JPH0876397A - Electrophotographic photoreceptor, its production and image forming method - Google Patents

Abstract

PURPOSE: To obtain an org. photoreceptor which can be produced at low temp., has high hardness, excellent wear resistance, and excellent optical characteristics and electric characteristics, and has a surface with low frictional force and low energy excellent in oxidation resistance. CONSTITUTION: This electrophotographic photoreceptor has at least an org. photoconductive layer 2 and a surface layer 3 on a conductive substrate 1. The surface layer 3 consists of amorphous silicon containing nitrogen, and if necessary, group III elements or group V elements. The absorbance by stretching vibration in the IR spectrum shows the relation of N-H>Si-H. Also, the production method of the photoreceptor and the image forming method is obtd. by this invention.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member having an organic photoconductive layer, a method for manufacturing the same, and a method for forming an image using the photosensitive member.

[0002]

2. Description of the Related Art Recently, as an electrophotographic photoreceptor, a photoreceptor having a photoconductive layer containing an organic photoconductor as a main component has been widely used. Such an organic photoconductor is superior in electrical characteristics such as charging property, dark decay, and infrared sensitivity to a selenium-based photoconductor or an amorphous silicon photoconductor, and is used as a low-cost photoconductor. There is. However, when this organic photoconductor is used in an electrophotographic process, it is oxidized by ozone generated in the charging step and further deteriorated by nitrogen oxides, and the residual toner cleaning step after transfer of a developed image is performed. However, there is a problem in that the filming phenomenon in which fine particles used as an external additive for toner adhere to the surface of the photoconductor is apt to occur, and image fogging, stains, and white spots occur, thereby deteriorating the image quality. Further, the organic photoreceptor has a drawback that it is easily worn by a cleaning blade, a carrier, or toner after long-term use, and has a shorter life than the selenium-based photoreceptor or the amorphous silicon photoreceptor.

On the other hand, by laminating an a-Si layer as a photoconductor and a surface Si ₃ N ₄ film on the organic photoconductor by the plasma CVD method, versatility of sensitivity and durability are improved. It has been proposed (Japanese Patent Laid-Open No. 58-806).
47 gazette). However, the organic photoconductor and a-Si:
It was difficult to match the injection and transport properties of the photo-generated carriers at the interface with H, and it was also difficult to obtain the photoconductivity of amorphous silicon at a low temperature according to the heat resistance of the organic photoconductor.

As a hard surface layer material, aC: H
Alternatively, a surface modification treatment using a material such as a-C: H, F or other amorphous carbon or diamond carbon has been proposed (see Japanese Patent Laid-Open No. 1-219755). However, the adhesiveness with the organic photoconductive layer is insufficient, cracks and cracks occur due to hardness difference, and further, the hardness is insufficient due to low temperature film formation, and the discharge product adsorption due to surface activity and the adhesion of toner image There was a problem that the quality deteriorated. Therefore, by heating the photoreceptor and keeping it in a dry state at all times, or by treating the surface of the photoreceptor with an abrasive or the like,
It was necessary to prevent foreign matter from sticking.

Since the above method requires constant heating, there is a problem in usage, such as a reduction in energy consumption and a long period of time from when the copying machine or printer is powered on until it can be operated. In addition, since the temperature of the photoconductor is high, the temperature inside the developing machine becomes 45 ° C or higher in the summer and high temperature areas, which causes the developer to block and makes the conveyance uneven, resulting in image defects such as white streaks and black streaks. It tends to occur. As a result, there is a problem that the low temperature fixing toner cannot be used while the material of the toner is limited and the energy saving is demanded in recent years.

[0006]

Therefore, the present invention solves the above-mentioned drawbacks in the electrophotographic photoreceptor having an organic photoconductive layer and a surface layer on a conductive substrate, and makes it possible to produce a photoreceptor at a low temperature. Possible, high hardness, excellent wear resistance, optical characteristics,
It is an object of the present invention to provide an organic photoreceptor having excellent electrical characteristics, a low friction surface and a low energy surface, and having oxidation resistance.

Another object of the present invention is to provide an organic photoconductor which does not require a drum heater, facilitates cleaning of residual toner, and can be downsized at low cost. Furthermore, the present invention has sufficient resistance to ultraviolet rays and organic solvents, has a long life, is highly reliable, and is capable of realizing high-quality imaged organic photoreceptor, a method for producing the same, and the photoreceptor. It is intended to provide an image forming method used. Specifically, the present invention aims to provide an organic photoreceptor having good abrasion resistance, good adhesion to an organic photosensitive layer, and good images over a large number of sheets. Another object of the present invention is to provide an organic photoreceptor in which the surface layer has good electrical and optical characteristics.

[0008]

The present invention makes it possible to solve the above problems by adopting the following configuration. (1) In an electrophotographic photosensitive member having at least an organic photoconductive layer and a surface layer on a conductive substrate, the surface layer is made of amorphous silicon containing nitrogen, and the surface layer has an absorbance of infrared spectrum stretching vibration of N. An electrophotographic photoreceptor having a relationship of -H> Si-H.

(2) In an electrophotographic photoreceptor having at least an organic photoconductive layer and a surface layer on a conductive substrate, the surface layer is made of amorphous silicon containing nitrogen, and the infrared spectrum stretching vibration of the surface layer. Absorbance of NH>
An electrophotographic photosensitive member having a relationship of Si-H and having a hydrogen amount in a range of 1 to 10 atomic%.

(3) In an electrophotographic photosensitive member having at least an organic photoconductive layer and a surface layer on a conductive substrate, the surface layer contains nitrogen and a group III element and / or a group V element. It is made of amorphous silicon, and the absorbance of the infrared spectrum stretching vibration of the surface layer is NH> S.
An electrophotographic photoreceptor having an i-H relationship and having a hydrogen content in the range of 1 to 10 atomic%.

(4) In an electrophotographic photoreceptor having at least an organic photoconductive layer and a surface layer on a conductive substrate, the surface layer is made of amorphous silicon containing nitrogen and halogen, and the infrared spectrum expansion and contraction of the surface layer. An electrophotographic photosensitive member characterized in that the absorbance of vibration has a relationship of N-H> Si-H.

(5) In an electrophotographic photoreceptor having at least an organic photoconductive layer and a surface layer on a conductive substrate, the surface layer is made of amorphous silicon containing nitrogen and halogen, and the infrared spectrum of the surface layer. The absorption of stretching vibration has a relationship of N-H> Si-H, and the amount of hydrogen is 1 to 10
An electrophotographic photosensitive member characterized by being in the range of atomic%.

(6) In an electrophotographic photosensitive member having at least an organic photoconductive layer and a surface layer on a conductive substrate, the surface layer contains nitrogen, halogen, and a group III element and / or a group V element. Consisting of containing amorphous silicon,
Moreover, the absorbance of infrared spectrum stretching vibration of the surface layer has a relationship of N-H> Si-H, and the amount of hydrogen is in the range of 1 to 10 atomic%.

(7) The contact angle of the surface layer with pure water is 85 ° to 1
The electrophotographic photosensitive member according to any one of the above (1) to (6), which is in the range of 40 °. (8) The electrophotographic photoreceptor according to any one of the above (1) to (7), wherein an intermediate layer is provided between the surface layer and the photoconductive layer. (9) The electrophotographic photoconductor according to any one of (1) to (8) above, wherein the organic photoconductive layer comprises a charge transport layer and a charge generation layer.

(10) In a method of forming at least an organic photoconductive layer and a surface layer on a conductive substrate, a hydrogen gas is used as a raw material from a silicon hydride gas and / or a silicon halide gas and a nitrogen gas. The substrate temperature is 80 to 2 without addition.
A method for producing an electrophotographic photosensitive member, characterized in that the surface layer is decomposed by a glow discharge method while being heated to 00 ° C., and the absorbance of infrared spectrum stretching vibration has a relationship of N—H> Si—H. .

(11) In a method of forming at least an organic photoconductive layer and a surface layer on a conductive substrate, a hydrogenated silicon gas and / or a halogenated silicon gas, and a Group III element or a Group V element Using nitrogen gas with added ingredients as a raw material,
The surface layer is decomposed by the glow discharge method while heating the substrate temperature to 80 to 200 ° C. without adding hydrogen gas, and the absorbance of infrared spectrum stretching vibration has a relationship of NH> Si—H. A method of manufacturing an electrophotographic photosensitive member, comprising:

(12) In the image forming method, comprising the steps of charging the image forming member, forming a latent image on the image forming member, and developing the latent image on the image forming member.
An image forming method using the photoconductor according to any one of (1) to (9).

[0018]

In the present invention, by providing a specific amorphous silicon surface layer on the organic photoconductive layer, the adhesiveness between the two can be improved and cracks and breakage can be prevented. Further, by stacking the surface layers or changing the gas, a concentration gradient can be provided, and by providing the high surface energy portion and the low surface energy portion, a photoreceptor having more excellent durability can be obtained.

1 to 4 are schematic cross-sectional views of an electrophotographic photosensitive member which is one specific example of the present invention. FIG. 1 shows a photoconductor in which an organic photoconductive layer 2 and a surface layer 3 are laminated on a conductive substrate 1. FIG. 2 shows a photoconductor in which a charge injection blocking layer 4 is provided between the conductive substrate 1 and the photoconductive layer 2 of FIG. FIG.
The photoconductive layer is a photoreceptor having a charge generation layer 5 and a charge transport layer 6. FIG. 4 shows a photoconductor in which the intermediate layer 7 is provided between the surface layer and the photoconductive layer.

Examples of the conductive substrate used in the present invention include metals such as aluminum, stainless steel, nickel and chromium, and alloys thereof. Alternatively, an insulative substrate whose surface has been subjected to a conductive treatment may be used. As the insulating substrate, polyester, polyethylene, polycarbonate, polystyrene, polyamide,
Polymer film or sheet such as polyimide, glass,
Ceramics etc. can be mentioned. The conductive treatment is performed by depositing the above metal, gold, silver, copper or the like by a vapor deposition method, a sputtering method, an ion plating method or the like.

The conductive support used in the present invention can be formed of Cr-Ni-containing steel which is an austenitic stainless steel, and the surface of which is a conductive material containing Mo, Cr, Mn, W or Ti as a main component. It is preferable to form a layer.
These conductive layers can be formed by a plating method, a sputtering method, an evaporation method, or the like. Further, the conductive support used in the present invention is made of Cr, T on an aluminum substrate.
What formed the conductive layer which has i, W, or Mo as a main component can be used. Further, a conductive support made of Mo, W or Ti can also be used.

The thickness of the conductive support is 0.5 to 50 m.
A range of m, preferably 1 to 20 mm is suitable. The conductive support used in the present invention may have a surface that has been subjected to an uneven treatment by sandblasting, honing, buffing, whetstone polishing, or the like.

If desired, a charge injection blocking layer can be provided on the conductive support. The charge injection blocking layer is obtained by drying and solidifying an alkoxide or an acetylacetone chelate compound, an anodized metal oxide layer, or
It is made of amorphous silicon to which a group III element or a group V element is added. Whether a Group III element or a Group V element is used as an additive is determined by the charge polarity of the photoconductor. The charge injection blocking layer may contain at least one of nitrogen, oxygen, carbon and halogen in addition to the Group III element or the Group V element. The film thickness is 0.
It is 1 to 10 μm, preferably 0.1 to 5 μm.

The organic photoconductive layer may be a single layer or a structure in which the charge generation layer and the charge transport layer are separated. A single layer in which the charge generating material and the charge transporting material are dispersed in the binder resin, or a single layer structure in which the charge generating material is dispersed in the binder resin and the charge transporting material is formed as a uniform film thereon by vapor deposition or the like Good. Further, a laminated structure including a charge generation layer and a charge transport layer in which the charge generation material and the charge transport material are dispersed in respective binder resins may be used.

Examples of organic photoconductors that can be used include high molecular weight semiconductors such as polyvinylcarbazole and trinitrofluorenone, bisazo pigments, phthalocyanine pigments, squarylium pigments and the like dispersed in a high molecular weight material, a pigment-dispersed charge generating material, triphenyl. It is possible to use a low molecular weight dispersion type charge transport material in which an amine type or pyrazoline type low molecule is dispersed in a polymer material. As the binder resin, a thermoplastic resin having a glass transition point of 150 ° C. or higher, a polyester having a glass transition point of 150 ° C. or higher, an unsaturated polyester, a heat-effective resin such as melamine, a polyurethane, a polyacryl urethane A cross-linking resin such as epoxy resin, a heat resistant resin such as polyimide, polysulfone, and silicone resin can be used. The thickness of the photoconductive layer is 1 to 100 μm, preferably 5
A range of -60 μm is suitable.

The surface layer, which is a feature of the present invention, includes a silicon hydride and / or a silicon halide gas and a nitrogen gas, if necessary, a halogen, and further a II-th gas without adding hydrogen.
It is formed by decomposing a Group I element and / or a Group V element component as a raw material gas by a glow discharge method, and includes nitrogen-containing amorphous silicon, nitrogen- and halogen-containing amorphous silicon, or nitrogen, halogen and Group III. It is made of amorphous silicon containing a group element and / or a group V element. In this surface layer, the absorbance of infrared spectrum stretching vibration has a relationship of N-H> Si-H. This film is not oxidized over a long period of time. The absorbance is N−H <
Si-H is not preferable because it has poor surface wettability and changes with time.

The contact angle between the generated surface layer and pure water is 85 to
A range of 140 °, preferably 90-140 °, more preferably 95-140 ° is suitable. When the contact angle is less than 85 °, corona discharge is generated at high humidity and the image is apt to be blurred. Further, the composition ratio of N / Si is 0.3 to 1.
3, preferably 0.4 to 1.2, more preferably 0.5.
A range of up to 1.1 is suitable. The composition ratio of N / Si is 0.
When it is less than 3, the absorption in the visible region to the infrared region increases, the absorption amount of the photoconductive layer decreases, and the sensitivity of the photoreceptor tends to decrease. On the other hand, when it exceeds 1.3, the resistance of the surface layer becomes high and the residual potential tends to rise.

The amount of hydrogen in the surface layer is preferably in the range of 1 to 10 atomic%, preferably 2 to 7 atomic%, more preferably 2 to 5 atomic%. Below 1 atomic%, dangling is achieved. Since the number of bonds is increased, the wettability is increased, and corona discharge is generated at high humidity to easily cause image blur. 10
If it exceeds atomic%, the contact angle tends to deteriorate over time,
As a result, image blurring occurs.

Further, the amount of halogen in the surface layer is 1 to 20.
Atomic%, preferably 2 to 15 atomic%, more preferably 5
The range of 10 atom% is suitable, and if it exceeds 20 atom%, the initial wettability is lowered, and although it is good, the change over time is large and image blurring easily occurs.

The Group III element and the Group V element to be added to the surface layer are selected according to the charging polarity of the photoconductor, and when functioning as a charge injection blocking layer, a positively chargeable Group V element, It is negatively charged and contains a Group III element. It is suitable that the content of the group V element is 0.1 to 100 ppm and the content of the group III element is 0.01 to 10000 ppm. Also, in the case of the resistance control function, it is positively charged and
The group I element may be negatively charged and may contain a group V element.

Further, the surface layer may contain oxygen and / or carbon for the purpose of controlling charge injection blocking property, improving surface hardness and the like. Oxygen and / or carbon content is 0.1
A range of -10 atomic% is suitable. The thickness of the surface layer is
A range of 0.01 to 5 μm, preferably 0.1 to 3 μm is suitable. If it is less than 0.01 μm, the charge injection blocking property is insufficient, and if it exceeds 3 μm, the residual charge becomes high, and the repeated potential stability deteriorates.

The intermediate layer may be provided to improve the adhesion between the organic photoconductive layer and the surface layer. This intermediate layer is formed of carbon, oxygen, nitrogen, and / or a group III element and / or a group V element.
It is also possible to form a plurality of layers by using amorphous silicon containing a group element. The nitrogen atom concentration of the intermediate layer is lower than that of the surface layer, the nitrogen atom ratio to the silicon atom is in the range of 0.1 to 1.0, and the film thickness is 0.
A range of 01 to 0.1 μm is suitable. The Group III element or Group V element is selected according to the charging polarity of the photoconductor. When functioning as a charge injection blocking layer,
A positively charged group V element is contained, and a negatively charged group III element is contained. The amount of Group V element is 0.1 to 100 pp
The amount of m and the group III element is in the range of 0.01 to 10,000 ppm. If you want it to function as resistance control,
A group III element having a positive charging property and a group V element having a negative charging property may be contained. Further, the intermediate layer may contain oxygen and / or carbon for the purpose of controlling charge injection blocking property and improving surface hardness.

Next, a method for forming each of the above layers on the conductive support will be described. The photoconductive layer formed on the conductive support is formed by a spray coating method or a dipping method. The surface layer can be formed by a glow discharge decomposition method using a plasma CVD method, a sputtering method, an ion plating method, a vacuum deposition method, or the like. At that time, a main raw material gas containing silicon atoms is used as the raw material gas.

The glow discharge decomposition method will be described below as an example. As a raw material gas, a gas containing an additive element is added to the above main raw material gas and used as a mixed gas. If necessary, hydrogen or an inert gas such as helium, argon or neon can be used as a carrier gas. For the glow discharge decomposition method, either direct current discharge or alternating current discharge may be adopted, and the film forming conditions are frequency 0-5.
GHz, reactor internal pressure 0.001 to 1333 Pa, discharge power 10 to 3000 W, and support temperature 30 to 300
It can be appropriately set within the range of ° C. When forming a surface layer, it sets in 50-200 degreeC. If the temperature is lower than 50 ° C, the desired properties as a surface layer cannot be obtained, and if the temperature is higher than 200 ° C, the properties of the organic photoreceptor are deteriorated.

The surface layer is produced by using SiH as a source gas.
₄ , silicon hydride gas such as Si ₂ H ₆ , SiH ₃ F,
Hydrogen halide such as SiH ₂ F ₂ , SiHF ₃ and SiF ₄ and N ₂ are used. The gas containing silicon may be 100% or diluted with N ₂ . The ratio of silicon to nitrogen of the gas containing silicon is suitably in the range of 1:10 to 1:50, the substrate temperature is 100 to 300 ° C., the frequency is 0 to 5 GHz, and the internal pressure of the reactor is 0.1 to 1333 Pa. , Discharge power is 100
~ 3000 W is suitable.

As the source gas containing a Group III element,
As a model, diborane (B₂H₆), But B_FourH
_Ten, B_FiveH₉, B_FiveH₁₁In addition to AlH₃Etc.
You can also do it. Also, a source gas containing a group V element gas
As typically PH ₃, AsH₃, SbH₃,
BiH₃Etc. can be used.

In order to improve the charge injection blocking ability of the surface layer and improve the chargeability, or to control the electric resistance and stabilize or reduce the residual potential after photoexposure, a Group III element or a Group V element is used. A group element may be included. In particular, when the Group III element is contained, the gas used may be 100% gas or diluted with nitrogen. In the case of a Group III element, the range of 10 to 10,000 ppm with respect to silicon is suitable. Below 10 ppm, there is no effect and 10,000 pp
When it exceeds m, the wettability of the surface increases and the change with time becomes large. If Group V is included, the gas used is 1
The gas may be 00% or may be diluted with nitrogen. V
The range of the group is 1 to 10000 ppm with respect to silicon.
If it exceeds ppm, the wettability of the surface increases and the change over time becomes large.

As the raw material gas containing carbon, paraffin hydrocarbons represented by the general formula C _n H _{2n + 2} such as methane, ethane, propane and pentane; general formula C _n H such as ethylene, propylene, butylene and pentene _2n olefinic hydrocarbons; acetylene, arylene, butyne and other general formulas C _n H _2n-2 acetylene hydrocarbons and other aliphatic hydrocarbons; cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptene, Examples thereof include alicyclic hydrocarbons such as cyclobutene, cyclopentene, and cyclohexene; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, anthracene, and their substitution products. These hydrocarbons may have a branched structure or may be a halogen-substituted product.
For example, halogenated hydrocarbons such as carbon tetrachloride, chloroform, carbon tetrafluoride, trifluoromethane, chlorotrifluoromethane, dichlorodifluoromethane, bromotrifluoromethane, perfluoroethane and perfluoropropane can be used. The carbonization raw materials listed above may be gaseous at room temperature, solid, or liquid. When it is in a solid or liquid state, it is vaporized before use. As the source gas containing oxygen, O ₂ , N
₂ O, CO, CO ₂ or the like can be used.

[0039]

EXAMPLES Next, the present invention will be described in detail with reference to Examples and Comparative Examples. [Example 1] An organic photoreceptor having a total thickness of 20 µm, comprising a charge injection blocking layer, a charge generating layer and a charge transporting layer on an Al cylindrical support having a thickness of 1 mm, and having a thickness of 20 µm. A photoconductor having a surface layer of 0.3 μm was prepared.

The charge injection blocking layer was prepared by dissolving a zirconium acetylacetone alkoxide compound and a silane coupling agent in a solvent in a weight ratio of 1: 1 and applying a drying effect to obtain a layer thickness of 1 μm. Next, a charge generation layer in which a phthalocyanine pigment was dispersed in a polyvinylidene resin at a weight ratio of 5: 2 was formed by 0.1 μm dip coating. in addition,
Triphenylamine-based hole-transporting molecules were dispersed in a polycarbonate resin at a weight ratio of 3: 2.

Next, this organic photoreceptor was placed in a vacuum chamber and heated to 150 ° C. while being evacuated. Next, a mixed gas of silane gas and nitrogen gas was introduced and glow discharge decomposition was performed to form a surface layer having a film thickness of 0.5 μm.
The film forming conditions at that time were as follows. 100% Silane gas flow rate: 10 cm ³ / min Nitrogen gas flow rate: 200 cm ³ / min Reactor internal pressure: 66.6 Pa Discharge power: 400 W Discharge time: 10 min Discharge frequency: 13.56 MHz Support temperature: 150 ° C

The N / Si atomic ratio of the obtained surface layer was 0.
It was 9 and the amount of hydrogen was 7 atomic%. Further, the absorbance of the infrared spectrum stretching vibration of the surface layer had a relationship of NH> Si-H (relative ratio was 3: 1). The contact angle of the electrophotographic photosensitive member surface with pure water was 95 °. In addition,
The atomic ratio is measured by using XPS (X-ray photoelectron spectroscopy), and the hydrogen content is measured by an infrared spectrophotometer (FT-IR) using N.
The absorption intensity of stretching vibration of —H and Ge—H was measured, and the amount of hydrogen was determined by a conventional method. Further, when the adhesiveness of this surface layer was measured with an adhesive tape, it was not peeled off when there was no scratch. When the surface layer was scratched with a knife or the like and measured, some peeling was observed.

The electrophotographic photosensitive member was incorporated into an XP-11 printer manufactured by Fuji Xerox Co., Ltd. which was modified for experiments, and a print test was conducted. This printer does not have a drum heater, and cleaning is blade cleaning. The charging potential was 550V and the residual potential was 50V. Moreover, the electrical characteristics were stable even after repeated use. Magnetic brush development was performed using a one-component developer as the developer. The image obtained was clear and no fog was observed. Even after printing 100,000 sheets, image blurring and image unevenness due to filming of toner on the surface of the photoconductor were not observed. The amount of wear of the surface layer at that time was less than a measurable amount (0.01 μm). When the surface layer was omitted, the film thickness was reduced from 20 μm to 11 μm.

Example 2 An intermediate layer and a surface layer were formed on the same organic photoreceptor as in Example 1. Next, a mixed gas of silane gas and nitrogen gas was introduced and glow discharge decomposition was performed to form an intermediate layer having a film thickness of 0.1 μm on the photoconductive layer. The film forming conditions at that time were as follows. 100% Silane gas flow rate: 10 cm ³ / min Nitrogen gas flow rate: 100 cm ³ / min Reactor internal pressure: 66.6 Pa Discharge power: 200 W Discharge time: 10 min Substrate temperature: 150 ° C

Then, a surface layer having a thickness of 0.3 μm was formed on the intermediate layer. The film forming conditions at that time were as follows. 100% silane gas flow rate: 10 cm ³ / min 100% nitrogen gas flow rate: 200 cm ³ / min Reactor internal pressure: 66.6 Pa Discharge power: 400 W Discharge time: 10 min Substrate temperature: 150 ° C

The N / Si atomic ratio of the obtained surface layer was 1.
1, and the amount of hydrogen was 5 atomic%. Further, the absorbance of the infrared spectrum stretching vibration of the surface layer had a relationship of N-H> Si-H. The contact angle of pure water on the surface of the electrophotographic photosensitive member was 97 °. A print test was conducted on this electrophotographic photosensitive member in the same manner as in Example 1. The charging potential is −
At 550V, the residual potential was -50V. Moreover, the electrical characteristics were stable even after repeated use. The image obtained was clear and no fog was observed.
Even after printing 100,000 sheets, image blurring and image unevenness due to filming of toner on the surface of the photoconductor were not observed. Also,
When the adhesiveness of this surface layer was measured with an adhesive tape, it was not peeled when there was no scratch. Further, the surface layer was scratched with a knife or the like, but the peeling was not observed.

Example 3 The same electrophotographic photosensitive member as in Example 2 was used except that the surface layer was doped with boron.
Was prepared in the same manner as in. The conditions for forming the surface layer were as follows. 100% Silane gas flow rate: 10 cm ³ / min Nitrogen gas dilution 100 ppm B ₂ H ₆ gas flow rate: 200 cm ³ / min Reactor internal pressure: 66.6 Pa Discharge power: 400 W Discharge time: 10 min Substrate temperature: 150 ° C.

The N / Si atomic ratio of the obtained surface layer was 1.
It was 0 and the amount of hydrogen was 10 atomic%. The absorbance of the infrared spectrum stretching vibration of the surface layer is N-H> Si-H.
Had a relationship. The contact angle of the surface of the electrophotographic photosensitive member with pure water was 95 °. A print test was conducted on this electrophotographic photosensitive member in the same manner as in Example 1. The charging potential is -530V and the residual potential is -20V by adding boron.
Became low. Moreover, the electrical characteristics were stable even after repeated use. The image obtained was clear and no fog was observed. Even after printing 100,000 sheets, image blurring and image unevenness due to filming of toner on the surface of the photoconductor were not observed. Further, when the adhesiveness of this surface layer was measured with an adhesive tape, it was not peeled off when there was no scratch. Further, the surface layer was scratched with a knife or the like, but the peeling was not observed.

Example 4 A film was prepared by introducing a mixed gas of silane gas, SiF ₄ gas and nitrogen diluted B ₂ H ₆ onto the intermediate layer of the same organic photoreceptor as in Example 1 and performing glow discharge decomposition. A surface layer having a thickness of 0.3 μm was formed. The film forming conditions at that time were as follows. 100% Silane gas flow rate: 5 cm ³ / min 100% SiF ₄ gas flow rate: 5 cm ³ / min Nitrogen diluted B ₂ H ₆ gas flow rate: 200 cm ³ / min Reactor internal pressure: 66.6 Pa Discharge power: 400 W Discharge time: 5 min Substrate temperature : 150 ° C

The N / Si atomic ratio of the obtained surface layer was 0.
9. The amount of hydrogen was 8 atom%, the amount of boron was 0.1 atom%, and the amount of fluorine was 5 atom%. Further, the absorbance of the infrared spectrum stretching vibration of the surface layer had a relationship of N-H> Si-H. The contact angle of pure water on the surface of the electrophotographic photosensitive member is 100 °
Met. A print test was conducted on this electrophotographic photosensitive member in the same manner as in Example 1. The charging potential was -550V, and the residual potential was lowered to -20V by adding boron. Moreover, the electrical characteristics were stable even after repeated use. The image obtained was clear and no fog was observed. Even after printing 100,000 sheets, image blurring and image unevenness due to filming of toner on the surface of the photoconductor were not observed. Further, when the adhesiveness of this surface layer was measured with an adhesive tape, it was not peeled off when there was no scratch. Further, the surface layer was scratched with a knife or the like, but the peeling was not observed.

[0051]

EFFECTS OF THE INVENTION By adopting the above constitution, the present invention has high hardness and excellent wear resistance, has a low wear force surface and a low energy surface, has good oxidation resistance, and has excellent electrical resistance. It is possible to provide an organic photoreceptor having excellent characteristics and optical characteristics and capable of obtaining excellent images on a large number of sheets.

[Brief description of drawings]

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

FIG. 2 is a schematic cross-sectional view showing another example of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a schematic cross-sectional view showing another example of the electrophotographic photosensitive member of the present invention.

FIG. 4 is a schematic cross-sectional view showing another example of the electrophotographic photosensitive member of the present invention.

Claims (12)

[Claims] 1. An electrophotographic photoreceptor having at least an organic photoconductive layer and a surface layer on a conductive substrate, wherein the surface layer is made of amorphous silicon containing nitrogen, and the absorbance of infrared spectrum stretching vibration of the surface layer. Is N-H> Si-
An electrophotographic photosensitive member having a relationship of H. 2. An electrophotographic photoreceptor having at least an organic photoconductive layer and a surface layer on a conductive substrate, wherein the surface layer is made of amorphous silicon containing nitrogen, and the infrared spectrum stretching vibration of the surface layer is suppressed. Absorbance is N-H> S
An electrophotographic photoreceptor having an i-H relationship and having a hydrogen content in the range of 1 to 10 atomic%. 3. An electrophotographic photoreceptor having at least an organic photoconductive layer and a surface layer on a conductive substrate, wherein the surface layer is an amorphous material containing nitrogen and a group III element and / or a group V element. It is made of silicon and has an absorbance of infrared spectrum stretching vibration of the surface layer of N-H> Si.
An electrophotographic photosensitive member having a relationship of —H and having a hydrogen content in a range of 1 to 10 atomic%. 4. An electrophotographic photoreceptor having at least an organic photoconductive layer and a surface layer on a conductive substrate, wherein the surface layer is made of amorphous silicon containing nitrogen and halogen, and the infrared spectrum stretching vibration of the surface layer. Absorbance of N
An electrophotographic photoreceptor having a relationship of -H> Si-H. 5. An electrophotographic photoreceptor having at least an organic photoconductive layer and a surface layer on a conductive substrate, wherein the surface layer is made of amorphous silicon containing nitrogen and halogen, and the infrared spectrum expansion and contraction of the surface layer. An electrophotographic photosensitive member characterized by having a vibration absorbance of N-H> Si-H and having a hydrogen amount in the range of 1 to 10 atom%. 6. An electrophotographic photoreceptor having at least an organic photoconductive layer and a surface layer on a conductive substrate, wherein the surface layer contains nitrogen, halogen, and a group III element and / or a group V element. Of the amorphous silicon, and the absorbance of the infrared spectrum stretching vibration of the surface layer is N
-H> Si-H, and the amount of hydrogen is 1 to 10 atom%.
The electrophotographic photosensitive member is characterized in that 7. The surface layer has a contact angle of 85 ° to 14 with pure water.
7. The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is in the range of 0 °. 8. The electrophotographic photosensitive member according to claim 1, further comprising an intermediate layer provided between the surface layer and the photoconductive layer. 9. The electrophotographic photoconductor according to claim 1, wherein the organic photoconductive layer comprises a charge transport layer and a charge generation layer. 10. A method of forming at least an organic photoconductive layer and a surface layer on a conductive substrate, wherein silicon hydride gas and / or silicon halide gas and nitrogen gas are used as raw materials, and hydrogen gas is added. Without adjusting the substrate temperature to 80-2
A method for producing an electrophotographic photosensitive member, characterized in that the surface layer is decomposed by a glow discharge method while being heated to 00 ° C., and the absorbance of infrared spectrum stretching vibration has a relationship of N—H> Si—H. . 11. A method for forming at least an organic photoconductive layer and a surface layer on a conductive substrate, comprising a silicon hydride gas and / or a silicon halide gas, and a Group III element or Group V element component. With nitrogen gas added as a raw material,
The surface layer is decomposed by the glow discharge method while heating the substrate temperature to 80 to 200 ° C. without adding hydrogen gas, and the absorbance of infrared spectrum stretching vibration has a relationship of NH> Si—H. A method of manufacturing an electrophotographic photosensitive member, comprising: 12. An image forming method comprising: a step of charging an image forming member; a step of forming a latent image on the image forming member; and a step of developing a latent image on the image forming member. An image forming method using the photoconductor according to any one of the items.