.
00 mTorr or less, more preferably 3 mTorr or more and 300 mTorr or less, most preferably 5 mTorr.
It is desirable to set it to not less than 100 mTorr.

The size and shape of the electrodes provided in the discharge space in the VHF-PCVD method may be any as long as they do not disturb the discharge, but practically 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.

The electrode may be made of any material as long as its surface becomes conductive. For example, stainless steel, Al, Cr, Mo, Au, In, Nb, Te, V,
Metals such as Ti, Pt, Pb, and Fe, alloys thereof, and glass, ceramics, and plastics whose surfaces are subjected to a conductive treatment are generally used.

[0200] As described above, the present invention has been improved from a conventional system for dehumidifying at a relatively low temperature which does not deteriorate the photoreceptor even when exposed to the photoreceptor for a long time with an improved heater and an improved heater. It has been found that extremely suitable image stabilization can be achieved by shifting to a dehumidification system of an electrophotographic device that gives an extremely high temperature to the photoconductor in a short time, that is, a system that became possible for the first time in combination with the photoconductor. .

The electrophotographic photosensitive member of the present invention has the specific configuration as described above, whereby various problems in the conventional electrophotographic photosensitive member composed of OPC and a-Si can be solved. It has been found that it brings out excellent electrical characteristics, optical characteristics, photoconductive characteristics, image characteristics, durability and use environment characteristics.

[0202]

EXAMPLES The effects of the present invention will be specifically described below with reference to examples. (1) Example 1 An aluminum cylinder having an outer diameter of 80 mm and a length of 358 mm was used as a base, and an alkoxymethylated nylon 5
% Methanol solution was applied by an immersion method to provide an undercoat layer (intermediate layer) having a thickness of 1 μm.

Next, titanyl phthalocyanine pigment was added to 10
Parts (parts by weight, hereinafter the same), 8 parts of polyvinyl butyral,
And 50 parts of cyclohexanone were mixed and dispersed in a sand mill using 100 parts of glass beads having a diameter of 1 mm for 20 hours. This dispersion is added with methyl ethyl ketone 70-120.
(Appropriate) parts were added and applied on the undercoat layer (intermediate layer).
After drying at 00 ° C. for 5 minutes, a 0.2 μm charge generation layer 15 was formed.

Next, on this charge generation layer 15, 10 parts of a styryl compound of the following structural formula was added.

[0205]

Embedded image 10 parts of bisphenol Z-type polycarbonate was dissolved in 65 parts of monochlorobenzene. This solution was applied on the substrate 11 by dipping, and dried with hot air at 120 ° C. for 60 minutes to form the charge transport layer 16 having a thickness of 20 μm.

Next, a protective layer having a thickness of 1.0 μm was provided on the charge transport layer 16 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: 0.1.
70 dl / g, melting point 258 ° C. (1 using a differential calorimeter)
The measurement was performed at a heating rate of 0 ° C./min. The measurement sample was 5 mg, and the polyester resin to be measured was 2 mg.
After melting at 80 ° C, it was quenched with 0 ° C ice water 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 (manufactured by Yuka Shell Epoxy)] in 100 ml of a phenol / tetrachloroethane (1: 1) mixed solution. I let it. Next, 3 parts of triphenylsulfonium hexafluoroantimonate (C) was added as a photopolymerization initiator to prepare a resin composition solution.

Light irradiation was performed by irradiating a 2 kW high-pressure mercury lamp (30 W / cm) at a temperature of 130 ° C. for 8 seconds from a position 20 cm away from the light source to cure.

The photosensitive drum of the photosensitive member 10 thus prepared is mounted on a copier [trade name: NP-4050 (manufactured by Canon Inc.)] in which an external heater and a heater inside the photosensitive body have been added and modified. The surface temperature of the photosensitive drum was adjusted to 40 ° C. under the heater setting conditions shown in Tables 1 to 4, and an endurance test of 200,000 sheets passed at a temperature of 24 ° C. and a relative humidity of 55% was performed. Further, after the endurance, the image was evaluated after being left overnight in a high temperature and high humidity environment of 32 ° C. and a relative humidity of 80%. Tables 1 to 4 show the results. (2) Comparative Example 1 A photoconductor was prepared in the same manner as in Example 1 except that the protective layer used in Example 1 was not used, and a durability test was performed as in Example 1. The results are shown in Tables 1 to 4. (3) Comparative Example 2 Instead of the protective layer used in Example 1, bisphenol Z was used as the same binder as that used in the charge transport layer 16.
4 parts of mold polycarbonate and 70 parts of monochlorobenzene,
One part of PTFE fine powder was mixed and dispersed in a sand mill for 10 hours to prepare a coating liquid. This coating liquid was applied on the charge transport layer 16 by a spray method so as to have a thickness of 1.0 μm to form a protective layer. A durability test was performed in the same manner as in Example 1. The results are shown in Tables 1 to 4.

In Tables 1 to 4, the temperature dependency indicates that when a certain receptive potential is applied, more specifically, when a constant high voltage is supplied to the main charger 102 or 402 in FIG. 1 or FIG. The temperature of 101 or 401 was changed from 25 ° C. (room temperature) to about 45 ° C., and the potential was measured. The change in the potential per 1 ° C. at this time was measured and expressed as a rate of change with respect to the receptive potential. More specifically, 0.5% / de
g is 3 V / de when the dark part receiving potential is 600 V.
g.

In Table 1, the temperature difference A is obtained by measuring the temperature of the surface of the photoreceptor and the back surface of the base with a thermocouple, and is obtained by measuring the temperature at the time when the surface of the photoreceptor reaches room temperature + 10 ° C. (Substrate back surface temperature ° C).

In Table 1, the image findings were evaluated as follows: first, so-called high-humidity flow, and second, damage and image defects due to damage on the surface of the photoreceptor due to heat from the heater.

In Table 1, power consumption was evaluated in terms of power consumed by the heater. In the comprehensive judgment, it was judged from the above results whether or not the object of the present invention was achieved.

In Table 1, the symbols are ：: excellent,
Δ: No problem in practical use, ×: Inferior.

As a result, the temperature difference between the surface of the photoreceptor and the back surface of the substrate is increased by a heat source close to the surface of the photoreceptor, and a temperature gradient of 1 deg. Good results were obtained for the high humidity image run.

In particular, in the case of the external heater A in which a heat source was provided with a heat-generating sintered body on a long ceramic substrate, this was remarkable.

[0217]

[Table 1] Next, in Table 2, under the conditions in Example 1, the temperature of the photoconductor back surface of the modified copier [trade name: NP-4050 (manufactured by Canon Inc.)] was measured with a thermocouple, and the temperature of the photoconductor surface temperature increase was measured. The image was printed under the condition that the heater was energized so as to increase.

In Table 2, the temperature difference B is obtained by measuring the temperature of the surface of the photoreceptor and the back surface of the photoreceptor with a thermocouple. -(Substrate back surface temperature ° C).

In Table 2, the image findings are as follows: first, a so-called high-humidity flow; second, damage due to photoreceptor surface damage;
The image density unevenness due to the eccentricity of the developing sleeve was evaluated.

In Table 2, the power consumption was evaluated with respect to the power consumed by the heater.

In the comprehensive judgment, it was judged from the above results whether or not the object of the present invention was achieved.

In Table 2, the symbols are ○: excellent,
Δ: No problem in practical use, ×: Inferior.

As a result, the temperature rise on the surface of the photoreceptor is made larger than the temperature rise on the back surface of the substrate by the heat source close to the surface of the photoreceptor. I got

In particular, in the case of the external heater A in which a heat source was provided with a heat generating sintered body on a long ceramic substrate, this was remarkable.

[0225]

[Table 2] In Table 3, under the conditions in Example 1, the temperature near the cleaner of the modified copier [trade name: NP-4050 (manufactured by Canon)] was measured, and the temperature rise of the surface of the photoconductor became larger. Image transfer was performed under the condition of energizing the heater.

In Table 3, the temperature difference C is obtained by measuring the temperature between the surface of the photoconductor and the vicinity of the cleaner with a thermocouple, and when the surface of the photoconductor reaches room temperature + 10 ° C. after the start of heating (temperature rise of the photoconductor surface). -(Temperature rise near the photoreceptor ° C).

In Table 3, the image findings are as follows: first, a so-called high-humidity flow; second, damage due to photoconductor surface damage;
In addition, image defects due to poor cleaning caused by cleaner blocking and the like were evaluated.

In Table 3, the power consumption was evaluated with respect to the power consumed by the heater.

In the comprehensive judgment, it was judged from the above results whether or not the object of the present invention was achieved.

In Table 3, the symbols are ：: excellent,
Δ: No problem in practical use, ×: Inferior.

As a result, when the surface of the photosensitive member is heated by a heat source close to the surface of the photosensitive member so that the temperature rise on the surface of the photosensitive member is larger than the temperature rise near the photosensitive member, good results without cleaning failure can be obtained. Obtained.

In particular, in the case of the external heater A in which the heat source was provided with a heat-generating sintered body on a long ceramic substrate, the temperature rise of the cleaner was drastically suppressed, and the effect was remarkable.

[0233]

[Table 3] In Table 4, under the conditions in Example 1, the single copy (one copy) of the modified copier [trade name: NP-4050 (manufactured by Canon)] was set to 10 seconds in the pre-rotation and 15 seconds to the discharge, and only during this time, the heater was used. The image transfer was performed under the condition of energizing.

In Table 4, the image findings were evaluated as follows: first, the so-called high-humidity flow, and second, the scratches and image defects due to the photoconductor surface damage by the heater.

In Table 4, the power consumption was evaluated with respect to the power consumed by the heater.

In the overall judgment, it was judged from the above results whether or not the object of the present invention was achieved.

In Table 4, the symbols are ：: excellent,
Δ: No problem in practical use, ×: Inferior.

As a result, when the temperature difference between the surface of the photoreceptor and the back surface of the substrate was increased by a heat source close to the surface of the photoreceptor and a temperature gradient of 1 deg. Despite very little heating time, good results have been obtained for high humidity image runs.

In particular, in the case of the external heater A in which a heat source was provided with a heat generating sintered body on a long ceramic substrate, this was remarkable.

[0240]

[Table 4] 4. Example 2 Using the apparatus for manufacturing an electrophotographic photoreceptor by the RF-PCDV method shown in FIG. 2, a charge injection blocking layer 12 was formed on a mirror-finished aluminum cylinder having a diameter of 108 mm under the conditions shown in Table 5. The photoconductor 10 including the photoconductive layer 13 and the surface layer 14 was manufactured. Further, SiH ₄ and H ₂ are added to the photoconductive layer 13.
Various photoconductors 10 were prepared by changing the mixing ratio and the discharge power.

The prepared photoreceptor 10 was set in an electrophotographic apparatus (a NP6150 manufactured by Canon was modified for testing).
The temperature dependence (temperature characteristics) of the charging ability, memory and image defects were evaluated.

The temperature characteristics were measured by changing the temperature of the photoreceptor from 25 ° C. (room temperature) to about 45 ° C., and measuring the change in charging power per 1 ° C. at this time. | 0.5% / deg | or less was judged to be acceptable. Specifically, the dark part receiving potential was set to 400 V, and | 2 V / deg | or less was determined to be acceptable.

Regarding the memory and the image deletion, the image was judged by visual observation.
3: No problem in practical use, 4: Rank in four stages: practically somewhat difficult. On the other hand, a film thickness of about 1 μm was formed on a glass substrate (Corning 7059) and a Si wafer placed on a cylindrical sample holder under the conditions for forming a photoconductive layer.
A-Si film was deposited. A for the deposited film on the glass substrate
Then, the characteristic energy (Eu) of the exponential function tail and the localized level density (DOS) are measured by CPM, and the hydrogen content of the deposited film on the Si wafer is measured by FTIR. It was measured. FIG. 5 shows the relationship between Eu and temperature characteristics at this time. O. 6 and 7 show the relationship between S, the memory, and the image flow. Each sample had a hydrogen content of 10
30 atomic%. As is clear from FIGS. 5, 6 and 7, Eu = 50 to 60 meV; O.
It has been found that it is necessary to set S = 1 × 10 ^{14 to} 5 × 10 ¹⁵ cm ⁻³ in order to obtain good electrophotographic characteristics. Below, blank

[0244]

[Table 5] With respect to the photoconductors having various electrophotographic characteristics having different temperature characteristics, the internal heater, the external heater A, and the external heater B are further applied to the above-described electrophotographic apparatus (a Canon NP6150 is modified for testing). The drum surface temperature was adjusted to 40 ° C. under each heater setting condition, and the temperature was set to 24 ° C.
And a durability test of 200,000 sheets passed at a relative humidity of 55%. Further, after the durability test, the image was evaluated after being left overnight in a high-temperature and high-humidity environment of 32 ° C. and a relative humidity of 80%.
Tables 8 to 9 and Tables 10 to 11 summarize the results.

In Tables 6 to 7, the temperature difference A is obtained by measuring the temperature between the surface of the photoreceptor and the back surface of the substrate with a thermocouple and measuring the temperature at the time when the surface of the photoreceptor reaches room temperature + 10 ° C. after the start of heating. ° C)-(substrate back surface temperature ° C).

In Tables 6 to 7, the image findings were evaluated as follows: first, the so-called high-humidity flow, and secondly, the potential fluctuation due to the fluctuation of the photosensitive member surface temperature caused by the heat from the heater, that is, the image density fluctuation caused by the temperature characteristics. did.

In Tables 6 to 7, the power consumption was evaluated with respect to the power consumed by the heater.

In Tables 6 to 7, the symbols ○: excellent, Δ: no problem in practical use, ×: inferior.

As a result, the temperature dependence of the receptive potential of the photoreceptor at 25 ° C. to 45 ° C. was | 0.5% / deg | or less, and the surface of the photoreceptor was heated by a heat source close to the surface of the photoreceptor. The temperature difference between the surface of the photoreceptor and the temperature of the back surface of the substrate is high, and a temperature gradient of 1 deg to 100 deg is provided and heating is performed. .

In particular, in the case of the external heater A in which the heat source for dehumidification was provided with a heat generating sintered body on a long ceramic substrate, the effect was remarkable.

[0251]

[Table 6]

[0252]

[Table 7] Similarly, a difference in temperature rise between the photoconductor surface and the back surface of the substrate is given,
Tables 8 to 9 summarize the effects of improving the high humidity image flow and the unevenness of the developing sleeve around the image density.

In Tables 8 to 9, the temperature of the back surface of the photoreceptor of the modified copier [trade name: NP-6150 (manufactured by Canon)] was measured with a thermocouple under the conditions in Example 2, and the surface temperature of the photoreceptor increased. The image was printed under the condition that the heater was energized so that the value of “” became larger.

In Tables 8 to 9, the temperature difference B was obtained by measuring the temperature of the surface of the photoreceptor and the back surface of the photoreceptor with a thermocouple. Temperature (° C)-(substrate back surface temperature ° C).

In Tables 8 to 9, the image findings were evaluated as follows: first, the so-called high-humidity flow, and second, the image density unevenness caused by sleeve eccentricity due to heat transfer from the drum heater to the developing sleeve.

In Tables 8 to 9, the power consumption was evaluated with respect to the power consumed by the heater.

In Tables 8 to 9, the symbols are:
Excellent, Δ: No problem in practical use, ×: Inferior.

As a result, the photosensitive member was heated so that the temperature dependency of the receptive potential at 25 ° C. to 45 ° C. was not more than | 0.5% / deg | and the rise in surface temperature was larger than the rise in back surface temperature of the substrate. , High humidity image flow, and unevenness in the periphery were obtained.

In particular, in the case of the external heater A in which a heat source was provided with a heat generating sintered body on a long ceramic substrate, this was remarkable.

[0260]

[Table 8]

[Table 9] Similarly, a difference in temperature rise between the photoconductor surface and the back surface of the substrate is given,
Tables 10 to 11 summarize the effects of improving high humidity image deletion and cleaner blocking.

In Table 10 to Table 11, the temperature difference C was measured by measuring the temperature of the surface of the photoreceptor and the vicinity of the cleaner with a thermocouple. Temperature rise (° C.) − (Temperature rise near the photoreceptor ° C.)

In Tables 10 to 11, the image findings were evaluated as follows: first, the so-called high-humidity flow, and second, image defects due to poor cleaning caused by cleaner blocking and the like.

In Tables 10 to 11, the power consumption was evaluated with respect to the power consumed by the heater.

In Tables 10 to 11, the symbols are as follows:
：: excellent, △: no problem in practical use, x: poor.

As a result, the photosensitive member was heated so that the temperature dependence of the receptive potential at 25 ° C. to 45 ° C. was not more than | 0.5% / deg | and the surface temperature rise was greater than the temperature rise near the photosensitive member. By doing so, good results were obtained for the high-humidity image flow.

In particular, in the case of the external heater A in which a heat source was provided with a heat generating sintered body on a long ceramic substrate, the effect was remarkable.

[0267]

[Table 10]

[0268]

[Table 11] Similarly, under the conditions in the second embodiment, a single copy (one copy) of the modified copier [trade name: NP-6150 (manufactured by Canon)] is set to 10 seconds in front rotation and 15 seconds to ejection,
Only during this time, the image was printed under the condition that the heater was energized.

In Tables 12 and 13, the image findings were evaluated firstly for a so-called high-humidity flow, and secondly for potential fluctuations due to fluctuations in the surface temperature of the photosensitive member due to heat from the heater, ie, image density fluctuations due to temperature characteristics. did.

In Tables 12 to 13, the power consumption was evaluated with respect to the power consumed by the heater.

In Tables 12 to 13, the symbols are ○: excellent, Δ: no problem in practical use, x: inferior.

As a result, the temperature dependence of the receptive potential of the photoreceptor at 25 ° C. to 45 ° C. was | 0.5% / deg | or less, and the surface of the photoreceptor was heated by a heat source close to the surface of the photoreceptor. The temperature difference between the surface of the photoreceptor and the temperature of the back surface of the substrate was high, and a temperature gradient of 1 deg. To 100 deg. Was provided.

In particular, in the case of the external heater A in which the heat source was provided with a heat generating sintered body on a long ceramic substrate, this was remarkable.

[0274]

[Table 12]

[0275]

[Table 13] 5. Example 3 Using the apparatus for manufacturing an electrophotographic photosensitive member shown in FIG.
An electrophotographic photoconductor was manufactured under the following manufacturing conditions. At this time, Eu of the photoconductive layer and D.E. O. S is 55me each
V, 2 × 10 ¹⁵ cm ⁻³ , and temperature characteristics were 1.1 V / deg. The temperature difference between the surface of the photoconductor and the temperature of the back surface of the substrate is increased by the external heater A to 1.5 deg.
The sample was heated with a temperature gradient of 2 and evaluated in the same manner as in Example 2. As a result, good electrophotographic characteristics were obtained as in Example 2.

[0276]

[Table 14] 6. Example 4 Using the apparatus for manufacturing an electrophotographic photosensitive member shown in FIG.
An electrophotographic photoconductor was manufactured under the following manufacturing conditions. At this time, Eu of the photoconductive layer and D.E. O. S is 50me each
V, 8 × 10 ¹⁴ cm ^-3 , temperature characteristic is -0.5 V / deg
Met. Then, the difference in temperature between the surface of the photoconductor and the temperature of the back surface of the substrate was increased by 2 ° C. by the external heater A, and the same evaluation as in Example 2 was performed. Obtained.

[0277]

[Table 15] 7. Example 5 Using the apparatus for manufacturing an electrophotographic photosensitive member shown in FIG.
An electrophotographic photoconductor was manufactured under the following manufacturing conditions. At this time, Eu of the photoconductive layer and D.E. O. S is 60me each
V, 5 × 10 ¹⁵ cm ⁻³ , and temperature characteristics were 0.8 V / deg. Then, the temperature rise difference between the surface of the photoconductor and the temperature near the photoconductor (upper of the cleaner) was increased by 3 ° C. using the external heater A, and the same evaluation as in Example 2 was performed. No blocking of waste toner,
Good electrophotographic properties were obtained.

[0278]

[Table 16]

[0279]

As described above, the present invention provides an improved heater and an improved heater from a conventional system for dehumidifying at a relatively low temperature, which does not deteriorate the photoreceptor even when exposed to the photoreceptor for a long period of time. Very suitable image stabilization can be achieved by shifting to a system that has become possible for the first time by combining with an improved photoreceptor, that is, a dehumidification system of an electrophotographic apparatus that applies an extremely high temperature to a photoreceptor in a short time. It became possible.

By using the electrophotographic photosensitive member of the present invention in the specific configuration as described above, various problems in the conventional electrophotographic photosensitive member composed of OPC and a-Si can be solved. In particular, it has become possible to bring out extremely excellent electrical characteristics, optical characteristics, photoconductive characteristics, image characteristics, durability and use environment characteristics.

In particular, in the present invention, the photoconductive layer is made of a-Si whose level in the gap is remarkably reduced, whereby the change of the surface potential due to the fluctuation of the surrounding environment is suppressed. It is characterized in that the occurrence of fatigue and optical memory becomes substantially negligible, and that it has extremely excellent potential characteristics and image characteristics.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view for explaining a conventional electrophotographic apparatus.

FIG. 2 is an example of an apparatus for forming a photoreceptive layer of the electrophotographic photosensitive member according to the present invention, and is a schematic explanatory view of an apparatus for manufacturing an electrophotographic photosensitive member by a glow discharge method using a high frequency in an RF band. It is.

FIG. 3 is an example of an apparatus for forming a photoreceptive layer of the electrophotographic photoreceptor of the present invention, and is a schematic explanatory view of an apparatus for producing an electrophotographic photoreceptor by a glow discharge method using VHF band high frequency. It is.

FIG. 4 is a schematic cross-sectional view illustrating an electrophotographic apparatus according to one embodiment of the present invention.

FIG. 5 is a diagram illustrating a relationship between characteristic energy (Eu) of an Urbach tail of a photoconductive layer in an electrophotographic photoreceptor and temperature characteristics.

FIG. 6 is a diagram showing the relationship between the local density of state (DOS) of the photoconductive layer and the optical memory in the electrophotographic photoreceptor of the present invention.

FIG. 7 is a diagram showing the relationship between the local density of state (DOS) of the photoconductive layer and the image deletion in the electrophotographic photoreceptor of the present invention.

FIG. 8 is a diagram showing the relationship between the absorption peak intensity ratio of the Si—H ₂ bond and the Si—H bond of the photoconductive layer and the halftone density unevenness (roughness) in the electrophotographic photoreceptor of the present invention.

FIG. 9 is a schematic view of a ceramic heater and a nichrome heater, which are one mode of the heating element of the present invention.

FIG. 10 is a diagram illustrating a heating rate and output characteristics of a heating element according to the present invention.

FIG. 11 is a diagram illustrating a layer configuration of an amorphous silicon photoconductor used in the present invention.

FIG. 12 is a diagram illustrating a layer configuration of an OPC photosensitive member used in the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 10 electrophotographic photoreceptor 11 support 12 charge absorption blocking layer 13 photoconductive layer 14 surface layer 15 charge generation layer 16 charge transport layer 17 photosensitive layer 101 photoreceptor 102 main charger 103 electrostatic latent image forming portion 104 developer 107 Cleaner 123 Heat source (inner heater) 401 Photoconductor 402 Main charger 403 Electrostatic latent image forming portion 404 Developing device 407 Cleaner 423 Heat source (external heater) 901 Ceramic substrate 902 Electric heating element 903 Protective film 911 Base 912 Nichrome electric heating element 110 Support 1102 Photosensitive layer 1103 Photoconductive layer 1104 Amorphous silicon based surface layer 1105 Amorphous silicon based charge injection blocking layer 1106 Charge generating layer 1107 Charge transporting layer 1203 Support 1202 Photosensitive layer 1205 Charge generating layer 1204 Charge transporting layer 120 Protective layer or surface layer 2100 Deposition device 2111 Reaction container 2112 Cylindrical support 2113 Support heating heater 2114 Source gas introduction pipe 2115 Matching box 2116 Source gas pipe 2117 Reaction vessel leak valve 2118 Main exhaust valve 2119 Vacuum gauge 2200 Source gas supply Apparatus 2211 to 2216 Mass flow controller 2221 to 2226 Raw material gas cylinder 2231 to 2236 Raw material gas cylinder valve 2241 to 2246 Gas inflow valve 2251 to 2256 Gas outflow valve 2261 to 2266 Pressure regulator 3100 Deposition device 3111 Reaction vessel 3112 Cylindrical support 3113 Support heating Heater 3114 source gas piping 3116 matching box

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-273253 (JP, A) JP-A-61-69087 (JP, A) JP-A-3-168677 (JP, A) JP-A-59-1984 9666 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 21/20 G03G 5/00 101

Claims (6)

(57) [Claims] 1. A method according to claim 1, wherein a silicon atom is a base material on the conductive substrate.
Non-single bond containing hydrogen atom and / or halogen atom
Having photoconductive layer made of crystalline material and exhibiting photoconductivity
Have a cylindrical photosensitive member formed by laminating a formed photosensitive layer from the layer
And, the photoreceptor is rotated repeatedly charging, exposure, development, transfer and cleaning Oite electrophotographic equipment, temperature dependency of receptive potential at 45 ° C. from 25 ° C. of the photoreceptor | 0.5% / deg | or less, and the temperature difference between the surface temperature of the photoconductor and the back surface temperature of the substrate is increased by the heat source close to the outer surface of the photoconductor on the photoconductor surface side, and 1 deg.
g and a temperature difference of 100 deg.
Heating is applied in which the rise in
An electrophotographic apparatus comprising a wetting device . 2. The electrophotographic apparatus according to claim 1, wherein said heat source is provided with a heat generating sintered body on a long ceramic substrate. 3. The electrophotographic apparatus according to claim 1, wherein the degree of increase in the front surface temperature is larger than the increase in the back surface temperature of the base. 4. The electrophotographic apparatus according to claim 1, wherein the degree of increase in the surface temperature is larger than the increase in the temperature near the photoconductor. 5. The electrophotographic apparatus according to claim 1, wherein the heat source is energized and heated only during image formation. Wherein said photosensitive member, the photoconductive layer 10-3
It contains 0 atomic% of hydrogen, and has a characteristic energy of 50-60 mem of an exponential function tail obtained from a sub-bandgap light absorption spectrum at least in a portion where light is incident.
V, and the density of localized states in the photoconductive layer is 1 × 10
^{2. The method according} to claim 1, wherein the size is ^{14 to} 5 × 10 ¹⁶ cm ^−3.
6. The electrophotographic apparatus according to any one of claims 1 to 5,