JPS6315255A - Photosensitive body - Google Patents

Abstract

PURPOSE:To provide a high visible light transmittance and to assure the quantity of incident light to a photosensitive body consisting of Se-As or Se/Te by forming a surface protective layer of an amorphous hydrocarbon film which is formed by a glow discharge method and contains halogen atoms. CONSTITUTION:The photosensitive body consisting of the Se-As or Se/Te is provided with the surface protective film 3 consisting of the amorphous hydrocarbon film which is formed by the glow discharge in a low vacuum on the surface of said body and contains the halogen atoms. Gaseous hydrocarbon and gaseous halogen compd. are used as the raw gas of the gases for forming the a-C:X film by the glow discharge method and generally and commonly used gaseous hydrogen or gaseous argon, etc., are used for the carrier gas thereof. The phase state of the gaseous hydrocarbon is not always required to be in the gaseous phase at and under an ordinary temp. and atm. pressure and said gas is usable in either liquid or solid phase if the gas can be evaporated through melting evaporation, sublimation, etc., by heating or pressure reduction, etc. For example, satd. hydrocarbon, unsatd. hydrocarbon, alicyclic hydrocarbon, arom. hydrocarbon, etc., are used for the hydrocarbon.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a photoreceptor having a surface protective layer formed in a single layer structure of a selenium arsenic alloy or a laminated structure of a 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 photoreceptors.

The main photoreceptor materials conventionally used include inorganic substances such as selenium, selenium arsenide, selenium tellurium, cadmium sulfide, zinc oxide, amorphous silicon, polyvinyl carbazole, metal phthalocyanine, disazo pigments,
Trisazo pigment, perylene pigment, triphenylmethane compound, triphenylamine compound, hydrazone compound,
Examples include organic substances such as styryl compounds, birapurin compounds, oxazole compounds, and oxadiazole compounds.

On the other hand, in recent years, there has been a remarkable tendency for the amount of information in each weighing field to increase, and in order to copy a large amount of information in a short period of time, faster systems are required, even for electrophotography. In such high-speed copying systems, photoreceptor materials are also required to have high sensitivity, and among these materials, selenium arsenide alloy (hereinafter referred to as 5e
The photoreceptor (denoted as -As) has the highest sensitivity in terms of physical properties in the relative luminous efficiency range, and has been put into practical use in many cases. Other materials have many aspects of insufficient sensitivity and have not been applied to high-speed copying systems.

Further, in recent years, with the remarkable development of digital image processing technology, laser beam printers using semiconductor laser light as a light source are being put into practical use, and there is also a need for higher speeds. Among the above-mentioned materials, a so-called selenitellium (hereinafter referred to as Se/Te) photoconductor, which is formed by laminating a selenium layer on a selenium layer, is one of the photoconductors that has good sensitivity to the emission wavelength of a semiconductor laser. is considered suitable.

However, the conventionally used 5e-As and Se
/Te photoreceptor had the following drawbacks. One of them is its toxicity 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, its fine powder will be transferred to the copy due to surface abrasion caused by friction with transfer paper, cleaning members, developer, etc. It sticks to the image and is ejected from the machine. Therefore, when a copy is obtained, it is indirectly contaminated with selenium, arsenic, and tellurium, and there are concerns about its harmful effects. Another reason is that it lacks durability. 5e-As and Se/
The surface hardness of the Te photoreceptor is only about H or less based on the JIS standard pencil hardness, and therefore it is subject to wear during actual use as described above, or is susceptible to human operations during paper jams and recovery. The surface is often subjected to harsh surface contact due to such factors, and the surface is easily damaged. These scratches appear as so-called white spots on the copied image, significantly reducing the image quality and shortening the life of these photoreceptor materials. This lifespan varies depending on the design of the copying machine installed, but normally it can withstand at most 100,000 copies. In high-speed, large-scale copying, if the lifespan is short, it becomes necessary to frequently replace or maintain the photoreceptor, which results in a reduction in the usage efficiency of the copying machine.

In order to eliminate these drawbacks, 5e-As or Se/
The surface of the Te photoconductor is coated with a protective layer to avoid direct contact with copy paper, prevent harmful substances from being discharged outside the copy machine, and
An effective method is to improve the wear resistance by using a hard film as the protective layer.

However, to coat the surface of a 5e-As or Se/Te photoreceptor, it is not possible to use a random film material, and it is necessary to use a film that satisfies all of the following requirements. , originality is required for film materials and film-forming methods.

First, the visible light transmittance is high <5e-As or Se/
It is required that the film be able to secure a sufficient amount of light incident on the Te photoreceptor and take advantage of the high sensitivity inherent in these photoreceptors. Second, during actual use in a copying machine, the surface of the dura must not be damaged. Third,
It is required that the film has excellent adhesion to the 5e-As or Se/Te photoreceptor and does not peel off due to mechanical force or changes in temperature and humidity when used in a copying machine. Fourth,
It is required to be harmless. Fifth, it has excellent electrical compatibility with the 5e-AS or Se/Te photoreceptor, and does not generate residual potential, or when copying multiple sheets, the previous image appears as a positive or negative image on the next image. It is required that the film does not contribute to the occurrence of a memory phenomenon, and furthermore, does not contribute to the occurrence of so-called image drift due to the lateral flow of charges at the mismatched interface. Sixth,
In the environment in which a copying machine is actually used, especially under high temperature and high humidity conditions, it is required that image quality is not impaired and that so-called image deletion does not occur.

From this point of view, several film materials and film-forming methods have been disclosed for the surface protective layer of selenium-based photoreceptors, not only 5e-As and Se/Te photoreceptors. It has become one of the most important technical fields.

One method is a coating method. For example, JP-A-50-3
Japanese Patent No. 0526 discloses a photoreceptor in which a polyurethane coating layer of 0.5 to 2.5 μm in thickness is provided on the surface of a photosensitive layer made of a mixture of Cd5Se and ZnO by coating or spraying. JP-A-53-23636 and JP-A-53-111734 disclose insulating materials in which a specific silicon compound is coated and hardened on a photoconductive layer including selenium, selenium tellurium alloy, and selenium cadmium alloy. A layered photoreceptor is disclosed. Japanese Patent Publication No. 54-115134
The publication discloses a photoreceptor in which a selenium photoconductive layer is provided on a support other than at both ends, and a resin layer is provided only on the selenium photoconductive layer by dip coating and curing.

These disclosures are possible by coating an organic compound on the surface of a selenium-based photoreceptor and curing it! ¥! ff problem, and in addition to these, there are also
64239, JP-A-58-139154, JP-A-60-
101541 etc., similar disclosures are made.

In recent years, there have been many attempts to apply a vacuum film forming method using glow discharge as another method. For example, JP-A-59-58
No. 437 discloses that amorphous Si:N is formed by glow discharge on a selenium arsenic alloy photosensitive layer using silane gas and ammonia gas or silane gas and nitrous oxide gas as raw materials.
Alternatively, a photoreceptor in which Si:○ is provided in a thickness of 50 to 2 μm is disclosed. JP-A No. 60-249155 discloses that a layer of amorphous carbon or hard carbon of 0.05 to 5 μm is formed by glow discharge on a photosensitive layer of selenium, selenium tellurium alloy, etc. using methane or acetylene as a raw material. A photoreceptor is disclosed.

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

The present inventors have been studying for many years how to make 5e-As and Se/Te photoreceptors harmless and extend their service life, and found that an amorphous hydrocarbon film formed by a glow discharge method has excellent hardness and a surface It was found that it is effective as a protective layer. Furthermore, it has been found that adding at least halogen atoms as a chemical decoration substance to the amorphous hydrocarbon film has the effect of ensuring suitable adhesion and electrical integrity of the surface protective layer.

The present invention utilizes this new knowledge to achieve 5e-
It provides a surface protective layer suitable for As and Se/Te photoreceptors.

The present invention aims to solve the essential problems of conventional 5e-As and Se/Te photoreceptors, namely, their toxicity and low durability. Regarding the body. Furthermore,
The present invention relates to a photoreceptor having a surface protective layer that can satisfy the following requirements, which are often hindered in the formation of random protective films.

First, the visible light transmittance is high <Se-ΔS or Se/
The film must be able to ensure a sufficient amount of light incident on the T e photoreceptor and take advantage of the inherent high sensitivity of these photoreceptors. Second, the dura mater should not be scratched on the surface during actual use in a copying machine. Thirdly, the film must have excellent adhesion to the 5e-As or Se/Te photoreceptor and will 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 membrane. Fifth, 5e-As or S
It has excellent electrostatic compatibility with the e/Te photoreceptor, and prevents the generation of residual potential or the so-called memory phenomenon in which the previous image appears as a positive or negative image in the next image when copying multiple sheets. The film must not contribute to the occurrence of so-called image blurring due to the lateral flow of charges at the mismatched interface. Sixth, the film must not impair image quality or cause so-called image deletion under the environment in which the copying machine is actually used, especially under high temperature and high humidity conditions. To provide a photoreceptor capable of solving the above problems, the present invention provides a means for solving the above problem. Regarding a photoreceptor having a surface protective layer made of an amorphous hydrocarbon film containing halogen atoms formed by glow discharge in a photosensitive member (hereinafter, the amorphous hydrocarbon film containing halogen atoms according to the present invention is -C: referred to as X film).

In the present invention, hydrocarbon gas and halogen compound gas are used as raw material gases to form the a-C:X film by the glow discharge method, and commonly used hydrogen gas is used as the carrier gas. Alternatively, argon gas or the like may be used.

The phase state of the hydrocarbon gas does not necessarily have to be a gas phase at room temperature and pressure, but can be melted, evaporated, or evaporated by heating or reduced pressure.
As long as it can be vaporized through sublimation or the like, it can be used either in liquid phase or in the same phase. Examples of the hydrocarbons used include saturated hydrocarbons, unsaturated hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

There are many types of hydrocarbons that can be used, but examples of saturated hydrocarbons include methane, ethane, propane, butane,
Pentane, hexane, heptane, octane, isobutane, isopentane, neopentane, isohexane, neohexane, dimethylbutane, methylhexane, ethylpentane, dimethylpentane, tributane, methylhebutane, dimethylhexane, trimethylpentane, isonanone, etc. are used. For example, f1 is an unsaturated hydrocarbon.
Ethylene, propylene, isobutylene, butene, pentene, methylbutene, hexene, tetramethylethylene,
Heptene, octene, allene, methylalene, butadiene, pentadiene, hexadiene, cyclopentadiene, ocimene, allocimene, myrcene, hexatriene,
Acetylene, methylacetylene, butyne, pentyne, hexyne, heptyne, octyne, etc. are used. Examples of alicyclic hydrocarbons include cyclopropane, cyclobutane, cyclopenkune, cyclohexane, cyclohebutane, cyclooctane, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, limonene, terbirun, phelandrene,
sylvestrene, thuene, carene, pinene, bornylene, camphuene, fenchen, cyclobutanethiene, tricyclene, bisabolene, zingiberene, curcumene,
Humulene, kajinensesesquivenichen, selinene, caryophyllene, santarene, cedrene, campholene, phylloclatene, bodocarbrene, mylene, etc. are used. Examples of aromatic hydrocarbons include benzene, toluene,
xylene, hemime1notene, pseudocumene, mesitylene, prenitene, isodurene, durene, pentamethylbenzene, hexamethylbenzene, ethylbenzene,
Propylbenzene, cumene, styrene, piphenyl, terphenyl, diphenylmethane, triphenylmethane,
Dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, phenanthrene, etc. are used.

The amount of hydrogen atoms contained in a-C:XFa in the present invention is approximately 30 to 60 at % based on the total amount of carbon atoms and hydrogen atoms.

In the present invention, the nature of hydrogen atoms contained in the a-C film changes depending on the form of the film forming apparatus and the conditions during film forming, and when the amount of hydrogen decreases, for example, by increasing the substrate temperature, Lowering the pressure, lowering the dilution rate of the raw material hydrocarbon gas, using a raw material gas with a lower hydrogen content, increasing the applied power, lowering the frequency of the alternating electric field, increasing the strength of the DC electric field superimposed on the alternating electric field. Cases such as high (to do), etc. are mentioned.

In the present invention, in addition to hydrocarbon gas, a halogen compound gas is used to add at least halogen atoms into the a-C:X film. Here, the halogen atom refers to a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The phase state of the halogen compound gas does not necessarily have to be a gas phase at normal temperature and pressure, but may be a liquid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. It can also be used in the same phase. Examples of halogen compounds include fluorine, chlorine, bromine, iodine, hydrogen fluoride, chlorine fluoride, bromine fluoride, iodine fluoride, hydrogen chloride, bromine chloride, iodine chloride, hydrogen bromide, iodine bromide, Inorganic compounds such as hydrogenide, alkyl halides, metal alkyl halides, aryl halides, halogenated silicate esters, halogenated styrene,
Organic compounds such as halogenated polymethylene, halogen-substituted organosilane, and heroform are used.

Examples of the alkyl halide include methyl fluoride,
Methyl chloride, methyl bromide, methyl iodide, ethyl fluoride, ethyl chloride, ethyl bromide, ethyl iodide, propyl fluoride, propyl chloride, propyl bromide, propyl iodide,
Butyl fluoride, butyl chloride, butyl bromide, butyl iodide, amyl fluoride, amyl chloride, amyl bromide, amyl iodide, hexyl fluoride, hexyl chloride, hexyl bromide, hexyl iodide, heptyl fluoride, chloride Hebutyl, hebutyl bromide, hepdyl iodide, etc. are used. Examples of the alkyl metal halides include dimethylaluminum chloride, dimethylaluminum bromide, diethylaluminum chloride, diethylaluminum iodide, methylaluminum dichloride, methylaluminum tribromide, ethylaluminum diodide, trimethyltin chloride, and Trimedeltin, trimethyltin iodide, triethyltin chloride, triethyltin bromide, dimethyltin dichloride, dimethyltin tribromide, dimethyltin dichloride, diethyltin dichloride, diethyltin tribromide, diethyltin dichloride, methyltin trichloride, methyltin tribromide , methyltin triiodide, ethyltin tribromide, etc. are used. Examples of the halogenated aryl include fluorobenzene, chlorobenzene, brombenzene, iodobenzene, chlorotoluene, bromotoluene, chlornaphthalene, and bromnaphthalene. Examples of the halogenated silicic acid ester include monomethoxytrichlorosilane, dimethoxydichlorosilane, trimethoxymonochlorosilane, monoethoxytricumylsilane, jetoxydichlorosilane, triethoxymonochlorosilane, monoallyloxytrichlorosilane, and diaryloxy Dichlorosilane, triethoxymonochlorosilane, etc. are used. As the halogenated styrene, for example, chlorstyrene, bromustyrene, iodostyrene, fluorostyrene, etc. are used. Examples of halogenated polymethylene include methylene chloride, methylene bromide, methylene iodide, ethylene chloride, ethylene bromide, ethylene iodide, trimethylene chloride, trimethylene bromide, trimethylene iodide, butane dichloride, butane dibromide, Butane dichloride, pentane dichloride, pentane dibromide, pentane dichloride, hexane dichloride, hexane dibromide, hexane dichloride, hebutane dichloride, hebutane dibromide, hebutane dichloride, octane dichloride, Octane dibromide, octane shoide, nonane dichloride, nonane dibromide, etc. are used. As a halogen-substituted organosilane,
For example, chloromethyltrimethylsilane, dichloroethyltriethylsilane, bischloromethyldimethylsilane, trischlormethylmethylsilane, chlorethyltriethylsilane, dichloroethyltriethylsilane, bromomethyltrimethylsilane, iodomethyltrimethylsilane, bisiodomethyldimethyl Silane, chlorphenyltrimethylsilane, bromphenyltrimethylsilane, chlorphenyltriethylsilane, bromphenyltriethylsilane, iodophenyltriethylsilane, etc. are used. As heroform, for example, fluoroform, chloroform, bromoform, iodoform, etc. are used.

In the present invention, when the surface protective layer does not contain halogen atoms, for example, when halogen atoms are not detected by Auger analysis, 5e-As or Se
/ Te Due to electrical mismatch with the photoreceptor, residual potential may occur, or the so-called memory phenomenon may occur where the previous image appears as a positive or negative image on the next image when multiple copies are made, and furthermore, This tends to cause so-called image blur due to the lateral flow of charges at the matching interface. Also, 5e-As or S e
/ T The adhesiveness with the e layer becomes poor, and 8! ! The surface M retaining layer is likely to peel off due to mechanical force or changes in temperature and humidity. The electrical inconsistency described above is also considered to be due to this poor adhesiveness.

In the present invention, the amount of halogen atoms contained as a chemical modifier can be controlled to some extent mainly by increasing or decreasing the amount of the halogen compound gas introduced into the reaction chamber in which the plasma reaction is performed. be. By increasing the amount of halogen compound gas introduced, it is possible to increase the amount of halogen atoms added to the a-C film according to the present invention, and conversely, by decreasing the amount of halogen compound introduced, it is possible to increase the amount of halogen atoms added to the a-C film according to the present invention. According to the invention, it is possible to reduce the amount of halogen atoms added to the a-C film.

In the present invention, the halogen atom content may be 0.1% or more, and the maximum content is not particularly limited, but is inevitably determined from the structure of the surface protective layer and the production aspect of glow discharge.

In the present invention, the thickness of the a-C:χ film as the surface protective layer of the 5e-As or Se/Te photoreceptor is preferably approximately 0.2 to 5 μm. If the film thickness is less than 12 μm, the surface hardness is easily affected by the low hardness of the underlying 5e-As or Se/Te layer, and suitable durability cannot be ensured. Further, due to the diffusion of atoms in the film after the surface protective layer is formed, harmful atoms may be deposited even on the surface of the photoreceptor, so that the effect of preventing harmful effects is not necessarily achieved. If the film thickness is thicker than 5 μm, it is not necessarily possible to secure suitable visible light transmittance, and 5e-As or Se/T
e The high sensitivity performance originally possessed by the photoreceptor is impaired.

In the process of forming an a-C:X film from a source gas in the present invention, the source gas is in a plasma state generated by a so-called plasma method using direct current, low frequency, high frequency, microwave, etc. It is formed using

The 5e-As and Se/Te photoreceptors used in the present invention are formed by vacuum deposition using a resistance heating method in accordance with a conventional method.

Figure 1 shows a single layer of 5e-As or S on a conductive substrate (1).
S e / with a 5e-Te layer laminated sequentially on it
T e photosensitive layer (2) and surface protective layer (3), i.e. a-C
: This figure shows the structure of the photoreceptor according to the present invention in which the X layer is sequentially laminated on top of the X layer.

FIG. 2 shows the surface protective layer of the photoreceptor according to the present invention, that is, a
-C: Shows the manufacturing equipment for forming the X film, and in the figure (70
1) to (706) are first to sixth tanks in which raw materials and carrier gas in a gaseous state at room temperature are sealed, and each tank has first to sixth control valves (707) to (712). It is connected to the first to sixth flow rate controllers (713) to (718). In the figure, (719) to (721) are first to third containers filled with raw materials that are in a liquid or solid phase at room temperature, and each container is connected to a first to third temperature controller for vaporization. (7
22) to (724), and each container is further connected to seventh to ninth control valves (725) to (727) and seventh to ninth flow rate controllers (728) to (730). has been done. These gases are mixed in a mixer (731) and then sent into a reaction chamber (733) via a main pipe (732). The pipes along the way can be heated by appropriately placed pipe heating M (734) so that the gas, which is the vaporized raw material compound that is in a liquid or solid state at room temperature, does not condense on the way. .

Inside the reaction chamber, there is a ground electrode (735) and a power application electrode (73).
6) are installed facing each other, and each i-pole is connected to an electrode heater (7).
37) allows for heating. Power application electrode (7
36) is connected to a high frequency power source (739) via a high frequency power matching box (738), a low frequency power source (741) via a low frequency power matching box (740), and a low pass filter (74).
A DC power source (743) is connected through the power source 2), and power with different frequencies can be applied by a connection selection switch (744). The pressure inside the reaction chamber (733) can be adjusted by a pressure control valve (745).
33) is reduced through the exhaust system selection valve (746).
This is carried out by a diffusion pump (747), an oil rotary pump (748), a cooling exclusion device (749), a mechanical booster pump (750), or an oil rotary pump (74 white). For exhaust gases, suitable exclusion devices (75
After making it safe and harmless according to 3), it is exhausted into the atmosphere. These exhaust system pipings are also equipped with appropriately placed piping heaters (734) to prevent the vaporized gas from the raw material compound, which is in a liquid or solid phase at room temperature, from condensing on the way. It is said that heating is possible. The reaction chamber (733) can also be heated by the reaction chamber heater (751) for the same reason.
A substrate (752), on which a 5e-As or Se/Te photosensitive layer is previously formed on a conductive substrate, is placed on the electrodes arranged inside. In FIG. 2, the substrate (752) is fixed to the ground electrode (735), but it may be fixed to the power application electrode (736), or it may be fixed to both. .

FIG. 3 shows the surface protective layer of the photoreceptor according to the present invention, that is, a
This figure shows another form of the manufacturing apparatus for forming the -C:X film, and is the same as the manufacturing apparatus according to the present invention shown in FIG. 2 except for the internal form of the reaction chamber (733). In Figure 3,
Inside the reaction chamber (733), there is a ground 'Ti' in Figure 2.
A cylindrical substrate (752) on which a selenium-based photoreceptor layer is previously formed on a conductive substrate using another vacuum evaporation device is installed, which also serves as a pole (735).
) are arranged. A similarly cylindrical power application electrode (736) is arranged around the substrate (752), and an electrode heater (737) is arranged outside. 5e-Asori
The substrate (752) on which the Se/Te photosensitive layer is formed can be rotated using a drive motor (754) from the outside.
The pressure is reduced to about 10"6 Torr, and the degree of vacuum is checked and the gas adsorbed inside the device is desorbed. At the same time, the electrode and the substrate fixed to the electrode are heated to a predetermined temperature using an electrode heater. At this time, 5e-As and S
In the case of a photosensitive layer having a selenium layer to prevent thermal alteration of the e/Te photosensitive layer, the substrate temperature is approximately 90°C or less, and in the case of a photosensitive layer consisting only of a selenium arsenic alloy, the substrate temperature is approximately 250T.
It is preferable to set the temperature as follows; the time for raising and maintaining the temperature is preferably within about 30 minutes, and the time required for raising and lowering the temperature is preferably within about 1 hour. Next, raw material gases consisting of hydrocarbons and halogen compounds are introduced into the reaction chamber from the first to sixth tanks and the first to third containers while maintaining a constant flow rate using the first to ninth flow rate controllers, and the pressure is adjusted to Hfm. A valve maintains a constant reduced pressure inside the reaction chamber. After the gas flow rate is stabilized, a connection selection switch is used to select, for example, a high frequency power source, and high frequency power is applied to the power application electrode. A discharge is started between the two electrodes, and a solid phase film is formed on the substrate over time. The film thickness is controlled by the reaction time, and when a predetermined film thickness is reached, the discharge is stopped to obtain an a-02X film as a surface protective layer of the photoreceptor according to the present invention. This a-C
:X film is an amorphous hydrocarbon film containing halogen atoms produced according to the present invention. Through the above process, a photoreceptor having a surface protective layer according to the present invention is obtained.

The present invention will be described below with reference to Examples.

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

First, the inside of the reactor (733) is 10-5 to 1O-
After creating a high vacuum of about 6 Torr, the first, second, and
Release the third control valve (707, 708, and 709),
Hydrogen gas from the first tank (701), hydrogen gas from the second tank (70
2) Acetylene gas from the third tank (703) and carbon tetrafluoride gas from the third tank (703) are supplied to the first, second, and third flow rate controllers (713, 714) under an output pressure of 1-OKg/cm2, respectively.
, and 715). Then, adjust the scales of each flow rate controller so that the flow rate of hydrogen gas is 40 sec and the flow rate of acetylene gas is 40 sec cr? +, and the flow rate of carbon tetrafluoride gas to be 40 sec cm, the main pipe (732
) into the reaction chamber (733). After each flow rate stabilized, the pressure inside the reaction chamber (733) was reduced to 1.0 Torr.
The pressure control valve (745) was adjusted so that the temperature was r.

On the other hand, the board (752) has a height of 50 x width of 50 x thickness of 3
A 5e-As photosensitive layer (Example 1) and S
An e/Te photosensitive layer (Example 2) formed with a thickness of about 50 μm was used. The temperature of the substrate (752) was raised from room temperature to 80° C. over about 15 minutes before introducing the gas. With the gas flow rate and pressure stable, the high frequency power source (739) is connected in advance using the connection selection switch (744).
was applied to the power application electrode (736) at a frequency of 13.56MHz to perform a plasma polymerization reaction for about 10 minutes, and a 0.6t1m thick a-C: An X film was formed as a surface protective layer. After the film formation is completed, the power application is stopped, the control valves other than hydrogen gas are closed, and only hydrogen gas is supplied into the reaction chamber (733).
The pressure was maintained at 10 Torr, and the temperature was lowered to 50'C in about 15 minutes. Thereafter, the hydrogen gas control valve is closed, the inside of the reaction chamber (733) is sufficiently evacuated, and when the substrate temperature has decreased to 30°C, the reaction chamber (733) is
), and the photoreceptor having the surface protective layer according to the present invention was taken out.

a-C obtained as above: CH per Xff1
When N quantitative analysis was performed, the amount of hydrogen atoms contained was 45 at% based on the total amount of carbon atoms and hydrogen atoms, and roughly from Auger analysis, the amount of contained halogen atoms, i.e.
The amount of fluorine atoms was 2.5 at% based on the total constituent atoms.

Characteristics: The pencil hardness of the surface of the photoreceptor obtained was measured based on the JIS-5400 standard and was approximately 6H in both Examples 1 and 2, indicating that the surface protection of the photoreceptor according to the present invention It was understood that the hardness can be increased depending on the layer.

In addition, when the white light sensitivity of the photoreceptor obtained in Example 1 was measured using the normal Carlson method, the hand exposure amount was approximately 0.99 lux·sec, and θ was
1j was approximately 0.93 lux·sec, the surface protective layer of the photoreceptor according to the present invention was 5e-A.
It was understood that this does not impair the inherent sensitivity of the photoreceptor.

In addition, when the 780 nm photosensitivity of the photoreceptor obtained in Example 2 was measured using a normal Carlson method, the half-decreased exposure amount was approximately 5.2 erg/am2, which was compared to that measured before the surface protective layer was formed. The surface protective layer of the photoreceptor according to the present invention has a Se/
It was understood that this does not impair the inherent sensitivity of the Te photoreceptor.

Further, the photoreceptors obtained in Example 1 and Example 2 were heated to a temperature of 1
When left for 6 hours in an environment where a low temperature, low humidity atmosphere at 0°C relative humidity 30% and a high temperature high humidity atmosphere at 50°C relative humidity 90% were alternately repeated every 30 minutes, the surface protective layer peeled 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 with excellent adhesion to 5e-As and Se/Te photoreceptors.

EXAMPLE 1 A surface protective layer of a photoreceptor according to the present invention was prepared in a glow discharge decomposition apparatus shown in FIG.

First, the inside of the reactor (733) is 10-5 to 1O-
After creating a high vacuum of about 6 Torr, the 11th, 2nd, and
Release the 3rd m section valves (707, 708, and 709),
Hydrogen gas from the first tank (701), hydrogen gas from the second tank (70
2) Acetylene gas from the third tank (703) and carbon tetrafluoride gas from the third tank (703) are supplied to the first, second, and third flow rate controllers (713, 714,
and 715). Then, adjust the scales of each flow rate controller to set the flow rate of hydrogen gas to 250 seconds, the flow rate of acetylene gas to 200 seconds, and the flow rate of carbon tetrafluoride gas to 200 scan, and then turn on the intermediate mixer (731). Flowed into the reaction chamber (733) from the main pipe (732) through the main pipe (732). After each flow rate stabilizes,
The pressure control valve (745) was adjusted so that the pressure inside the reaction chamber (733) was 1.0 Torr. On the other hand, the board (75
For 2), on an aluminum substrate with a diameter of 80 mm and a length of 329 mm, a separate vacuum evaporation device was used in advance in accordance with a conventional method.
5e-As photosensitive layer (Example 3) and Se/Te photosensitive layer (
Example 4) formed with a film thickness of about 50 μm was used. The substrate (752) is heated from room temperature to 80° C. over about 20 minutes before the gas is introduced. When the gas flow rate and pressure are stable, turn on the high frequency power source (739) that was previously connected using the connection selection switch (744), and apply 250 Watt power to the power application electrode (736) at frequency 13.
．． A plasma polymerization reaction was performed for about 15 minutes by applying a frequency of 56 MHz, and a 0.8 μm thick a-
A C:X film was formed as a surface protective layer. After the film formation is completed,
The application of electric power was stopped, the control valves other than hydrogen gas were closed, and only hydrogen gas was flowed into the reaction chamber (733) for 600 seconds, the pressure was maintained at 10 Torr, and the temperature was lowered to 50° C. in about 20 minutes. Thereafter, the hydrogen gas control valve is closed, the inside of the reaction chamber (733) is sufficiently evacuated, and when the substrate temperature has decreased to 30° C., the vacuum in the reaction chamber (733) is broken and the surface protective layer according to the present invention is formed. The photoreceptor was taken out.

When CHN quantitative analysis was performed on the a-C: The amount of halogen atoms, ie, fluorine atoms, contained was 2.7 at % based on the total constituent atoms.

Characteristics: When the pencil hardness of the surface of the photoreceptor obtained was measured based on the JIS-5400 standard, it was 7H or higher in both Example 3 and Example 4, indicating that the surface protection of the photoreceptor according to the present invention It was understood that the hardness can be increased depending on the layer.

Furthermore, when the white light sensitivity of the photoreceptor obtained in Example 3 was measured using the normal Carlson method, the half-decrease exposure amount was approximately 0.95 lux·sec, which was measured before the surface protective layer was formed. It was understood that the surface protective layer of the photoreceptor according to the present invention does not impair the inherent sensitivity of the 5e-As photoreceptor.

In addition, when the 780 nm photosensitivity of the photoreceptor obtained in Example 4 was measured using a normal Carlson method, the half-decreased exposure amount was approximately 5.3 erg/cm2, which was compared to that measured before the surface protective layer was formed. The value of Se
It was understood that the sensitivity of the /Te photoreceptor is not impaired.

Further, the photoreceptors obtained in Example 3 and Example 4 were heated to a temperature of 1
When left for 6 hours in an environment where a low temperature, low humidity atmosphere at 0°C relative humidity of 30% and a high temperature and high humidity atmosphere at 50°C and 90% relative humidity were alternately repeated every 30 minutes, the surface protective layer peeled off or No cracks or the like were observed, indicating that the surface protective layer of the photoreceptor according to the present invention is a film with excellent adhesion to the 5e-As and Se/Te photoreceptors.

Further, the photoreceptor obtained in Example 3 was used in a Minolta copier EP.
When mounted on the 650Z and photographed, clear images were obtained without so-called memory images, and furthermore, the temperature was 35 degrees Celsius and the relative humidity was 8 degrees.
Even when photographing in a 0% environment, so-called image blur was not observed. Furthermore, no peeling of the surface protective layer was observed upon contact with the developer, transfer paper, and cleaning member in the copying machine. Furthermore, when live shooting was carried out for 250,000 degrees in a normal room, clear images were obtained to the end.

Furthermore, after 250,000 copies were printed, the composition of the surface was analyzed by Auger analysis, and no selenium or arsenic was detected. From these facts, it was understood that the surface protective layer of the photoreceptor according to the present invention can improve durability and reduce harmfulness without impairing image quality.

Further, the photoreceptor obtained in Example 4 was used in a Minolta copier EP.
When I mounted it on the 450Z and changed the optical system to a commonly used semiconductor laser exposure system consisting of a semiconductor laser, polygon mirror scanner, drive system, etc., I was able to obtain clear images without so-called memory images. Even when photographed under an environment of 35° C. and 80% relative humidity, no so-called image blurring was observed. Furthermore, no peeling of the surface protective layer was observed upon contact with the developer, transfer paper, and cleaning member in the copying machine. Furthermore, when we shot 200,000 images in a normal room, we were able to obtain clear images to the end. Furthermore, when the surface composition was analyzed by Auger analysis after 200,000 copies were taken, selenium, tellurium, etc. were not detected.From these facts, the surface protective layer of the photoreceptor according to the present invention improves the image quality. It was understood that this would improve durability and reduce toxicity without impairing the properties of the material.

EXAMPLE 1 A surface protective layer of a photoreceptor according to the present invention was prepared in a glow discharge decomposition apparatus shown in FIG.

First, the inside of the reactor (733) is 10-5 to 1O-
After creating a high vacuum of about 6 Torr, the first and third control valves (707 and 709) are opened, and the first tank (709) is opened.
01) and ethylene gas from the third tank (703) into the first and third flow rate controllers (713 and 715) under an output pressure of 1.0 Kg/cm2, respectively.
At the same time, the seventh and eighth control valves (725 and 726) are opened, and the styrene gas is supplied from the first container (719) to the first temperature controller (722) at a temperature of 60°C, and then to the second container (720).
From LH,LH,5H-octafluoropendel methacrylate CH2=C(CH3)C00CH2(CF2)
The 4H gas is sent to the second temperature controller (723) at a temperature of 60°C.
and flowed into the eighth flow rate controller (728 and 729). Then, adjust the scale of each flow rate controller to increase the flow rate of argon gas to 200 secms and the flow rate of ethylene gas to 1 secms.
50sec, styrene gas flow rate 101005c,
The flow rate of LH, IH, 5H-octafluoropentyl methacrylate gas was set to 50 seconds, and the gas flowed into the reaction chamber (733) from the main pipe (732) via an intermediate mixer (731). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 1.0 Torr. On the other hand, as a substrate (752), a 5e-As photosensitive layer (Example 5) and a Se/Te layer were deposited on an aluminum base with a diameter of 80 mm and a length of 329 mm using a separate vacuum evaporation apparatus in advance according to a conventional method.
A photoreceptor layer (Example 6) formed with a film thickness of about 50 μm was used. The temperature of the substrate (752) was raised from room temperature to 80° C. over about 20 minutes before introducing the gas. When the gas flow rate and pressure are stable, press the connection selection switch (74) in advance.
The low frequency power supply (741) connected in step 4) is turned on, and a power of 100Wa11 is applied to the power application electrode (736) at a frequency of 30KHz to perform a plasma polymerization reaction for about 10 minutes, and then the substrate (752) An aC:X film having a thickness of 2.5 μm was formed thereon as a surface protective layer. After the film formation is completed, power application is stopped, the control valves other than argon gas are closed, and only argon gas is supplied into the reaction chamber (733) for 600 seconds.
ecm flows in and maintains the pressure at 10Torr, approx.
The temperature was lowered to 50°C in 5 minutes. Thereafter, the hydrogen gas control valve is closed, the inside of the reaction chamber (733) is sufficiently evacuated, and when the substrate temperature has decreased to 30° C., the vacuum in the reaction chamber (733) is broken and the surface protective layer according to the present invention is formed. The photoreceptor was taken out.

a-c obtained as above: xMff Nikki CH
Quantitative analysis of N revealed that the amount of hydrogen atoms contained was 37 at% with respect to the amount of P3 of carbon atoms and hydrogen atoms.Rough Auger analysis revealed that the amount of halogen atoms, i.e., fluorine atoms, contained was 37 at%. The amount was 17 at% based on the total constituent atoms.

Characteristics: When the pencil hardness of the surface of the photoreceptor obtained was measured based on the JIS-5400 standard, it was 7H or higher in both Examples 5 and 6, and the surface protection of the photoreceptor according to the present invention was found to be 7H or higher. It was understood that the hardness can be increased depending on the layer.

In addition, when the white light sensitivity of the photoreceptor obtained in Example 5 was measured using the normal Carlson method, the half-decrease exposure amount was approximately 1.1 lux·sec, which was measured before the surface protective layer was formed. The value was approximately 0.93 lux·sec, which indicates that the surface protective layer of the photoreceptor according to the present invention does not impair the inherent sensitivity of the 5e-As photoreceptor. or,
When the 780 nm photosensitivity of the photoreceptor obtained in Example 6 was measured using the normal Carlson method, the half-decrease exposure amount was approximately 5.6 erg/cm2, which was the same as the value measured before the surface protective layer was prepared. was approximately 5.4 erg/cm2, the surface protective layer of the photoreceptor according to the present invention was made of Se/Te.
It was understood that the inherent sensitivity of the photoreceptor is not impaired.

Further, the photoreceptors obtained in Example 5 and Example 6 were heated to a temperature of 1
When left for 6 hours in an environment where a low temperature, low humidity atmosphere at 0°C relative humidity of 30% and a high temperature and high humidity atmosphere at 50°C and 90% relative humidity were alternately repeated every 30 minutes, the surface protective layer peeled 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 with excellent adhesion to 5e-As and Se/Te photoreceptors.

Furthermore, when the photoreceptors 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, adhesion, environmental resistance, durability, and,
Confirmed to be non-polluting.

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

First, the inside of the reactor (733) is 10-5 to 1O-
After creating a high vacuum of about 6 Torr, the first and third control valves (707 and 709) are opened, and the first tank (709) is opened.
01) Argon gas from the third tank (703) and butadiene gas from the third tank (703) are respectively fed into the first and Chiku3 flow rate controllers (713 and 715) under an output pressure of 1.0 Kg/am2, and simultaneously into the seventh control valve. (725) and release the first container (725).
From 19), chloroform gas was flowed into the seventh cascade (728) at a first temperature control N (722) of 15°C. Then, adjust the scale of each flow rate side container to set the argon gas flow rate to 200 sec.

The flow rates of butadiene gas and chloroform gas were set to 150 sec and 150 sec, respectively, and flowed into the reaction chamber (733) from the main pipe (732) via an intermediate mixer (731). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 1.0 Torr. On the other hand, the substrate (752) used was an aluminum base with a diameter of 80 mm and a length of 329 mm, on which a 5e-As photosensitive layer was formed in advance to a thickness of about 50 Ltm using a separate vacuum evaporation apparatus according to a conventional method. . The substrate (752) is approximately 3
The temperature was raised from room temperature to 200°C over 0 minutes. The low frequency power source (741) is connected in advance using the connection selection switch (744) when the gas flow rate and pressure are stable.
was applied to the power application electrode (736) at a frequency of 30 KHz to carry out a plasma polymerization reaction for about 10 minutes, and the substrate (752) was coated with a thickness of 1.5 watts.
A μm a-C:χ film was formed as a surface protective layer. After the film formation is completed, the power application is stopped, the control valves other than argon gas are closed, and only argon gas is supplied to the reaction chamber (733).
The pressure was maintained at 10 Torr, and the temperature was lowered to 50° C. in about 30 minutes. Thereafter, the hydrogen gas control valve is closed, the reaction chamber (733) is sufficiently evacuated, and when the substrate temperature has decreased to 30°C, the reaction chamber (733) is
The vacuum was broken and the photoreceptor having the surface protective layer according to the present invention was taken out.

Quantitative analysis of CHN on the a-C+X film obtained as described above revealed that the amount of hydrogen atoms contained was 50 atomic% based on the total amount of carbon atoms and hydrogen atoms. The amount of halogen atoms, ie, chlorine atoms, was 25 at % based on the total constituent atoms.

Characteristics: The pencil hardness of the surface of the photoreceptor obtained was measured in accordance with the JIS-5400 standard and was approximately 7H, indicating that the surface protective layer of the photoreceptor according to the present invention increases the hardness. Ta.

In addition, when white light sensitivity was measured using the normal Carlson method, the half-decrease exposure amount was approximately 1.0 lux·sec, and the value measured before forming the surface protective layer was approximately 0.89 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 5e-As photoreceptor.

In addition, when the surface protective layer was left for 6 hours in an environment in which a hot, low-humidity atmosphere with a temperature of 10°C and a relative humidity of 30% and a high-temperature and high-humidity atmosphere with a temperature of 50°C and a relative humidity of 90% were alternately repeated every 30 minutes, the surface protective layer No peeling or cracking was observed, indicating that the surface protective layer of the photoreceptor according to the present invention was a film with excellent adhesion to the 5e-As photoreceptor.

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

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

First, after making the inside of reactor II (733) a high vacuum of about 10-5 to 10-6 Torr, the first and
Release the third control valve (7o7, and 709), and hydrogen gas flows from the first tank (701) and the third tank (703).
Then, carbon tetrafluoride gas was introduced into the first and third landscape controllers (713 and 715) under an output pressure of 1.0 Kg/cm2, and at the same time, the seventh control valve (725) was released, and the first container(
71,9), myrcene gas was allowed to flow into the seventh flow rate restrictor (728) at a first temperature controller (722) temperature of 85°C. Then, adjust the scales of each flow rate regulator to set the hydrogen gas flow rate to 50sec and the carbon tetrafluoride gas flow rate to 15sec.
cm, and the flow rate of myrcene gas was set to 101005e, and the gas flowed into the reaction chamber (733) from the main pipe (732) via the 8 combiner (731) on the way. After each flow rate stabilizes, the pressure in the reaction chamber (733) decreases to 1.
O.T.

The pressure regulating valve (745) was adjusted so that rr. On the other hand, the board (752) has a diameter of 80 m and a length of 329 m.
A 5e-As photosensitive layer having a thickness of about 50 .mu.m was formed on an aluminum substrate having a thickness of about 50 .mu.m using a separate vacuum evaporation apparatus in accordance with a conventional method. The substrate (752) is heated from room temperature to 200° C. over about 30 minutes before the gas is introduced. When the gas flow rate and pressure are stable, turn on the low frequency power supply (744) connected in advance using the connection selection switch (744).
41) and apply 120W to the power application electrode (736).
A plasma polymerization reaction was carried out for about 10 minutes by applying power of tt at a frequency of 45 KHz to form a 4.5 μm thick a-COX film as a surface protective layer on the substrate (752). After the film formation is completed, the power application is stopped, the control valves other than hydrogen gas are closed, and only hydrogen gas is supplied into the reaction chamber (733) for 60 minutes.
The flow rate is 0sec, the pressure is maintained at 10Torr, and the pressure is maintained at about 3
The temperature was lowered to 50°C in 0 minutes. Thereafter, the hydrogen gas control valve is closed, the inside of the reaction chamber (733) is sufficiently evacuated, and when the substrate temperature has decreased to 30° C., the vacuum in the reaction chamber (733) is broken and the surface protective layer according to the present invention is formed. The photoreceptor was taken out.

When the a-C: Auger analysis revealed that the amount of halogen atoms, ie, fluorine atoms, contained was 0.2 at % based on the total constituent atoms.

Characteristics: The pencil hardness of the surface of the photoreceptor obtained was determined according to JIS-
The hardness was approximately 6H when measured based on the -5400 standard, and it was understood that the hardness was increased by the surface protective layer of the photoreceptor according to the present invention.

In addition, in the normal Carlson method, the white light sensitivity is
1, the half-reduced exposure amount was about 1.05 lux·sec, and the value measured before forming the surface protective layer was about 0.05 lux·sec.
8 flux·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 5e-As photoreceptor.

Furthermore, when the surface protective layer was left for 6 hours in an environment where a low temperature, low humidity atmosphere at a temperature of 10°C and a relative humidity of 30% and a high temperature and high humidity atmosphere at a temperature of 50°C and a relative humidity of 90% were alternately repeated every 30 minutes, the surface protective layer peeled off. In addition, no cracks or the like were observed, indicating that the surface protective layer of the photoreceptor according to the present invention was a film with excellent adhesiveness to the 5e-As photoreceptor.

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

Comparative Examples 1 to 2 5e-As (Comparative Example 1) and Se
/Te (Comparative Example 2) A surface layer was formed on a photoreceptor.

When Auger analysis was performed on this surface layer, no halogen atoms, that is, fluorine atoms, were detected, and even though fluorine atoms were present due to contamination, the amount was at the detection limit of Auger analysis. O,
It is understood that it is less than lat%.

The initial characteristics all showed values similar to those in Examples 3 and 4, but when actual copying was performed, during continuous copying,
A so-called memory phenomenon, in which the previous image appears as a negative image on the next image, occurred, and a practically suitable image could not be obtained. From this, it can be understood that the addition of halogen atoms improves electrical consistency and, as a result, improves image quality.

Furthermore, after actual shooting, the photoreceptors obtained in Comparative Example 1 and Comparative Example 2 were exposed to a low-temperature, low-humidity atmosphere at a temperature of 10°C and a relative humidity of 30% and a high-temperature and high-humidity atmosphere at a temperature of 50°C and a relative humidity of 90% every 30 minutes. When the surface protective layer was left for 6 hours in an environment that was alternately repeated, most of the surface protective layer peeled off.
The effect of improving adhesion to the Se/Te photoreceptor was also demonstrated.

Comparative Examples 3-4 13(, IH, 58-octafluoropentyl methacrylate CH2=C(CH3)COOCH2(CF2)4
5e-As (Comparative Example 3) and Se/Te (
Comparative Example 4) A surface layer was formed on a photoreceptor.

When Auger analysis was performed on this surface layer, no halogen atoms, that is, fluorine atoms, were detected, and even though a very large amount of fluorine atoms were present due to contamination, the amount was at the detection limit of Auger analysis. O, l
It is understood that it is less than at%.

The initial characteristics both showed values similar to those of Examples 5 and 6, but when actual copying was performed, during continuous copying,
A so-called memory phenomenon, in which the previous image appears as a negative image on the next image, occurred, and a practically suitable image could not be obtained. From this, it can be understood that the addition of halogen atoms improves electrical consistency and, as a result, improves image quality.

[Brief explanation of drawings]

FIG. 1 shows the structure of a photoreceptor according to the present invention, and FIGS. 2 and 3 show a manufacturing apparatus for manufacturing the photoreceptor according to the invention.

Claims (1)

[Claims] In a photoreceptor consisting of a single layer of selenium arsenic alloy or a laminated structure of selenium and selenium tellurium alloy in this order on a conductive substrate, a surface protective layer is provided, and the surface protective layer is generated by a glow discharge method and contains at least halogen atoms. A photoreceptor characterized by being an amorphous hydrocarbon film containing.