JPH0731410B2 - Photoconductor - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoconductor in which a surface protective layer is formed in a single layer structure of selenium-arsenic alloy or a laminated structure of selenium and selenium tellurium alloy.

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.

The main photosensitive materials that have been conventionally used are selenium, selenium arsenic, celenium tellurium, cadmium sulfide, zinc oxide, inorganic substances such as amorphous silicon, polyvinylcarbazole, metal phthalocyanine, disazo pigment,
Trisazo pigment, perylene pigment, triphenylmethane compound, triphenylamine compound, hydrazone compound,
Organic substances such as styryl compounds, pyrazoline compounds, oxazole compounds and oxadiazole compounds can be mentioned.

On the other hand, in recent years, the amount of information has increased remarkably in various fields, but in order to reproduce a large amount of information in a short time, it is necessary to speed up the system even in electrophotography. In such a high-speed copying system, the photoconductor material is also required to have high sensitivity and high-speed responsiveness. Among the above substances, the selenium-arsenic alloy (hereinafter referred to as Se-As) photoconductor is in the range of specific visual sensitivity. Among them, it is most practically used because it has the highest physical properties and high sensitivity and high-speed response performance. Many of the other substances have insufficient sensitivity and high-speed response, and have not been applied to high-speed copying systems.

Further, in recent years, with the remarkable development of digital image processing technology, a laser beam printer using a semiconductor laser beam as a light source has been actively put into practical use, and similarly, high speed is required. As one of the photoconductors having good sensitivity to the emission wavelength of a semiconductor laser, among the above substances, a so-called selentellurium (hereinafter, referred to as Se / Te) photoconductor formed by laminating a selentellurium alloy layer on a selenium layer. Is preferred.

However, the conventionally used Se-As and Se / Te photoreceptors have the following drawbacks. One of them is harmful to the human body. There is almost no chance that the photoconductor will come into direct contact with the human body, but when the photoconductor is actually used in a copying machine, the fine powder is generated due to surface friction caused by friction with transfer paper, a cleaning member, a developer, etc. It adheres to the copied image and is discharged outside the machine. Therefore, when you get a copy, you will be indirectly contaminated with selenium, arsenic, and tellurium, and there is concern about its harmfulness. Another is that it has poor durability. The surface hardness of the Se-As and Se / Te photoconductors is only about H or less in terms of JIS standard pencil hardness.
Alternatively, the paper is often subjected to severe surface contact 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 copy surface image, significantly reducing the image quality, and shortening the life of these photoreceptor materials.

This life varies depending on the design of the copier to be mounted, but it is usually about at most 100,000 copies. In high-speed mass copying, if the life is short, it is necessary to frequently replace or maintain the photoconductor.
Use efficiency of the copying machine is reduced.

In order to eliminate these drawbacks, the surface of the Se-As or Se / Te photoconductor is covered with a protective layer to avoid direct contact with copy paper and prevent harmful substances from being discharged outside the copier. Furthermore, a method of improving wear resistance by using a hard film for the protective layer is effective.

However, in order to coat the surface of the Se-As or Se / Te photoreceptor, a random film material cannot be used, and it is necessary to use a film that satisfies all the following necessary items. Ingenuity is required for the material and the film forming method thereof.

First, it is necessary that the film has a high visible light transmittance and can secure a sufficient amount of incident light to the Se-As or Se / Te photoconductor, and can utilize the high sensitivity inherent in these photoconductors. It Secondly, in actual use in a copying machine, it is necessary that the dura be a surface that is not scratched. Third, Se-As or Se / T
e It must be a film that has excellent adhesion to the photoconductor and does not peel off due to mechanical force or changes in temperature and humidity in actual use in a copying machine. Fourth, it needs to be harmless. Fifth, the so-called “Se-As” or “Se / Te” photoconductor is excellent in electrical matching property, a residual potential is generated, or a so-called “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 is a film that does not contribute to the occurrence of the memory phenomenon and the so-called image deletion due to the lateral flow of charges at the mismatched interface. Sixth, under the environment where the copying machine is actually used, especially under high temperature and high humidity conditions, it is necessary that the image quality is not deteriorated and so-called image deletion does not occur.

From this point of view, not only for the Se-As and Se / Te photoconductors but also for the surface protective layer of the selenium-based photoconductor, several film materials and film forming methods thereof are disclosed. It has become one of the important technical fields.

One method is a coating method. For example, JP-A-50-3052
No. 6, gazette discloses that a polyurethane coating layer of 0.5 to 2.5 is formed by coating or spraying on the surface of a photosensitive layer with a mixture of CdSSe and ZnO.
A photoconductor provided with a thickness of μm is disclosed. Japanese Patent Laid-Open No. 53
-23636, and JP-A-53-111734,
A photoreceptor is disclosed in which an insulating layer formed by coating and curing a specific silicon compound is provided on a photoconductive layer including selenium, a selenium tellurium alloy, and a selenium cadmium alloy. JP-A-54
Japanese Patent Laid-Open No. 115134 discloses a photoconductor in which a selenium photoconductive layer is provided on both sides of a support, and a resin layer formed by dip coating and curing is provided only on the selenium photoconductive layer.

These disclosures are intended to solve the above problems by coating an organic compound on the surface of a selenium-based photoreceptor and curing it. In addition to these, JP-A-57-64239 and JP-A-58-64239 Similar disclosures are made in 139154, JP-A-60-101541 and the like.

In recent years, as another method, attempts to apply a vacuum film forming method by glow discharge have been popular. For example, JP-A-59-58437
In the publication, silane gas and ammonia gas or silane gas and nitrous oxide gas are used as raw materials to form amorphous Si: N or Si: O by glow discharge on a selenium-arsenic alloy photosensitive layer.
A photoreceptor provided with 50Å to 2 μm is disclosed. JP 60
JP-A-249155 discloses that methane or acetylene is used as a raw material, and a layer made of amorphous carbon or hard carbon by glow discharge is formed on a photosensitive layer of selenium, a selenium tellurium alloy, etc.
A photoreceptor provided with 5 μm is disclosed.

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 studied the detoxification and the prolongation of the life of Se-As and Se / Te photoconductors for many years, and the amorphous hydrocarbon film formed by the glow discharge method has excellent hardness and surface. It was found to be effective as a protective layer. Furthermore, it has been found that adding at least nitrogen atom as a chemical modifier to the amorphous hydrocarbon film has the effect of ensuring suitable adhesiveness and electrical compatibility of the surface protective layer.

The present invention uses Se-As by utilizing this new finding.
And a surface protective layer suitable for a Se / Te photoreceptor.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention is an essential problem of conventional Se-As and Se / Te photoconductors, that is, a photosensitizer having a surface protective layer for solving harmfulness and low durability. Regarding the body Further, the present invention relates to a photoreceptor having a surface protective layer which can satisfy the following necessary items, which are often hindered in forming a random protective film.

That is, first, the film has a high visible light transmittance and can secure a sufficient amount of incident light to the Se-As or Se / Te photoconductor, and can utilize the high sensitivity inherent in these photoconductors. Secondly, it is a dura that does not scratch the surface when it is actually used in a copying machine. Thirdly, it is a film that has excellent adhesiveness to the Se-As or Se / Te photoconductor and does not peel off due to mechanical force or changes in temperature and humidity during actual use in a copying machine. Fourth, it is a harmless film. Fifth, it has excellent electrostatic compatibility with Se-As or Se / Te photoconductors and causes residual potential, or when copying multiple sheets, the previous image appears as a positive or negative image in the next image. It is a film that does not contribute to the occurrence of so-called memory phenomenon and the so-called image deletion due to lateral flow of charges at the mismatched interface. Sixth, in the environment where the copying machine is actually used, particularly under high temperature and high humidity conditions, it is a film that does not impair image quality and does not cause so-called image deletion. The present invention provides a photoconductor that can solve the above problems.

Means for Solving the Problems That is, the present invention relates to a Se-As or Se / Te photoconductor in which at least a nitrogen atom-containing amorphous film formed on its surface by glow discharge in a low vacuum is formed. The present invention relates to a photoconductor having a surface protective layer composed of a high-quality hydrocarbon film (hereinafter, an amorphous hydrocarbon film containing at least nitrogen atoms according to the present invention is referred to as an aC: N film).

In the present invention, as the gas for forming the aC: N film by the glow discharge method, a hydrocarbon gas and a nitrogen compound gas are used as a source gas, and a hydrogen gas which is generally used as a carrier gas. Alternatively, argon gas or the like is used.

The phase state of the hydrocarbon gas does not necessarily have to be in the gas phase at room temperature and normal pressure, and is melted or evaporated by heating or depressurization.
A liquid phase or a solid phase can be used as long as it can be vaporized through sublimation or the like. As the hydrocarbon, for example, saturated hydrocarbon, unsaturated hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon and the like 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 and the like are used. Examples of unsaturated hydrocarbons include:
Ethylene, propylene, isobutylene, butene, pentene, methylbutene, hexene, tetramethylethylene,
Heptene, octene, allene, methylarene, butadiene, pentadiene, hexadiene, cyclopentadiene, ocimene, alocymene, myrcene, hexatriene, acetylene, methylacetylene, butyne, pentine, hexine, 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, cyclbestrene, and tsuen. , Karen, Pinene,
Bornylene, camphene, fenchen, cyclophenchen, tricyclene, pisabolene, zingiberene, curcumene, humulene, kazinenseskibenihen, serinene, cariophyllene, santalen, sedrene, campholene, philocladen, podocarprene, milen and the like are used. Examples of aromatic hydrocarbons include benzene and
Toluene, xylene, hemimelliten, pseudocumene,
Mesitylene, prenitene, isodulene, durene, pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, cumene, styrene, biphenyl, terphenyl, diphenylmethane, triphenylmethane, dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, phenanthrene, etc. Is used.

The amount of hydrogen atoms contained in the aC: N 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: N 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 decreases, for example, the substrate temperature is increased and the pressure is decreased. Reduce the dilution rate of the raw material hydrocarbon gas. Examples include the case of using a raw material gas having a low hydrogen content, increasing the applied power, lowering the frequency of the alternating electric field, and increasing the strength of the DC electric field superposed on the alternating electric field.

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: N film. The phase state of the nitrogen compound gas does not necessarily have to be a gas phase at room temperature and an ordinary pressure, and may be a liquid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or pressure reduction. It can also be used in the solid phase. As the nitrogen compounds, for example, nitrogen, ammonia, nitrogen monoxide, nitrogen dioxide, dinitrogen trioxide, dinitrogen pentoxide, nitrogen trioxide, inorganic compounds such as amino (-NH _2), cyano group (-CN ),
A nitro group (-NO _2), nitroso group (-NO), isocyanate ester bond (-NCO), isothiocyanate coupling (-NCS), an azo thioether bond (-N = NS
-), A peptide bond (-CONH-), an organic compound having a functional group or bond such as a nitrogen-containing heterocycle, or the like 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, propionitrile, butyronitrile, valeronitrile, capronitrile, enanthnitrile, caprylonitrile, ferralgon nitrile, caprynitrile, lauronitrile, palmitonitrile, stearonitrile, and clon. Nitrile, malon nitrile, succinonitrile, dalutar nitrile, adiponitrile, benzonitrile, tolunitrile, benzyl cinnamic acid nitrile cyanide, naphthonitrile, cyan pyridine and the like are used. Examples of the organic compound having a nitro group include nitrobenzene, nitrotoluene,
Nitroxylene, nitronaphthalene, etc. are used.
Examples of the organic compound having a nitroso group include nitrosobenzene, nitrosotoluene, nitrosonaphthalene, and nitrosocresol. 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 benzisothiocyanate. Examples of the organic compound having an azothioether bond include benzenediazothiophenyl ether, chlorobenzenediazothiophenyl ether, bromobenzenediazothiophenyl ether, nitrobenzenediazothiophenyl ether, phenyldiazomercaptonaphthalene, methoxyphenyldiazomercaptonaphthalene, benzene. Diazothioglycolic acid,
Brombenzenediazothioglycolic acid, nitrobenzenediazothioglycolic acid and the like are used. As the organic compound having a peptide bond, for example, glyceroglycopeptide, glyceroid peptide and the like are used. Heterocyclic compounds include pyrrole, pyrroline, pyrrolidine,
Oxazole, thiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, pyrazolidine, triazole, tetrazole, pyridine, piperidine, oxazine, morpholine, thiazine, pyritazine, pyrimidine, pyrazine, piperazine, triazine,
Indole, indoline, benzoxazole, indazole, benzimidazole, quinoline, cinnoline,
Phthalazine, phthalocyanine, quinazoline, quinxaline, carbazole, acridine, phenanthridine, phenazine, phenoxazine, indolizine, quinolidine, minuclidine, naphthyridine, purine, pteridine, aziridine, azepine, oxadiazine, dithiazine, benzoquinoline, imidazothiazole, etc. are used. To be

In the present invention, when the surface protective layer does not contain nitrogen atoms, for example, when nitrogen is not detected by Auger analysis, electrical failure with the Se-As or Se / Te photoreceptor is caused. Due to matching, a residual potential is generated, or a so-called memory phenomenon occurs in which the previous image appears as a positive or negative image in the next image when a plurality of sheets are copied, and a so-called image due to lateral flow of charges at the mismatched interface. It is easy to induce flow generation. or,
Adhesion to the Se-As or Se / Te photoconductor becomes poor, and peeling of the surface protective layer easily occurs due to mechanical force in actual use in a copying machine, or temperature / humidity change. . The electrical inconsistency described above is also considered to be due to this poor adhesion.

In the present invention, the amount of nitrogen atoms contained in the surface protective layer 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: N film according to the present invention to some extent, and conversely decrease the amount of nitrogen compound introduced. For example, it is possible to reduce the amount of nitrogen atoms added to the aC: N film according to the present invention.

In the present invention, the oxygen atom content is 0.1% or more, and the maximum content is not particularly limited, but it is necessarily limited from the viewpoint of the structure of the surface protective layer and the production of glow discharge.

In the present invention, the film thickness of the aC: N film as the surface protective layer of the Se-As or Se / Te photoconductor is preferably about 0.2 to 5 μm. When the film thickness is less than 0.2 μm, the surface hardness is easily affected by the low hardness of these underlying photoconductors, and suitable durability cannot be ensured. Further, since harmful atoms may be deposited even on the surface of the photoconductor due to diffusion of atoms in the film after forming the surface protective layer, the effect of preventing harmfulness is not always achieved. 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 Se-As or Se / Te photoreceptor is impaired.

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

The Se-As and Se / Te layers used in the present invention are formed by a conventional method by vacuum vapor deposition by a resistance heating method.

FIG. 1 shows a Se / Te photosensitive layer (2) formed by sequentially stacking a Se-As single layer or Se and a Se-Te layer on the conductive substrate (1).
And a surface protective layer (3), that is, an aC: N layer, are sequentially laminated in this order, showing the constitution of a photoreceptor according to the present invention.

FIG. 2 is a surface protective layer of the photoreceptor according to the present invention, that is, a
− Shows a manufacturing apparatus for forming a C: N film, and shows (701) to
Reference numeral (706) is a first to sixth tanks in which a raw material and a carrier gas which are in a vapor phase state at room temperature are sealed, and each tank is provided with first to sixth control valves (707) to (712) and first to sixth tanks. It is connected to the sixth flow rate controllers (713) to (718). In the figure (71
9) to (721) are 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 (722) are provided because each container vaporizes. ~ (724) can be heated, and each container is equipped with a seventh to ninth control valve (72
5) to (727) and the seventh to ninth flow rate controllers (728) to (73
0) is connected. These gases are mixed in the mixer (731) and then fed into the reaction chamber (733) via the main pipe (732). The piping in the middle is capable of being heated by a properly arranged pipe heater (734) so that the vaporized gas of the raw material compound in the liquid phase or the solid phase at room temperature does not condense in the middle. . Ground electrode (73
5) and the power application electrode (736) are installed facing each other, and each electrode can be heated by the electrode heater (737). The matching electrode for high frequency power (7
38), high frequency power supply (739), low frequency power matching device (740), low frequency power supply (741), low pass filter (742) and direct current power supply (743). Electric power with different frequencies can be applied by the selection switch (744). The pressure in the reaction chamber (733) can be adjusted by the pressure control valve (745), and the decompression in the reaction chamber (733) is performed by the diffusion pump (7) via the exhaust system selection valve (746).
47), oil rotary pump (748), or cooling exclusion device (74
9), mechanical booster pump (750), oil rotary pump (748). Regarding the exhaust gas, it is further safety-detoxified by an appropriate exclusion device (753) and then exhausted to the atmosphere. Even with regard to these exhaust system pipes, a gas is vaporized from the raw material compounds that were in a liquid phase or solid phase at room temperature. It is possible to heat. Reaction chamber (73
3) is also heatable by the reaction chamber heater (751) for the same reason, and the Se-As or Se / Te photosensitive layer is previously conductive on the electrode arranged inside by another vacuum deposition device. A substrate (752) formed on the flexible substrate is placed. Although the substrate (752) is fixedly arranged on the ground electrode (735) in FIG. 2, it may be fixedly arranged on the power applying electrode (736).
Furthermore, it may be arranged on both sides.

FIG. 3 is a surface protective layer of the photoreceptor according to the present invention, that is, a
-Shows another form of a manufacturing apparatus for forming a C: N film,
Except for the internal form of the reaction chamber (733), it is the same as the manufacturing apparatus according to the present invention shown in FIG. In FIG. 3, inside the reaction chamber (733), a selenium-based photoreceptor layer is previously formed on the conductive substrate by another vacuum vapor deposition device which also serves as the ground electrode (735) in FIG. A cylindrical substrate (752) is installed and an electrode heater (737) is arranged inside.
A power application electrode (736) having the same cylindrical shape is arranged around the substrate (752), and an electrode heater (737) is arranged outside. The substrate (752) on which the Se-As or Se / Te photosensitive layer is formed can rotate from the outside by using a drive motor (754).

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 heater raises the temperature of the electrode and the substrate fixed to the electrode to a predetermined temperature. At this time, in the case of a photosensitive layer having a selenium layer in order to prevent thermal transformation of the Se-As and Se / Te photosensitive layers, the substrate temperature is approximately 90 ° C. or less, and the photosensitive layer made of only a selenium-arsenic alloy is used. In this case, it is preferable to set the temperature to about 250 ° C. or less, the time during which the temperature is maintained to be raised is within about 30 minutes, and the time required for raising and lowering the temperature is preferably within about 1 hour. Then the first
To 6th tank and 1st to 3rd container are introduced into the reaction chamber while constant flow rate of the raw material gas composed of hydrocarbon and nitrogen compound is made by using the 1st to 9th flow controllers, and the pressure control valve is used to introduce the reaction chamber. To maintain a constant vacuum. After the gas flow rate is stabilized, for example, a high frequency power source is selected by the connection selection switch, and 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 the aC: N film according to the present invention is obtained as the surface protective layer of the photoreceptor. This aC: N film is an amorphous hydrocarbon 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.

Examples 1 and 2 In the glow discharge decomposition apparatus shown in FIG. 2, the surface protective layer of the photoreceptor according to the present invention was prepared.

First, the inside of the reactor (733) is evacuated to a high vacuum of about 10 ^-6 Torr, and then the first, second, and third control valves (707, 708,
, 709) and hydrogen gas from the first tank (701),
Acetylene gas from the second tank (702) and nitrogen gas from the third tank (703) under the output pressure of 1.0 kg / cm ² , respectively, the first, second and third flow rate controllers (713, 714, and 713). 715)
It was made to flow in. Then, adjust the scale of each flow rate controller so that the flow rate of hydrogen gas is 40 sccm and the flow rate of acetylene gas is
The flow rate of 40 sccm and the flow rate of nitrogen gas were set to 40 sccm, and the mixture flowed from the main pipe (732) into the reaction chamber (733) through the intermediate mixer (731). After each flow rate was stabilized, the pressure adjusting valve (745) was adjusted so that the pressure in the reaction chamber (733) became 1.0 Torr. On the other hand, as the substrate (752), a Se--As photosensitive layer (Example 1) and a Se / Te photosensitive layer were prepared on an aluminum substrate having a length of 50 mm, a width of 50 mm and a thickness of 3 mm according to a conventional method using another vacuum deposition apparatus in advance. A layer (Example 2) having a film thickness of about 50 μm was used. The substrate (752) was heated from room temperature to 80 ° C. over about 15 minutes before introducing gas. With the gas flow rate and pressure stable, turn on the high-frequency power supply (739) that was previously connected by the connection selection switch (744) and apply 200 Watt of power to the power application electrode (736) at a frequency of 1
A voltage of 3.56 MHz was applied to perform a plasma polymerization reaction for about 10 minutes to form an aC: N film having a thickness of 0.5 μm on the substrate (752) as a surface protective layer. After the film formation is complete, stop applying power, close the control valves other than hydrogen gas, flow only 200 sccm of hydrogen gas into the reaction chamber (733), keep the pressure at 10 Torr, and keep the temperature up to 50 ° C in about 15 minutes. The temperature dropped. After that, the hydrogen gas control valve was closed, the reaction chamber (733) was sufficiently evacuated, and when the substrate temperature was lowered to 30 ° C., the vacuum of the reaction chamber (733) was broken and the surface protective layer according to the present invention was provided. The photoconductor was taken out.

When CHN quantitative analysis was performed on the aC: N film obtained as described above, the amount of hydrogen atoms contained was 45 atom% with respect to the total amount of carbon atoms and hydrogen atoms. The amount of nitrogen atoms contained is 1.
It was 2 atomic%.

Characteristics: The surface of the obtained photoreceptor has a pencil hardness of JIS-K-5.
When measured based on the 400 standard, both of Example 1 and Example 2 were about 7H, and it was understood that the surface protection layer of the photoreceptor according to the present invention increased the hardness.

When the white light sensitivity of the photoconductor obtained in Example 1 was measured by a usual Carlson method, the half-exposure amount was about 0.92 lux · sec, which was measured before the preparation of the surface protective layer. Since the value was about 0.88 lux · sec, it was understood that the surface protective layer of the photoreceptor according to the present invention did not impair the inherent sensitivity of the Se-As photoreceptor. Also, in the usual Carlson system, 780n of the photoconductor obtained in Example 2
When the photosensitivity was measured, the half exposure was about 5.7 erg / cm ²
And the value measured before preparing the surface protective layer was about 5.7e.
Since it was rg / cm ^2, it was understood that the surface protective layer of the photoreceptor according to the present invention does not impair the inherent sensitivity of the Se / Te photoreceptor.

In addition, the photoconductors obtained in Examples 1 and 2 were heated at a temperature of 10
Low temperature and low humidity atmosphere with ℃ relative humidity 30% and temperature 50 ℃ relative humidity 90
% High-temperature and high-humidity atmosphere is alternately repeated every 30 minutes, left for 6 hours, the surface protective layer peels off, or
No cracks or the like were observed, and it was understood that the surface protective layer of the photoreceptor according to the present invention was a film having excellent adhesiveness to Se-As and Se / Te photoreceptors.

Examples 3 to 4 The surface protective layer of the photoreceptor according to the present invention was prepared in the glow discharge decomposition apparatus shown in FIG.

First, the inside of the reactor (733) is evacuated to a high vacuum of about 10 ^-6 Torr, and then the first, second, and third control valves (707, 708,
, 709) and hydrogen gas from the first tank (701),
Acetylene gas from the second tank (702) and nitrogen gas from the third tank (703) under the output pressure of 1.0 kg / cm ² , respectively, the first, second and third flow rate controllers (713, 714, and 713). 715)
It was made to flow in. Then, adjust the scale of each flow rate controller so that the flow rate of hydrogen gas is 250 sccm, the flow rate of acetylene gas is 200 sccm, and the flow rate of nitrogen gas is 200 sccm, and the intermediate mixer (731) is used. , Flowed into the reaction chamber (733) through the main pipe (732). After each flow rate was stabilized, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) became 1.0 Torr. On the other hand, as the substrate (752), an Se-As photosensitive layer (Example 3) and an Se / Te photosensitive layer (Example 3) were prepared on an aluminum substrate having a diameter of 80 mm and a length of 329 mm in advance using another vacuum vapor deposition apparatus according to a conventional method. What was formed in Example 4) with a film thickness of about 50 μm was used. The substrate (752) was heated from room temperature to 80 ° C. for about 20 minutes before introducing gas. With the gas flow rate and pressure stable, turn on the high-frequency power supply (739) that was previously connected by the connection selection switch (744), and apply 250 Watt of power to the power application electrode (736) at a frequency of 1
A voltage of 3.56 MHz was applied to carry out a plasma polymerization reaction for about 15 minutes to form a 0.7 μm thick aC: N film as a surface protective layer on the substrate (752). After film formation is complete, stop applying power, close the control valves other than hydrogen gas, flow 600 sccm of hydrogen gas only into the reaction chamber (733), keep the pressure at 10 Torr, and keep the temperature up to 50 ° C in about 25 minutes. The temperature dropped. After that, the hydrogen gas control valve was closed, the reaction chamber (733) was sufficiently evacuated, and when the substrate temperature was lowered to 30 ° C., the vacuum of the reaction chamber (733) was broken and the surface protective layer according to the present invention was provided. The photoconductor was taken out.

When CHN quantitative analysis was performed on the aC: N film obtained as described above, the amount of contained hydrogen atoms was 43 atom% with respect to the total amount of carbon atoms and hydrogen atoms, and from Auger analysis, The amount of nitrogen atoms contained is 1.
It was 3 atomic%.

Characteristics: The surface of the obtained photoreceptor has a pencil hardness of JIS-K-5.
When measured based on the 400 standard, both of Example 3 and Example 4 were 7H or more, and it was understood that the surface protective layer of the photoreceptor according to the present invention increased the hardness.

Further, when the white light sensitivity of the photoreceptor obtained in Example 3 was measured by a usual Carlson method, the half-exposure amount was about 1.1 lux · second, which was measured before the preparation of the surface protective layer. Since the value was about 0.96 lux · sec, it was understood that the surface protective layer of the photoreceptor according to the present invention did not impair the inherent sensitivity of the Se-As photoreceptor. Also, in the usual Carlson method, 780n of the photoconductor obtained in Example 4 was used.
When the photosensitivity was measured, the half-exposure amount was about 5.5 erg / cm ²
And the value measured before preparing the surface protective layer was about 5.3e.
Since it was rg / cm ^2, it was understood that the surface protective layer of the photoreceptor according to the present invention does not impair the inherent sensitivity of the Se / Te photoreceptor.

Also, the photoconductors obtained in Examples 3 and 4 were heated at a temperature of 10
Low temperature and low humidity atmosphere with ℃ relative humidity 30% and temperature 50 ℃ relative humidity 90
% High-temperature and high-humidity atmosphere is alternately repeated every 30 minutes, left for 6 hours, the surface protective layer peels off, or
No cracks or the like were observed, and it was understood that the surface protective layer of the photoreceptor according to the present invention was a film having excellent adhesiveness to Se-As and Se / Te photoreceptors.

In addition, the photoconductor obtained in Example 3 was manufactured by Minolta Copier EP65.
When it was mounted on 0Z and actually shot, a so-called clear image without a so-called memory image was obtained, and so-called image deletion was not observed even when actually shot in an environment of a temperature of 35 ° C. and a relative humidity of 80%.
Further, the peeling of the surface protective layer was not observed even when the developer, the transfer paper, and the cleaning member were contacted in the copying machine. Also, when 250,000 actual photographs were taken in a normal room, a clear image was obtained to the end. Moreover, after the actual copying of 250,000 sheets, the composition of the surface was analyzed by Auger analysis, and selenium or arsenic was not detected. From these, it was understood that the surface protective layer of the photoreceptor according to the present invention achieves improvement in durability and improvement in harmfulness without impairing image quality.

Further, the photoconductor obtained in Example 4 was used as a copying machine EP45 manufactured by Minolta.
When mounted on 0Z, the optical system was changed to a normal semiconductor laser exposure system consisting of a semiconductor laser, a polygon mirror scanner, and a drive system, and when it was actually shot, a clear image without a so-called memory image was obtained. , Temperature 35 ℃, relative humidity 80%
The so-called image deletion was not recognized even when the image was taken in the environment. Further, the peeling of the surface protective layer was not observed even when the developer, the transfer paper, and the cleaning member were contacted in the copying machine. In addition, when 200,000 actual photographs were taken in a normal room, a clear image was obtained to the end. Also, after the actual copying of 200,000 sheets, the composition of the surface was analyzed by Auger analysis, and selenium, tellurium, etc. were not detected. From these, it was understood that the surface protective layer of the photoreceptor according to the present invention achieves improvement in durability and improvement in harmfulness without impairing image quality.

Examples 5 to 6 The surface protective layer of the photoreceptor according to the present invention was produced in the glow discharge decomposition apparatus shown in FIG.

First, after the inside of the reactor (733) was evacuated to a high vacuum of about 10 ^-6 Torr, the first and third control valves (707 and 709) were opened, and the argon gas was discharged from the first tank (701). , And the output pressure of ethylene gas from the third tank (703) is 1.0 kg / c, respectively.
Under m ² , into the 1st and 3rd flow controllers (713 and 715), simultaneously release the 7th and 8th control valves (725 and 726), and from the 1st container (719) styrene gas The first temperature controller (722) is at a temperature of 60 ° C, and the aniline gas is supplied from the second container (720) at a second temperature controller (723) at a temperature of 120 ° C.
It flowed into the flow controllers (728 and 729). Then adjust the scale of each flow rate controller to adjust the flow rate of argon gas to 20
The flow rate of ethylene gas is 150 sccm, the flow rate of styrene gas is 100 sccm, and the flow rate of aniline gas is 60 sccm, and the flow rate of the aniline gas is 60 sccm. ). After each flow rate was stabilized, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) became 1.0 Torr. On the other hand, the substrate (75
As 2), an aluminum substrate having a diameter of 80 and a length of 329 mm was previously prepared by using another vacuum deposition apparatus according to a conventional method, and Se-As was prepared.
The photosensitive layer (Example 3) and the Se / Te photosensitive layer (Example 6) each contained about 5 parts.
A film having a film thickness of 0 μm was used. The board (752) is
The temperature was raised from room temperature to 80 ° C. over about 20 minutes before introducing the gas. With the gas flow rate and pressure stable, the low-frequency power source (7
41), 100Watt of power is applied to the power application electrode (736) at a frequency of 30KHz to carry out plasma polymerization reaction for about 10 minutes, and a 3.3 μm thick aC: N film is applied on the substrate (752). The film was formed as a surface protective layer. After the film formation was completed, the power application was stopped, the control valves other than argon gas were closed, and the reaction chamber (73
3) Close the control valves other than argon gas in the reaction chamber (73
3) Argon gas is introduced into the inside of 600sccm and the pressure is 10To.
The temperature was maintained at rr and the temperature was lowered to 50 ° C. in about 15 minutes. After that, the hydrogen gas control valve was closed, the inside of the reaction chamber (733) was sufficiently exhausted, and when the temperature of the substrate was lowered to 30 ° C., the reaction chamber (73
The vacuum of 3) was broken and the photoreceptor having the surface protective layer according to the present invention was taken out.

When CHN quantitative analysis was performed on the aC: N film obtained as described above, the amount of hydrogen atoms contained was 37 atom% with respect to the total amount of carbon atoms and hydrogen atoms, and from Auger analysis, The amount of nitrogen atoms contained is 6.
It was 8 atomic%.

Characteristics: The surface of the obtained photoreceptor has a pencil hardness of JIS-K-5.
When measured based on the 400 standard, both Example 5 and Example 6 have 7H or more, and it was understood that the surface protection layer of the photoreceptor according to the present invention provides high hardness.

Further, when the white light sensitivity of the photoreceptor obtained in Example 5 was measured by a usual Carlson method, the half-exposure amount was about 1.15 lux · second, which was measured before the surface protective layer was prepared. Since the value was about 0.96 lux · sec, it was understood that the surface protective layer of the photoreceptor according to the present invention did not impair the inherent sensitivity of the Se-As photoreceptor.

Further, when the photosensitivity of the photoconductor obtained in Example 6 was measured at 780 nm in a usual Carlson method, the half-exposure amount was about 5.5 erg / cm ² , which was measured before the surface protective layer was formed. Since the value was about 5.3 erg / cm ^2, it was understood that the surface protective layer of the photoreceptor according to the present invention does not impair the inherent sensitivity of the Se / Te photoreceptor.

Also, the photoconductors obtained in Examples 5 and 6 were heated at a temperature of 10
Low temperature and low humidity atmosphere with ℃ relative humidity 30% and temperature 50 ℃ relative humidity 90
% High-temperature and high-humidity atmosphere is alternately repeated every 30 minutes, left for 6 hours, the surface protective layer peels off, or
No cracks or the like were observed, and it was understood that the surface protective layer of the photoreceptor according to the present invention was a film having excellent adhesiveness to Se-As and Se / Te photoreceptors.

Further, when the photoconductors obtained in Examples 5 and 6 were actually copied in a copying machine in the same manner as in Examples 3 and 4, good images, adhesiveness, environmental resistance, durability, And
Pollution-free was confirmed.

Example 7 A surface protective layer for a photoreceptor according to the present invention was prepared in the glow discharge decomposition apparatus shown in FIG.

First, after the inside of the reactor (733) was evacuated to a high vacuum of about 10 ^-6 Torr, the first and third control valves (707 and 709) were opened, and the argon gas was discharged from the first tank (701). , And the output pressure of butadiene gas from the third tank (703) is 1.0 kg.
/ cm ² into the first and third flow controllers (713 and 715), at the same time releasing the seventh control valve (725), the first container (71
From 9), pyridine gas was allowed to flow into the seventh flow controller (728) under the temperature of the first temperature controller (722) of 40 ° C. Then adjust the scale of each flow rate controller to adjust the flow rate of argon gas to 200s.
The flow rate of ccm, the flow rate of butadiene gas was set to 150 sccm, and the flow rate of pyridine gas was set to 150 sccm, and the mixture flowed from the main pipe (732) into the reaction chamber (733) through the intermediate mixer (731). After stabilizing each flow rate, the reaction chamber (733)
The pressure control valve (745) was adjusted so that the internal pressure was 1.0 Torr. On the other hand, the substrate (752) has a diameter of 80 and a length of 329.
A Se--As photosensitive layer having a thickness of about 50 μm was previously formed on an aluminum substrate having a thickness of mm by a conventional method using another vacuum vapor deposition apparatus. Substrate (752) is approximately 30 before gas introduction
The temperature was raised from room temperature to 180 ° C over a period of time. When the gas flow rate and pressure are stable, the connection selection switch (74
Turn on the low frequency power supply (741) that was connected by 4),
The power of 150Watt is applied to the power application electrode (736) at a frequency of 30KHz, and the plasma polymerization reaction is performed for about 10 minutes. The 2.4μm thick aC: N film is used as the surface protection layer on the substrate (752). Formed. After the film formation was completed, the power application was stopped, the control valves other than argon gas were closed, only 600 sccm of argon gas was flowed into the reaction chamber (733), and the pressure was kept at 10 Torr.
The temperature was lowered to 50 ° C in about 30 minutes. After that, the hydrogen gas control valve was closed, the reaction chamber (733) was sufficiently evacuated, and when the substrate temperature was lowered to 30 ° C., the vacuum of the reaction chamber (733) was broken and the surface protective layer according to the present invention was provided. The photoconductor was taken out.

When CHN quantitative analysis was performed on the aC: N film obtained as described above, the amount of hydrogen atoms contained was 52 atom% with respect to the total amount of carbon atoms and hydrogen atoms. The amount of nitrogen atoms contained is 7 for all constituent atoms.
It was atomic%.

Characteristics: The surface of the obtained photoreceptor has a pencil hardness of JIS-K-5.
It was about 7H when measured based on the 400 standard, and it was understood that the surface protection layer of the photoreceptor according to the present invention increased the hardness.

In addition, when the white light sensitivity was measured in the usual Carlson method, the half-exposure amount was about 1.1 lux · second,
Since the value measured before the preparation of the surface protective layer was about 0.92 lux · sec, it is understood that the surface protective layer of the photoreceptor according to the present invention does not impair the inherent sensitivity of the Se-As photoreceptor. It was

Also, the temperature is 10 ℃ and the relative humidity is 30%.
When left for 6 hours in an environment in which a high temperature and high humidity atmosphere with a relative humidity of 90% is alternately repeated every 30 minutes, no peeling of the surface protective layer or cracking was observed. It was understood that the surface protective layer was a film having excellent adhesiveness to the Se-As photoconductor.

In addition, when the image was actually taken in a copying machine in the same manner as in Example 3,
Good images, adhesion, environmental resistance, durability, and pollution-free were confirmed.

Example 8 A surface protective layer for a photoreceptor according to the present invention was produced in the glow discharge decomposition apparatus shown in FIG.

First, the inside of the reactor (733) is evacuated to a high vacuum of about 10 ^-6 Torr, and then the first and third control valves (707 and 709) are opened, and hydrogen gas is discharged from the first tank (701). , And the output pressure of ammonia gas from the third tank (703) is 1.0 kg / cm ^{2 respectively.}
Below into the first and third flow controllers (713 and 715),
At the same time, the seventh control valve (725) was opened, and Milsen gas was allowed to flow from the first container (719) into the seventh flow controller (728) under the temperature of the first temperature controller (722) of 85 ° C. Then, adjust the scale of each flow rate controller so that the flow rate of hydrogen gas is 50 sccm, the flow rate of ammonia gas is 10 sccm, and the flow rate of myrcene gas is
The flow rate was set to 100 sccm, and the mixture flowed from the main pipe (732) into the reaction chamber (733) through the mixer (731) on the way. After each flow rate is stabilized, the pressure in the reaction chamber (733) becomes 1.0
The pressure control valve (745) was adjusted to Torr. On the other hand, as the substrate (752), an Se-As photosensitive layer having a film thickness of about 50 μm is formed on an aluminum substrate having a diameter of 80 mm and a length of 329 mm in advance according to a conventional method using another vacuum vapor deposition device. Using. The substrate (752) was heated from room temperature to 200 ° C. over about 30 minutes before introducing gas. With the gas flow rate and pressure stable, turn on the low-frequency power supply (741) that was previously connected by the connection selection switch (744) and apply 120Watt of power to the power application electrode (736) at a frequency of 45KHz. And carry out plasma polymerization reaction for about 10 minutes, substrate (752)
An aC: N film having a thickness of 4.1 μm was formed thereon as a surface protective layer. After film formation, stop applying power, close control valves other than hydrogen gas, and add only 600 sc of hydrogen gas into the reaction chamber (733).
cm, the pressure was maintained at 10 Torr, and the temperature was lowered to 50 ° C. in about 30 minutes. After that, the hydrogen gas control valve was closed, the reaction chamber (733) was sufficiently evacuated, and when the substrate temperature was lowered to 30 ° C., the vacuum of the reaction chamber (733) was broken and the surface protective layer according to the present invention was provided. The photoconductor was taken out.

When CHN quantitative analysis was performed on the aC: N film obtained as described above, the amount of contained hydrogen atoms was 36 atom% with respect to the total amount of carbon atoms and hydrogen atoms. The amount of nitrogen atoms contained is 0 for all constituent atoms.
It was 2 atomic%.

Characteristics: The surface of the obtained photoreceptor has a pencil hardness of JIS-K-5.
It was 7H or more when measured based on the 400 standard, and it was understood that the surface protection layer of the photoreceptor according to the present invention increased the hardness.

In addition, when the white light sensitivity was measured in the ordinary Carlson method, the half-exposure amount was about 0.91 lux · second,
Since the value measured before preparation of the surface protective layer was about 0.9 lux · sec, it was understood that the surface protective layer of the photoreceptor according to the present invention does not impair the inherent sensitivity of the Se-As photoreceptor. It was

Also, the temperature is 10 ℃ and the relative humidity is 30%.
When left for 6 hours in an environment in which a high temperature and high humidity atmosphere with a relative humidity of 90% is alternately repeated every 30 minutes, no peeling of the surface protective layer or cracking was observed. It was understood that the surface protective layer was a film having excellent adhesiveness to the Se-As photoconductor.

In addition, when the image was actually taken in a copying machine in the same manner as in Example 3,
Good images, adhesiveness, environmental resistance, durability, and pollution-free were recognized.

Comparative Examples 1 and 2 Example 3 and Example 4 except that nitrogen gas was not introduced.
A surface layer was formed on the Se-As (Comparative Example 1) and Se / Te (Comparative Example 2) photoconductors in the same manner as.

When Auger analysis was performed on this surface layer, nitrogen atoms were not detected, and even if a very small amount of nitrogen atoms were mixed in due to contamination, the amount was less than 0.1 at% which is the detection limit of Auger analysis. It is understood that there is.

The various characteristics showed values similar to those of Example 3 and Example 4, but when a real image was taken, there was a so-called memory phenomenon in which the previous image appeared as a negative image on the next image during continuous copying. Occurred, and a practically suitable image was not obtained. From this fact, it is understood that the addition of nitrogen atoms improves the electrical compatibility and, as a result, the image quality.

Also, after the actual copying, the photoconductors obtained in Comparative Example 1 and Comparative Example 2 were subjected to a low temperature and low humidity atmosphere at a temperature of 10 ° C and a relative humidity of 30% and a temperature of 50 ° C.
When left for 6 hours in an environment in which a high temperature and high humidity atmosphere with a relative humidity of 90% is repeated alternately every 30 minutes, the surface protective layer gradually and finally from the end of the drum-shaped photoreceptor Peels off or cracks, and Se-As by nitrogen addition in the surface protective layer of the photoreceptor according to the present invention
And the effect of improving the adhesiveness with the Se / Te photoreceptor was understood.

Comparative Examples 3 to 4 A surface layer was formed on the Se-As (Comparative Example 3) and Se / Te (Comparative Example 4) photoreceptors in the same manner as in Example 5 and Example 6 except that aniline gas was not introduced. did.

When Auger analysis was performed on this surface layer, nitrogen atoms were not detected, and even if a very small amount of nitrogen atoms were mixed in due to contamination, the amount was less than 0.1 at% which is the detection limit of Auger analysis. It is understood that there is.

The various characteristics showed values similar to those of Example 5 and Example 6, but when a real image was taken, there was a so-called memory phenomenon in which the previous image appeared as a negative image on the next image during continuous copying. Occurred, and a practically suitable image was not obtained. From this, the effect of improving the image quality by adding nitrogen atoms can be understood.

Also, after the actual copying, the photoconductors obtained in Comparative Example 3 and Comparative Example 4 were subjected to a low temperature and low humidity atmosphere of 10 ° C. and a relative humidity of 30% and a temperature of 50 ° C.
When left for 6 hours in an environment in which a high temperature and high humidity atmosphere with a relative humidity of 90% is alternately repeated every 30 minutes, the entire surface protective layer is peeled off, and the surface protective layer of the photoreceptor according to the present invention is It was understood that the effect of improving the adhesiveness with the Se-As and Se / Te photoconductors by adding oxygen.

[Brief description of drawings]

FIG. 1 is a diagram showing the structure of a photoconductor according to the present invention, and FIGS. 2 and 3 are diagrams showing a manufacturing apparatus for producing the photoconductor according to the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Iyoyo Osawa Inventor Iyosei Osawa 2-30, Azuchi-cho, Osaka-city Osaka Prefecture Osaka Osaka International Building Minolta Camera Co., Ltd. Inspector Kayoko Yasuda (56) References JP-A-60-249155 (JP, A) JP-A-61-94056 (JP, A)

Claims (1)

[Claims] 1. A photoreceptor having a selenium-arsenic alloy single layer structure or a laminated structure in which selenium and a selenium tellurium alloy are provided in this order on a conductive substrate, and a surface protection layer is provided by a glow discharge method. A photoconductor characterized by being an amorphous hydrocarbon film which is generated and contains at least nitrogen atoms.