JP2002311612A - Electrophotographic method, electrophotographic photoreceptor and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic method which well functions a cleanerless toner recycling process when an amorphous silicon photoreceptor is used, an electrophotographic device and an electrophotographic photoreceptor. SOLUTION: The electrophotographic method and electrophotographic device are characterized in that the electrophotographic photoreceptor has a photoconductive layer composed of a non-single crystalline material consisting of silicon atoms as a base body and a first substrate layer composed of the non-single crystalline material on a conductive substrate and is laminated with a second surface layer containing the compound formed by polymerizing a compound having at least a chain polymerizable functional group by irradiation with electrons and conductive particles in the first surface layer and the electrostatic charging process step of electrostatically charges the surface of a body to be electrostatically charged by bringing electrostatic charging particles essentially consisting of the conductive particles of 10 nm to 10 μm in grain size into contact with the body to be electrostatically charged by an electrostatic charging particles carrier provided with a surface of electrical conductivity and elasticity and is absent of the cleaning process step from between the transfer to the electrostatic charging and the electrophotographic photoreceptor used for this method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic method, an electrophotographic apparatus, and an electrophotographic photoreceptor. More specifically, the present invention relates to an electrophotographic method and an electrophotographic apparatus for a specific system in which there is no cleaning step between transfer and charging. And an amorphous silicon electrophotographic photosensitive member to which a specific surface layer made of an electron beam curing compound is added.

[0002]

2. Description of the Related Art Conventionally, an electrophotographic method generally repeats a cycle of charging-exposure-development-transfer-cleaning of toner remaining after transfer-discharging of residual charges of a photoconductor-charging. In this method, transfer residual toner remaining on the photoreceptor (electrophotographic photoreceptor) after transfer is removed from the photoreceptor surface by a cleaner (cleaning device) to become waste toner. This waste toner is environmentally friendly. It is also preferable that this does not occur. Therefore, the electrophotographic device of the toner recycling process, which removes the cleaner and removes the transfer residual toner on the photoreceptor after transfer from the photoreceptor by "development simultaneous cleaning" by the developing device and collects and reuses it in the developing device Has also appeared.

[0003] Japanese Patent Application Laid-Open No. 10-307455 discloses such an electrophotographic apparatus. Simultaneous development and cleaning means that the toner remaining on the photoreceptor after transfer is developed during the next and subsequent steps, that is, the photoreceptor is subsequently charged and exposed to form a latent image. This is a method of recovering by a fog removal potential difference (Vback) which is a potential difference between a DC voltage applied to the developing device and a surface potential of the photoconductor. According to this method, the transfer residual toner is collected in the developing device and reused in the subsequent process and thereafter,
By eliminating waste toner, it is possible to reduce troublesome maintenance. In addition, the cleaner-less system has a great advantage in terms of space, and can greatly reduce the size of the electrophotographic apparatus.

Hereinafter, a toner recycling process will be briefly described with reference to FIG.

(1) The photosensitive member 201 is a contact charging member 202
As a result, a voltage is applied and the substrate is uniformly charged. In the case of this figure, it is negatively charged.

(2) On the photosensitive member 201 uniformly negatively charged, the exposure light 203 of the reversal development system corresponding to the image information is given to form a latent image.

(3) The toner 205, which is a colored powder to which a charge is applied from the developing unit 204, is supplied to the surface of the photoconductor 201 in a form corresponding to the latent image to form a visible image.

(4) The toner image is transferred to the transfer material 207 by applying a voltage by the transfer member 206 or applying an electrostatic attraction force, and is fixed by the fixing device 209. At this time, a part of the toner is transferred and remains, and a part of the toner is charged to a polarity opposite to the original polarity by a transfer charging member to which a voltage having a polarity opposite to that of the toner is applied. This is called a reversal toner 208.

(5) The transfer residual toner remaining on the photoreceptor surface has the same polarity as the charging polarity including the reversal toner due to the friction between the contact charging member 202 to which the voltage of (1) is applied and the photoreceptor 201. Is re-applied to the photoreceptor and discharged again onto the photoreceptor. Hereinafter, the toner at this stage is referred to as “discharge toner”. Aligning the inverted toner in the discharged toner to the original polarity is called "normalization of toner polarity". As a method for quantitatively measuring this degree, a charge amount measuring device “E-SPARTANAL” manufactured by Hosokawa Micron Corporation is used.
There is a method using “YZER MODEL EST-II”. A specific example will be described later.

(6) The toner 205 recharged with a charge having the same polarity as the charged polarity is again collected by the developing device 204 together with surplus toner during development by the developing bias of the developing device.

[0011] By such a series of cycles, a system that does not generate waste toner can be realized. The explanation here is
It is an overview and is not intended to be limiting.

Amorphous silicon photoreceptors have unmatched potential stability and are used especially in high-speed copying machines and high-speed printers. In particular, a photoconductor in which a photoconductive layer formed of a non-single-crystal material having silicon atoms as a base on a conductive substrate and a surface layer formed of a non-single-crystal material having carbon atoms as a base is laminated, Lubricating properties, high hardness,
It has excellent performance such as anti-fusing, long life and environmental stability from oxidation resistance.

There has been a great demand for excellent potential stability even in the field of small-sized machines and popularized machines, but the number of prints before the main body is rejected is at most one million, and amorphous silicon Due to the mismatch with the durable life of millions of bodies, it is not widely used.

In the cleanerless system described above, the amorphous silicon photoreceptor contains a charge series with toner and a charging member, specifically, a mismatch in work function and electronegativity of the photoreceptor surface. In the step (5), there is a phenomenon that the inverted toner in the discharged toner is converted into a polarity distribution that is difficult to be recovered even by the fog removing bias, specifically, an average polarity in a direction opposite to the charging polarity. There is a problem that a cleanerless system to which the merits of a silicon photoreceptor are sufficiently added cannot be achieved.

As a specific example, Comparative Example 1 indicated by a broken line in the charge amount distribution of the toner in FIG. 4 is a polarity distribution that is difficult to collect, in other words, an example where normalization is insufficient, and Example 1 indicated by a solid line. This is a normalized example of the polarity distribution that is easily collected.

In particular, a surface layer composed of a non-single-crystal material having carbon atoms as a matrix tends to be less normalized than a surface layer composed of an organic substance such as a resin. Image troubles such as thinness sometimes occurred.

Incidentally, Japanese Patent Application Laid-Open No. 8-220784 discloses that the charge transport layer of the photoreceptor is made of a cured product by an electron beam. JP-A-11-265085 discloses that the surface layer of a photoreceptor is cured by irradiation with radiation. JP-A-10-307455 discloses a toner recycling process for an amorphous silicon photoreceptor. JP-A-2000-98846 discloses that
There is a disclosure related to contact charging of an amorphous silicon photoconductor, particularly an amorphous silicon photoconductor having a surface layer made of amorphous carbon.

[0018]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned technical problems. Even when an amorphous silicon photoreceptor is used, the cleaner-less toner recycling process can function well. An object of the present invention is to provide an electrophotographic method, an electrophotographic apparatus, and an electrophotographic photosensitive member.

Another object of the present invention is to provide a novel amorphous silicon photosensitive member having a recycling effect and an image defect preventing effect which can be widely used in small-sized machines and popularized machines, and an electrophotography having the photosensitive body. A method and an electrophotographic apparatus are provided.

[0020]

According to the present invention, there is provided an electrophotographic photosensitive member, a charging step for charging a surface of the electrophotographic photosensitive member, and a latent image for forming an electrostatic latent image on a charged surface of the electrophotographic photosensitive member. An image forming step, a developing step of developing the electrostatic latent image as a toner image, and an electrophotographic method having a transfer step of transferring the toner image to a recording medium, wherein the electrophotographic photosensitive member is
There is a photoconductive layer made of a non-single-crystal material mainly composed of silicon atoms on a conductive substrate and a first surface layer made of a non-single-crystal material, and at least a chain is formed on the first surface layer. A second surface layer containing a compound obtained by polymerizing a compound having a polymerizable functional group by electron beam irradiation and conductive particles is laminated, and the charging step mainly includes conductive particles having a particle size of 10 nm to 10 μm. The charged particles are brought into contact with the charged object by a charged particle carrier having a surface having conductivity and elasticity, and the surface of the charged object is charged, and there is no cleaning process between transfer and charging. An electrophotographic method and an electrophotographic apparatus are provided.

According to the present invention, there is further provided a photoconductive layer composed of a non-single-crystal material mainly composed of silicon atoms on a conductive substrate, and a first surface layer composed of a non-single-crystal material. An electrophotographic photoreceptor having a second surface layer containing a compound obtained by polymerizing at least a compound having a chain polymerizable functional group on a first surface layer by electron beam irradiation and conductive particles is provided. You.

[0022]

Embodiments of the present invention will be described below in detail.

In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the step (5) of normalizing the reversal toner. It has been found that this process can be performed extremely smoothly and stably by using a high quality silicon photoreceptor.

More specifically, a photoconductive layer composed of a non-single-crystal material containing silicon atoms as a base material and a first surface layer are formed on a conductive substrate, and at least a chain polymerization is formed on the first surface layer. An electrophotographic photoreceptor having a second surface layer containing conductive particles and a compound obtained by polymerizing a compound having a functional functional group by electron beam irradiation, and the charging means having a particle size of 10
a charged particle mainly composed of conductive particles having a thickness of 10 nm to 10 μm, and a surface provided with conductivity and elasticity, comprising a charged particle carrier for supporting the charged particle, wherein the charged particle is An extremely good toner recycling process has been achieved by an electrophotographic method and apparatus using a charging means for contacting and charging the surface of an object to be charged and having no cleaning step from transfer to charging.

According to the study of the present inventors, it is a phenomenon that is controlled by the rubbing contact of the four elements on the contact charging member, the conductive particles, the toner, and the photoreceptor surface in the step (5). The most important parameter is the difference of the photoconductor surface.

It is clear why the surface layer made of an amorphous material has a difference in the normalized state and whether the surface layer made of a compound having a chain polymerizable functional group has a good effect on the normalization. Although the reason is not clear, Quas of the material
It is considered that there is a correlation between the value of i Fermi Level (eV) and the ratio of constituent elements of the material.

Specifically, when the value of QFL is large, the material itself tends to be negative and the other party tends to be positive.

The QFL of the surface layer was measured using a low energy photoelectron measuring device (manufactured by Riken Keiki Co., Ltd., surface analyzer AC-1 type). Specifically, photoelectrons excited by ultraviolet light in the atmosphere are measured. The excitation energy is changed by changing the wavelength of the ultraviolet light, and the excitation energy at which photoelectrons begin to be detected is determined. This value is QFL.
It is known that QFL is not a work function itself, but is effective as a value correlated with the work function.

The QFL of the surface layer mainly composed of amorphous silicon atoms used as the first surface layer is 4.2 to 5.0 eV.
The film obtained by polymerizing a compound having a chain polymerizable functional group as a main component by electron beam irradiation had a value of about 6 eV. When used as the second surface layer, the conductive particles mixed with the film, for example, tin oxide had a value of about 4 eV. The present inventors presume that the QFL of the conductive particles greatly contributes to the normalization of the discharged toner according to the present invention. That is, it is presumed that how small the QFL is contained in the surface layer is dominant.

The electrophotographic photoreceptor used in the present invention comprises a photoconductive layer made of a non-single-crystal material having silicon atoms as a base on a conductive substrate and a first surface layer. A second surface layer containing conductive particles and a compound obtained by polymerizing a compound having at least a chain polymerizable functional group by electron beam irradiation is provided thereon.

FIG. 1 is an example of a schematic sectional view of an electrophotographic photosensitive member 100 used in the present invention.

The a-Si photosensitive member shown in FIG. 1A has a conductive substrate 101 made of aluminum or the like, a charge injection blocking layer 102, a photoconductive layer 103, and a first conductive layer 103 sequentially laminated on the surface of the conductive substrate 101. , And a second surface layer 105. Here, the charge injection blocking layer 102 blocks charge injection from the conductive substrate 101 to the photoconductive layer 103, and is provided as necessary. Also, the photoconductive layer 1
Numeral 03 is made of an amorphous material containing at least silicon atoms and shows photoconductivity. Further, the first surface layer 1
04 and the second surface layer 105 are layers having an ability to retain a latent image in an electrophotographic apparatus.

As shown in FIG. 1B, the photoconductive layer 103
Are a charge transport layer 107 made of an amorphous material containing at least silicon atoms and carbon atoms, and a charge generation layer 106 made of an amorphous material containing at least silicon atoms.
May be a function-separated type having a configuration in which are sequentially stacked.

First, an outline of manufacturing a non-single-crystal silicon photoreceptor portion serving as a base will be described.

<Conductive Substrate> The substrate of the conductive substrate may be either conductive or electrically insulating. Examples of the conductive substrate include Al, Cr, Mo, Au, In, and N.
Examples include metals such as b, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof, for example, stainless steel. Also, polyester, polyethylene, polycarbonate,
Films or sheets of synthetic resins such as cellulose acetate, polypropylene, polyvinyl chloride, polystyrene and polyamide, and electrically insulating supports such as glass and ceramics at least on the surface on which the photosensitive layer is to be formed are also conductive substrates. Can be used as

<Photoconductive Layer> The photoconductive layer can be formed by, 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, or a vacuum method. It can be formed by various thin film deposition methods such as an evaporation method, an ion plating method, an optical 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 an electrophotographic photosensitive member for an image forming apparatus to be manufactured. The glow discharge method, especially in the RF band, μW band or V, is used because it is relatively easy to control the conditions for manufacturing an electrophotographic photosensitive member for an image forming apparatus having desired characteristics.
A high-frequency glow discharge method using a power supply frequency in the HF band is preferable.

In order to form the photoconductive layer 103 by the glow discharge method, it is basically known that silicon atoms (S
At least one of a source gas for supplying Si that can supply i), a source gas for supplying H that can supply hydrogen atoms (H), and a source gas for supplying X that can supply halogen atoms (X) Is introduced in a desired gas state into a reaction vessel in which the pressure can be reduced, a glow discharge is generated in the reaction vessel, the introduced raw material gas is decomposed, and a predetermined gas which is previously set at a predetermined position is introduced. A-Si on conductive substrate 101:
What is necessary is just to form the layer which consists of H and X.

Further, the dangling bonds of silicon atoms are compensated,
In order to improve the layer quality, in particular, the photoconductivity and the charge retention characteristics, it is necessary that the photoconductive layer 103 contains at least one of a hydrogen atom and a halogen atom. The content of atoms or the sum of hydrogen atoms and halogen atoms is preferably from 10 to 30 at%, more preferably from 15 to 25 at%, based on the sum of silicon, hydrogen and halogen atoms.

As the halogen compound which can be suitably used in the present invention, specifically, fluorine gas (F ₂ ), Br
_{F, ClF, ClF 3, BrF} 3, BrF 5, IF 3 and I
It can be exemplified interhalogen compounds such as F _7. Specific examples of the silicon compound containing a halogen atom, ie, a silane derivative substituted with a halogen atom, include, for example, S
Silicon fluoride such as iF ₄ or Si ₂ F ₆ can be mentioned as a preferable example.

In the present invention, it is preferable that the photoconductive layer 103 contains atoms for controlling conductivity as necessary. The atoms that control the conductivity may be contained in the photoconductive layer 103 in a uniformly distributed state, or may be contained in the layer thickness direction in a non-uniform distribution state. Is also good.

Examples of the atoms for controlling the conductivity include so-called impurities in the semiconductor field.
An atom belonging to Group 13 of the periodic table that gives p-type conduction properties (hereinafter abbreviated as “Group 13 atom”) or an atom belonging to Group 15 of the periodic table that gives n-type conduction properties (hereinafter “Group 15 atom”)
May be used.

Specific examples of Group 13 atoms include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). It is suitable. Specific examples of Group 15 atoms include phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi).
s is preferred.

The content of atoms for controlling the conductivity contained in the photoconductive layer 103 is preferably 1 × 10 ^-2 to 1
× 10 ⁴ atomic ppm, more preferably 5 × 10 ^{-2 to} 5 ×
Preferably, it is 10 ³ atomic ppm, most preferably 1 × 10 ^-1 to 1 × 10 ³ atomic ppm.

In order to structurally introduce an atom for controlling conductivity, for example, a group 13 atom or a group 15 atom, a source material for introducing a group 13 atom or a group 15 atom during formation of a layer. The raw material for introduction may be introduced into the reaction vessel in a gaseous state together with another gas for forming the photoconductive layer 103. As a raw material for introducing a Group 13 atom or a raw material for introducing a Group 15 atom, a material which is gaseous at ordinary temperature and normal pressure or which can be easily gasified at least under layer forming conditions is employed. Is preferred.

These raw materials for introducing atoms for controlling conductivity may be diluted with H ₂ , He or the like as necessary.

Further, in the present invention, the photoconductive layer 103
It is also effective to contain singly or plural kinds of atoms such as carbon atom, oxygen atom and nitrogen atom. The content of carbon atom, oxygen atom and nitrogen atom is preferably 1 to the sum of silicon atom, carbon atom, oxygen atom and nitrogen atom.
× 10 ^-5 to 10 atomic%, more preferably 1 × 10 ^-4 to 8
Atomic%, optimally 1 × 10 ^{−3 to} 5 atomic% is preferred. Carbon atoms, oxygen atoms and nitrogen atoms may be uniformly contained in the photoconductive layer, or may have a non-uniform distribution such that the content changes in the thickness direction of the photoconductive layer. There may be.

In the present invention, the thickness of the photoconductive layer 103 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, and is preferably 15 to 60 μm, more preferably 20 to 60 μm. It is preferably from 50 to 50 μm, most preferably from 20 to 40 μm. If it is less than 15 μm, the amount of current passing through the charging member increases, and the deterioration tends to be quick. When the thickness exceeds 60 μm, the abnormally grown portion of the a-Si photoreceptor becomes large.
μm, and 5 to 20 μm in the height direction, so that damage to the charging member rubbing the surface cannot be ignored.

The thickness of the photoconductive layer 103 can be adjusted by the film forming conditions such as the amount of the source gas introduced, and the like (a film thickness meter HELMUT FISHER GMBH).
It can be measured by using FisherScope mms (manufactured by Co., Ltd.), and the thickness of the photoconductive layer 103 can be confirmed.

Further, the temperature of the conductive substrate 101 is appropriately selected in an optimum range according to the layer design, but is usually preferably 200 to 350 ° C., and more preferably 23 ° C.
The temperature is preferably from 0 to 330C, most preferably from 250 to 310C.

<First Surface Layer> The electrophotographic photosensitive member used in the present invention has a first surface layer made of an amorphous material. Specifically, at least one of hydrogen (H) and halogen (X) and silicon (S
i), a-Si (C, O, N) formed by carbon (C), oxygen (O), and nitrogen (N): H (X) to a-C
(N): having a first surface layer composed of H (X).

Among them, a-SiC: H (X) and a-SiC: H (X)
C: H (X) has high hardness and excellent durability. In addition,
The thickness of the first surface layer is determined by measuring the degree of interference with a reflection spectroscopic interferometer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.).
The film thickness is calculated from this value and the known refractive index. The thickness of the surface layer described later can be adjusted by the film formation conditions. A preferable range of the film thickness is 0.01 μm to 5 μm.
m is preferable, and particularly preferably 0.1 μm to 2 μm.

The refractive index of the surface layer is 1.6 to 2.8.
It is suitably used if it is on the order of magnitude, preferably from 1.6 to 2.
2, particularly preferably 1.6 to 2.0. Here, the refractive index is measured by long-wavelength light multiplex interference. Specifically, a sample in which a surface layer is formed on a glass substrate (7059 manufactured by Coating) is applied to a visible spectroscope (330 manufactured by Hitachi, etc.).
Spectral transmittance is measured on the short wavelength side from around 2500 nm (wavelength range in which 4 to 5 extreme values are found), and the refractive index is calculated using the obtained extreme value wavelength / transmittance. The relative dielectric constant of the first surface layer 104 is obtained by squaring the refractive index.

The surface layer 104 is formed by, for example, a glow discharge method.
It can be formed by a known thin film deposition method such as 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
It is 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 photosensitive member for an image forming apparatus to be manufactured. Therefore, it is preferable to use a deposition method equivalent to that of the photoconductive layer.

The high-frequency power for decomposing the raw material gas is preferably as high as possible because the decomposition of the hydrocarbon proceeds sufficiently. Specifically, the unit time (min) of the raw material gas and the standard state (normal) ) Is 5 W · mi per unit volume (ml) of gas.
Although it is preferably n / ml (normal) or more, if it is too high, an abnormal discharge occurs and the characteristics of the electrophotographic photoreceptor deteriorate. Therefore, it is necessary to suppress the electric power to a level that does not cause the abnormal discharge. Regarding the pressure in the discharge space, when using normal RF (specifically, 13.56 MHz) power, 13.3 Pa to 1333 Pa (0.1 Torr) is used.
-10 Torr), VHF band (specifically, 50-450 Torr)
MHz) when using 0.133 Pa to 13.3 P
a (0.1 mTorr to 100 mTorr).

Further, in the present invention, it is preferable that the surface layer 104 contains atoms for controlling conductivity as necessary. The atoms for controlling the conductivity may be contained in the surface layer 104 in a state of being uniformly distributed without unevenness,
Alternatively, there may be a portion contained in a non-uniform distribution state in the layer thickness direction.

Examples of the atoms for controlling the conductivity include so-called impurities in the field of semiconductors, and "Group 13 atoms" or "Group 15 atoms" can be used.

Further, between the surface layer 104 and the photoconductive layer 103, the content of oxygen atoms and nitrogen atoms is reduced.
A region that changes so as to decrease toward may be provided. This improves the adhesion between the surface layer and the photoconductive layer,
The influence of interference due to light reflection at the interface can be further reduced.

Hereinafter, an example of a procedure for manufacturing an amorphous silicon photoreceptor using the apparatus shown in FIG. 3 will be described.

FIG. 3 is a diagram schematically showing an example of an electrophotographic photosensitive member deposition apparatus by an RF plasma CVD method using a high-frequency power supply.

This apparatus is roughly classified into a reaction vessel 2110
Device 2100 having source gas, source gas supply device 220
0, an exhaust device (not shown) for reducing the pressure inside the reaction vessel 2110. The conductive substrate 2 connected to the ground is provided in the reaction vessel 2110 in the deposition apparatus 2100.
112, a heater 2113 for heating the conductive substrate, and a raw material gas introduction pipe 2114 are provided, and a high frequency power supply 2120 is connected via a high frequency matching box 2115.

The raw material gas supply device 2200 includes SiH ₄ ,
_{H 2, CH 4, NO,} B 2 H 6 and CF _4, etc. of the raw material gas cylinders 2221 to 2226 and the valve 2231 to 2236, pressure regulators 2261 to 2266, flow-in valves 2241 to 2
246, outflow valves 2251 to 2256, and mass flow controllers 2211 to 2216. A gas cylinder filled with each source gas is connected to a source gas introduction pipe 2114 in a reaction vessel 2110 via an auxiliary valve 2260.

The conductive base 2112 is provided on the conductive pedestal 21.
23 is connected to the ground.

Hereinafter, an example of a procedure for producing an electrophotographic photosensitive member using the apparatus shown in FIG. 3 will be described.

A conductive substrate 2112 is placed in a reaction vessel 2110.
Is installed, and the inside of the reaction vessel 2110 is exhausted by an exhaust device (not shown) (for example, a vacuum pump). Subsequently, the temperature of the conductive substrate 2112 is controlled to a desired temperature of 20 ° C. to 500 ° C. by the heater 2113 for heating the conductive substrate. Then
A source gas for forming an electrophotographic photosensitive member is caused to flow into the reaction vessel 2110. The introduction of the raw material gas is performed by the valves 2231 to 2236 of the gas cylinder and the leak valve 2117 of the reaction vessel.
Is closed, and the inlet valve 22
After confirming that 41 to 2246, the outflow valves 2251 to 2256, and the auxiliary valve 2260 are open, the main valve 2118 is opened to exhaust the reaction vessel 2110 and the gas supply pipe 2116.

Thereafter, the reading of the vacuum gauge 2119 becomes 0.67.
When the pressure reaches mPa, the auxiliary valve 2260 and the outflow valves 2251 to 2256 are closed. Then the raw material gas cylinder 2
From 221 to 2226, each gas is supplied to a valve 2231 to 223.
6 is opened and introduced, and each gas pressure is adjusted to 2 kg / cm ² (0.2 MPa) by the pressure adjusters 2261 to 2266. Next, the inflow valves 2241 to 2246 are gradually opened, and each gas is supplied to the mass flow controllers 2211 to 221.
6 is introduced.

After the preparation for film formation is completed by the above procedure, first, a photoconductive layer is formed on the conductive base 2112.

That is, when the temperature of the conductive substrate 2112 reaches a desired temperature, each of the outflow valves 2251 to 2256
Are gradually opened, and the auxiliary valve 2260 is gradually opened, and a desired source gas is supplied from each source gas cylinder 2221 to 2226 through the source gas introduction pipe 2114 to the reaction vessel 21.
Introduce into 10. Next, each mass flow controller 2211 to 2216 adjusts each raw material gas to a desired flow rate. At this time, the inside of the reaction vessel 2110 is 1
Vacuum gauge 21 is set to a desired pressure of 33.3 Pa or less.
Adjust the opening of the main valve 2118 while looking at 19.

When the internal pressure becomes stable, the high-frequency power supply 21
20 is set to a desired power, for example, a frequency of 1 MHz to
A high frequency power of 450 MHz, for example, 13.56 MHz is supplied to the cathode electrode 2111 through the high frequency matching box 2115 to generate a high frequency glow discharge.
Each source gas introduced into the reaction vessel 2110 is decomposed by this discharge energy, and a photoconductive layer mainly containing silicon atoms is deposited on the conductive base 2112. After the desired layer thickness is formed, the supply of the high-frequency power is stopped, the outlet valves 2251 to 2256 are closed to stop the flow of the source gases into the reaction vessel 2110, and the formation of the photoconductive layer is completed.

Known compositions and thicknesses of the photoconductive layer can be used. When a surface layer is formed on the photoconductive layer, basically, the above operation may be repeated. In the case of lamination, the interface between the layers can be eliminated or continuously changed by continuously flowing a gas or continuously supplying high-frequency power.

Next, an outline of preparation of the second surface layer will be described.

The conductive particles contained in the second surface layer include metals, metal oxides and carbon black. Examples of the metal include aluminum, zinc, copper, nickel, silver, and stainless steel, and those obtained by vapor-depositing these metals on the surface of plastic particles. Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony and tantalum-doped tin oxide, and antimony-doped zirconium oxide. . These can be used alone or in combination of two or more. When used in combination of two or more, they may be simply mixed, or may be in a solid solution or fused form.

The average particle size of the conductive particles used in the present invention is preferably 0.3 μm or less, particularly preferably 0.1 μm or less, in view of the transparency of the second surface layer. In the present invention, among the above-described conductive particles, it is particularly preferable to use a metal oxide from the viewpoint of transparency.

Further, fluorine atom-containing resin particles can be dispersed in the second surface layer in order to improve the slipperiness of the photosensitive member surface. Examples of the fluorine atom-containing particles include ethylene tetrafluoride resin, ethylene trifluoride chloride resin, ethylene hexafluoride propylene resin, vinyl fluoride resin, vinylidene fluoride resin, ethylene dichloride diethylene resin, and copolymers thereof. It is preferable to appropriately select one kind or two or more kinds selected from the following, and particularly preferable are a tetrafluoroethylene resin and a vinylidene fluoride resin. The molecular weight of the resin particles and the particle size of the particles can be appropriately selected and are not particularly limited.

Further, a charge transporting material can be positively mixed into the second surface layer. Examples of the charge transport material include electron-withdrawing materials such as 2,4,7-trinitrofluorenone and 2,4,5,7-tetranitrofluorenone, and those obtained by polymerizing these electron-withdrawing materials. Can be Examples of the hole transport material include polycyclic aromatic compounds such as pyrene and anthracene; carbazole, indole, imidazole, oxazole, thiazole, oxydiazole, pyrazole, pyrazoline, thiadiazole and triazole compounds And the like. In addition to these organic charge transport materials, inorganic materials such as selenium, selenium-tellurium, and amorphous silicon can be used.

The compound having a chain polymerizable functional group contained in the second surface layer will be described below.

The chain polymerization in the present invention refers to the former type of polymerization reaction when the formation reaction of a high molecular compound is largely divided into chain polymerization and sequential polymerization, and is described in detail in “Basic Synthetic Resin” Chemistry (New Edition) "1995
July 25 (1st edition, 8th press) As described in 24, the form mainly refers to unsaturated polymerization, ring-opening polymerization, isomerization polymerization, and the like in which the reaction proceeds mainly through intermediates such as radicals or ions. The chain polymerizable functional group in the general formula (1) means a functional group capable of unsaturated polymerization in the above-mentioned reaction form, and specific examples of the unsaturated polymerizable functional group are shown below.

Unsaturated polymerization refers to an unsaturated group such as C ＝ C, C≡C, C ＝ O, C ＝
This is a reaction in which N or C≡N is polymerized.
It is. Specific examples of the unsaturated polymerizable functional group are shown in Table 1 below, but are not limited thereto.

[0078]

[Table 1]

In Table 1, the acryloyloxy group (6) and the methacryloyloxy group (7) are preferred from the viewpoint of polymerization characteristics.

Among the chain polymerizable functional groups according to the present invention as described above, those represented by the following general formula (1) are preferable.

[0081]

Embedded image

In the formula, E represents a hydrogen atom, a halogen atom,
An alkyl group which may have a group;
Reel group, cyano group, nitro group, alkoxy group, -CO
OR ¹(R¹Has a hydrogen atom, a halogen atom and a substituent
Alkyl group, aralkyl group which may have a substituent
Or an aryl group which may have a substituent) or -CONR
^TwoR^Three(R^TwoAnd R^ThreeRepresents a hydrogen atom, a halogen atom,
Alkyl group which may have, aral which may have a substituent
An aryl group which may have a kill group or a substituent;
May be the same or different), and W is
A divalent alkylene group which may have a substituent,
Divalent arylene group, -COO-, -CH_Two
-, -O-, -OO-, -S- or -CONR^Four− (R^Four
Represents a hydrogen atom, a halogen atom, and an optionally substituted
Kill group, aralkyl group or substituent which may have a substituent
An aryl group which may have a). f represents 0 or 1
You.

In the general formula (1), the halogen atom represented by E is a fluorine atom, a chlorine atom, a bromine atom or the like; the alkyl group is a methyl group, an ethyl group, a propyl group or a butyl group; Group, naphthyl group, anthryl group, pyrenyl group, thiophenyl group, furyl group and the like, and alkoxy group include methoxy group, ethoxy group and propoxy group.

Examples of the alkylene group represented by W include a methylene group, an ethylene group and a butylene group, and examples of the arylene group include a phenylene group, a naphthylene group and an anthracenylene group.

The halogen atom represented by R ¹ , R ² , R ³ and R ⁴ includes a fluorine atom, a chlorine atom and a bromine atom, and the alkyl group includes a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group and a thienyl group, and the aryl group includes a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a thiophenyl group and a furyl group. No.

Substituents which may be present in E and W include halogen atoms such as fluorine and chlorine atoms; nitro groups; cyano groups; hydroxyl groups; alkyl groups such as methyl and ethyl groups; Alkoxy such as an ethoxy group and the like can be mentioned.

The compound having a chain polymerizable functional group represented by the general formula (1) in the present invention is roughly classified into a monomer and an oligomer by repeating its structural unit. The monomer refers to a monomer having a relatively small molecular weight without repeating the structural unit having a chain polymerizable functional group represented by the general formula (1), and the oligomer refers to a chain polymerizable functional group represented by the general formula (1). The number of repetitions of the unit structure having the formula is 2 to 2
It is a polymer of about 0. Further, a macronomer having a chain polymerizable functional group represented by the general formula (1) only at the terminal of the polymer or oligomer can also be used as the second surface layer polymerizable compound of the present invention.

In the present invention, it is preferable to use a monomer from the viewpoint of achieving both durability and electrical characteristics of the photosensitive member. In addition, monomers having a functional group represented by the general formula (1) can be further classified according to the number of functional groups in one molecule, and those having one functional group in one molecule are called monofunctional monomers. Are called polyfunctional monomers.

In the present invention, it is preferable to use a polyfunctional monomer in order to sufficiently secure the hardness of the second surface layer, and more preferably a polyfunctional monomer having three or more chain-polymerizable functional groups in one molecule. It is preferred to use

As the oligomer having a chain-polymerizable functional group represented by the general formula (1), the repeating structural unit includes a chain-polymerizable functional group represented by the general formula (1) as shown in the compound example of Table 1. You only need to have a group.

In the solution in which the compound having a chain polymerizable functional group is dissolved, not only aromatic solvents such as toluene, xylene and monochlorobenzene but also ethers and ketones can be used as the solvent. In the present invention, it is necessary that the conductive particles are uniformly dispersed in the solution, and the mixing ratio of the conductive particles and the compound greatly changes depending on the particle size and resistivity of the conductive particles. It is appropriately selected depending on the combination.

As described above, the conductive particles are uniformly dispersed.
A solution comprising a compound having a chain polymerizable functional group is generally formed as a second surface layer by performing a polymerization / curing reaction after being applied on the first surface layer. However, it is also possible to form by applying a solution that has been dispersed or dissolved in a solvent again after a cured product is obtained by reacting the solution in advance.

[0093] The method of coating includes, for example, a dip coating method, a spray coating method, a curtain coating method and a spin coating method.

In providing the second surface layer on the first surface layer, it is preferable to polish the projections of the a-Si photosensitive member. Japanese Patent Publication No. 7-77702 discloses a polishing apparatus for a-Si photoreceptor.

FIG. 5 shows an example of the polishing apparatus. In FIG. 5, 500 is an a-Si photoreceptor, 520 is an elastic supporting mechanism and a rotating mechanism, specifically a pneumatic holder. In this experiment, a pneumatic holder made by Bridgestone Corporation (trade name: air pick, model number: PO45TCA *) 820) connected to a motor. 530 is a pressing elastic roller for winding a polishing tape and pressing the a-Si photoreceptor 500, 531 is a polishing tape, 532 is a delivery roll, 5
Reference numeral 33 denotes a take-up roll, and 534 and 535 denote fixed-rate feeding rolls and capstan rollers. The polishing tape 531 is preferably usually called a wrapping tape, and SiC, Al ₂ O ₃ , Fe ₂ O ₃ or the like is used as abrasive grains. Here, a wrapping tape LT-C2000 manufactured by Fuji Film Co., Ltd. was used.

Reference numeral 540 denotes a table for holding the photosensitive member support mechanism.
The photosensitive member 500 is rotated so as to be able to move back and forth with an accuracy of about 0.01 mm, and polishing is performed while adjusting the pressure with the polishing tape pressing roller 530.

In the present invention, the compound having a chain polymerizable functional group constituting the second surface layer applied on the first surface layer is polymerized by electron beam irradiation. When irradiating with an electron beam, any type of accelerator such as a scanning type, an electro-curtain type, a broad peak type, and a pulse type can be used. When irradiating with an electron beam, in the present invention, the acceleration voltage is preferably 250 kV or less, particularly preferably 150 kV or less. The dose is preferably 1 × 10 ⁴ Gy (1 Mra
d) to 1 × 10 ⁶ Gy (100 Mrad), more preferably 3 × 10 ⁴ Gy to ⁵ × 10 ⁵ Gy. When the acceleration voltage exceeds 250 kV, the damage of the electron beam irradiation to the photoconductor characteristics becomes remarkable. If the dose is 1
When the amount is less than × 10 ⁴ Gy, the polymerization becomes insufficient, and when the amount is more than 1 × 10 ⁶ Gy, the characteristics of the photoreceptor are adversely affected.

The thickness of the second surface layer by the above method is 1 to
It is preferably 50 μm, particularly preferably 1 to 30 μm.

Next, an outline of the electrophotographic method and the electrophotographic apparatus will be described.

FIG. 2 is a schematic diagram showing an example of a cleanerless image forming apparatus according to the present invention.

<Electrophotographic photosensitive member> 201 is a rotating drum type electrophotographic photosensitive member as the electrophotographic photosensitive member. The copying machine of the present embodiment employs reversal development, and the electrophotographic photosensitive member 201 is an a-Si based electron in which the above-mentioned second surface layer is formed on a negative a-Si photosensitive member having a diameter of, for example, 30 mm. It is a photoreceptor. The electrophotographic photosensitive member 201 is driven to rotate in the direction of the arrow at a peripheral speed of, for example, 200 mm / sec.

<Charging> It is essential that the charging device of the present invention has a charge providing ability for normalizing the transfer residual toner. In this category, corona charging, a method of applying a high voltage to a conductive member such as a roller to charge the photosensitive member in contact is not to be excluded, but the generation of ozone products is suppressed, and the transfer residual toner is suppressed. From the viewpoint of improving the normalization probability, a method in which charged particles are present between the conductive elastic roller and the photoconductor and a voltage close to the photoconductor charging potential is preferably applied.

Reference numeral 202 denotes a conductive elastic roller which is a charged particle carrier serving as a flexible contact charging member disposed in contact with the electrophotographic photosensitive member 201 with a predetermined pressing force. The outer periphery of the charging roller 202 is coated with and charged with charged particles M, and the charged particles M are present in a charging nip portion between the charging roller 202 and the electrophotographic photosensitive member 201.

In this embodiment, the charging roller 202 is rotationally driven at a peripheral speed of 50% in a direction (counter) opposite to the rotation direction of the electrophotographic photosensitive member 201 in the charging nip portion. Contact the surface with a speed difference. Then, a predetermined charging bias is applied to the charging roller 202 from a charging bias power supply.
Thus, the outer peripheral surface of the electrophotographic photosensitive member 201 is uniformly contact-charged to a predetermined polarity and potential by the injection charging method.

In the present embodiment, the developing site potential of the electrophotographic photosensitive member 201 is preferably 150 V to 800 V, particularly preferably 250 V to 600 V, and more preferably 300 V.
A charging bias is applied to the charging roller 202 from a charging bias power source so that the charging process is uniformly performed to 450 V. If the voltage is less than 150 V, the toner
−Si photoconductors cannot be developed, which accumulates and may cause adverse effects such as low image density. Also,
If the voltage exceeds 800 V, the amount of current passing through the charging member increases, and the deterioration of the charging member is accelerated, and the applied voltage is increased, which may cause partial discharge, which is not preferable.

The charging roller, charged particles M, injection charging and the like will be described in detail in another section.

<Exposure> 203 is intensity-modulated from a laser beam scanner (exposure device) as latent image forming means including a laser diode, a polygon mirror, and the like in accordance with a time-series electric digital pixel signal of target image information. Exposure light that outputs a laser beam and scans and exposes the uniformly charged surface of the electrophotographic photosensitive member 201 with the laser beam.
By this scanning exposure, an electrostatic latent image corresponding to the target image information is formed on the surface of the electrophotographic photosensitive member 201.

The light source used for the electrostatic latent image forming means is not limited to the above laser beam scanner, but may be an LED array. In this case, the LED at the position corresponding to the target image information is turned on, An electrostatic latent image is formed on the surface of the photoconductor 201.

<Developing> 204 is a developing device as a developing means. The electrostatic latent image formed on the electrophotographic photosensitive member 201 is developed by the developing device 204 as a toner image, here, a negatively charged toner 205.

<Transfer> Reference numeral 206 denotes a transfer roller of medium resistance, which is a transfer means as a contact transfer means, and is brought into predetermined contact with the electrophotographic photosensitive member 201 to form a transfer nip portion. A transfer material 20 as a recording medium (recording medium) is supplied to the transfer nip from a paper supply unit (not shown) at a predetermined timing.
7 is supplied, and a predetermined transfer bias voltage, here a positive charge is applied to the transfer roller 206, so that a toner image on the electrophotographic photosensitive member 201 side, here a negatively charged toner, is fed to the transfer nip portion. The transfer material 207 is sequentially transferred to the surface of the transferred transfer material 207 by electrostatic force and pressing force.

<Fixing> 209 is a fixing device such as a heat fixing system. The transfer material 207 to which the toner image on the electrophotographic photosensitive member 201 has been transferred is separated from the surface of the electrophotographic photosensitive member 201 and introduced into the fixing device 209, where the toner image is fixed and an image forming material (print or (Copy) is discharged out of the apparatus.

<Charging Roller> The charging roller 202 as a contact charging member in the present embodiment is manufactured by forming a medium-resistance layer of rubber or foam on a cored bar.

The medium resistance layer is formulated with a resin (eg, urethane), conductive particles (eg, carbon black), a sulfide agent, a foaming agent, and the like, and is formed in a roller shape on a cored bar.
Thereafter, the surface is polished if necessary.

When the roller resistance of the charging roller 202 of this embodiment was measured, the resistance was 100 kΩ. The roller resistance was measured by applying a voltage of 100 V between the core metal and the aluminum substrate in a state where the charging roller 202 was pressed against an aluminum substrate having a diameter of 30 mm so that a total pressure of 1 kg was applied to the core metal of the charging roller 202. .

Here, it is important that the charging roller 202 as a contact charging member functions as an electrode. That is, it is necessary to obtain a sufficient contact state with the member to be charged by providing elasticity, and at the same time, it is necessary to have a resistance low enough to charge the moving member to be charged. On the other hand, it is necessary to prevent voltage leakage when a low breakdown voltage defect site such as a pinhole is present in the charged body. When an electrophotographic photosensitive member for electrophotography is used as a member to be charged, a resistance of 10 ⁴ to 10 ⁷ Ω is preferable in order to obtain sufficient chargeability and leakage resistance.

The surface of the charging roller 202 is charged with the charged particles M
It is preferable that the substrate has microscopic irregularities so that the surface roughness can be maintained.

If the hardness of the charging roller 202 is too low, the shape is not stable, so that the contact property with the member to be charged is deteriorated. If the hardness is too high, only a charging nip portion cannot be secured between the roller and the member to be charged. However, since the microscopic contact with the surface of the member to be charged is deteriorated, the Asker C hardness is preferably in the range of 25 to 50 degrees. The hardness of the charging roller 202 can be measured using an Asker-C micro rubber hardness meter manufactured by Kobunshi Keiki Co., Ltd. More specifically,
The hardness meter measures the rubber hardness at any five points of the charging member, and the average value of the five points is defined as the hardness of the charging member.

The material of the charging roller 202 is not limited to an elastic foam.
EPDM, urethane, NBR, silicone rubber, IR
For example, a rubber material in which a conductive material such as carbon black or a metal oxide is dispersed for resistance adjustment, or a foamed material thereof is used. Further, it is also possible to adjust the resistance by using an ionic conductive material without dispersing the conductive substance.

The charging roller 202 is disposed so as to be pressed against the electrophotographic photosensitive member 201 as a member to be charged with a predetermined pressing force against elasticity. In this embodiment, a charging nip portion having a width of several mm is provided. It has been formed.

<Charged Particles> The charged particles used in the present invention are mainly composed of conductive particles having a particle size of 10 nm to 10 μm. In the present embodiment, conductive zinc oxide particles having a specific resistance of 10 ⁵ Ω · cm and an average particle diameter of 1.5 μm are used as the charged particles M. There is no problem that the charged particles exist not only in the state of primary particles but also in the state of aggregation of secondary particles. Regardless of the state of aggregation, the form is not important as long as the function as charged particles can be realized as an aggregate.

When the particles constitute an aggregate, the particle size is defined as the average particle size of the aggregate. The particle size was measured by observation using an optical or electron microscope.
Zero or more were extracted, the volume particle size distribution was calculated using the maximum chord length in the horizontal direction, and the 50% average particle size was determined.

The resistance value of the charged particles M is 10^TenOver Ω · cm
The charging property is easily impaired. Therefore, if the resistance value is 10
^TenΩ · cm or less, more preferably
10 ⁸Ω · cm or less. In this embodiment, 1 × 10^FiveΩ
・ Use the one of cm. Resistance is measured by the tablet method
And normalized. That is, the bottom area is 2.26 cm. ^Two
About 0.5 g of a powder sample is placed in a cylinder of
While applying 5 kg of pressure, a voltage of 100 V
The resistance was measured and then normalized to calculate the specific resistance.

The charged particles M are preferably white or nearly transparent so as not to hinder the exposure of the latent image, and are therefore preferably non-magnetic. Further, considering that the charged particles are partially transferred from the photoreceptor to the transfer material P, color recording is preferably colorless or white. If the particle size is not more than about 1/2 of the particle size of the toner, image exposure may be interrupted. Therefore, the particle size of the charged particles M is preferably smaller than 1/2 of the particle size of the toner. The lower limit of the particle size is considered to be 10 nm as a limit so that the particles can be stably obtained. In order to obtain good charging uniformity, the thickness is preferably 10 μm or less.

As the material of the charged particles M, zinc oxide is used in the present embodiment, but the material is not limited to zinc oxide. In addition, a mixture of other metal oxides such as titanium oxide and alumina with conductive inorganic particles and organic substances. Alternatively, various conductive particles such as those obtained by subjecting them to a surface treatment can be used. Also, 2
You may mix and use two or more.

In order for the conductive fine powder to be interposed in the contact portion, the charging means may be provided with a conductive fine powder replenishing means for supplying the conductive fine powder to the surface of the charging member, or the conductive fine powder may be added to the toner. There is a method of externally adding and indirectly intervening.

<Injection Charging> By interposing the charged particles M in the charging nip between the photosensitive member 201 and the charging roller 202 serving as a contact charging member, the frictional effect of the charged particles M causes a large frictional resistance. Even if it is difficult for the charging roller to make contact with the photoconductor 201 with a speed difference, the charging roller can be easily and effectively brought into contact with the surface of the photoconductor 201 with a speed difference. And the charging roller 20
2 comes into close contact with the surface of the photoconductor 201 via the charged particles M, and comes into contact with the surface of the photoconductor 201 more frequently.

By providing a sufficient speed difference between the charging roller 202 and the photosensitive member 201, the charging roller 20
In the charging nip portion of the photoconductor 201 and the photoconductor 201, the chance of the charged particles M coming into contact with the photoconductor 201 is significantly increased, and a high contact property can be obtained.
01 in the charging nip portion of the photoconductor 20
By rubbing one surface without gaps, electric charge can be directly injected into the photoconductor 201. Contact charging of the photoconductor 201 by the charging roller 202 is controlled by the injection charging mechanism due to the interposition of the charged particles M.

As a configuration for providing a speed difference, the charging roller 202 is driven to rotate or fixed to provide a speed difference from the photosensitive member 201. Preferably, the charging roller 202
, And the rotation direction is preferably rotated in a direction opposite to the moving direction of the surface of the photoconductor 201.

[0129]

The present invention will be described below in more detail with reference to specific examples. In addition, "part" in an Example shows a mass part.

Example 1 Manufacturing Example 1 of Electrophotographic Photoreceptor First, the RF shown in FIG.
Electrophotographic photoreceptor used for negative charging in which a lower blocking layer, a photoconductive layer, and a surface layer are sequentially laminated on an aluminum substrate having a diameter of 30 mm and a thickness of 2.5 mm using a plasma CVD apparatus according to the following conditions. Was prepared. After the fabrication, the abnormal projections of the a-Si photoreceptor were polished to a height of 1 μm or less by the polishing apparatus shown in FIG.

Lower blocking layer SiH ₄ 150 ml / min (normal) PH ₃ 500 ppm NO 10 ml / min (normal) Power 200 W Internal pressure 67 Pa Base temperature 240 ° C. Film thickness 1 μm Photoconductive layer SiH ₄ 200 ml / min (normal) Power 500 W Internal pressure 67 Pa Base temperature 240 ° C. Film thickness 25 μm First surface layer SiH ₄ 50 ml / min (normal) CH ₄ 500 ml / min (normal) Power 1500 w Internal pressure 67 Pa Base temperature 240 ° C. Film thickness 0.7 μm

Next, 25 parts of a compound having an acryloyloxy group and the following structural formula (11)

[0133]

Embedded image 50 parts of antimony-doped tin oxide ultrafine particles surface-treated (7% treatment amount) with the compound of
The mixture was dissolved in a mixed solvent of 140 parts by mass and dichloromethane of 140 parts, and tin oxide ultrafine particles were dispersed in a sand mill over 66 hours to prepare a second surface layer coating material. This paint was applied on the first surface layer of the non-single-crystal silicon photoreceptor by a spray coating method, and dried at 120 ° C. for 60 minutes.
An electron beam was irradiated under the conditions of an acceleration voltage of 150 KV and a dose of 3 × 10 ⁵ Gy to polymerize / harden the resin, thereby forming a second surface layer having a thickness of 3 μm, thereby producing an electrophotographic photosensitive member.

As the toner, a magnetic negative toner was used. Specifically, 0.1M-Na ₃ PO ₄ was added to 709 parts of ion-exchanged water.
After adding 451 parts of an aqueous solution and heating to 60 ° C., hydrochloric acid is added so that the pH after the addition of calcium chloride becomes 6.0, and then 67.7 parts of a 1.0 M CaCl ₂ aqueous solution is added. An aqueous medium containing a calcium phosphate salt was obtained.

Then, 78 parts of styrene and 22 parts of n-butyl acrylate O. And E. O. Unsaturated polyester resin obtained by condensation reaction between adduct and fumaric acid 2 parts Bisphenol A O. And E. O. Saturated polyester resin obtained by condensation reaction between adduct and terephthalic acid 3 parts Negative charge control agent (monoazo dye-based Fe compound) 1 part Surface-treated magnetic substance 1 90 parts Attritor (Mitsui Miike Chemical Co., Ltd. )) To uniformly disperse and mix.

The monomer composition was heated to 60 ° C., and 6 parts of an ester wax (maximum endothermic peak in DSC: 72 ° C.) was added thereto, mixed and dissolved, and the polymerization initiator 2,2′- 5 parts of azobis (2,4-dimethylvaleronitrile) [t1 / 2 = 140 minutes, at 60 ° C.] were dissolved.

The above-mentioned polymerizable monomer system was charged into the aqueous medium, and the mixture was heated at 10,000 rpm at 60 ° C. in a N ₂ atmosphere at 10,000 rpm with a TK type homomixer.
Stir for minutes and granulate. Thereafter, the mixture was reacted at 60 ° C. for 6 hours while stirring with a paddle stirring blade. Thereafter, the liquid temperature is set to 80
C. and continued stirring for another 4 hours. After completion of the reaction, distillation was further performed at 80 ° C. for 2 hours. Thereafter, the suspension was cooled, hydrochloric acid was added to dissolve the calcium phosphate salt, filtered, washed with water, and dried to obtain black particles having a weight average particle size of 7.0 μm. 1 was obtained.

The black particles (100 parts) were treated with hexamethyldisilazane, and then treated with silicone oil. After the treatment, 0.9 parts of a hydrophobic silica fine powder having a BET value of 180 m ² / g and charged particles were used. Specific resistance is 10 ⁵ Ω · c
m, conductive zinc oxide particles having an average particle diameter (secondary particle) of 1.5 μm and a Henschel mixer (Mitsui Miike Kakoki Co., Ltd.)
And mixed.

The produced electrophotographic photosensitive member was evaluated for the degree of normalization and the image quality of the discharged toner by an electrophotographic apparatus having the structure shown in FIG.

At the exposure site of the electrophotographic apparatus shown in FIG. 2, toner is discharged from the photoreceptor 201 and collected, and a charge amount measuring device “E-SPART AN” manufactured by Hosokawa Micron Corporation is used.
ALYZER MODEL EST-II "was used to measure the charge amount distribution. FIG. 4 shows the results of Example 1. As shown in FIG. 4, a negative charge distribution which was easily collected by the collection bias was shown.

As for the image quality, development fog caused by the reversal toner component was evaluated. As shown in FIG. 6, a solid black image was imaged only in a part, and the amount of transfer residual toner was changed in the longitudinal direction, and the degree of fog deterioration in the part where the transfer residual toner was increased was evaluated. There was almost no difference in fog between the solid black portion and the solid white portion, and the fog itself was also slight.

(Comparative Example 1) Next, FIG.
The lower blocking layer, the photoconductive layer, and the surface layer are sequentially laminated on a conductive substrate made of aluminum having a diameter of 30 mm and a thickness of 2.5 mm under the conditions shown below using the plasma CVD apparatus described in An electrophotographic photosensitive member was manufactured. After the fabrication, the abnormal projections of the a-Si photoreceptor were polished to a height of 1 μm or less by the polishing apparatus shown in FIG.

<Comparative Production Example 1 of Electrophotographic Photoreceptor> Lower Blocking Layer SiH ₄ 150 ml / min (normal) PH ₃ 500 ppm NO 10 ml / min (normal) Power 200 W Internal Pressure 67 Pa Base Temperature 240 ° C. Film Thickness 1 μm Photoconductive Layer SiH ₄ 200 ml / min (normal) Power 500 W Internal pressure 67 Pa Base temperature 240 ° C. Film thickness 25 μm Buffer layer SiH ₄ 50 mL / min (normal) CH ₄ 500 ml / min (normal) Power 1500 W Internal pressure 67 Pa Base temperature 240 ° C. Film thickness 0 0.7 μm ・ Surface layer CH ₄ 100 ml / min (normal) Power 800 w Internal pressure 47 Pa Base temperature 100 ° C. Film thickness 0.2 μm

The produced electrophotographic photosensitive member was evaluated for the degree of normalization and the image quality of the discharged toner by an electrophotographic apparatus having the structure shown in FIG. FIG. 4 shows the results of Comparative Example 1. FIG.
As shown in the figure, the charge distribution was relatively difficult to recover by the recovery bias.

Regarding the image quality, development fogging caused by the same reversal toner component as in Example 1 was evaluated. A difference in fog was observed between the solid black portion and the solid white portion, and fog after the solid black portion was observed.

(Example 2) A lower blocking layer, a photoconductive layer, and a surface layer were sequentially laminated on an aluminum conductive substrate having a diameter of 30 mm and a thickness of 2.5 mm according to the conditions described above used in Comparative Example 1. An electrophotographic photosensitive member used for negative charging was produced. After the fabrication, the abnormal projections of the a-Si photoreceptor were polished to a height of 1 μm or less by the polishing apparatus shown in FIG.

As the toner, a magnetic negative toner was used.

Specifically, a styrene / n-butyl acrylate copolymer (mass ratio 80/20) 100 parts Unsaturated polyester resin 2 parts Saturated polyester resin 3 parts Load control agent (monoazo dye-based Fe compound) 1 part Surface-treated magnetic substance 1 90 parts Ester wax used in developer 1 5 parts The above materials were mixed by a blender, melted and kneaded by a twin-screw extruder heated to 110 ° C, and the cooled kneaded material was hammer milled. After coarse pulverization, the coarsely pulverized product was finely pulverized by a jet mill, and the obtained finely pulverized product was subjected to air classification to obtain black particles 2 having a weight average particle size of 8.9 μm. A mixture obtained by adding 1.2 parts of hydrophobic silica fine powder to 100 parts of the black particles and conductive zinc oxide particles having an average particle size of 1.5 μm as charged particles was mixed and produced using a Henschel mixer.

Next, the second surface layer used in Example 1 was formed, and the produced electrophotographic photosensitive member was copied on an A4 paper sheet for one million sheets using an electrophotographic apparatus having the structure shown in FIG. . Although fog changed favorably, some circumferential scratches were observed in the image at 1 million sheets.

The photosensitive member was replaced with a polishing tape 531 of the polishing apparatus shown in FIG. 5 having a relatively soft and coarse abrasive, specifically, an abrasive having an alumina abrasive, and peeling off the second surface layer. Processed.

Next, the second surface layer used in Example 1 was formed again, and the produced electrophotographic photosensitive member was subjected to image evaluation using an electrophotographic apparatus having the structure shown in FIG. The image was reproduced so that good image quality without fog and scratches could be obtained.

[0152]

As described above, a photoconductive layer and a first surface layer made of a non-single-crystal material having silicon atoms as a base are provided on a conductive substrate. A second compound containing a compound obtained by polymerizing a compound having at least a chain polymerizable functional group by electron beam irradiation and a conductive particle
An electrophotographic photosensitive member having a surface layer. Further, using the photoreceptor, a charged particle having a conductive particle having a particle size of 10 nm to 10 μm as a main component, and a charged particle carrier having a surface having conductivity and elasticity, and carrying the charged particle. The charged particles are in contact with the member to be charged, and a charging means for charging the surface of the member to be charged is used.
While making use of the extremely stable latent image characteristics of the Si photoreceptor, the control of the charge amount of the discharged toner (toner to be recovered) in the recovery process cycle is stabilized, so that the cleaner-less toner recycling process can function well for a long time. became.

Further, the first surface layer having high hardness makes it easy to peel off the second surface layer, and achieves a system for reusing the a-Si photosensitive member having an extremely stable latent image characteristic many times. Was done.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a layer structure of an electrophotographic photosensitive member according to the present invention.

FIG. 2 is a schematic configuration diagram illustrating an embodiment of an image forming apparatus according to the present invention.

FIG. 3 is a schematic view showing an example of an apparatus for manufacturing an amorphous silicon electrophotographic photosensitive member by glow discharge using high frequency.

FIG. 4 is an example of a toner charge amount distribution measured by a charge amount measuring device.

FIG. 5 is a schematic view showing an example of an apparatus for polishing the surface of an amorphous silicon electrophotographic photosensitive member.

FIG. 6 is a diagram showing a method for evaluating development fog in an example.

[Explanation of symbols]

Reference Signs List 101 conductive substrate 102 charge injection blocking layer 103 photoconductive layer 104 first surface layer made of an amorphous material 105 containing a compound obtained by polymerizing a compound having a chain polymerizable functional group by electron beam irradiation and conductive particles Second
Surface layer 106 Charge generation layer 107 Charge transport layer 201 Electrophotographic photoreceptor 202 Contact charging member 203 Exposure light 204 Developing device 205 Toner 206 Transfer member 207 Transfer material 208 Inverted toner 209 Fixing device 2100 Deposition device 2110 Reaction container 2112 Conductive substrate 2113 Heating heater 2114 Gas introduction pipe 2115 Matching box 2116 Gas supply pipe 2117 Leak valve 2118 Main valve 2119 Vacuum gauge 2120 High frequency power supply 2123 Conductive pedestal 2200 Raw material gas supply device 2211 to 2216 Mass flow controller 2221 to 2226 Raw material gas cylinder 2231 to 2236 Valves 2241 to 2246 Inflow valves 2251 to 2256 Outflow valves 2260 Auxiliary valves 500 a-Si photoconductor 520 Air hose Rudder 530 Pressure elastic roller 531 Abrasive tape 532 Delivery roll 533 Take-up roll 534,535 Campstan roll 540 Holder

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) G03G 15/08 507 G03G 15/08 507B (72) Inventor Minoru Shimojo 3-30-2 Shimomaruko, Ota-ku, Tokyo No. Canon Inc. (72) Inventor Shoji Amemiya 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term (reference) 2H068 AA03 AA04 AA05 BA15 BB02 BB10 BB18 BB31 CA03 DA05 DA13 DA19 EA18 EA38 EA47 FC01 FC15 2H077 AA37 AC16 AD06 DB12 GA04 GA17 2H200 FA08 FA12 GA18 GA23 GA33 GA34 GA44 GA49 GA59 GB22 GB25 GB37 HA03 HA21 HA28 HB12 HB17 HB22 HB45 HB46 HB47 JA02 JA26 JB10 JB46 MA03 MA04 MA08 MA14 MA20 MC01 MB06 MC01

Claims (34)

[Claims] An electrophotographic photosensitive member, a charging step of charging a surface of the electrophotographic photosensitive member, a latent image forming step of forming an electrostatic latent image on a charged surface of the electrophotographic photosensitive member, An electrophotographic method comprising: a developing step of developing a latent image as a toner image; and a transfer step of transferring the toner image to a recording medium, wherein the electrophotographic photoreceptor includes a non-monolithic material having a silicon atom as a base on a conductive substrate. There is a photoconductive layer made of a crystalline material and a first surface layer made of a non-single-crystal material, and a compound having at least a chain polymerizable functional group on the first surface layer is polymerized by electron beam irradiation. A second surface layer containing the compound and the conductive particles is laminated, and the charging step includes charging the conductive particles having a particle diameter of 10 nm to 10 μm as a main component and having conductivity and elasticity. Covered by charged particle carrier with surface In contact with the body, the electrophotographic method, wherein the cleaning step is not between the charged and the charged surface, from the transfer to the charge. 2. The chain polymerizable functional group represented by the following general formula (1)
2. The electrode according to claim 1, which is an unsaturated polymerizable functional group represented by the formula:
Child photography method. Embedded imageＥ In the formula, E has a hydrogen atom, a halogen atom,
An alkyl group, an aryl group which may have a substituent,
Cyano group, nitro group, alkoxy group, -COOR ¹(R¹
Represents a hydrogen atom, a halogen atom, and an optionally substituted
Kill group, aralkyl group or substituent which may have a substituent
An aryl group optionally having) or -CONR^TwoR^Three(R^Two
And R^ThreeHas a hydrogen atom, a halogen atom, and a substituent
A good alkyl group, an aralkyl group which may have a substituent or
Represents an aryl group which may have a substituent, and is the same as each other
May be different from each other), and W represents a substituent
Alkylene group which may have, ant which may have a substituent
-Lene group, -COO-, -CH _Two-, -O-, -OO
-, -S- or -CONR^Four− (R^FourIs hydrogen atom, halogen
Atom, an alkyl group which may have a substituent,
Aralkyl group or ant which may have a substituent
Group). f represents 0 or 1; 3. The electrophotographic method according to claim 1, wherein the compound having a chain polymerizable functional group has two or more chain polymerizable functional groups in one molecule. 4. The chain polymerizable functional group represented by the general formula (1) is represented by the following structural formula (2) or (3).
The electrophotographic method according to any one of the above. Embedded image 5. The method according to claim 1, wherein W in the general formula (1) is an arylene group obtained by removing two hydrogen atoms from an aromatic hydrocarbon selected from benzene, naphthalene, anthracene and pyrene which may have a substituent. The electrophotographic method according to any one of 1 to 3. 6. The electrophotographic method according to claim 1, wherein the chain polymerizable functional group represented by the general formula (1) is represented by the following structural formula (4). Embedded image 7. The electrophotographic method according to claim 1, wherein the second surface layer contains a charge transport material. 8. The method according to claim 1, wherein the second surface layer is an ethylene tetrafluoride resin,
It is selected from the group consisting of ethylene trifluoride chloride resin, hexafluoroethylene propylene resin, vinyl fluoride resin, vinylidene fluoride resin, ethylene difluoride ethylene chloride resin and fluorine atom-containing resin particles composed of a copolymer thereof. The electrophotographic method according to any one of claims 1 to 7, comprising one or more kinds. 9. The electrophotographic method according to claim 1, wherein the acceleration voltage for electron beam irradiation is 250 KV or less. 10. The dose of electron beam irradiation is 1 × 10 ⁴ Gy or more.
The electrophotographic method according to claim 1, wherein the electrophotographic method is 1 × 10 ⁶ Gy. 11. The electrophotographic method according to claim 1, wherein the first surface layer is mainly composed of amorphous carbon. 12. The electrophotographic method according to claim 1, wherein the second surface layer is peeled off and re-laminated to form an image. 13. A photoconductive layer composed of a non-single-crystal material mainly composed of silicon atoms on a conductive substrate and a first surface layer composed of a non-single-crystal material, and further comprising the first surface. An electrophotographic photoreceptor having a second surface layer containing conductive particles and a compound obtained by polymerizing a compound having at least a chain polymerizable functional group by electron beam irradiation on a layer. 14. The electrophotographic photosensitive member according to claim 13, wherein the chain polymerizable functional group is an unsaturated polymerizable functional group represented by the general formula (1). 15. The compound having a chain polymerizable functional group is 1
14. A molecule having two or more chain polymerizable functional groups in the molecule.
Or the electrophotographic photosensitive member according to 14. 16. The chain polymerizable functional group represented by the general formula (1) is a structural formula (2) or a formula (3).
5. The electrophotographic photosensitive member according to any one of 5. 17. The method according to claim 1, wherein W in the general formula (1) is an arylene group obtained by removing two hydrogen atoms from an aromatic hydrocarbon selected from benzene, naphthalene, anthracene and pyrene which may have a substituent. The electrophotographic photosensitive member according to any one of 13 to 15, wherein 18. The electrophotographic photoreceptor according to claim 13, wherein the chain polymerizable functional group represented by the general formula (1) is a structural formula (4). 19. The electrophotographic photosensitive member according to claim 13, wherein the second surface layer contains a charge transport material. 20. A second surface layer comprising an ethylene tetrafluoride resin, an ethylene trifluoride chloride resin, a hexafluoroethylene propylene resin, a vinyl fluoride resin, a vinylidene fluoride resin, an ethylene dichloride ethylene chloride resin and the like. 20. The electrophotographic photosensitive member according to any one of claims 13 to 19, comprising one or more members selected from the group consisting of fluorine atom-containing resin particles made of a copolymer of 21. The electrophotographic photosensitive member according to claim 13, wherein an acceleration voltage of electron beam irradiation is 250 KV or less. 22. An electron beam irradiation dose of 1 × 10 ⁴ Gy to
The electrophotographic photoreceptor according to any one of claims 13 to 21, wherein the electrophotographic photoreceptor has 1 x 10 ⁶ Gy. 23. The electrophotographic photosensitive member according to claim 13, wherein the first surface layer is mainly composed of amorphous carbon. 24. An electrophotographic photosensitive member, charging means for charging a surface of the electrophotographic photosensitive member, latent image forming means for forming an electrostatic latent image on a charged surface of the electrophotographic photosensitive member, An electrophotographic apparatus comprising: developing means for developing a latent image as a toner image; and transfer means for transferring the toner image to a recording medium, wherein the electrophotographic photoreceptor includes a non-conductive material having silicon atoms as a base on a conductive substrate. A photoconductive layer made of a single-crystal material and a first surface layer made of a non-single-crystal material;
A second surface layer containing a compound obtained by polymerizing at least a compound having a chain-polymerizable functional group by electron beam irradiation and a conductive particle on the surface layer, wherein the charging means has a particle size of 10 nm to 10 μm. A charged particle having a conductive particle as a main component, and a charged particle carrier having a surface having conductivity and elasticity and supporting the charged particle, the charged particle is brought into contact with the charged object, An electrophotographic apparatus characterized in that a charged body surface is charged, and there is no cleaning process between transfer and charging. 25. The electrophotographic apparatus according to claim 24, wherein the chain polymerizable functional group is an unsaturated polymerizable functional group represented by the general formula (1). 26. The compound having a chain polymerizable functional group is 1
25. A molecule having two or more chain polymerizable functional groups in the molecule.
Or the electrophotographic apparatus according to 25. 27. The chain polymerizable functional group represented by the general formula (1) is a structural formula (2) or (3).
An electrophotographic apparatus according to any one of the above. 28. The method according to claim 1, wherein W in the general formula (1) is an arylene group obtained by removing two hydrogen atoms from an aromatic hydrocarbon selected from benzene, naphthalene, anthracene and pyrene which may have a substituent. The electrophotographic apparatus according to any one of 24 to 27. 29. The electrophotographic apparatus according to claim 24, wherein the chain polymerizable functional group represented by the general formula (1) is a structural formula (4). 30. The electrophotographic apparatus according to claim 24, wherein the second surface layer contains a charge transport material. 31. A second surface layer comprising an ethylene tetrafluoride resin, an ethylene trifluoride chloride resin, a hexafluoroethylene propylene resin, a vinyl fluoride resin, a vinylidene fluoride resin, an ethylene difluoride ethylene chloride resin and the like. 31. The electrophotographic apparatus according to claim 24, wherein the electrophotographic apparatus contains one or more kinds selected from the group consisting of fluorine atom-containing resin particles made of a copolymer of 32. The electrophotographic apparatus according to claim 24, wherein an acceleration voltage of electron beam irradiation is 250 KV or less. 33. The electrophotographic apparatus according to claim 24, wherein the dose of electron beam irradiation is 1 × 10 ⁴ Gy or more and 1 × 10 ⁶ Gy or less. 34. The electrophotographic apparatus according to claim 24, wherein the first surface layer is mainly composed of amorphous carbon.