JPH07122756B2 - Photoreceptor and manufacturing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photoreceptor having a surface protective layer formed on an organic photosensitive layer, and a method for producing the same.

2. Description of the Related Art Since the invention of the Carlson method, the application field of electrophotography has continued to make remarkable progress, and various materials have been developed and put into practical use for photoconductors. Among them, in recent years, the development of organic photoconductors is superior in terms of hygiene and has high sensitivity as compared with photoconductors such as selenium, selenium arsenic, celenium tellurium, cadmium sulfide, and zinc oxide which have been used so far. Is remarkable.

Generally, as a material used for producing the organic photosensitive layer, as a photoconductive material that contributes to charge generation, for example,
Phthalocyanine-based pigments, azo-based pigments, perylene-based pigments and the like are used, and examples of charge-transporting materials that contribute to charge transport include triphenylmethane compounds, triphenylamine compounds, hydrazone compounds, styryl compounds, pyrazoline compounds, and oxazole compounds. Oxadiazole compounds and the like are used, and as the binder material for dispersing and coating them, for example, resins such as polyester, polyvinyl butyral, polycarbonate, polyarylate, and styrene acryl are used.

However, any of the organic photosensitive layers produced using these materials has a low surface hardness and usually has a pencil hardness according to JIS-K-5400 standard of at most about 5B to 4B. Therefore, when such a photosensitive layer is used as a photoconductor as it is, it has excellent performances in terms of charging ability and photosensitivity, but in actual use in a copying machine, a transfer paper, a cleaning member, a developer, The surface is often scratched due to surface abrasion due to friction with the like, or due to an artificial operation at the time of paper jam and its restoration, and the surface is easily scratched. These scratches appear as so-called white spots on the copied image, significantly reducing the image quality,
Shorten photoreceptor life. Further, the surface abrasion gradually scrapes off the photosensitive layer, so that the film thickness of the photosensitive layer is reduced, so that a desired charging potential cannot be obtained and the life of the photoreceptor is shortened. The abrasion effect on the surface of the photosensitive layer changes depending on the design of the copying machine, but the life of the organic photosensitive layer is usually such that it can withstand the copying of tens of thousands to 100,000 sheets at most.

In order to eliminate such a defect, a method of providing a protective layer having high hardness on the surface of the organic photosensitive layer and improving the abrasion resistance against a contact member in a copying machine or artificial contact is effective. .

However, in order to cover the surface of the organic photosensitive layer with the protective layer, random film materials and film forming methods cannot be used,
It is necessary to use a film that satisfies all of the following necessary items, and the film material and its film forming method require originality and ingenuity.

First, it is necessary that the film has a high visible light transmittance and can secure a sufficient amount of light incident on the organic photosensitive layer and does not impair the excellent sensitivity inherent in the photosensitive layer. Secondly, in actual use in a copying machine, it is necessary that the surface of the dura be not damaged. Thirdly, it is required that the film has excellent adhesiveness to the organic photosensitive layer and does not peel off due to mechanical contact or changes in temperature and humidity in actual use in a copying machine. Fourth, it needs to be harmless. Fifth, it is excellent in electrical matching with the organic photosensitive layer, and a residual potential is generated, or a so-called memory phenomenon in which the previous image appears as a positive or negative image in the next image when a plurality of sheets are copied, It is necessary that the film does not contribute to the occurrence of so-called image deletion due to the lateral flow of charges at the mismatched interface. In other words, the surface protective layer is required to have excellent electrical compatibility with the organic photosensitive layer. Sixth, in the environment where the copying machine is actually used, particularly under high temperature and high humidity conditions, it is necessary that the film does not impair the image quality and does not cause so-called image deletion.

Furthermore, most of the organic photosensitive layer materials have poor heat resistance, and cannot be heated to a high temperature when the protective film is formed. For example, if a thermosetting resin is applied and heat-cured, a hard film of about 3H to 6H can be obtained, but the photosensitive layer is modified by the heat treatment, and suitable sensitivity cannot be obtained. Therefore, although it depends on the type of the organic photosensitive layer material, the protective film forming temperature is most preferably room temperature, and even if it is slightly heated, the maximum temperature must be suppressed to 100 ° C. at most.

From such a point of view, several film materials and a film forming method for the surface protective layer of the organic photoconductor are disclosed, and they are important technical fields in electrophotography.

One method is a coating method. For example, JP-A-53-23636
The publication discloses a photoconductor in which an insulating layer obtained by coating and curing a specific silicon compound is provided on various photoconductive layers including organic systems. JP-A-54-17732 discloses a photoconductor in which an overcoat layer (surface protection layer) containing nitrocellulose as a main component is applied and dried on the surface of a photoconductive layer in which a phthalocyanine photoconductor is dispersed in a resin. It is disclosed.
JP-A-57-89764 discloses a photoreceptor in which a resin such as a polyurethane resin is applied and cured on various photosensitive layers including organic systems.

These disclosures are intended to solve the above problems by applying an organic compound again to the surface of an organic photoreceptor and curing the same.

However, generally, when an organic compound is formed as a surface protective layer by a coating method, only a pencil hardness of about 2H to 3H is obtained, and the surface hardness is not always sufficient.

As another method, Japanese Patent Laid-Open No. 57-89765 discloses a photoconductor in which a vacuum deposition film of a metal oxide or a metal halide is formed as a surface protective layer on an organic photoconductive layer.

This disclosure is also the same as the present invention for the purpose of solving the above-mentioned problems by using an overcoat film forming method at around room temperature.
Essentially different from the present invention. Further, generally, even when it is formed as a surface protective layer by a vacuum vapor deposition method, only a pencil hardness of about 2H to 3H can be obtained, and the surface hardness is not always sufficient.

On the other hand, the plasma organic polymerized film itself has been known for a long time, for example, Journal of Applied, published in 1973 by M. Shen and At Bell.
Polymer Science (Journal of Applied Polymer S
cience, Vol. 17, pages 885-892, that they can be made from gases of any organic compound, and also by the same authors, that the American Chemical Society of 1979 (American Chemical Society
The film forming property is also discussed in Plasma Polymerization issued by an Chemical Society. However, its application is not mentioned.

As a concrete application example to the photoconductor, for example, JP-A-59-59
JP-A-214859 discloses a technique for forming a film of about 5 μm by plasma polymerization of an organic hydrocarbon monomer as a protective layer on the surface of an amorphous silicon photoconductor. Japanese Unexamined Patent Publication (Kokai) No. 60-61761 discloses a photoconductor provided with a diamond-like carbon thin film of 500 Å to 2 μm as a surface protective layer of an amorphous silicon photoconductor, and the film thickness is 2 μm or less from the viewpoint of translucency. It is said to be preferable. Japanese Unexamined Patent Publication (Kokai) No. 60-249115 discloses a technique in which an amorphous carbon or hard carbon film of about 0.05 to 5 μm is used as a surface protective layer of an amorphous silicon photoconductor, and when the film thickness exceeds 5 μm, the photoconductor becomes active. It is said to have an adverse effect. Japanese Unexamined Patent Publication No. 61-94056 discloses an amorphous silicon photoreceptor using an amorphous carbon film having excellent hydrophobicity as a protective layer on the surface of amorphous silicon.

All of these disclosures attempt to improve the image quality at high humidity by coating the surface of an amorphous silicon photoreceptor, which has high hardness but poor moisture resistance and is apt to cause so-called image deletion, with a carbon-based film. It is a thing. In addition, since the amorphous silicon photoconductor, which is an inorganic photoconductor, is originally excellent in heat resistance, a film is formed at high temperature. Therefore, it is essentially different from the present invention.

Further, Japanese Patent Application Laid-Open No. 50-20728 discloses a photoconductor in which a polymer film formed by glow discharge polymerization is provided on the surface of a polyvinylcarbazole-selenium photoconductor as a protective layer in a thickness of 0.1 to 1 μm. Japanese Patent Application Laid-Open No. 51-46130 discloses an electrophotographic photosensitive plate in which a polyvinylcarbazole-based electrophotographic photosensitive member is subjected to glow discharge polymerization to form a polymer film of 0.001 to 3 μm.

All of these disclosures are intended to improve solvent resistance when a liquid development method is adopted, or to adjust charge polarity, and improve abrasion resistance of an organic photoreceptor by increasing hardness. Is not mentioned at all, including the composition and film forming method, and is essentially different from the present invention.

The present invention solves the above-mentioned problems while satisfying all the above-mentioned necessary items by using a material composition that is essentially different from those disclosed above.

The present inventors have been investigating a long-life type organic photoconductor by improving the surface hardness, and a plasma organic polymerized film formed by a glow discharge method is excellent in translucency and hardness, and is used as a surface protective layer. It was found to be effective. Furthermore, by including a nitrogen atom in the plasma organic polymerized film,
It was found that a surface protective layer having excellent adhesiveness, electrical compatibility, and environmental resistance can be obtained. Then, they have found that by forming the plasma organic polymerized film at a low temperature of 100 ° C. or lower, the film can be formed without modification of the organic photosensitive layer.

The present invention, by using these new findings, provides a suitable surface protective layer on the organic photosensitive layer, and provides an organic photosensitive member having excellent wear resistance and a long life, and a method for producing the same. Is.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention solves an essential problem of a conventional organic photosensitive layer, that is, poor wear resistance and short life due to low hardness of the photosensitive layer surface. Therefore, the present invention relates to a novel organic photoreceptor having a surface protective layer. Further, the present invention provides
The present invention relates to a novel organic photoreceptor having a surface protective layer that can sufficiently satisfy the following necessary items, which is often hindered in the formation of a random protective film, and a method for producing the same.

First, it is necessary that the surface protective layer has a high visible light transmittance and can secure a sufficient amount of incident light to the organic photosensitive layer and does not impair the excellent sensitivity inherent in the photosensitive layer. Secondly, in actual use in a copying machine, it is necessary that the surface protection layer has a high hardness so that the surface is not damaged. Thirdly, it is required that the surface protective layer has excellent adhesiveness to the organic photosensitive layer and is not peeled off due to mechanical contact or change in temperature and humidity in actual use in a copying machine.
Fourth, it needs to be a harmless surface protective layer. Fifth, it is excellent in electrical matching with the organic photosensitive layer, and a residual potential is generated, or a so-called memory phenomenon in which the previous image appears as a positive or negative image in the next image when a plurality of sheets are copied, It is necessary that the surface protection layer does not contribute to the generation of so-called image deletion due to the lateral flow of charges at the mismatched interface. In other words, the surface protective layer is required to have excellent electrical compatibility with the organic photosensitive layer. Sixth,
Under the environment where the copying machine is actually used, especially under high temperature and high humidity conditions, it is necessary to be a surface protective layer which does not impair the image quality and does not cause so-called image deletion. Furthermore, in most organic photosensitive layer materials, compounds having poor heat resistance cannot be subjected to high-temperature heating when forming a protective film, so it is necessary to form a surface protective layer at room temperature to 100 ° C. .

The present invention provides a photoreceptor capable of solving the above and a method for producing the same.

Means for Solving the Problems That is, the present invention relates to an organic photoreceptor in which an organic photosensitive layer is provided on a conductive substrate and a surface protective layer is provided thereon, wherein the organic photosensitive layer is a binder resin, a charge. A photoconductor comprising a generating material and a charge transporting material, wherein the surface protective layer is a plasma organic polymerized film of a hydrocarbon compound, and the plasma organic polymerized film contains at least a nitrogen atom (hereinafter The plasma organic polymerized film containing nitrogen atoms according to the present invention is referred to as an aC: X film). Furthermore, the plasma organic polymerized film is formed at a substrate temperature of 100 ° C. or less, and relates to a method for producing a photoreceptor.

In the present invention, as a gas for forming an aC: X film by a glow discharge method, a hydrocarbon gas and a nitrogen compound gas are used as a source gas, and a commonly used hydrogen gas or a nitrogen gas is used as a carrier gas. Argon gas or the like is used.

The phase state of the hydrocarbon gas does not necessarily have to be a gas phase at room temperature and normal pressure, and it can be used in a liquid phase or a solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or decompression. It is possible. As the hydrocarbon, for example,
Saturated hydrocarbons, unsaturated hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, etc. are used.

Although there are many types of hydrocarbons that can be used, examples of saturated hydrocarbons include methane, ethane, propane, butane,
Pentane, hexane, heptane, octane, isobutane, isopentane, neopentane, isohexane, neohexane, dimethylbutane, methylhexane, ethylpentane, dimethylpentane, triptan, methylheptane, dimethylhexane, trimethylpentane, isonanone, etc. are used. Examples of unsaturated hydrocarbons include ethylene, propylene, isobutylene, butene, pentene, methylbutene, hexene, tetramethylethylene, heptene, octene, allene, methylarene, butadiene, pentadiene, hexadiene, cyclopentadiene, ocimene, arocymene, myrcene. , Hexatriene, acetylene, diacetylene, methylacetylene, butyne, pentine, hexyne, heptin, octyne and the like are used. Examples of the alicyclic hydrocarbon include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclopropene, cyclobutene, cyclopentene, cyclohexene,
Cycloheptene, cyclooctene, limonene, terbinolene, ferrandrene, silvestrene, tsuen, karen, pinene, bornylene, camphene, fenchen,
Cyclophenchen, tricyclene, pisabolene, zingiberene, curcumene, humulene, kazinensesquibenijen, serinen, cariophyllene, santalen, sedrene, camphorene, phyllocladen, podocarprene, mylene and the like are used. As the aromatic hydrocarbon, for example, benzene, toluene, xylene, hemimelitene, pseudocumene, mesitylene, prenitene, isodulene, durene, pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, cumene,
Styrene, biphenyl, terphenyl, diphenylmethane, triphenylmethane, dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, phenanthrene and the like are used.

The amount of hydrogen atoms contained in the aC: X film in the present invention is about 30 to 60 atom% with respect to the total amount of carbon atoms and hydrogen atoms.

The amount of hydrogen atoms contained in the aC: X film in the present invention changes depending on the form of the film forming apparatus and the conditions during film formation,
When the amount of hydrogen becomes low, for example, the substrate temperature is raised, the pressure is lowered, the dilution ratio of the raw hydrocarbon gas is lowered, the raw material gas having a low hydrogen content is used, the applied power is raised, and the alternating voltage is increased. Examples include cases where the frequency of the electric field is lowered, and the strength of the DC electric field superposed on the alternating electric field is increased.

In the present invention, in addition to the hydrocarbon gas, a nitrogen compound gas is used to add at least nitrogen atoms into the aC: X film. The phase state of the nitrogen compound gas does not necessarily have to be a gas phase at room temperature and normal pressure, and it can be used in a liquid phase or a solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or decompression. It is possible. As the nitrogen compound, for example, nitrogen, ammonia, nitric oxide, nitrogen dioxide, dinitrogen trioxide, dinitrogen pentoxide, nitric oxide,
Inorganic compounds such as amino (-NH _2), cyano (-C
N), nitro group (-NO _2), nitroso group (-NO), isocyanate ester bond (-NCO), isothiocyanate coupling (-NCS), an azo thioether bond (-N = NS
-), Peptide bond (-CONH-), nitrogen-containing heterocycle,
An organic compound having a functional group or bond such as is used.
Examples of the organic compound having an amino group include, for example, methylamine, ethylamine, propylamine, butylamine, amylamine, hexylamine, heptylamine,
Octylamine, cetylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, allylamine, diallylamine, triallylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine , Cyclohexylamine, aniline,
Methylaniline, dimethylaniline, ethylaniline,
Diethylaniline, toluidine, benzylamine, dibenzylamine, tribenzylamine, diphenylamine, triphenylamine, naphthylamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, diaminoheptane, diaminooctane, phenylenediamine , Etc. are used. Examples of the organic compound having a cyano group include, for example, acetonitrile, flopionitrile, butyronitrile, valeronitrile, capronitrile, enanthnitrile, caprylonitrile, ferralgon nitrile, caprynitrile, lauronitrile, palmitonitrile, stearonitrile, croton. Nitrile, malon nitrile, succinonitrile, dartar nitrile,
Adiponitrile, benzonitrile, tolunitrile, benzyl cyanocinnamate nitrile, naphthonitrile, cyan pyridine, etc. are used. Examples of the organic compound having a nitro group include nitrobenzene, nitrotoluene, nitroxylene, nitronaphthalene, and the like. As the organic compound having a nitroso group, for example,
Nitrosobenzene, nitrosotoluene, nitrosonaphthalene, nitrosocresol, etc. are used. Examples of the organic compound having an isocyanate bond include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, phenyl isocyanate, naphthyl isocyanate, and the like. Examples of the organic compound having an isothiocyanate bond include methyl isothiocyanate, ethyl isothiocyanate, propyl isothiocyanate, butyl isothiocyanate, amyl isothiocyanate, allyl isothiocyanate, phenyl isothiocyanate, and benzyl isothiocyanate. Examples of the organic compound having an azothioether bond include benzenediazothiophenyl ether, chlorobenzenediazothiophenyl ether, bromobenzenediazothiophenyl ether, nitrobenzenediazothiophenyl ether, phenyldiazomercaptonaphthalene, methoxyphenyldiazomercaptonaphthalene, benzene. Diazothioglycolic acid, bromobenzenediazothioglycolic acid, nitrobenzenediazothioglycolic acid, etc. are used.
As the organic compound having a peptide bond, for example, glyceroglycopeptide, glyceroid peptide, etc. are used. Heterocyclic compounds include pyrrole, pyrroline,
Pyrrolidine, oxazole, thiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, pyrazolidine, triazole, tetrazole,
Pyridine, piperidine, oxazine, morpholine, thiazine, pyridazine, pyrimidine, pyrazine, piperazine, triazine, indole, indoline, benzoxazole, indazole, benzimidazole, quinoline, cinnoline, phthalazine, phthalocyanine, quinazoline, quinxaline, carbazole, acridine, phenant. Lysine, phenazine, phenoxazine, indolizine, quinolidine, quinuclidine, naphthyridine, purine, pteridine, aziridine, azepine, oxadiazine, dithiazine, benzoquinoline, imidazothiazole, etc. are used.

In the present invention, when the surface protective layer does not contain a nitrogen atom, for example, when the nitrogen atom is not detected by Auger analysis, it is left unresolved due to electrical inconsistency with the organic photosensitive layer. Occurrence of electric potential, or occurrence of so-called memory phenomenon in which the previous image appears as a positive or negative image in the next image at the time of copying a plurality of sheets, and further, occurrence of so-called image deletion due to lateral flow of charges at the mismatched interface, etc. It is easy to induce. Further, the adhesiveness to the organic photosensitive layer becomes poor, and the surface protective layer is liable to peel off due to mechanical force during actual use in a copying machine or due to changes in temperature and humidity. The electrical inconsistency described above is also considered to be due to this poor adhesion.

The amount of nitrogen atoms contained as a chemical modifier in the present invention can be controlled mainly by increasing or decreasing the amount of the above-mentioned nitrogen compound gas introduced into the reaction chamber where the plasma reaction is performed. By increasing the amount of nitrogen compound gas introduced, it is possible to increase the amount of nitrogen atoms added to the aC: X film according to the present invention, and conversely, by decreasing the amount of nitrogen compound introduced. It is possible to reduce the amount of nitrogen atoms added to the aC: X film according to the present invention.

In the present invention, the nitrogen atom content may be 0.1 atomic% or more, and the maximum content is not particularly limited, but it is necessarily determined from the structure of the surface protective layer and the manufacturing aspect of glow discharge.

A- as a surface protective layer of the organic photosensitive layer in the present invention
The thickness of the C: X film is preferably about 0.2 to 5 μm. When the film thickness is less than 0.2 μm, the surface hardness is likely to be affected by the low hardness of the underlying organic photosensitive layer, and suitable durability cannot be secured. Further, when the film thickness is thicker than 5 μm, it is not always possible to secure a suitable visible light transmittance, and the high sensitivity performance originally possessed by the organic photosensitive layer is impaired.

In the process of forming the aC: X film from the raw material gas in the present invention, the raw material gas uses a plasma state generated by a so-called plasma method using direct current, low frequency, high frequency, or microwave. It is formed.

The organic photosensitive layer used in the present invention is formed by a conventional coating method.

FIG. 1 shows the structure of a photoreceptor according to the present invention, in which an organic photosensitive layer (2) and a surface protective layer (3), that is, aC: X layer, are sequentially laminated in this order on a conductive substrate (1). Is shown. The photosensitive layer may be a single layer having both charge generation and charge transport, or may be two layers having both functions separated.

FIG. 2 is a surface protective layer of the photoreceptor according to the present invention, that is, a
-C: shows the manufacturing equipment for forming the X film, (201) in the figure
Numerals (206) are first to sixth tanks for sealing the raw material and carrier gas in a gas phase at room temperature, and each of the tanks is composed of first to sixth control valves (207) to (212) and first to sixth tanks. 6 flow controllers (213) to (218) are connected. In the figure, reference numerals (219) to (221) denote first to third containers in which raw materials in a liquid phase or a solid phase at room temperature are enclosed, and the first to third temperature controllers (222) are provided for each container for vaporization. )-(224), and each container has seventh to ninth control valves (225) to (227) and seventh to ninth flow controllers (22).
8) to (230). These gases are mixed in the mixer (231) and then fed into the reaction chamber (233) through the main pipe (232). The pipes on the way can be heated by a pipe heater (234) arranged appropriately so that the vaporized gas of the raw material compound in the liquid or solid state at room temperature does not condense on the way. . A ground electrode (235) and a power application electrode (236) are installed in the reaction chamber so as to face each other, and each electrode can be heated by an electrode heater (237). A high frequency power source (239) via a high frequency power matching box (238), a low frequency power source (241) and a low pass filter (242) via a low frequency power matching box (240) to the power application electrode (236). A direct current power source (243) is connected via the, and power of different frequencies can be applied by the connection selection switch (244). The pressure in the reaction chamber (233) can be adjusted by the pressure control valve (245), and the pressure reduction in the reaction chamber (233) is controlled by the diffusion pump (247) and the oil rotation via the exhaust system selection valve (246). Pump (248) or
Cooling exclusion device (249), mechanical booster pump (2
50), an oil rotary pump (248). Exhaust gas is further safety-detoxified by an appropriate exclusion device (253), and then discharged into the atmosphere. Even if these exhaust system pipes are used, the vaporized gas of the raw material compound that was in the liquid phase or solid phase at room temperature should be prevented from condensing during the process.
It can be heated by a pipe heater (234) arranged appropriately. For the same reason, the reaction chamber (233) can be heated by the reaction chamber heater (251), and a substrate (in which an organic photosensitive layer is previously formed on a conductive substrate is formed on the electrode arranged inside) 252) is installed. In FIG. 2, the substrate (2
Although 52) is fixedly arranged on the ground electrode (235), it may be fixedly arranged on the power applying electrode (236) or may be arranged on both sides.

FIG. 3 is a surface protective layer of the photoreceptor according to the present invention, that is, a
-C: shows another form of the manufacturing apparatus for forming the X film, and is the same as the manufacturing apparatus according to the present invention shown in FIG. 2 except the shape inside the reaction chamber (333). That is, the numbers in the 200s in FIG. 2 may be replaced with the 300s in FIG.

In FIG. 3, inside the reaction chamber (333), a cylindrical substrate (352), which also serves as the ground electrode (235) in FIG. 2 and on which an organic photosensitive layer is previously formed on a conductive substrate, is installed. The electrode heater (337) is arranged inside. Around the substrate (352), a cylindrical power applying electrode (3
36) is arranged, and an electrode heater (337) is arranged outside. The substrate (352) on which the organic photosensitive layer is formed is
It can rotate from the outside using a drive motor (354).

The pressure in the reaction chamber is reduced to about 10 ^{−4 to} 10 ⁻⁶ Torr in advance by a diffusion pump, and the degree of vacuum is confirmed and the gas adsorbed inside the apparatus is desorbed. At the same time, the electrode and the substrate fixedly mounted on the electrode are heated to a predetermined temperature by the electrode heater. At this time, the substrate temperature is set to 100 ° C. or lower (normal temperature to 100 ° C.) in order to prevent thermal denaturation of the organic photosensitive layer. Next, the first to sixth tanks and the first
Through the third to third containers, a raw material gas consisting of hydrocarbons and nitrogen compounds is introduced into the reaction chamber while making the flow rate constant by using the first to ninth flow rate controllers, and the pressure control valve keeps the reaction chamber at a constant reduced pressure state. . After the gas flow rate is stabilized, select the high frequency power supply, for example, with the connection selection switch,
High frequency power is applied to the power application electrode. Discharge is started between both electrodes, and a solid phase film is formed on the substrate with time. The film thickness is controlled by the reaction time, the discharge is stopped when the film thickness reaches a predetermined value, and an aC: X film is obtained as the surface protective layer of the photoreceptor according to the present invention. This aC: X film is a plasma organic polymerized film containing nitrogen atoms produced by the present invention. Through the above process, the photoreceptor having the surface protective layer according to the present invention is obtained.

Hereinafter, the present invention will be described with reference to examples.

First, the organic photosensitive layers A to D were manufactured. Below, vertical
The organic photosensitive layers Ap to Dp are formed on a flat aluminum substrate of 50 × width 50 × thickness 3 mm by using an auxiliary symbol p.
Which is formed on a cylindrical aluminum substrate having a diameter of 80 mm and a length of 330 mm, is referred to as an organic photosensitive layer using an auxiliary symbol d.
Called Ad ~ Dd.

Preparation of Organic Photosensitive Layer A A mixed solution of 1 g of chlorodian blue (CDB) as a disazo pigment, 1 g of polyester resin (V-200 manufactured by Toyobo Co., Ltd.), and 98 g of cyclohexanone was dispersed for 13 hours with a sand blinder. This dispersion was applied on a flat aluminum substrate having a length of 50 × width of 50 × thickness of 3 mm by using a bar coater so that the film thickness after drying would be 0.3 μm, and dried to form a charge generation layer.

Then, 5 g of 4-diethylaminobenzaldehyde-diphenylhydrazone (DEH) and 5 g of polycarbonate (K-1300 manufactured by Teijin Chemicals Ltd.) are dissolved in 30 g of THF, and this solution is dried on the charge generation layer to have a thickness of 15 μm. On the organic photosensitive layer.
Got an Ap.

In the same process, using dipping, an organic photosensitive layer Ad is formed on a cylindrical aluminum substrate with a diameter of 80 mm and a length of 330 mm.
Was formed.

Comparative Example 1 The obtained organic photosensitive layer Ap was charged to −600 V by corona discharge in a conventional Carlson process, and the half-quantity of white light (hereinafter, referred to as E1 / 2) was measured. -Second, the residual potential was 5V. Also, JIS-K-540
When the pencil hardness according to 0 standard was measured, it had a surface hardness of about 5B.

The same performance was also confirmed for the obtained organic photosensitive layer Ad. However, when the organic photosensitive layer Ad was further mounted on an actual copying machine and a printing durability test was conducted, it was found that A4 copy paper In the printing durability test of 5,000 sheets, a film thickness reduction of 1 μm was observed. Therefore, it was understood that although the electrostatic property was excellent, the durability was poor.

Preparation of Organic Photosensitive Layer B The organic photosensitive layers Bp and Bd were prepared in the same manner as the organic photosensitive layers Ap and Ad except that the polycarbonate for forming the charge transport layer was replaced with methyl methacrylate PMMA (BR-85 manufactured by Mitsubishi Rayon Co., Ltd.).
Was produced.

Comparative Example 2 The obtained organic photosensitive layer Bp was charged to −600 V by corona discharge in a conventional Carlson process, and E1 / 2 was measured to be 6.2 lux · sec and residual potential was 12 V. .
Moreover, when the pencil hardness according to JIS-K-5400 standard was measured, it had a surface hardness of about B.

Also, similar performance was observed for the obtained organic photosensitive layer Bd, but when the organic photosensitive layer Bd was mounted on an actual copying machine and a printing durability test was conducted, it was found that In the printing durability test of 8,000 sheets, a film thickness reduction of 1 μm was observed. Therefore, it was understood that although the electrostatic property was excellent, the durability was poor.

Preparation of Organic Photosensitive Layer C Polycarbonate is polyarylate (U- manufactured by Unitika Ltd.)
The organic photosensitive layers Cp and Cd were produced in the same manner as the organic photosensitive layers Ap and Ad except that the organic photosensitive layers Ap and Ad were replaced with 4000).

Comparative Example 3 The obtained organic photosensitive layer Cp was charged to −600 V by corona discharge in a conventional Carlson process, and E1 / 2 was measured to be 2.3 lux · second and residual potential was 8 V. .
Moreover, when the pencil hardness according to JIS-K-5400 standard was measured, it had a surface hardness of about 5B.

The same performance was also confirmed for the obtained organic photosensitive layer Cd. However, when the organic photosensitive layer Cd was mounted on an actual copying machine and a printing durability test was conducted, it was found that In the printing durability test of 4,000 sheets, a film thickness reduction of 1 μm was observed. Therefore, it was understood that although the electrostatic property was excellent, the durability was poor.

Preparation of Organic Photosensitive Layer D Polycarbonate is made of polyester (V-20 manufactured by Toyobo Co., Ltd.).
Organic photosensitive layers Dp and Dd were prepared in the same manner as the organic photosensitive layers Ap and Ad except that the organic photosensitive layers Ap and Ad were replaced.

Comparative Example 4 The obtained organic photosensitive layer Dp was charged to −600 V by corona discharge in a conventional Carlson process, and E1 / 2 was measured to be 2.2 lux · second and residual potential was 7 V. .
Moreover, when the pencil hardness according to JIS-K-5400 standard was measured, it had a surface hardness of about 5B.

Further, similar performance was observed for the obtained organic photosensitive layer Dd, but when the organic photosensitive layer Dd was further mounted on an actual copying machine and a printing durability test was conducted, it was found that In the printing durability test of 5,000 sheets, a film thickness reduction of 1 μm was observed. Therefore, it was understood that although the electrostatic property was excellent, the durability was poor.

Example 1 Using the manufacturing apparatus according to the present invention, a photoconductor of the present invention having a conductive substrate, an organic photosensitive layer, and a surface protective layer as shown in FIG. 1 was prepared in this order.

In the glow discharge decomposition apparatus shown in FIG. 2, first, the inside of the reactor (233) is evacuated to a high vacuum of about 10 ⁻⁶ Torr,
The first, second, and third control valves (207, 208, and 209) are opened, and hydrogen gas is supplied from the first tank (201), ethylene gas is supplied from the second tank (202), and the third tank (203). More nitrogen gas under the output pressure of 1.0 Kg / cm ² , the first, second,
And into the third flow controller (213, 214, and 215). Then, adjust the scale of each flow rate controller so that the flow rate of hydrogen gas is 40 sccm, the flow rate of ethylene gas is 30 sccm, and the flow rate of nitrogen gas is 30 sccm, and the interim mixer (231) is used. , And flowed into the reaction chamber (233) through the main pipe (232). After stabilizing each flow rate, the reaction chamber (23
3) Pressure control valve (245) so that the pressure inside becomes 0.5 Torr
Was adjusted. On the other hand, as the substrate (252), the organic photosensitive layer Ap is used and preheated to 100 ° C., and the connection selection switch (24
Turn on the high frequency power supply (239) connected by 4),
Power of 200Watt is applied to the power application electrode (236) at a frequency of 13.56MHz.
And a plasma polymerization reaction was carried out for about 10 minutes to form a 0.32 μm thick aC: X film as a surface protective layer on the substrate (252). After the film formation was completed, the power application was stopped, the control valve was closed, the reaction chamber (233) was sufficiently evacuated, and then the vacuum was broken to take out the photoconductor of the present invention.

When CHN quantitative analysis was performed on the aC: X film obtained as described above, the amount of hydrogen atoms contained was about 47 atom% with respect to the total amount of carbon atoms and hydrogen atoms. , The amount of nitrogen atoms contained was about 1.3 atom% with respect to all the constituent atoms.

Characteristics: The obtained photoreceptor of the present invention was charged to −600 V by corona discharge in a conventional Carlson process, and E1 / 2 was measured. As a result, it was 2.1 lux · second and the residual potential was 5 V. From this, it was understood that the photoreceptor of the present invention is a photoreceptor having a surface protective layer which does not impair the excellent sensitivity performance originally possessed by the organic photosensitive layer. Moreover, when the pencil hardness according to JIS-K-5400 standard was measured, it was found that the pencil hardness was 7H or more, and the surface hardness was remarkably improved.

Example 2 Using the manufacturing apparatus according to the present invention, a photoconductor of the present invention having a conductive substrate, an organic photosensitive layer and a surface protective layer as shown in FIG. 1 was provided in this order.

In the glow discharge decomposition apparatus shown in FIG. 3, first, the inside of the reactor (333) is evacuated to a high vacuum of about 10 ⁻⁶ Torr, and then the first, second, and third control valves (307, 308, and 309). ) Is released, hydrogen gas is discharged from the first tank (301), and the second tank (3
Ethylene gas from 02) and nitrogen gas from the third tank (303) under the output pressure of 1.0 kg / cm ² in the first, second and third flow controllers (313, 314 and 315). Was made to flow into. Then, adjust the scale of each flow rate controller so that the flow rate of hydrogen gas is 120 sccm, the flow rate of ethylene gas is 90 sccm, and the flow rate of nitrogen gas is 65 sccm, and the intermediate mixer (331) is used. , Flowed into the reaction chamber (333) through the main pipe (332). After stabilizing each flow rate, the reaction chamber (33
3) Pressure control valve (345) so that the pressure inside becomes 0.8 Torr
Was adjusted. On the other hand, as the substrate (352), an organic photosensitive layer Ad is used and preheated to 75 ° C., and in a state where the gas flow rate and pressure are stable, the connection selection switch (344) is previously set.
The high frequency power source (339) connected by the above is turned on, 250 Watt of power is applied to the power application electrode (336) at a frequency of 13.56 MHz, and a plasma polymerization reaction is performed for about 5 minutes, and then it is placed on the substrate (352). An aC: X film having a thickness of 0.2 μm was formed as a surface protective layer. After the film formation was completed, the power application was stopped, the control valve was closed, the reaction chamber (333) was sufficiently evacuated, the vacuum was broken, and the photoreceptor of the present invention was taken out.

When CHN quantitative analysis was performed on the aC: X film obtained as described above, the amount of hydrogen atoms contained was about 31 atom% with respect to the total amount of carbon atoms and hydrogen atoms. , The amount of nitrogen atoms contained was about 2.1 atom% with respect to all the constituent atoms.

Characteristics: The obtained photoreceptor of the present invention was charged to −600 V by corona discharge in a usual Carlson process, and E1 / 2 was measured. As a result, it was 2.0 lux · second and the residual potential was 7 V. From this, it was understood that the photoreceptor of the present invention is a photoreceptor having a surface protective layer which does not impair the excellent sensitivity performance originally possessed by the organic photosensitive layer. Moreover, when the pencil hardness according to JIS-K-5400 standard was measured, it was found that the pencil hardness was 7H or more, and the surface hardness was remarkably improved.

Further, when this photoreceptor of the present invention was mounted on an actual copying machine and a printing durability test was conducted, a clear image was always obtained even when copying about 100,000 A4 copy papers, and a decrease in film thickness was observed. However, it was understood that the durability was excellent. Also, at the time of normal temperature and normal humidity and high temperature and high humidity, so-called image deletion is not observed, and the photoreceptor is excellent in electrical matching between the organic photosensitive layer and the surface protective layer, and is also excellent in environmental resistance. I understood something. Furthermore, peeling of the surface protective layer was not observed even after a printing durability test of 100,000 sheets, and it was understood that the photoconductor has excellent adhesiveness between the organic photosensitive layer and the surface protective layer.

Example 3 Using the manufacturing apparatus according to the present invention, a photoconductor of the present invention having a conductive substrate, an organic photosensitive layer and a surface protective layer as shown in FIG. 1 was prepared in this order.

In the glow discharge decomposition apparatus shown in FIG. 2, first, the inside of the reactor (233) is evacuated to a high vacuum of about 10 ⁻⁶ Torr,
The first, second, and seventh control valves (207, 208, and 225) are opened, and hydrogen gas from the first tank (201) and nitrogen gas from the second tank (202) output pressure of 1.0 kg / cm, respectively. ² and the styrene gas from the first container (219) to the first temperature controller (2
22) Flowed into the first, second and seventh flow controllers (213, 214 and 228) at a temperature of 35 ° C. And adjust the scale of each flow rate controller, the flow rate of hydrogen gas is 40sccm, the flow rate of nitrogen gas is 3sccm, and the flow rate of styrene gas is 10scc.
Set it to be m, and through the mixer (231) on the way,
It flowed into the reaction chamber (233) from the main pipe (232). After each flow rate is stabilized, the pressure in the reaction chamber (233) becomes 0.25 Torr.
The pressure control valve (245) was adjusted so that On the other hand, as the substrate (252), the organic photosensitive layer Bp is used, and the
With the gas flow rate and pressure stable after being heated to ℃, turn on the low-frequency power supply (241) that was connected in advance by the connection selection switch (244), and then turn on the power application electrode (236).
120Watt power is applied under the frequency of 100KHz to carry out plasma polymerization reaction for about 45 seconds, and the thickness is 0.5μ on the substrate (252).
m a-C: X film was formed as a surface protection layer. After the film formation is completed, the power application is stopped, the control valve is closed, and the reaction chamber (23
3) After exhausting the inside sufficiently, the vacuum was broken and the photoreceptor of the present invention was taken out.

When CHN quantitative analysis was performed on the aC: X film obtained as described above, the amount of hydrogen atoms contained was about 41% atomic% based on the total amount of carbon atoms and hydrogen atoms. Therefore, the amount of nitrogen atoms contained was about 0.15 atom% with respect to all the constituent atoms.

Characteristics: The obtained photoreceptor of the present invention was charged to −600 V by corona discharge in a conventional Carlson process, and E1 / 2 was measured. As a result, it was 6.2 lux · sec and the residual potential was 11 V. From this, it was understood that the photoreceptor of the present invention is a photoreceptor having a surface protective layer which does not impair the excellent sensitivity performance originally possessed by the organic photosensitive layer. Moreover, when the pencil hardness according to JIS-K-5400 standard was measured, it was found that it had a surface hardness of about 7H, and the surface hardness was remarkably improved.

Example 4 Using the manufacturing apparatus according to the present invention, a photoconductor of the present invention having a conductive substrate, an organic photosensitive layer and a surface protective layer as shown in FIG. 1 was provided in this order.

In the glow discharge decomposition apparatus shown in Fig. 3, first, the inside of the reaction device (333) is evacuated to a high vacuum of about 10 ^-6 Torr,
The first, second, and seventh control valves (307, 308, and 325) are opened, and hydrogen gas from the first tank (301) and nitrogen gas from the second tank (302) output pressure of 1.0 kg / cm, respectively. ² and the styrene gas from the first container (319) to the first temperature controller (3
22) Flowed into the first, second, and seventh flow controllers (313, 314, and 328) at a temperature of 45 ° C. Then, adjust the scale of each flow rate controller so that the flow rate of hydrogen gas is 90 sccm, the flow rate of nitrogen gas is 30 sccm, and the flow rate of styrene gas is 18 sccm.
The flow rate was set to cm, and the mixture flowed into the reaction chamber (333) from the main pipe (332) through the mixer (331) in the middle. After each flow rate became stable, the pressure in the reaction chamber (333) was 0.28T.
The pressure control valve (345) was adjusted to be orr. on the other hand,
As the substrate (352), the organic photosensitive layer Bd is used, and the low-frequency power source (341) is connected in advance by the connection selection switch (344) in a state where the gas flow rate and pressure are stable at room temperature. Power is applied to the power application electrode (336) at a frequency of 150 KHz at a frequency of 150 KHz to carry out a plasma polymerization reaction for about 50 seconds, and a 1 μm thick aC: X film is formed on the substrate (352).
The film was formed as a surface protective layer. After the film formation was completed, the power application was stopped, the control valve was closed, the reaction chamber (333) was sufficiently evacuated, the vacuum was broken, and the photoreceptor of the present invention was taken out.

When CHN quantitative analysis was performed on the aC: X film obtained as described above, the amount of hydrogen atoms contained was about 47 atom% with respect to the total amount of carbon atoms and hydrogen atoms. , The amount of nitrogen atoms contained was about 1.4 atom% with respect to all the constituent atoms.

Characteristics: The obtained photoreceptor of the present invention was charged to −600 V by corona discharge in a conventional Carlson process, and E1 / 2 was measured. As a result, it was 6.4 lux · sec and the residual potential was 10 V. From this, it was understood that the photoreceptor of the present invention is a photoreceptor having a surface protective layer which does not impair the excellent sensitivity performance originally possessed by the organic photosensitive layer. Moreover, when the pencil hardness according to JIS-K-5400 standard was measured, it was found that the pencil hardness was 7H or more, and the surface hardness was remarkably improved.

Further, when this photoreceptor of the present invention was mounted on an actual copying machine and a printing durability test was conducted, a clear image was always obtained even when copying about 100,000 A4 copy papers, and a decrease in film thickness was observed. However, it was understood that the durability was excellent. Also, at the time of normal temperature and normal humidity and high temperature and high humidity, so-called image deletion is not observed, and the photoreceptor is excellent in electrical matching between the organic photosensitive layer and the surface protective layer, and is also excellent in environmental resistance. I understood something. Further, no peeling of the surface protective layer was observed even after a printing durability test of 100,000 sheets, and it was understood that the photoconductor has excellent adhesiveness between the organic photosensitive layer and the surface protective layer.

Example 5 Using the manufacturing apparatus according to the present invention, a photoconductor of the present invention having a conductive substrate, an organic photosensitive layer and a surface protective layer as shown in FIG. 1 was prepared in this order.

In the glow discharge decomposition apparatus shown in FIG. 2, first, the inside of the reactor (233) is evacuated to a high vacuum of about 10 ⁻⁶ Torr,
The first, second, and seventh control valves (207, 208, and 225) are released, and hydrogen gas from the first tank (201) and butadiene gas from the second tank (202) output pressure of 1.0 kg / cm, respectively. ² and the diethylamine gas from the first container (219) under the temperature of the first temperature controller (222) of 40 ° C., the first, second and seventh flow rate controllers (213, 214 and 228). Then, adjust the scale of each flow rate controller so that the flow rate of hydrogen gas is 60 sccm, the flow rate of butadiene gas is 60 sccm, and the flow rate of diethylamine gas is 25 sccm, and the intermediate mixer (231) is used. , And flowed into the reaction chamber (233) through the main pipe (232). After each flow rate stabilizes,
The pressure control valve (245) was adjusted so that the pressure in the reaction chamber (233) was 0.5 Torr. On the other hand, as the substrate (252), the organic photosensitive layer Cp was used, which was previously heated to 45 ° C., and was connected in advance by the connection selection switch (244) while the gas flow rate and pressure were stable. Turn on the low frequency power supply (239) and apply 100Watt of power to the power application electrode (236) at a frequency of 100K.
Applying under Hz to carry out plasma polymerization reaction for about 25 seconds,
On the substrate (252), a 0.5 μm thick aC: X film was formed as a surface protective layer. After the completion of the film formation, the power application was stopped, the control valve was closed, the reaction chamber (233) was sufficiently evacuated, the vacuum was broken, and the photoreceptor of the present invention was taken out.

When CHN quantitative analysis was performed on the aC: X film obtained as described above, the amount of hydrogen atoms contained was about 36 atom% with respect to the total amount of carbon atoms and hydrogen atoms. , The amount of nitrogen atoms contained was about 18 atom% with respect to all the constituent atoms.

Characteristics: The obtained photoreceptor of the present invention was charged to −600 V by corona discharge in a usual Carlson process, and E1 / 2 was measured. As a result, it was 2.4 lux · second and residual potential was 10 V. From this, it was understood that the photoreceptor of the present invention is a photoreceptor having a surface protective layer which does not impair the excellent sensitivity performance originally possessed by the organic photosensitive layer. Moreover, when the pencil hardness according to JIS-K-5400 standard was measured, it was found that the pencil hardness was 7H or more, and the surface hardness was remarkably improved.

Example 6 Using the manufacturing apparatus according to the present invention, a photoconductor of the present invention having a conductive substrate, an organic photosensitive layer and a surface protective layer as shown in FIG. 1 was prepared in this order.

In the glow discharge decomposition apparatus shown in Fig. 3, first, the inside of the reaction device (333) is evacuated to a high vacuum of about 10 ^-6 Torr,
The first, second, and seventh control valves (307, 308, and 325) are released, and hydrogen gas from the first tank (301) and butadiene gas from the second tank (302) are respectively output at a pressure of 1.0 kg / cm. ² and the diethylamine gas from the first container (319) under the first temperature controller (222) temperature of 45 ° C., the first, second and seventh flow rate controllers (213, 214, and 228). Then, the scale of each flow rate controller was adjusted so that the flow rate of hydrogen gas was 200 sccm, the flow rate of butadiene gas was 30 sccm, and the flow rate of diethylamine gas was 40 sccm, and the intermediate mixer (331) was used. , Flowed into the reaction chamber (333) through the main pipe (332). After each flow rate stabilizes,
The pressure control valve (345) was adjusted so that the pressure in the reaction chamber (333) was 0.7 Torr. On the other hand, the substrate (352) was previously heated to 30 ° C. using the organic photosensitive layer Cd, and was previously connected by the connection selection switch (344) while the gas flow rate and pressure were stable. Turn on the low frequency power supply (341) and apply 250Watt power to the power application electrode (336) at a frequency of 120K.
Applying under Hz to perform plasma polymerization reaction for about 30 seconds,
A 2.2 μm-thick aC: X film was formed as a surface protective layer on the substrate (252). After the film formation was completed, the power application was stopped, the control valve was closed, the reaction chamber (333) was sufficiently evacuated, the vacuum was broken, and the photoreceptor of the present invention was taken out.

When CHN quantitative analysis was performed on the aC: X film obtained as described above, the amount of hydrogen atoms contained was about 38 atomic% with respect to the total amount of carbon atoms and hydrogen atoms. , The amount of nitrogen atoms contained was about 20 atom% with respect to all the constituent atoms.

Characteristics: The obtained photoreceptor of the present invention was charged to −600 V by corona discharge in a conventional Carlson process, and E1 / 2 was measured. As a result, it was 2.3 lux · second and residual potential was 9 V. From this, it was understood that the photoreceptor of the present invention is a photoreceptor having a surface protective layer which does not impair the excellent sensitivity performance originally possessed by the organic photosensitive layer. Moreover, when the pencil hardness according to JIS-K-5400 standard was measured, it was found that the pencil hardness was 7H or more, and the surface hardness was remarkably improved.

Further, when this photoreceptor of the present invention was mounted on an actual copying machine and a printing durability test was conducted, a clear image was always obtained even when copying about 100,000 A4 copy papers, and a decrease in film thickness was observed. However, it was understood that the durability was excellent. Also, at the time of normal temperature and normal humidity and high temperature and high humidity, so-called image deletion is not observed, and the photoreceptor is excellent in electrical matching between the organic photosensitive layer and the surface protective layer, and is also excellent in environmental resistance. I understood something. Further, no peeling of the surface protective layer was observed even after a printing durability test of 100,000 sheets, and it was understood that the photoconductor has excellent adhesiveness between the organic photosensitive layer and the surface protective layer.

Example 7 Using the manufacturing apparatus according to the present invention, a photoconductor of the present invention having a conductive substrate, an organic photosensitive layer and a surface protective layer as shown in FIG. 1 was provided in this order.

In the glow discharge decomposition apparatus shown in FIG. 2, first, the inside of the reactor (233) is evacuated to a high vacuum of about 10 ⁻⁶ Torr,
The first, second, and seventh control valves (207, 208, and 225) are opened, and hydrogen gas from the first tank (201) and ammonia gas from the second tank (202) output pressure of 1.0 kg / cm, respectively. ² and under the temperature of the first temperature controller (222) at 145 ° C. for the Milsen gas from the first container (219), the first, second and seventh flow controllers (213, 214 and 228). ). Then adjust the scale of each flow rate controller to adjust the flow rate of hydrogen gas to 40
The flow rate of sccm and ammonia gas was set to 0.5 sccm, and the flow rate of myrcene gas was set to 15 sccm, and the mixture flowed into the reaction chamber (233) from the main pipe (232) through the midway mixer (231). After stabilizing each flow rate, the reaction chamber (233)
The pressure control valve (245) was adjusted so that the internal pressure was 0.23 Torr. On the other hand, as the substrate (252), the organic photosensitive layer D is used.
Using p, turn on the low-frequency power source (241) that was previously connected by the connection selection switch (244) with the gas flow rate and pressure stable at room temperature, and apply the power application electrode (2
36), 150Watt of power is applied under the frequency of 80KHz, and about 20
Plasma polymerization reaction for 2 seconds, thickness on substrate (252)
A 0.2 μm aC: X film was formed as a surface protective layer. After the completion of the film formation, the power application was stopped, the control valve was closed, the reaction chamber (233) was sufficiently evacuated, the vacuum was broken, and the photoreceptor of the present invention was taken out.

When CHN quantitative analysis was performed on the aC: X film obtained as described above, the amount of hydrogen atoms contained was about 56 atomic% with respect to the total amount of carbon atoms and hydrogen atoms. The amount of nitrogen atoms contained was about 3 atom% based on all the constituent atoms.

Characteristics: The obtained photoreceptor of the present invention was charged to −600 V by corona discharge in a usual Carlson process, and E1 / 2 was measured. As a result, it was 2.3 lux · second, and the residual potential was 7 V. From this, it was understood that the photoreceptor of the present invention is a photoreceptor having a surface protective layer which does not impair the excellent sensitivity performance originally possessed by the organic photosensitive layer. Moreover, when the pencil hardness according to JIS-K-5400 standard was measured, it was found that the pencil hardness was 7H or more, and the surface hardness was remarkably improved.

Example 8 Using the manufacturing apparatus according to the present invention, a photoconductor of the present invention having a conductive substrate, an organic photosensitive layer and a surface protective layer as shown in FIG. 1 was prepared in this order.

In the glow discharge decomposition apparatus shown in Fig. 3, first, the inside of the reaction device (333) is evacuated to a high vacuum of about 10 ^-6 Torr,
The first, second, and seventh control valves (307, 308, and 325) are released, and the output pressure of argon gas from the first tank (301) and nitrous oxide gas from the second tank (302) are 1.0 kg. / cm ²
The first, second, and seventh flow controllers (313, 314, and 328) under the temperature of the first temperature controller (322) at a temperature of 145 ° C. under the temperature of the first container (319). It was made to flow in.
Then, adjust the scale of each flow rate controller so that the flow rate of argon gas is 40 sccm, the flow rate of nitrous oxide gas is 8 sccm, and the flow rate of myrcene gas is 30 sccm, and the intermediate mixer (331) is used. From the main pipe (332) to the reaction chamber (33
3) It flowed in. After the respective flow rates have stabilized, the pressure control valve (3) is set so that the pressure in the reaction chamber (333) becomes 0.25 Torr.
45) was adjusted. On the other hand, as the substrate (352), the organic photosensitive layer Dd is used, and the low-frequency power source (previously connected by the connection selection switch (344) with the gas flow rate and pressure stabilized at room temperature ( 341), and 130Watt of power is applied to the power application electrode (336) at a frequency of 150 KHz to carry out plasma polymerization reaction for about 20 seconds, and the substrate (352)
An aC: X film having a thickness of 0.3 μm was formed on the surface as a surface protective layer. After film formation is complete, stop applying power, close the control valve,
After sufficiently exhausting the inside of the reaction chamber (333), the vacuum was broken and the photoreceptor of the present invention was taken out.

When CHN quantitative analysis was performed on the aC: X film obtained as described above, the amount of hydrogen atoms contained was about 55 atom% with respect to the total amount of carbon atoms and hydrogen atoms. The amount of nitrogen atoms contained was about 1.8 atom% with respect to all the constituent atoms.

Characteristics: The obtained photoreceptor of the present invention was charged to −600 V by corona discharge in a usual Carlson process, and E1 / 2 was measured. As a result, it was 2.2 lux · second and the residual potential was 8 V. From this, it was understood that the photoreceptor of the present invention is a photoreceptor having a surface protective layer which does not impair the excellent sensitivity performance originally possessed by the organic photosensitive layer. Moreover, when the pencil hardness according to JIS-K-5400 standard was measured, it was found that the pencil hardness was 7H or more, and the surface hardness was remarkably improved.

Further, when this photoreceptor of the present invention was mounted on an actual copying machine and a printing durability test was conducted, a clear image was always obtained even when copying about 100,000 A4 copy papers, and a decrease in film thickness was observed. However, it was understood that the durability was excellent. Also, at the time of normal temperature and normal humidity and high temperature and high humidity, so-called image deletion is not observed, and the photoreceptor is excellent in electrical matching between the organic photosensitive layer and the surface protective layer, and is also excellent in environmental resistance. I understood something. Further, no peeling of the surface protective layer was observed even after a printing durability test of 100,000 sheets, and it was understood that the photoconductor has excellent adhesiveness between the organic photosensitive layer and the surface protective layer.

Comparative Example 5 A photoconductor was produced in the same manner as in Example 2 except that nitrogen gas was not introduced. When the surface layer of the obtained photoreceptor was subjected to elemental analysis by Auger analysis, nitrogen atoms were not detected.

When this photoconductor was mounted on a copying machine and an attempt was made for actual copying, the surface layer was peeled off over the entire surface of the photoconductor due to contact with members inside the copying machine.

From this, the effect of securing the adhesiveness by the addition of nitrogen atoms in the present invention is understood.

Comparative Example 6 A photoconductor was prepared in the same manner as in Example 4 except that nitrogen gas was not introduced. When the surface layer of the obtained photoreceptor was subjected to elemental analysis by Auger analysis, nitrogen atoms were not detected.

When this photoconductor was mounted on a copying machine and an actual copying was attempted, it was observed that only an image in a so-called image deletion state was obtained, and the electrical compatibility between the organic photosensitive layer and the surface protective layer was poor.

From this, it is understood that the effect of ensuring the electrical compatibility by the addition of nitrogen atoms in the present invention.

Comparative Example 7 A photoconductor was produced in the same manner as in Example 3 except that the substrate temperature was 150 ° C. When the E1 / 2 of the obtained photoconductor was measured, it was found that a light amount of 30 lux · sec or more was required and the photoconductor sensitivity was significantly impaired.

From this fact, it is understood that the effect of producing the photoconductor at the substrate temperature of 100 ° C. or less in the present invention is achieved.

[Brief description of drawings]

FIG. 1 is a drawing showing the constitution of the photoconductor of the present invention, and FIGS. 2 to 3 are drawings showing the photoconductor manufacturing apparatus according to the present invention.

Continuation of front page (56) Reference JP-A-59-113447 (JP, A) JP-A-57-105744 (JP, A) JP-A-63-88560 (JP, A)

Claims (2)

[Claims] 1. An organic photoreceptor in which an organic photosensitive layer and a surface protective layer are provided on a conductive substrate, the organic photosensitive layer containing a binder resin, a charge generating material and a charge transporting material. The surface protective layer is a plasma organic polymerized film of a hydrocarbon compound, and the plasma organic polymerized film contains at least a nitrogen atom. 2. A step of forming an organic photosensitive layer containing a binder resin, a charge generating material and a charge transporting material on a conductive substrate, and the temperature of the conductive substrate on the photosensitive layer by glow discharge method. Forming a surface protective layer made of a plasma organic polymerized film of a hydrocarbon compound and a nitrogen compound while maintaining the temperature at 100 ° C. or lower.