JPS6161105B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an electrophotographic image that is used to form an image using electromagnetic waves such as light (herein, light in a broad sense refers to ultraviolet visible light, infrared light, X-rays, gamma rays, etc.). It relates to a forming member. Conventionally, photoconductive materials constituting the photoconductive layer of electrophotographic image forming members include inorganic photoconductive materials such as Se, CdS, and ZnO, poly-N vinyl carbazole (PVK), and trinitrofluorenone (TNF). Organic photoconductive materials (OPC) are commonly used. However, regarding electrophotographic image forming members using these photoconductive materials, there are still various issues that can be resolved, and the conditions may be relaxed to a certain extent to suit individual circumstances. The reality is that appropriate electrophotographic imaging members are used in each case, and improvements and improvements are made along the way. On the other hand, a new third material is also being developed as a photoconductive material constituting the photoconductive layer of an electrophotographic image forming member. Among such materials that have recently been viewed as promising is amorphous silicon (hereinafter abbreviated as a-Si). In the early stages of development, a-Si films exhibited various electrical and optical properties due to their structure being influenced by the manufacturing method and manufacturing conditions, which caused major problems in terms of reproducibility. I was holding it. For example, in the early stages, a-Si films formed by vacuum evaporation or sputtering methods contained a large number of defects such as voids, which greatly affected their electrical and optical properties. It did not receive much attention as a research material for fundamental physical properties, and no research and development was conducted for its application. However, in 1976, P and n control was thought to be impossible in amorphous a-Si.
At the beginning of 2018, it was reported that p-n junctions could be realized for the first time using amorphous materials (Applied Physics
Since its publication in 1976 (Vol. 28, No. 2, 15 January 1976), it has attracted a great deal of attention, and research and development efforts have since focused primarily on its application to solar cells. For this reason, the a-Si films reported so far are
Since it was developed for use in solar cells, it cannot currently be used as a photoconductive layer in an electrophotographic image forming member due to its electrical and optical properties. In other words, solar cells convert solar energy into current and extract it, so in order to have a good signal-to-noise ratio and efficiently extract current, a-Si
The resistance of the film must be relatively small, but if the resistance is too small, the photosensitivity will decrease and the signal-to-noise ratio will deteriorate, so one of its characteristics is resistance.
A resistance of about 10 ⁵ to ^{10 8} Ωcm is required. However, the resistance (dark resistance) of an a-Si film having this level of resistance (dark resistance) is too low to be used as a photoconductive layer of an electrophotographic image forming member. , it cannot be used at all by applying currently known electrophotographic methods. In addition, the material constituting the photoconductive layer of an electrophotographic image forming member is required to have a bright resistance (resistance when irradiated with light) that is about 2 to 4 orders of magnitude smaller than the dark resistance.
Since the a-Si films that have been reported so far have values of about two digits at most, in this respect as well, conventional a-Si films could not provide a photoconductive layer that fully satisfies these characteristics. In addition, previous reports on a-Si films have shown that increasing the dark resistance reduces photosensitivity; for example, in an a-Si film with a dark resistance of 10 ¹⁰ Ωcm, the bright resistance is also the same. Although it has been shown that the value of
In this respect as well, conventional a-Si films could not serve as photoconductive layers for electrophotographic image forming members. Therefore, it is necessary to develop an a-Si film having sufficient dark resistance and photosensitivity to be used as a photoconductive layer of an electrophotographic imaging member, taking into account reproducibility and productivity. Incidentally, the a-Si layer is generally formed on a suitable support by a deposition method utilizing a discharge phenomenon such as a glow discharge method or a sputtering method. When forming an a-Si layer by such a deposition method, various reports and literature have shown that the dark resistance and photosensitivity of the formed layer change depending on the temperature of the support during layer formation. ing. That is, for example, by forming a layer while maintaining the support temperature at a high temperature of about 400° C., it is possible to reduce the bright resistance, which is one of the electrical characteristics. However, since the layer growth rate of a-Si is much slower than that of, for example, Se, etc., the above-mentioned high temperatures can be applied with high precision to achieve the layer thickness required for the photoconductive layer of an electrophotographic image forming member. It is extremely difficult to maintain it constant. Furthermore, as the photoconductive layer of an electrophotographic image forming member, the total light-receiving surface requires a large area, for example, A4 size or B4 size or more, even in normal cases. With the current technology, it is extremely difficult to control the temperature in order to maintain the above-mentioned high-temperature state uniformly over the area until the layer formation is completed. However, even when changing the temperature of the support, it is difficult to control it over such a large area so that the rate of temperature change does not vary depending on location. As described above, it is extremely difficult to control the support temperature at a high temperature for a long time and over a large area without temperature unevenness in order to obtain the desired dark resistance and bright resistance. Therefore, temperature variations occur depending on the location and time during layer formation, and it is not only impossible to achieve uniform layer thickness over a large area, but also the electrical and optical properties required for the photoconductive layer of an electrophotographic image forming member. It is also impossible to measure the uniformity of characteristics. The present invention has been made in view of the above points, and it is possible to generate a-Si with extremely high photosensitivity by generating plasma under certain specific conditions described below in the presence of a material for forming a-Si. A-Si powder particles that can be obtained in large quantities in a single hour in powder form cannot be used as a photoconductive layer of an electrophotographic image forming member if they are used as a photoconductive layer of a single constituent material. However, it is based on the discovery that if the photoconductive layer is dispersed in a binder with affinity, it can be a photoconductive layer with extremely excellent electrophotographic properties. The electrophotographic imaging member of the present invention includes a support;
In an electrophotographic imaging member having a photoconductive layer formed by dispersing photoconductive material powder particles in a binder, the photoconductive material powder particles contain 10 to 40 atomic percent hydrogen. It is characterized by being amorphous silicon powder particles. In this way, when a-Si powder is dispersed in a binder to form a photoconductive layer, a-Si powder particles can be produced in large quantities in a short time, so glow discharge method, sputtering method, etc. can be used. Compared to forming an a-Si photoconductive layer by a deposition method that utilizes the discharge phenomenon of
There is no need to strictly control the temperature of the support for a long time, and the production efficiency is improved due to the slow layer growth rate, as in the case of forming an a-Si photoconductive layer by the above-mentioned deposition method. The above-mentioned deposition method has no disadvantages, does not require much capital investment in production equipment, photoconductive layers with any large area can be formed on supports of any shape, etc. Tsute a-
It has industrially excellent effects that are not available when forming a Si photoconductive layer. In addition, the formed electrophotographic image forming member has high sensitivity, is excellent in repeated use, has strong mechanical strength, is always stable against charging action and discharging action, and has excellent cleaning properties. It also has excellent transfer efficiency and can always provide a large number of high-quality copies. The electrophotographic image forming member of the present invention basically consists of a-Si powder particles produced by the method described below, which are kneaded together with a binder having predetermined properties using a solvent as necessary. It can be obtained by coating the photoconductive layer on a suitable support such as metal and solidifying it to form a photoconductive layer. In the present invention, most of the supports normally used in the field of electrophotography are effective as supports used, but depending on the form of the image forming member to be manufactured, e.g. The type of support used differs depending on whether or not charges need to be injected from the support side into the photoconductive layer during charging for formation. It is desirable to select the appropriate one and use the best one. In the present invention, examples of the support used include stainless steel, Al, Cr, Mo, Au, Ir,
Examples include conductive supports such as metals such as Nb, Ta, V, Ti, Pt, and Pd, or alloys thereof, films or sheets of synthetic resins, and electrically insulating supports such as glass and ceramics. The support is preferably subjected to a series of cleaning treatments before the photoconductive layer is formed thereon. In this kind of cleaning process,
Typically, for example, a metallic support is contacted with an alkaline or acidic solution which effectively cleans the surface by etching. The support is then dried in a clean atmosphere and, without further preparatory treatment, a photoconductive layer is then formed thereon. In the case of an electrically insulating support, its surface is subjected to conductive treatment, if necessary. For example, in the case of glass, its surface is conductively treated with In ₂ O ₃ or SnO ₂ , or in the case of a synthetic resin film such as polyimide film, it is treated with Al, Ag,
Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V,
The surface is treated with a metal such as Ti or Pt by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal, so that the surface thereof is conductive. The shape of the support body is cylindrical, belt-shaped,
It can be of any shape, such as a plate shape, and the shape is determined as desired, but in the case of continuous high-speed copying,
It is desirable to have an endless belt shape or a cylindrical shape. The thickness of the support is determined appropriately so that the desired image forming member is formed, but when flexibility is required as an image forming member, the support function can be fully demonstrated. Within this range, it is made as thin as possible. However, in such cases, the thickness is usually set to 10μ or more in view of manufacturing and handling of the support, mechanical strength, etc. The binder, which is a material constituting the photoconductive layer together with the a-Si powder particles, is suitable for achieving the purpose of the present invention and is suitable for the electrical properties, optical properties, and the a-Si powder particles produced. - The material is appropriately selected and used from desired materials, taking into consideration the chemical and physical affinity with the Si powder particles. Such materials include
Usually used in the electrophotographic field,
Many resin binders that have film-forming ability and are electrically insulating can be effectively used. Such resin binders include thermosetting resins,
These include thermoplastic resins, photocurable resins, electron beam curable resins, X-ray curable resins, etc. Specifically, phenol resins: furan resins: xylene resins: formaldehyde resins: urea resins: melamine resins: aniline resins: Sulfonamide resin: Alkyd resin:
Unsaturated polyester resin: Epoxy resin: Triallyl cyanurate resin: Polyethylene: Polypropylene: Polystyrene: Polyvinyl acetate: Polyacrylate: Polymethacrylate: Polyvinyl chloride: Polyvinylidene chloride: Polytetrafluoroethylene: Polychlorotrifluoroethylene: Polyfts Vinyl chloride: Polyvinylidene fluoride: Tetrafluoroethylene: Hexafluoropropylene copolymer: Chlorotrifluoroethylene: Fluororesin such as vinylidene fluoride copolymer: Polyacrylonitrile; Polyvinyl ether: Polyvinyl ketone: Polyether: Polycarbonate: Polyester :
Examples include polyamides such as nylon 6, nylon 66, and nylon 6/66; polyurethanes; cellulose derivatives such as silicone cellulose acetate, ethyl cellulose, propionic cellulose acetate, etc., and two or more of these may be mixed as necessary. You can use it as well. In the present invention, the binder constituting the photoconductive layer is appropriately selected from the resin binders described above, but also a binder chemically similar to a-Si powder particles is used. From the viewpoint of properties, silicone compounds such as silicone varnish and silicone rubber that have film-forming ability can also be effectively used as the binder. Examples of silicone varnishes include silicone varnishes used for coating film formation, vehicles for various paints, and base ranges for molding materials. For example, pure silicone varnishes mainly composed of polysiloxane as shown by the following formula: , A silicone intermediate mainly composed of a low molecular weight polysiloxane having a hydroxyl group or an alkoxy group bonded to a silicon atom, such as the following formula, In addition, examples include silicone-modified varnishes of various resins obtained by reacting various resins with silicone intermediates, silane coupling agents, and pure silicone varnishes.For example, alkyd-modified silicone varnishes include For example, epoxy silicone varnishes have the following structure: There are polyester-modified silicone varnishes, acrylic-modified silicone varnishes, phenol-modified silicone varnishes, polyurethane-modified silicone varnishes, melamine-modified silicone varnishes, etc. Furthermore, examples of solvent-free silicone varnishes include silicone varnishes represented by the following formula. (φ: C ₆ H ₅ , Me; CH ₃ , V; CH ₂ =CH) Silicone rubber is classified into thermosetting type and room temperature curing type (generally referred to as RTV), but in the present invention, room temperature curing type (RTV type) is more preferably used. RTV silicone rubber comes in one-component and two-component types, both of which can be selected. General formula for one-component RTV silicone rubber (Here, R ₁ and R ₂ are alkyl groups, phenyl groups, vinyl groups, propyl trifluoride groups, etc.) with an acetoxy group, oxime group, acoxyl group, or alkyl group attached to the end of the main chain, Condensation reactions of deacetic acid, deoxime, alcohol, and deamine proceed due to moisture in the air, forming a crosslinked structure at a relatively low temperature from room temperature. Curing silicone rubber,
Deoxidized one-component room-temperature-curing silicone rubber, alcohol-dealing one-component room-temperature-curing silicone rubber,
Deamined one-component room-temperature curing silicone rubber 4
Two types can be mentioned. Next, two-component room-temperature curing silicone rubber can also be used, and this silicone rubber is composed of diorganopolysiloxane as a base oil, a trifunctional or higher functional silane or siloxane as a crosslinking agent, and a curing catalyst, and the curing mechanism is condensation. There are reaction types (dealcoholization condensation reaction type, dehydration condensation reaction type, dehydrogenation condensation reaction type) and addition reaction types. As the silicone compound used as a binder to achieve the purpose of the present invention, many commercially available silicone varnishes, rubbers, etc. can be effectively used. KR251, KR255 from Kagaku Kogyo Co., Ltd.
KR5240, KR114, KE10RTV, KE66RTV,
KE1204(B), KE104Gel, KE103RTV,
KE111RTV, KE1400RTV, KE41RTV,
KE44RTV, KE445RTV, KE42S−RTV,
KE441RTV, KE45S−RTV, KE48RTV,
KE102RTV, KE1206RTV, KE16,
KE1091RTV, KE12RTV, KE112RTV,
KJR601, KJR4010, Toshiba Silicone Corporation
TSR144, TSR1205, TSR1291, YR3110,
TSE370RTV, TSE328RTV, TSE371RTV,
TSE353RTV, TSE380RTV, TSE3402RTV,
TSE3503RTV, TSE−350−5RTV,
TSE300RTV, RTV11, TSE370−RTV,
YE3085, YE5505, Toray Silicone Co., Ltd. SH630, SH850, SH6005, R4−3117,
SH649, SH6101, SH6100, SE5011RTV,
SH780, SH738, SH9551, SH9583, SH9731,
SH1820, SH1840, SH643, SH2104, Fuji Polymer Industries Co., Ltd.'s Bergan C, Bergan D, Bergan F, FSXR-2622, Silascon RTV6501, Silascon RTV6521, Silascon RTV6700, Silascon RTV6601, Silascon RTV6589, FSXS-
2279, Silpot 200, Silaseal 3FW, Sirotex 32B, FSXF-2500, etc., and if necessary, two or more of these compounds used as a binder may be used in combination. Furthermore, in the present invention, many synthetic rubbers that are electrically insulating and have film-forming properties can be effectively used as the binder. Specifically, examples thereof include polybutadiene rubber, butadiene acrylonitole rubber, acrylic rubber, urethane rubber, and the like. Among the binders listed so far, those with a volume resistivity of 10 ¹² Ω·cm or more, preferably 10 ¹³ Ω·cm or more, most preferably 10 ¹⁴ Ω·cm or more are selected. It is desirable to use the In addition, the dielectric strength is usually selected from those having a dielectric strength of 10 KV/mm or more, preferably 15 KV/mm or more, and optimally 20 KV/mm or more. In the present invention, the amount of the binder used in forming the photoconductive layer is determined as appropriate so that a photoconductive layer having desired electrophotographic properties can be formed. Weight ratio with Si powder particles is usually 5~
60wt%, preferably 8-50wt% optimally 10-40wt
%. The solvent for kneading and dispersing the a-Si powder particles together with the binder is selected from solvents that do not adversely affect the a-Si powder particles, depending on the type of binder used. As such a solvent, many commercially available organic solvents can be effectively used. Specifically, for example, methylene chloride, chloroform, ethane dichloride, 1,1,2 ethane trichloride, retylene trichloride, ethane tetrachloride, carbon tetrachloride, propane 1,2 chloride, 1,1,1 trichloride. Ethane, ethylene tetrachloride, ethyl acetate, butyl acetate, isoamyl acetate, cellosorbiacetate,
Examples include alcohols such as toluene, xylene, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, dimethylamide, N-methylpyrrolidone, methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol. In the present invention, in addition to the above-mentioned materials, so-called organic photoelectric materials are used as the binder constituting the photoconductive layer for the purpose of improving photosensitivity, improving charge mobility in the layer, etc. It's okay. The organic photoconductive material to be used is selected from those having the same properties as those described above for the binder in terms of resistance when not irradiated with light (dark resistance) and film forming properties. is desirable. Such organic photoconductive materials include PVK, carbazole,
N-ethylcarbazole, N-isopropylcarbazole, N-phenylcarbazole, tetraphenylpyrene, 1-methylpyrene, perylene, chrysene, atracene, tetracene, tetraphene, 2-phenylnaphthalene, azapyrene, fluorene, fluorenone, 1-ethylpyrene , acetylpyrene, 2,3-benzoglycerin, 3,4
-Benzopyrene, 1,4-bromopyrene, phenylindole, polyvinylpyrene, polyvinyltetracene, polyvinylberylene, polyvinyltetraphene, polyacrylonitrile, PVK: TNF
(Molar ratio of monomers 1:1) includes tetranitrofluorenone, dinitroanthracene, dinitroacridene, tetracyanophylene, dinitroanthraquinone, and the like. These organic photoconductive materials may be used in combination of two or more types as long as the required properties are not deteriorated, or they may be used in combination with the electrically insulating binder described above. It's okay. The layer thickness of the a-Si photoconductive layer depends on the desired electrophotographic properties and usage conditions, such as whether flexibility is required, the particle size of the a-Si powder particles to be applied, and the darkness. It may be determined as appropriate depending on the attenuation characteristics or the uniformity of the electrical and optical characteristics of the photoconductive layer formed, but usually 10 to 80
μ, preferably 15 to 70μ, most preferably 20 to 50μ. The electrophotographic image forming member of the present invention has a basic layer structure consisting of a support and a photoconductive layer as described above, but also has a so-called protective layer and an electrically insulating layer on the photoconductive layer. A so-called surface coating layer may also be provided. In the present invention, the characteristics required of the surface coating layer differ depending on the electrophotographic process to which it is applied. That is, for example, Japanese Patent Publication No. 42-23910,
If an electrophotographic process such as the NP method described in Publication No. 43-24748 is applied, the surface coating layer should be electrically insulating and have a high ability to retain static charge when subjected to charging treatment. It is required to have sufficient thickness and a certain level of thickness, for example,
If an electrophotographic process such as the Carlson process is applied, it is desirable that the potential of the bright area after electrostatic image formation be very small, so the thickness of the surface coating layer is required to be very thin. In addition to satisfying the desired electrical properties, the surface coating layer should also have no adverse chemical or physical effects on the photoconductive layer, good electrical contact and adhesive properties with the photoconductive layer, and is formed taking into consideration moisture resistance, abrasion resistance, cleanability, etc. Typical materials effectively used for forming the surface coating layer include polyethylene terephthalate, polycarbonate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, polyamide,
Polytetrafluoroethylene, polytrifluorochloroethylene,
Synthetic resins such as polyvinyl fluoride, polyvinylidene fluoride, propylene hexafluoride-tetrafluoroethylene copolymer, ethylene trifluoride monofluoride vinylidene copolymer, polybutene, polyvinyl butyral, polyurethane, cellulose derivatives such as cyacetate and triacetate etc. These synthetic resins or cellulose derivatives may be formed into a film and laminated onto the photoconductive layer, or a coating solution thereof may be formed and applied onto the photoconductive layer to form a layer. Also good. The thickness of the surface coating layer is appropriately determined depending on the desired characteristics and the material used, but is usually about 0.5 to 70 μm. In particular, when the surface coating layer is required to function as the above-mentioned protective layer, it is usually 10μ or less,
On the other hand, when a function as an electrically insulating layer is required, the thickness is usually set to 10μ or more. However, the layer thickness value that distinguishes between the protective layer and the electrically insulating layer varies depending on the materials used, the applied electrophotographic process, and the structure of the designed electrophotographic imaging member. The value of 10μ is not absolute. The basic structure is a support and a photoconductive layer, and either the photoconductive layer has a free surface, or a surface coating layer as a so-called protective layer provided on the photoconductive layer has a free surface, and the photoconductive layer has a free surface. In an image forming member in which the free surface of a highly conductive layer or a protective layer is subjected to charging treatment for forming an electrostatic image, an electrostatic line forming layer is formed between a support and a layer provided on the support. It is more preferable to provide a barrier layer that acts to prevent carrier injection from the support side during the charging process.
Materials for forming a barrier layer that acts to prevent carrier injection from the support side include:
The type of support to be selected is appropriately selected depending on the electrical characteristics of the photoconductive layer, and an appropriate support is used.
Examples of such barrier layer forming materials include:
Inorganic insulating compounds such as Al ₂ O ₃ , SiO, SiO ₂ , organic insulating compounds such as polyethylene, polycarbonate, polyurethane, parylene, Au, Ir, Pt, Rh,
Metals such as Pd and Mo. In the present invention, the transfer image properties, durability, and repeatability of the formed electrophotographic image forming member, or the interlayers such as the photoconductive layer, the support, the surface coating layer, the barrier layer, etc. In order to further improve the electrical properties, etc., it is preferable to surface-treat the support or the surface of the layer that has already been formed with a silane-based treatment agent when forming the layer. In the present invention, examples of the silane treatment agent suitably used include compounds represented by the following chemical formula. That is, Examples include a methanol solution of aminosilane. As the silane treatment agent used in the present invention, many commercially available silane treatment agents are effectively used, such as those available from Toray Silicone Co., Ltd.
SH6020, SH6026, SH6031, DC6032, SH6040,
SH6062, SH6075, SH6076, DC5456, X1−
6000, PRX-11, PRX-19, PRX-24,
SH6070, SH6079, SH2260, KA1003, KBE1003, KBC1003 of Shin-Etsu Chemical Co., Ltd.
KBM403, KBM503, KBM602, KBM603, Primer MT, Primer U, Primer W, Primer D, Primer T, Primer A, Primer S, Primer No. 4, Primer No. 5, Toshiba Silicone Corporation's ME11, ME13, ME121,
ME123, ME124, ME151, ME152, ME20,
Examples include ME21 and FS Primer S from Fuji Polymer Industries Co., Ltd. These silane-based treatment agents are organic solvents or water,
Alternatively, the surface is diluted with a solution containing a binder, or the surface is directly treated with a silane-based treatment agent without any dilution. Application methods include spray coating, brush coating, spin coating, coating rod coating, dipping method, etc. It is coated with a thickness ranging from a monomolecular layer to several tens of microns. In the present invention, the a-Si powder particles used are prepared by using a capacitance type or inductance type gas discharge device to form a raw material gas for forming the a-Si powder particles, such as SiH ₄ , Si ₂ Manufactured by introducing diluent gas such _as He, Ne, etc. mixed as necessary into a gas discharge chamber that can reduce the pressure, and generating a glow discharge in the discharge chamber to form a plasma atmosphere. be done. In the present invention, a-
In order to obtain Si powder particles, the conditions for generating a discharge phenomenon in the discharge chamber that are effective for forming a desired plasma atmosphere are the electrode arrangement of the gas discharge device used, the shape of the electrodes, the internal volume and internal shape of the discharge chamber. , the distance between the electrodes, the electric field strength between the electrodes when maintaining gas discharge, the type of gas introduced into the discharge chamber, etc., as appropriate. For example, as for electrical conditions, in the case of capacitance type, the voltage between the electrodes is usually 20~
It is good to adjust it to 2000V, preferably 50 to 1500V. The input power is usually 0.05 for both capacitance and inductance types.
~500w, preferably 0.1~300w, optimally 1~
It is better to set it to 200w, or even more, in the case of AC,
The frequency is usually 0.2~30MHz, preferably 5~
It is desirable to set it to 20MHz. The a-Si powder particles formed have characteristics that enable the formation of a photoconductive layer for intended electrophotography, and their dark resistance and photoelectric gain can be controlled by incorporating H during formation. be done. Here, "H is contained in the a-Si powder particles" means "a state where H is combined with Si" or "a state where H is ionized and incorporated into the powder particles".
or "a state in which H ₂ is incorporated into powder particles" or a combination thereof. The inclusion of H in the a-Si powder particles is
When forming a-Si powder particles, inside the manufacturing equipment system
Introduced in the form of compounds such as SiH ₄ , Si ₂ H ₆ or H ₂ , these compounds or H are decomposed by gas discharge, and are added to the a-Si powder particles along with the formation of powder particles. Contain. According to the findings of the present inventors, the H content in the a-Si powder particles has a large effect on whether or not the formed photoconductive layer can actually be applied for electrophotography. This is one of the factors, and it has been found to be extremely important. In the present invention, in order to make the formed photoconductive layer sufficiently applicable to practical applications, the amount of H contained in the a-Si powder particles is usually 10 to 40 atomic.
%, preferably 15 to 30 atomie%. The a-Si powder particles can be made intrinsic by doping with impurities during manufacture and their conductivity type can be controlled. In order to make the a-Si powder particles P-type, impurities doped into the a-Si powder particles include elements of group A of the periodic table, such as B, Al, Ga, In,
Preferred examples include Tl, and when n-type, elements of group V A of the periodic table, for example,
Preferred examples include N, P, As, Sb, Bi, and the like. The amount of impurity doped into the a-Si powder particles is appropriately determined depending on the desired electrical and optical properties, but in the case of impurities in group A of the periodic table, it is usually 10 ^-6 ~ 10 ^-3 atomic%, preferably 10 ^-3 ~
10 ^-4 atomic%, in the case of impurities of group V A of the periodic table, usually 10 ^-8 to 10 ^-5 atomic%, preferably 10 ^-3 to
It is desirable to set it to 10 ^-7 atomic%. The amount of gas introduced into the discharge chamber is usually 0.1 to 20 Torr, preferably 0.5 to 20 Torr, as indicated by the pressure inside the discharge chamber.
10 Torr, and the raw material gas pressure for forming a-Si powder is usually 10 ^-2 to 10 Torr, preferably 10 ^-2 to
A value of 5 Torr, optimally 10 ^-1 to 2 Torr is desirable. In the present invention, a commonly used gas discharge device can be used to produce the a-Si powder particles used. An example of such a gas discharge device is shown in FIG. FIG. 1 is a schematic illustration of a gas discharge apparatus for producing a-Si powder particles by a capacitance type glow discharge method. Reference numeral 1 designates a glow discharge chamber, and capacitance type electrodes 3 and 4 connected to a high frequency power source 2 are wound around the upper outside of the chamber 1, and when the high frequency power source 2 is turned on, the electrodes High frequency power is applied to 3 and 4 to generate glow discharge within the chamber 1. A gas introduction pipe is connected to the upper end of the discharge chamber 1, so that the gas in each cylinder is introduced into the discharge chamber 1 from the gas cylinders 5, 6, 7, and 8 when necessary. Reference numerals 9, 10, 11 and 12 are flowmeters for detecting the flow rate of gas, 13, 14, 15 and 16 are flow rate adjustment valves, and valve 21 is an auxiliary valve. Further, the lower end of the discharge chamber 1 is connected to an exhaust device (not shown) via a main valve 22. 23 is a valve for breaking the vacuum in the discharge chamber 1. A conical collecting plate 24 with a hole in the center is attached to the lower end of the discharge chamber 1, and a conical collecting plate 24 with a hole in the center is installed in the collecting chamber 25 at a position directly below the hole of the collecting plate 24. A container 26 for storing a-Si powder is placed. 27 is an opening/closing door for taking in and out the storage container 26 in the collection chamber 25, and in the closed state,
The collection chamber 26 is designed to maintain sufficient vacuum. The collection plate 24 collects a-Si generated in the discharge chamber 1.
In addition to having the function of collecting the powder in its center, it also has the function of preventing the generated a-Si powder from being taken into the exhaust system. Reference numeral 28 is a gate valve, which is used to cut off and open the discharge chamber 1 and the collection chamber 25. 29 is a valve for breaking the vacuum in the collection chamber 25 after, for example, the gate valve 28 is closed and the discharge chamber 1 is sealed off. To produce a-Si powder using the apparatus shown in FIG. 1, first, the main valve 22 and gate valve 28 are fully opened to exhaust the air in the discharge chamber 1 and the collection chamber as shown by arrow A. to create a vacuum of about 10 ^-5 Torr. After the inside of the discharge chamber 1 reaches a predetermined degree of vacuum, the auxiliary valve 21 is then fully opened, and then the valve 17 of the gas cylinder 5 and the valve 1 of the gas cylinder 6 are opened.
Fully open 8. The gas cylinder 5 is for dilution gas such as Ar gas, and the gas cylinder 6 is for raw material gas for forming a-Si, for example,
SiH ₄ , Si ₂ H ₆ , Si ₄ H ₁₀ or mixtures thereof are stored. Further, the cylinders 7 and 8 are used for raw material gas to introduce impurities into the a-Si photoconductive layer as required.
PH ₃ , P ₂ H ₄ , B ₂ H ₆ and the like are stored in cylinder 8. After that, the flow rate adjustment valve 1 of gas cylinders 5 and 6
3 and 14 while looking at flow meters 9 and 10,
The discharge chamber 1 is gradually opened, and a diluent gas such as Ar gas and a raw material gas for forming a-Si such as SiH ₄ gas is introduced into the discharge chamber 1 . At this time, a diluent gas such as Ar gas is not necessarily required, and only the source gas such as SiH ₄ gas may be introduced. When Ar gas is introduced as a mixture with a raw material gas for a-Si formation such as SiH ₄ gas, the quantitative ratio is determined as desired. Gas is considered to be 10Vol% or more. Note that a rare gas such as He gas may be used as the diluent gas instead of Ar gas. When the desired gas is introduced into the discharge chamber 1 from the cylinders 5 and 6, the main valve 22 is adjusted to obtain a predetermined degree of vacuum, which is normally used to form a-Si powder. Keep total gas pressure between 0.1 and 20 Torr. Next, high frequency power of a predetermined frequency, usually 0.2 to 30 MHz, is applied from the high frequency power source 2 to the capacitance type electrodes 3 and 4 wound outside the discharge chamber 1 to generate a glow discharge inside the discharge chamber 1. When a plasma atmosphere is formed and, for example, SiH ₄ is used as a raw material gas for a-Si formation, the SiH ₄ is decomposed to form a-Si powder particles. formed a
- the Si powder particles are collected by the collection plate 24;
4 and stored in a storage container 26 in a collection chamber 25 installed below. When introducing impurities into the a-Si powder particles to be formed, a gas for impurity generation is supplied from the cylinder 7 and/or cylinder 8 to the discharge chamber 1 during the formation of the a-Si powder.
It would be better to introduce it internally. In this case, by appropriately adjusting the flow rate control valves 15 and 16, the amount of gas introduced into the discharge chamber 1 from the cylinders 7 and/or 8 can be appropriately controlled.
The amount of impurities introduced into the a-Si powder particles formed can be arbitrarily controlled. In the gas discharge device shown in FIG. 1, a capacitance type glow discharge method is employed, but an inductance type glow discharge method is also employed in the present invention. Further, the electrode for glow discharge may be provided inside the discharge chamber 1 or may be provided outside the discharge chamber 1. Hereinafter, the present invention will be specifically explained based on examples. Example 1 N-type a with an average particle size of 5 to 10μ as a photoconductive substance
- Form a photoconductive layer by mixing and dispersing 20 g of Si powder particles and 20 g of fluororesin (product name MP-10; Mitsui Fluorochemical Co., Ltd.) powder with an average particle size of 10 μ as a binder in 50 ml of Freon solution containing 2 g of trinitone. A dispersion liquid was prepared. An aluminum cylindrical drum support with a matte surface was immersed in this dispersion, then pulled up, thoroughly dried, and then baked at approximately 370°C for 60 minutes to form a photoconductive layer with a thickness of 20μ. This was used as an electrophotographic image forming member. The surface of the photoconductive layer of the obtained electrophotographic image forming member was extremely smooth and had a good appearance. In this electrophotographic imaging member, in a dark place,
A 6 KV corona was applied, image exposure was performed, development was performed using a charged toner, and the obtained toner image was transferred onto plain paper. For cleaning, a urethane rubber blade was used. After repeating this image reproduction process 100,000 times, there was no difference between the image quality of the 100,000th transferred image and the first transferred image, and it was clear and extremely good with no overlap. and
Furthermore, since the transferability is excellent, there is almost no need for cleaning every time the image reproduction process is repeated, and in this example, the cleaning process was applied every 30 sheets. In addition, the sensitivity is good at 10 lux.sec, and the charging property is 500V when a 6KV corona discharge is applied.
The surface potential was observed and proved to be sufficiently satisfactory for practical use. Example 2 P-type a-Si with an average particle size of 1μ as a photoconductive substance
A dispersion liquid for forming a photoconductive layer was prepared by mixing and dispersing 20 g of powder, 20 g of polyfluoroethylene propylene resin powder having an average particle size of 10 μm as a binder, and 1 g of Trinitone in 50 ml of Freon solution. An aluminum cylindrical drum support with a matte surface was immersed in this dispersion, then pulled up, thoroughly dried, and then baked at approximately 280°C for 60 minutes to form a photoconductive layer with a thickness of 30μ. This was used as an electrophotographic image forming member. The surface of the photoconductive layer of the obtained electrophotographic image forming member was extremely smooth and had a good appearance. In this electrophotographic imaging member, in a dark place,
A 6 KV corona discharge was applied and then imagewise exposed, the phenomenon was performed using a loaded toner, and the resulting toner image was transferred onto plain paper. For cleaning, a urethane rubber blade was used. After repeating this image reproduction process 100,000 times, there was no difference in the image quality between the 100,000th transferred image and the first transferred image, which was extremely good with no overlap. Also, since the transferability is excellent, there is almost no need for cleaning every time the image reproduction process is repeated, and in this example, even if the cleaning process is applied every 10 sheets, there is no need for cleaning at all. No problems occurred. In addition, the sensitivity was good at 7.0 lux.sec, and the charging characteristics were shown to be sufficiently satisfactory for practical use, as a surface potential of 500V was observed when a 6KV corona discharge was applied. Example 3 An n-type a-
A dispersion containing 100 parts by weight of Si powder and 50 parts by weight of aromatic polyester urethane resin (molecular weight approximately 30,000) (trade name: CA101, manufactured by NOF Corporation) as resin solid content was applied to a cylindrical aluminum drum and dried. ,
Next, after drying at 80° C. for 15 minutes, the film was cured by irradiation with light using a 4KW mercury lamp for 5 minutes to form a photoconductive layer with a thickness of 50 μm. Next, the surface of the photoconductive layer obtained was immersed in a solution of photocurable unsaturated polyester resin (trade name: UV-CM-102, manufactured by Kashiyu KK) diluted with methyl ethyl ketone so that the viscosity was 90 CPS. After pulling up at a speed of 10 min, it was irradiated with a 4KW mercury lamp for 5 minutes to cure. Repeat this operation three times
A 30μ insulating layer was provided. The surface of the insulating layer of the electrophotographic image forming member formed in this manner is primarily charged at a power supply voltage of 6,000 V.
When corona discharge was performed for 0.2 seconds,
Charged to 2000V. Next, as a secondary charge, corona discharge is performed at a power supply voltage of 5500V, and at the same time the exposure amount is 15V.
Image exposure was performed at lux.sec, and then the entire surface of the image forming member was uniformly irradiated to form an electrostatic image. When this electrostatic image was developed with toner charged by the cascade method and transferred and fixed onto transfer paper, an image of extremely good quality was obtained. In addition, after repeating the above image reproduction process 100,000 times, there was no difference in the image quality of the 100,000th transferred image and the first transferred image, and it was extremely high quality with no overlap. It was hot. Example 4 P-type a- manufactured by the apparatus shown in FIG.
100 parts by weight of Si powder, 10 parts by weight of vinyl chloride-vinyl acetate copolymer, and 10 parts by weight of methyl isobutyl ketone as a diluent were mixed and dispersed well with a roll mill to prepare a paste-like photoconductive composition, and then methyl ethyl ketone was added. The viscosity was adjusted to 700 cps at 20°C. The composition solution was coated by dipping an aluminum cylindrical drum at a speed of 30 mm/min, and was dried at 70° C. for 20 minutes to completely volatilize the solvent to form a photoconductive layer with a thickness of 50 μm. Next, the above drum was dipped in an aqueous dispersion (viscosity: 70 cps at 20°C) obtained by neutralizing the carboxyl groups of α, ω polybutadiene dicarboxylic acid resin with ammonia, and was coated by pulling up at a speed of 30 mm/min, and then heated at 70°C. The photoconductive layer was dried for 30 minutes to volatilize water and ammonia, and a sealing layer with a thickness of 4 μm was formed on the photoconductive layer. Furthermore, the drum was immersed in a solution of photocurable acrylated urethane resin diluted with ethyl alcohol (viscosity: 20°C, 70 cps) and pulled up at a speed of 30 mm/min to form a thin film of the above material on the sealing layer. In the ultraviolet irradiation equipment,
It was cured by irradiating ultraviolet light for 100 seconds to form an insulating layer. The thickness of this insulating layer was 10 μm after one application, and the same operation was repeated two more times to obtain an insulating layer with a total thickness of 30 μm. When a corona discharge was performed for 0.2 seconds at a power supply voltage of 6000V as a primary charge on the surface of the insulating layer of the electrophotographic image forming member manufactured in this way, the surface of the insulating layer was 2000V.
charged. Next, as a secondary charge, the power supply voltage
Corona discharge at 5500V and exposure amount 15 at the same time
Image exposure was performed at lux.sec, and then the entire surface of the image forming member was uniformly irradiated to form an electrostatic image. When this electrostatic image was developed with toner charged by the cascade method and transferred and fixed onto transfer paper, an image of extremely good quality was obtained. Also, after repeating the above image reproduction process 100,000 times, the image quality of the 100,000th transferred image and the image quality of the first transferred image are as follows.
There was no difference whatsoever, and it was of extremely high quality with no overlap. Example 5 A dispersion liquid for forming a photoconductive layer was prepared as shown in Table 1. These dispersions were coated on a stainless steel cylindrical drum support using a dipping method, and a predetermined curing treatment was performed to form a photoconductive layer approximately 35μ thick.
Electrophotographic imaging members of NosS ₅₁ to S ₅₆ were obtained. For the image forming members of samples NosS ₅₁ to _{S 53} among these image forming members, corona discharge was applied to the surface of the photoconductive layer in the dark with a power supply voltage of 5500 V, and then image exposure was performed at an exposure amount of 15 lux.sec. Then, an electrostatic image was formed, and the electrostatic image was developed with toner charged by a cascade method, and then transferred and fixed onto a transfer paper. An extremely clear image with high resolution was obtained. On the other hand, regarding the image forming members of samples NosS ₅₄ to _{S 56} ,
Corona discharge was applied in the dark with a power supply voltage of 6000V, then image exposure was performed with a light intensity of 15 lux.sec, and the image was created under the same conditions as when the image was created with the corona discharge described above. The image on the transfer paper had high resolution, was extremely clear, and was of good quality. The above-mentioned image forming process suitable for each was repeated and applied to the electrophotographic image forming members of samples NosS ₅₁ to S ₅₆ , and the durability of these electrophotographic image forming members was tested. The image obtained on the 10,000th sheet of transfer paper is also of extremely good quality, and there is no difference in quality compared to the image on the first sheet of transfer paper. It has been demonstrated that it has excellent abrasion resistance and is extremely durable.

【table】

[Table] Example 6 N-type a- manufactured by the apparatus shown in Fig. 1
10 parts by weight of Si powder, 10 parts by weight of vinyl chloride-vinyl acetate copolymer, and 10 parts by weight of methyl isobutyl ketone as a diluent were mixed and dispersed well with a roll mill to prepare a paste-like photoconductive composition, and then methyl ethyl ketone was added. The viscosity was adjusted to 700 cps at 20°C. An aluminum cylindrical drum was dropped into the composition solution, pulled up at a speed of 30 mm/min for coating, and dried at 70°C for 20 minutes to completely volatilize the solvent and form a photoconductive layer with a thickness of 50 μm. . Next, the drum was coated with an aqueous dispersion (viscosity: 20°C, 70 cps) of polyvinyl alcohol (trade name: Poval C-17, manufactured by Shin-Etsu Chemical Co., Ltd.), and the coating was applied by pulling up at a speed of 30 mm/min.
The photoconductive layer was dried for 30 minutes to evaporate the water and form a protective layer with a thickness of 2 μm on the photoconductive layer. The thus produced electrophotographic image forming member was subjected to corona discharge on the surface of the photoconductive layer in the dark at a power supply voltage of 5500 V, and then subjected to image exposure at an exposure dose of 15 lux.sec to form an electrostatic image. was formed, and the electrostatic image was developed with charged toner by a cascade method and transferred and fixed onto transfer paper, resulting in an extremely clear image with high resolution. Furthermore, after repeating the above image reproduction process 20,000 times, there was no difference in the image quality between the 20,000th transferred image and the first transferred image, and the image quality was extremely high with no overlap. It was hot. Example 7 Samples NosS ₇₁ to _{S 74} were prepared under the same conditions and procedures as in Example 6, except that the protective layer forming material shown in Table 2 was used instead of polyvinyl alcohol as the protective layer forming material in Example 6. An electrophotographic imaging member was manufactured. When these image forming members were subjected to the same image reproduction process as in Example 6, good results were obtained as in Example 6.

[Table] Example 8 Six cylindrical aluminum drums were prepared, and the surface of each drum was treated with the silane treatment agent shown in Table 3 (ethyl alcohol was used as the solvent). Separately, add vinyl chloride-vinyl acetate copolymer varnish (trade name V-1, manufactured by Morikawa Ink Co., Ltd.) to 100 parts by weight of n-type a-Si powder produced using the apparatus shown in Figure 1, and add 10 parts by weight of solid content, and a diluent. A paste-like photoconductive composition was prepared by mixing 5 parts by weight of methyl isobutyl ketone and thoroughly dispersing the mixture using a roll mill. Next, add methyl ethyl ketone to this composition to
The viscosity was 600C.PS. The above six aluminum cylindrical drums were individually dipped into the composition solution, pulled up at a speed of 30cm/min, and dried at 70°C for 20 minutes to completely volatilize the solvent and form a 35μ thick drum. A photoconductive layer was formed. Next, a 10% aqueous gelatin solution (manufactured by Nitta Gelatin Co., Ltd.) was prepared by heating and dissolving each of the above six drums at 40°C.
The photoconductive layer was dipped into the photoconductive layer and pulled up at a speed of about 4 cm/min to form a sealing layer with a thickness of 1 μm on the photoconductive layer. Furthermore, each of the above six drums was separately dropped into a solution of photocurable acrylic urethane resin (product name: Sonne, manufactured by Kansai Paint Co., Ltd.) diluted with ethyl alcohol to 100 C.PS, and pulled up at a speed of 4 cm/min. After forming a thin film of the above substance on the sealing layer, it was cured by irradiating it with ultraviolet rays for 120 seconds in an ultraviolet irradiation device. This coating was repeated three times on each of the six drums to form an insulating layer with a thickness of 30 μm to obtain electrophotographic imaging members of samples NosS ₈₁ to S ₈₅ . When corona discharge was performed for 0.2 seconds at a power supply voltage of 6000V as a primary charge on the surface of the insulating layer of these electrophotographic image forming members, the surface was charged to 2000V.
Next, as secondary charging, corona discharge was performed at a power supply voltage of 5500 V, and at the same time image exposure was performed at an exposure amount of 15 lux.sec, and then the entire surface of the image forming member was uniformly irradiated to form an electrostatic image. When this electrostatic image was developed with toner loaded by the cascade method and transferred and fixed onto transfer paper, an extremely high quality image was obtained. Furthermore, after repeating the above image reproduction process 100,000 times, there was no difference in the image quality between the 100,000th transfer image and the first transfer image, and they were of extremely high quality with no overlap. It was hot.

[Table] Values are the weight ratio of solvent and silane treatment agent.
Example 9 A silane treatment agent (CH ₃ O) ₃ Si(CH ₂ ) ₃ NHCH ₂ CH ₂ NH ₂ 2.0% by weight ethyl alcohol solution was applied by spraying onto the surface of an aluminum cylindrical drum. Separately, 100 parts by weight of n-type a-Si powder produced using the apparatus shown in Figure 1, 10 parts by weight of vinyl chloride-vinyl acetate copolymer varnish (trade name v-1, manufactured by Morikawa Ink Co., Ltd.) as a solid content, and a diluent. A paste-like photoconductive composition was prepared by mixing 5 parts by weight of methyl isobutyl ketone and thoroughly dispersing the mixture using a roll mill. Methyl ethyl ketone is then added to this composition to give approximately 550 C.P.
The viscosity is S. Dip the aluminum cylindrical drum into the composition solution and
The sample was pulled up at a speed of 10 min and dried at 70°C for 20 minutes to completely volatilize the solvent and form a photoconductive layer with a thickness of 35 μm. After the surface of this photoconductive layer was treated with the same silane treatment agent as described above, polycarbonate resin was applied to a dry thickness of 15 μm to form an electrically insulating layer. It was used as an image forming member.
As a primary charge on the surface of the insulating layer of this image forming member,
When corona discharge was performed for 0.2 seconds with a power supply voltage of 6000V, it was charged to 2000V. Next, as secondary charging, corona discharge was performed at a power supply voltage of 5500 V, and at the same time, image exposure was performed at an exposure amount of 15 lux.sec, and then the entire surface of the photoreceptor was uniformly irradiated to form an electrostatic image. When this electrostatic image was developed with toner charged by the cascade method and transferred and fixed onto transfer paper, an image of extremely good quality was obtained. Example 10 An electrophotographic image forming member was produced under the same conditions and procedures as in Example 6, except that the surface of the aluminum cylindrical drum in Example 6 was alumite-treated to form a barrier layer with a thickness of approximately 2 μm. Manufactured. When this image forming member was subjected to the same image reproduction process as in Example 6, a good transferred image was obtained as in Example 6.

[Brief explanation of the drawing]

FIG. 1 is a schematic explanatory diagram for explaining an example of a gas discharge apparatus for producing photoconductive material powder used in the present invention. 1...discharge chamber, 2...high frequency power supply, 3, 4...
Electrode, 5, 6, 7, 8...Cylinder, 25...Collection chamber, 26...Storage container, 27...Opening/closing door, 28...
gate valve.

Claims (1)

[Scope of Claims] 1. An electrophotographic imaging member comprising a support and a photoconductive layer formed by dispersing photoconductive material powder particles in a binder, wherein the photoconductive material powder particles are dispersed in a binder. An electrophotographic image forming member characterized by being amorphous silicon powder particles containing 10 to 40 atomic percent hydrogen. 2. The electrophotographic image forming member according to claim 1, wherein the binder is contained in a weight ratio of 5 to 60 wt% with respect to the amorphous silicon powder particles. 3. The electrophotographic imaging member according to claim 1, wherein the photoconductive layer has a thickness of 10 to 80 μm. 4. The electrophotographic image forming member according to claims 1 and 2, wherein the binder is a resin binder. 5. The electrophotographic image forming member according to claim 1, wherein the binder is a silicone compound. 6. The electrophotographic imaging member according to claim 1, wherein the binder is an organic photoconductive material. 7. The electrophotographic image forming member according to claim 1, wherein the binder has a dielectric strength of 10 KV/mm or more. 8. The electrophotographic image forming member according to claim 1, wherein the binder has a volume resistivity of 10 ¹² Ωcm or more. 9 Claims 1 to 8, wherein the interface between the support and the photoconductive layer is treated with a silane treatment agent.
1. Electrophotographic imaging member. 10. The electrophotographic image forming member according to claims 1 to 8, which has a surface coating layer on the photoconductive layer. 11. The electrophotographic imaging member according to claim 1, wherein a barrier layer is provided between the support and the photoconductive layer.