JPS6373260A - Photosensitive body - Google Patents

Abstract

PURPOSE:To enhance charge transfer performance and the performance of an electrophotographic sensitive body by forming as a charge transfer layer an organic plasma polymerized film produced by a low-pressure plasma polymerization reaction of an organic gas and containing alkali metal atoms and oxygen atoms as chemically modifying substances. CONSTITUTION:The photosensitive body is obtained by successively laminating on a conductive substrate 1 the charge transfer layer 2 and the charge generating layer 3. The charge transfer layer 2 is composed of an amorphous solid of carbon and hydrogen atoms produced by the plasma polymerization of hydrocarbon in a gas phase and containing as the chemical modifying substances at least the alkali metal atoms in an amount of 0.1-10atom% of the total constituent atoms and oxygen atoms in an amount of <=7atom% of them, thus permitting charge transfer performance to be stably retained without undergoing deterioration due to the lapse of time.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a photoreceptor having a charge generation layer and a charge transport layer.

BACKGROUND OF THE INVENTION Since the invention of the Carlson method, the field of electrophotography has continued to make remarkable progress, and various materials have been developed and put into practical use for electrophotographic photoreceptors.

The main electrophotographic photoreceptor materials conventionally used include inorganic substances such as amorphous selenium, selenium arsenide, selenium telluride, cadmium sulfide, zinc oxide, amorphous silicon, polyvinyl carbazole, metal phthalocyanine,
Examples include organic substances such as disazo pigments, trisazo pigments, perylene pigments, triphenylmethane compounds, triphenylamine compounds, hydrazone compounds, styryl compounds, pyrazoline compounds, oxazole compounds, and oxadiazole compounds. In addition, the configurations include a single-layer structure in which these substances are used alone, a binder-type structure in which they are dispersed in a binder, and a laminated structure in which a charge generation layer and a charge transport layer are provided for each function. Can be mentioned.

However, the electrophotographic photoreceptor materials conventionally used each have drawbacks. One of these is their toxicity to the human body, and all inorganic substances, except for the amorphous silicon mentioned above, have unfavorable properties. In addition, in order for an electrophotographic photoreceptor to be actually used in a copying machine, it must always maintain stable performance even when exposed to harsh environmental conditions such as charging, exposure, development, transfer, neutralization, and cleaning. However, all of the organic substances mentioned above have poor durability and many unstable factors in terms of performance.

In order to eliminate such drawbacks, in recent years, amorphous silicon produced by a glow discharge method has been increasingly applied to electrophotographic photoreceptors as a material with improved toxicity and high durability. However, since amorphous silicon requires highly ignitable silane gas as a raw material, it is highly dangerous to manufacture. Furthermore, although a large amount of silane gas is required, since it is an expensive gas, the resulting electrophotographic photoreceptor is also significantly more expensive than conventional photoreceptors. In addition, there are many inconveniences in production, such as the slow film formation rate and the generation of a large amount of explosive undecomposed silane products in the form of dust. If this dust gets mixed into the photosensitive layer during manufacturing, it will significantly adversely affect image quality. Furthermore, since amorphous silicon originally has a high dielectric constant, its charging performance is low, and in order to charge it to a predetermined surface potential in a copying machine, a high output power is required from a charger.

On the other hand, plasma organic polymerized films themselves have been known for a long time, such as diene (H, 5hen) and bell (A).

In 1973, the journal
Journal of Applied Polymer Science
alof Applied Polymer 5cie
nce), Volume 17, pp. 885-892, the same author also reported in the 1979 American Chemical Society that all organic compounds can be made from gas.
Plasma Volimalization (Pl) published by
Asma polymerization), its film formability is also being discussed.

However, plasma organic polymer films prepared by conventional methods are used only for applications that assume insulation properties, that is, they are considered to be insulating films with a specific resistance of about <1018 Ωcm, like ordinary polyethylene films. Or at least it was used with the recognition that it was such a membrane. Due to the same recognition, its actual use in electrophotographic photoreceptors has been limited to protective layers, adhesive layers, blocking layers, or insulating layers, and has only been used as so-called undercoat layers or overcoat layers. .

For example, JP-A-59-28161 discloses a photoreceptor in which a plasma-polymerized polymer layer having a network structure is provided on a substrate as a blocking layer and an adhesive layer, and an amorphous silicon layer is provided thereon. ing. Japanese Patent Application Publication No. 5
Publication No. 9-38753 discloses that a plasma polymerized film with a high resistance of 1013 to 1015 ΩCm generated from a mixed gas of oxygen, nitrogen, and hydrocarbons is provided on a substrate as a blocking layer and an adhesive layer by 10 to 100 people. A photoreceptor provided with an amorphous silicon layer has been disclosed. Unexamined Japanese Patent Publication 1987-
Publication No. 136742 discloses a photoreceptor in which a carbon film of approximately 1 to 5 μm is formed on the surface of the substrate as a protective layer to prevent aluminum atoms from diffusing into the amorphous silicon layer provided on the aluminum substrate during light irradiation. has been fully disclosed.

Japanese Unexamined Patent Publication No. 60-63541 discloses a photosensitive material in which a diamond-like carbon film with a thickness of 200 to 2 μm is provided in the middle as an adhesive layer in order to improve the adhesion between an aluminum substrate and an amorphous silicon layer provided thereon. It is disclosed that the film thickness is preferably 2 μm or less in terms of residual charge.

All of these disclosures are inventions in which a so-called undercoat layer is provided between the substrate and the amorphous silicon layer,
There is no disclosure regarding charge transport properties, and a-Si
However, it does not solve the above-mentioned essential problems.

Furthermore, for example, Japanese Patent Application Laid-Open No. 50-20728 and US Pat. No. 3,956.52.5 disclose that a polymer film formed by glow discharge polymerization is applied as a protective layer on the surface of a polyvinylcarbazole-selenium photoreceptor. A photoreceptor having a thickness of 1 to 1 μm is disclosed. Japanese Patent Publication No. 59-21485
No. 9 discloses a technique for forming a protective layer on the surface of an amorphous silicon photoreceptor by plasma polymerizing an organic hydrocarbon monomer such as styrene or acetylene to form a film of about 5 μm. JP-A-60-61761 discloses a photoreceptor provided with a diamond-like carbon thin film of 500 to 2 μm as a surface protective layer, and from the viewpoint of light transmission, the film thickness is preferably 2 μm or less. There is. JP-A-60-249115 discloses a technique using an amorphous carbon or hard carbon film with a thickness of about 0.05 to 5 μm as a surface protective layer, and if the film thickness exceeds 5 μm, the activity of the photoreceptor is adversely affected. It is said that Japanese Patent Publication BB61-9405
No. 6 discloses an amorphous silicon photoreceptor using an amorphous carbon film with excellent hydrophobicity as a protective layer on the surface of amorphous silicon.

All of these disclosures are inventions in which a so-called overcoat layer is provided on the surface of a photoreceptor, and there is no disclosure about charge transport properties, and they do not solve the above-mentioned essential problems of a-Si. .

Furthermore, JP-A-51-46130 discloses an electrophotographic photosensitive plate in which a polymer film of 0.001 to 3 μm is formed on the surface of a polyvinylcarbazole electrophotographic photoreceptor by glow discharge polymerization. However, there is no mention of charge transport properties at all, and it does not solve the above-mentioned essential problems of a-Si.

Q As mentioned above, plasma organic polymer films conventionally used in electrophotographic photoreceptors have been used as so-called undercoat layers or overcoat layers, but they are It is a film that does not require a function, and is used based on the judgment that the organic polymer film is insulating.-'
Therefore, it can only be used as an extremely thin film with a thickness of about 5 μm at most, and if the carriers pass through the film due to tunneling effect, or if tunneling effect cannot be expected, it will not be a problem as a practical residual potential. It is only used in thin films that are only small enough to last.

In a functionally separated electrophotographic photoreceptor, the charge transport layer must have carrier transport properties, and the carrier mobility must have a value of at least 10 cm2/V/5ec1 or more. In addition, in order to be used suitably in an electrophotographic system, it is necessary to have excellent charging performance, and a withstand voltage of at least 10 [V/μm] is required, and in order to roughly reduce the load on the charger, It is preferable to have a value of 6 or less in terms of ratio.

While considering the application of plasma organic polymer films to photoreceptors, the present inventors discovered that organic polymer films, which were originally thought to be insulating, contained appropriate amounts of alkali metal atoms as chemical modifiers. It has been found that the specific resistance decreases with the addition of 4 or more, and that suitable charge transport properties begin to be easily exhibited. Although the theoretical interpretation has many unclear points even for the present inventors, it is not possible to discuss it in detail, but electrons in a relatively unstable energy state that are trapped in the charge generation layer, such as
Unpaired electrons, residual free radicals, etc. are polarized due to the incorporation of alkali metal atoms or changes in steric structure, etc.
It is presumed that this is because it effectively contributes to charge transport properties.

Generally speaking, in the state where no alkali metal atoms are added, the polymer film is likely to exhibit a decrease in transport properties over time after film formation, that is, a decrease in sensitivity, but when alkali metal atoms are added as a chemical modifier, It has been found that by doing so, the charge transport properties of the charge transport layer can be stably ensured without being subject to deterioration over time. Furthermore, the addition of alkali metal atoms ensures suitable potential attenuation even in the light attenuation characteristic in the low electric field region of the photoreceptor, lowers the base of so-called LDC, and has the effect of significantly preventing the generation of residual potential. I found out. In general, we have found that the addition of alkali metal atoms significantly improves the film formation rate, which is essential in the production of a charge transport layer that requires a certain level of film thickness.

On the other hand, we found that when alkali metal atoms were added, apart from the above-mentioned features, there was a decrease in charge retention ability over time, in other words, a decrease in dark decay characteristics over time. The present inventors have also discovered that by adding a trace amount of oxygen atoms in addition to alkali metal atoms, it is possible to prevent the dark decay characteristics from deteriorating over time without impairing the above features.

The present invention utilizes these new findings to achieve a
-Providing a photoreceptor that eliminates all of the above-mentioned essential problems of Si photoreceptors and uses an organic polymer film, especially an organic plasma polymer film, as a charge transport layer, and has completely different purposes and characteristics from conventional ones. The purpose is to do.

The present invention solves the drawbacks of conventional electrophotographic photoreceptors, and uses a chemical modifier produced by plasma polymerization reaction of an organic gas under low pressure as a charge transport layer. The present invention relates to a photoreceptor characterized by having a plasma organic polymer film containing alkali metal atoms and oxygen atoms. Although the charge transport layer does not have clear photoconductivity for visible light or light with a wavelength near semiconductor laser light, it stably provides suitable charge transport properties, and also has charging ability, durability, It has excellent electrophotographic photoreceptor performance such as weather resistance and environmental pollution resistance, and is also excellent in light transmission, so it can provide an extremely high degree of freedom especially when forming a laminated structure as a functionally separated photoreceptor. It is.

Specifically, the present invention provides a photoreceptor having a charge generation layer and a charge transport layer, in which a hydrocarbon plasma polymerized film is provided as the charge transport layer, and at least an alkali metal atom is added as a chemical modifier in the polymer film. and oxygen atoms in an amount of 0.1 to 10 at% of alkali metal atoms based on the total constituent atoms.
, relates to a photoreceptor characterized by containing 7 at % or less of oxygen atoms. (Hereinafter, the polymer film according to the present invention is a-
Here, the amounts of carbon atoms, hydrogen atoms, alkali metal atoms, and oxygen atoms in the a-C film according to the present invention can be determined using conventional methods of elemental analysis, such as organic elemental analysis and Auger analysis. It is possible to know by facts.

In the present invention, hydrocarbons are used as the organic gas for forming the a-C film. The phase state of the hydrocarbon does not necessarily have to be a gas phase at room temperature and normal pressure; it can be used in either a liquid phase or a solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. It is. Examples of the hydrocarbons used include saturated hydrocarbons, unsaturated hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and the like.

There are many types of hydrocarbons that can be used, but examples of saturated hydrocarbons include methane, ethane, propane, butane,
Pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane,
tocosan, tricosane, tetracosan, pentacosan,
Normal paraffins such as hexacosane, heptacosane, 'octacosane, nonacosane, triacontane, todoriacontane, pentatriacontane, etc., as well as isobutane, isopentane, neopentane, isohexane, neohexane, 2.3-dimethylbutane, 2-methylhexane, 3 -ethylpentane, 2,2-dimethylpentane,
2.4-dimethylpentane, 3.3-dimethylpentane, tributane, 2-methylhebutane, 3-methylhebutane, 2.2-dimethylhexane, 2,2.5-dimethylhexane, 2.2.3- Trimethylpentane, 2.2.
4-trimethylpentane, 2゜3.3-trimethylpentane, 2,3.4-trimethylpentane, isonanone,
and other isoparaffins, etc. are used. Examples of unsaturated hydrocarbons include ethylene, propylene, isobutylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl -Olefins such as 2-butene, 1-hexene, tetramethylethylene, 1-heptene, 1-octene, 1-nonene, 1-decene, and allene, methylalene, butadiene, pentadiene, hexadiene, cyclopentadiene, diolefins such as ocimene, allocimene, myrcene, hexatriene, and acetylene, diacetylene,
Methylacetylene, 1-butyne, 2-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, 1
-nonine, 1-decyne, etc. are used. Examples of alicyclic hydrocarbons include cyclopropane, cyclobutane,
Cycloparaffins such as cyclobentane, cyclohexane, cyclohebutane, cyclooctane, cyclononane, cyclodecane, cyclobuntecane, cyclododecane, cyclobutecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, and cyclopropene,
Cycloolefins such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, limonene, terbirun, phelandrene, sylvestrene, thuen, carene, pinene, bornylene, kunghuen, fuenchen,
Cyclodecanethene, tricyclene, bisabolene, zingiberene, curcumene, humulene, kajinensesesquibenichen, selinene, caryophyllene, ren, santarene, cedrene, campholene, phylloclatene, bodocarprene,
Terpenes such as mylene, steroids, etc. are used. Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimelithene, pseudocumene, mesitylene, prenitene, isodurene, durene, pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, cumene, styrene, biphenyl, diphenylmethane, triphenylmethane, dibenzyl, stilbene, indene, naphthalene,
Tetralin, anthracene, phenanthrene, etc. are used.

The amount of hydrogen atoms contained in the a-C film in the present invention is 0.1 to 67 at.%, preferably 30 to 60 at.%, based on the total amount of carbon atoms and hydrogen atoms. If the amount of hydrogen atoms is less than 0.1 atomic %, transport performance deteriorates and suitable photosensitivity cannot necessarily be obtained. The amount of hydrogen atoms is 6
If it is higher than 7 at %, the charging ability will be lowered and the film forming properties will be deteriorated.

The amount of hydrogen atoms contained in the a-C film in the present invention can be changed depending on the form of the film forming apparatus and the conditions during film forming.In order to lower the hydrogen amount, for example, the substrate temperature can be changed. Increase the applied power, lower the pressure, lower the dilution rate of the raw material hydrocarbon gas, use a raw material gas with a lower hydrogen atom content, increase the applied power, lower the frequency of the alternating electric field, superimpose it on the alternating electric field. This can be controlled by means such as increasing the DC electric field strength, or by a combination of these means.

The thickness of the a-C film as the charge transport layer in the present invention is 5 to 5
0tim, especially 7 to 20L1m is blocking, 5μm
If the density is lower, the charged potential will be lower and sufficient density of the copied image cannot be obtained. Moreover, if it is thicker than 50 μm, it is not preferable in terms of productivity. This a-C film has high light transmittance, high dark resistance, and is rich in charge transport properties, and even if the film thickness is 5 μm or more as mentioned above, carriers are transported without being trapped, effectively reducing light attenuation. It is possible to contribute.

In the present invention, in addition to hydrocarbons, an alkali metal compound is used to add at least alkali metal atoms into the a-C film. Here, the alkali metal atom refers to a lithium atom, a sodium atom, a potassium atom, a rubidium atom, and a cesium atom. The phase state of the alkali metal compound gas does not necessarily have to be a gas phase at room temperature and normal pressure, and since there are few compounds in a gas phase, it is possible to vaporize through melting, evaporation, sublimation, etc. by heating or reduced pressure. As long as it can be obtained, either liquid phase or solid phase can be used. As the alkali metal compound, for example, metal alcoholade metal acrylic acid, metal methacrylic acid, metal phthalocyanine, etc. can be used.

In the present invention, the amount of alkali metal atoms contained as a chemical modifier is 0.1 to 10
% by atom, preferably from 0.3 to 5 atomic%. If the amount of alkali metal atoms is lower than 0.1 at%, it is not always possible to guarantee suitable charge transport properties, which tends to cause a decrease in sensitivity or the generation of residual potential, and also guarantees stability of sensitivity over time. When the amount of alkali metal atoms is higher than 10 atomic %, the alkali metal atoms, which had guaranteed suitable charge transport properties and prevention of residual potential generation when added in an appropriate amount, conversely deteriorate the charging ability. causing a decline.

In addition, film formability is not necessarily guaranteed, and film peeling and
It tends to become oily or powdery.

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

In the present invention, in addition to hydrocarbons and alkali metal compounds, oxygen compounds are used to add at least oxygen atoms into the a-C film. The phase state of the oxygen compound does not necessarily have to be a gas phase at room temperature and normal pressure; it can be used in either a liquid phase or a solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. It is. Examples of oxygen compounds include oxygen, ozone, and water (steam).
, hydrogen peroxide, -carbon oxide, carbon dioxide, carbon suboxide,
- Inorganic compounds such as nitrogen oxide, nitrogen dioxide, dinitrogen trioxide, dinitrogen pentoxide, nitrogen trioxide, hydroxyl group (-OH),
Aldehyde group (-CoH), acyl group (RC〇-, -C
R○), ketone group (>Co), nitro group (NO2), nitroso group (-NO), sulfone group (503H), :
L-thyl bond (-0-), ester bond (-000-
), a peptide bond (-CONH-), an oxygen-containing heterocycle, an organic compound having a functional group or bond, and also a metal alkoxide.

Examples of organic compounds having a hydroxyl group include methanol, ethanol, propatool, butanol, furyl alcohol, fluoroethanol, fluorobutanol,
Phenol, cyclohexanol, benzyl alcohol, furfuryl alcohol, etc. are used. Examples of the organic compound having an aldehyde group include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, glyoxal, acrolein, benzaldehyde, and furfural. Examples of organic compounds having an acyl group include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, valmitic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, benzoic acid, toluic acid, salicylic acid, and cinnamon. acid, naphthoic acid,
Phthalic acid, furanic acid, etc. are used. Examples of organic compounds having a ketone group include acetone, ethyl methyl ketone, methyl propyl ketone, butyl methyl ketone, binacolon, diethyl ketone, methyl vinyl ketone, mesityl oxide, methyl hebutenone, cyclobutanone, cyclopentanone, and cyclohexanone. , acetophenone, propiophenone, butyrophenone, valerophenone, dibenzylketone, acetonaphthone, acetochenone, acetofuron, etc. are used. As the organic compound having a nitro group, for example, 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 a sulfonic group include methanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and the like. Examples of organic compounds having an ether bond include methyl ether, ethyl ether, propyl ether, methyl, butyl ether, amyl ether, ethyl methyl ether, methyl propyl ether,
Methyl butyl ether, methyl amyl ether, ethyl propyl ether, ethyl butyl ether, ethyl amyl ether, vinyl ether, allyl ether, methyl vinyl ether, methylfuryl ether, ethyl vinyl ether, ethyl allyl ether, anisole, phenetol, phenyl ether, benzyl ether, phenylbenzyl ether , naphthyl ether, ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydrobilane, dioxane, etc. are used. Examples of organic compounds having an ester bond include methyl formate, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl propionate, ethyl propionate, and propion. propyl acid, butyl propionate, amyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, amyl butyrate, methyl valerate, ethyl valerate, propyl valerate, butyl valerate, amyl valerate, methyl benzoate, Ethyl benzoate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, methyl salicylate, ethyl salicylate, propyl salicylate,
Butyl salicylate, amyl salicylate, methyl anthranilate, ethyl anthranilate, butyl anthranilate, amyl anthranilate, methyl phthalate, ethyl phthalate, butyl phthalate, and the like are used. As the organic compound having a peptide bond, for example, glyceroglobebutide, glyceroid peptide, etc. are used. Examples of heterocyclic compounds include furan, oxazole, furazane,
Bilan, oxazine, morpholine, benzofuran, pandioxazole, chromene, chroman, dibenzofuran, xanthine, phenoxazine, oxolane, dioxolane, oxathiolane, oxadiazine, benzisoxazole, etc. are used. Examples of the metal alkoxide include lithium isopropylate, lithium tert-butyrate, sodium, thorium isopropylate,
potassium isopropylate, magnesium ethylate,
Calcium ethylate, strontium methylate, barium ethylate, barium isopropylate, boric acid methyl ester, boric acid ethyl ester, boric acid butyl ester, aluminum butyrate, aluminum isopropylate, aluminum butyrate, gallium isopropylate, silicic acid Methyl ester, ethyl silicate, isopropyl silicate, germanium methylate, germanium propylate, germanium methylate, methyl phosphate, antimony butyrate, antimony butyrate, indium isopropylate, zinc tylate, yttrium isopropylate ,
Lanthanum isopropylate, titanium isopropylate, titanium butyrate, zirconium ethylate,
Zirconium isopropylate, hafnium isopropylate, vanadium methylate, panadium ethylate, vanadium butyrate, vanadyl ethylate, vanadium, rutertiary butyrate, niopium ethylate,
Tantalum ethylate, iron isibrovirate, tin methylate, tin ethylate, tin isopropylate, tin butyrate, etc. are used.

In the present invention, the amount of oxygen atoms contained as a chemical modifier is 7.0 atom % or less, and optimally 4.7 atom % or less based on the total constituent atoms. Oxygen atoms are 7.0 at%
If it is contained in a larger amount, the sensitivity characteristics based on good charge transport properties due to the addition of alkali metal atoms cannot necessarily be guaranteed. On the other hand, if it does not contain any oxygen atoms, for example, if it is so oxygen-free that no oxygen is detected by Auger analysis, the effect of alkali metal atoms to lower the dark resistance over time, i.e., the electric charge during storage for several months. It becomes impossible to prevent effects that lead to a decrease in retention capacity.

In the present invention, the appearance of oxygen atoms contained as a chemical modifier can be controlled mainly by increasing or decreasing the amount of the aforementioned oxygen compound introduced into the reaction chamber in which the plasma reaction is performed. If the amount of oxygen compound introduced is increased,
It is possible to increase the amount of oxygen atoms added to the a-C film according to the present invention, and conversely, if the amount of oxygen compounds introduced can be reduced, the amount of oxygen atoms added to the a-C film according to the present invention can be increased. It is possible to reduce the amount added.

The process of forming an a-C film from a raw material gas in the present invention is a method in which the raw material gas is formed through a plasma state generated by a plasma method using direct current, low frequency, high frequency, microwave, etc. is the most preferable, but it may also be formed through an ionic state generated by ionization vapor deposition method, ion beam vapor deposition method, etc., or neutral state produced by vacuum vapor deposition method, sputtering method, etc. It may be formed from particles or a combination thereof. The important thing is that
The a-C film is formed so that the amount of alkali metal atoms and oxygen atoms contained in the a-C film falls within the above-mentioned range.

The charge generating layer used in the photoreceptor according to the present invention is not particularly limited, and examples thereof include amorphous selenium, selenium arsenic, selenium tellurium, cadmium sulfide, zinc oxide, and optionally different elements (such as hydrogen, boron, carbon, nitrogen,
Inorganic substances such as amorphous silicon containing oxygen, fluorine, phosphorus, sulfur, chlorine, bromine, germanium, etc.), polyvinyl carbazole, cyanine compounds, metal phthalocyanine compounds, Ab compounds, perylene compounds, triaryl Methane compounds, triphenylmethane compounds, triphenylamine compounds, hydrazone compounds, styryl compounds, pyrazoline compounds, oxazole compounds, oxazine compounds, oxadiazole compounds, thiazine compounds, xanthine compounds, Organic substances such as biryllium compounds, quinacridone compounds, indigo compounds, polycyclic quinone compounds, disbenzimidazole compounds, induthrone compounds, and squarylium compounds can be used. In addition to this, any material can be used as long as it can efficiently generate photo-excited carriers by irradiation light and can efficiently inject the carriers into the charge transport layer.

Further, the charge generation layer is not subject to any limitations in the manufacturing method, and for example, the charge transport ff1 (
It may be formed by the same manufacturing method as the a-C film), or by a vacuum evaporation method, an electrodeposition method in a liquid phase, a coating method by spraying or dipping, or the like. Among these, it is preferable to form the film by the same manufacturing method as that for the charge transport layer in the present invention, since this leads to reduction in manufacturing equipment cost and labor in the process.

The photoreceptor in the present invention is a photoreceptor comprising a charge generation layer and a charge transport layer, and the laminated structure of the charge generation layer and the charge transport layer can be appropriately selected as necessary.

FIG. 1 shows, as one form thereof, a structure in which a charge transport N (2) and a charge generation N (3) are sequentially laminated on a conductive substrate (1). FIG. 2 shows, as another embodiment, a structure in which a charge generation layer (3) and a charge transport layer (2) are sequentially laminated on a conductive substrate (1). FIG. 3 shows a structure in which a charge transport layer (2), a charge generation M (3), and a charge transport layer (2) are sequentially laminated on a conductive substrate (1) as a roughly different form. This is what is shown.

When the surface of the photoreceptor is positively charged using a corona charger or the like and then used for image exposure, in FIG. 1, holes generated in the charge generation layer (3) pass through the charge transport layer (2). Electrons travel toward the conductive substrate (1), and in Figure 2, electrons generated by charge generation N (3) travel through the charge transport layer (2) toward the surface of the photoreceptor; Holes generated in the layer (3) travel through the charge transport layer (2) toward the conductive substrate (1), and at the same time, electrons generated in the charge generation layer (3) travel through the charge transport layer (2) on the upper side. ) through which the photoreceptor surface travels, forming an electrostatic latent image with proper brightness attenuation. On the other hand, when the surface of the photoreceptor is negatively charged and then used for image exposure, the behavior of electrons and holes can be exchanged to understand the mobility of carriers. In FIGS. 2 and 3, the irradiation light for image exposure passes through the charge transport layer (2), but since the charge transport layer according to the present invention has excellent translucency, it is possible to form a suitable latent image. It is possible to carry out formation.

FIG. 4 shows a conductive substrate (1), a charge transport layer (2), a charge generation layer (3) and a surface protective layer (
4) is shown in a structure formed by sequentially stacking them. In other words, it corresponds to the form shown in Fig. 1 with a surface protective layer provided, but
In the embodiment shown in FIG. 1, since the outermost surface is a charge generation layer which is not particularly limited in the present invention, in many cases it is preferable to provide a surface protective layer in order to ensure practical durability. In the case of the configurations shown in FIGS. 2 and 3, since the outermost surface is the highly durable charge transport layer according to the present invention, there is no need to provide a surface protective layer. A surface protective layer may also be provided for the purpose of adjusting the consistency of various elements within the copying machine, such as preventing dirt on the copying machine.

FIG. 5 shows, as a further embodiment, an intermediate layer (5), a charge generation layer (3) and a charge transport N (2) on a conductive substrate (1).
This figure shows a structure in which these are sequentially laminated. That is, the second
This corresponds to the form shown in the figure with an intermediate layer provided, but in the form shown in Fig. 2, the bonding surface with the conductive substrate is a charge generation layer which is not particularly limited in the present invention, so in many cases It is preferable to provide a surface protective layer to ensure adhesion and injection blocking effect. In the case of the configurations shown in FIGS. 1 and 3, since the bonding surface with the conductive substrate is the charge transport layer according to the present invention, which has excellent adhesiveness and injection blocking effect, it is not necessary to provide an intermediate layer. For example, an intermediate layer may be provided for the purpose of adjusting compatibility with a manufacturing process before forming a photosensitive layer, such as a pretreatment method for a conductive substrate.

FIG. 6 shows, as a rough form, an intermediate layer (5), a charge transport layer (2), and a charge generation layer (3) on a conductive substrate (1).
This figure shows a structure in which a surface protection layer (4) and a surface protection layer (4) are sequentially laminated. In other words, it corresponds to the configuration in which an intermediate layer and a surface protective layer are provided in the configuration shown in FIG. It is also possible to provide a layer and a surface protective layer.

In the present invention, the intermediate layer and the surface protective layer are not particularly limited in terms of material or manufacturing method, and can be appropriately selected as long as a predetermined purpose can be achieved. An a-C film according to the invention may also be used. However, if the material used is, for example, an insulating material as described in the conventional example, the film thickness must be kept at 5 μm or less to prevent generation of residual potential.

The charge transport layer of the photoreceptor according to the present invention decomposes molecules in a gas phase by discharge decomposition under reduced pressure, and diffuses active neutral species or charged species contained in the generated plasma atmosphere onto the substrate, using electric force or magnetic force. It is preferable that the polymer be generated by a so-called plasma polymerization reaction, which is induced by force or the like and deposited as a solid phase by a recombination reaction on a substrate.

FIG. 7 shows a photoconductor manufacturing apparatus according to the present invention, and in the figure (701) to (706) are first to sixth tanks in which the raw material compound and carrier gas, which are in a gas phase at room temperature, are sealed, respectively. The tanks are the first to sixth control valves (707)
〜(712) and the first to sixth flow rate controllers (713)〜(
718) is not connected. (719) to (721) in the figure
) are first to third containers filled with raw material compounds that are in a liquid or solid state at room temperature, and each container is heated by the first to third temperature controllers (722) to (724) for vaporization. Roughly speaking, each container has seventh to ninth control valves (725) to (727) and seventh to ninth flow rate controllers (727).
28) to (730) are disconnected. After these gases are completely mixed in the mixer (731), they are sent into the reaction chamber (733) via the main pipe (732). The pipes along the way are
Heat can be applied to the gas obtained by vaporizing the raw material compound, which is in a liquid or solid phase at room temperature, by an appropriately placed pipe heater (734) so as not to condense on the way. Inside the reaction chamber, there is a ground electrode (735) and a power application electrode (
736) are installed facing each other, and each electrode can be heated by an electrode heater (737). A high frequency power supply (739) and a low frequency power matching box (740) are connected to the power applying electrode (736) via a matching box for high frequency power (738).
), low frequency power supply (741), low pass filter (
A DC power source (743) is connected via a power source (742), 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), and the pressure inside the reaction chamber (733) can be reduced through an exhaust system selection valve (746) by a diffusion pump (747), an oil Rotary pump (748)
, or by a cooling exclusion device (749), a mechanical booster pump (750), or an oil rotary pump (748). Regarding exhaust gas, use a suitable exclusion device (
753), and then exhausted into the atmosphere. These exhaust system pipings are also heated by appropriately placed piping systems to prevent gases produced by vaporizing raw material compounds that are in a liquid or solid phase state at room temperature from condensing on the way (73
4), heat can be applied. Reaction chamber (733)
For the same reason, the reaction chamber heater (751) can be used to heat the chamber, and a conductive substrate (752) is placed on the electrodes arranged inside the chamber.
) will be installed. In FIG. 7, the conductive substrate (752)
are fixedly arranged on the ground electrode (735), but may be fixedly arranged on the power application electrode (736), or may be arranged roughly on both sides.

FIG. 8 shows another embodiment of the photoconductor manufacturing apparatus according to the present invention, which is similar to the photoconductor manufacturing apparatus according to the present invention shown in FIG. 7 except for the internal configuration of the reaction chamber (833). can be,
The appended numbers can be interpreted by replacing the 700s with 800s. In FIG. 8, the reaction chamber (83
3) A cylindrical conductive substrate (852) which also serves as the ground electrode (735) in FIG. 7 can be installed inside, and an electrode adder P8 (837) is arranged inside. A similarly cylindrical power application electrode (836) is arranged around the conductive substrate (852), and an electrode heater (837) is arranged outside. The conductive substrate (852) is rotatable using an external drive motor (854).

The reaction chamber used for photoreceptor production is preliminarily heated by a diffusion pump.
The pressure is reduced to about 0-4 to 1 O-6 Torr, and the degree of vacuum is checked and the gas adsorbed inside the device is removed. At the same time, an electrode heater heats the electrode and the conductive substrate fixedly disposed on the electrode to a predetermined temperature. If necessary, an undercoat layer or a charge generation layer may be provided in advance on the conductive substrate in order to obtain a desired photoreceptor structure from among those described above. The present apparatus or a separate apparatus may be used to provide the undercoat layer or the charge generation layer. Next, raw material gases consisting of hydrocarbons and alkali metal compounds are introduced into the reaction chamber from the first to sixth tanks and the first to third containers while being kept at a constant flow rate using the first to ninth flow rate controllers, and the pressure is increased. A control 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 the a-C film according to the present invention as a charge transport layer.

This a-C film contains at least an alkali metal atom as a chemical modifier in an amorphous solid composed of carbon atoms and hydrogen atoms produced by the present invention at a rate of 0.1% relative to all constituent atoms.
This film is specially designed to contain 10 to 10 atomic percent. Next, the first to ninth control valves are closed to sufficiently exhaust the inside of the reaction chamber. If the desired photoreceptor configuration is obtained, the vacuum in the reaction chamber is broken and the photoreceptor according to the present invention is taken out from the reaction chamber. Furthermore, if a charge generation layer or an overcoat layer is required in the desired photoreceptor configuration, this device can be used as is, or these layers can be removed by breaking the vacuum and transferring to another device. to obtain a photoreceptor according to the present invention.

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

^Production 1 Using the manufacturing apparatus according to the present invention, as shown in FIG.
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided in this order.

Charge transport layer forming step: (CTL step) In the glow discharge decomposition apparatus shown in FIG.
) After creating a high vacuum of about 10-εTorr inside the first, second, and fourth control valves (7o7.708 and 71
0), hydrogen gas from the first tank (701), acetylene gas from the second tank (702), and nitrous oxide gas from the fourth tank (704), each at an output pressure of 1°0K.
g/cm2 under the first, second, and fourth flow controllers (7
13, 714, and 716). at the same time,
From the first container (719), the lithium tertiary-butylade gas was sublimed from the solid under the temperature of the first temperature controller (722) of 180°C, and was caused to flow into the seventh flow rate controller (728).

Then, adjust the scales of each flow rate controller to set the hydrogen gas flow rate to 40 sec and the acetylene gas flow rate to 40 sccm.
q Increase the flow rate of lithium tertiary-butyrad gas to 2.
8 sec1 and the flow rate of nitrous oxide gas 40 sec
The mixture was set so as to flow 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 0.5 Torr. On the other hand, as the conductive substrate (752), fir 5
A high frequency power source (739) using an aluminum substrate measuring 0 x width 50 x thickness 3 mm was heated to 200°C and connected in advance with a connection selection switch (744) with the gas flow rate and pressure stable. and applied a power of 200 Watts to the power application electrode (736) at a frequency of 13.5.
A plasma polymerization reaction was performed for about 3 hours by applying a frequency of 6 MHz, and a 10° 2 μm thick a was formed on the conductive substrate (752).
-C film was formed as a charge transport layer.

After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

CHN quantitative analysis was performed on the a-CPA obtained as above, and the amount of hydrogen atoms contained was 4.4 at% based on the total amount of carbon atoms and hydrogen atoms, roughly based on Auger analysis. The alkali metal atoms contained, i.e.
The amount of lithium atoms was 2.1 at% and the amount of oxygen atoms was 1.5 at% based on the total constituent atoms.

Charge generation layer forming step: (CGL step) Next, the first
Control valve (707), fourth control valve (710), and sixth control valve
Release the FA control valve (712) and supply hydrogen gas from the first tank (701), nitrous oxide gas from the fourth tank (704), and silane gas from the sixth tank (706) under an output pressure of IKg/cm2. 1st and 6th flow control devices (71
3,716, and 718). Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 100 sec.
The flow rate of cms nitrous oxide gas was set to 0.5scam and the flow rate of silane gas was set to 60sec, and the reaction chamber (
733). 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 conductive substrate (752) on which the a-C film is formed is heated to 20oC, and with the gas flow rate and pressure stabilized,
A power of 100 Watts was applied to the power application electrode (736) at a frequency of 13.56 MHz from the high frequency power source (739) to generate glow 1'J and electricity. This discharge is 20
This was carried out for 1 minute to form a 0.4 μm thick a-Si:H charge generation layer.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, the maximum charging potential (hereinafter referred to as Vmax) was -6
00V, that is, the total photoreceptor film thickness is 10.6 μm, so the charging capacity per 1 μm (hereinafter referred to as C, A) is extremely high at 56.6V, and from this, it has sufficient charging performance. Things were understood. Also, Vmax in the dark
The time required for the dark decay from the surface potential to 90% of Vmax (hereinafter referred to as Td) was about 15 seconds, and from this it was understood that it had sufficient charge retention performance. In addition, after initial charging to Vmax, V
The amount of light required to attenuate the brightness to a surface potential of 20% of max (hereinafter referred to as E) is 1. Flux・
It was understood from this that it had sufficient photosensitivity performance. Furthermore, when the surface potential was measured as a residual potential (hereinafter referred to as Vr) when irradiated with white light at 80 lux/second, it was found to be -10 V, which was found to be extremely good.

Furthermore, similar measurements were carried out after 3 months had passed since the fabrication, and it was found that Vmax' (hereinafter, symbols with ゛ are the measurements that are meant when the respective ゛ is not attached). ) is -580V
It was understood that there was almost no change in charging performance. Further, Td° was approximately 10 seconds, which indicates that the charge retention performance was hardly changed. Also, E
o was 1.4 lux·sec, Vr' was -8 V, and it was understood that good conditions were maintained with almost no change.

From the above, it is understood that the photoreceptor according to the present invention shown in this example has excellent performance, and when its stability over time and measurement errors are taken into account, it is second to none. Further, when an image was formed and transferred to this photoreceptor using the commonly used Carlson process, a clear image was obtained.

In the CTL process, the flow rate of the inflowing lithium tertiary butyrad gas is adjusted by adjusting the temperature of the first temperature controller (722) and the opening degree of the valve of the seventh flow rate controller (728). , respectively 2.4 (Example 2), 2.0 (Example 3), 1.5 (Example 4), 1.0 (Example 5) scc
A photoreceptor according to the present invention was produced in the same manner as in Example 1 except that m was used. When CHN quantitative analysis was performed on the a-C film obtained here, the amount of hydrogen atoms contained was 44.4% relative to the total amount of carbon atoms and hydrogen atoms.
7.45.5o atomic %, and from a rough Auger analysis, the amount of alkali metal atoms contained, that is, lithium atoms, is 1.7.1.2.0.7.0.3, respectively, based on the total constituent atoms.
Atomic % and oxygen atom ratio are respectively 1.5.1.4.1.3.
It was 1.3 at%. In addition, the film thickness of the a-C film is
7'10.12.3.11.4.10.8 μm.

Characteristics: When the obtained photoreceptor was used in a conventional Carlson process, VmaX was -600, -650, and -65, respectively.
0 and -650V, that is, the total photoreceptor film thickness is 10V, respectively.
．． 4.12.7.11°8.11.2μm, so C and A are 57.7.51.2.55.1.58 respectively
．． The OV was extremely high, and from this it was understood that it had sufficient charging performance. Moreover, Td is about 15.20.
20.20 seconds, and from this it was understood that it had sufficient charge retention performance. Also, E is 1.8.2, respectively.
4.3.1.3. flux seconds, and from this it was understood that it had sufficient photosensitivity performance. Also, Vr
It was understood that the values were -15, -15, -15, and -10, respectively, which were sufficiently good.

Roughly, Vmax', C, A,', Td', El, V
For rl, values almost equivalent to these were also obtained within the measurement error range.

From the above, the photoreceptor according to the present invention shown in this example has excellent performance and is also excellent in stability over time. Further, when an image was formed and transferred to this photoreceptor using the commonly used Carlson process, a clear image was obtained.

A photoreceptor according to the present invention was produced in the same manner as in Example 1, except that in the CTL process, the flow rate of the inflowing lithium tertiary-butylade gas was set to 0.5 seconds. When @CHN quantitative analysis was performed on the a-C film obtained here, the amount of hydrogen atoms contained was 53 at% based on the total amount of carbon atoms and hydrogen atoms, and furthermore, Auger analysis revealed that the amount of hydrogen atoms contained was 53 at%. The amount of alkali metal atoms, ie, lithium atoms, was 11 atomic % of O and the amount of oxygen atoms was 1.2 atomic % based on all the constituent atoms. Moreover, the film thickness of the a-C film is 10
．． It was 1 μm.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, VmaX was -650, that is, since the total photoreceptor film thickness was 10.5 μm, C and A were 61.
The voltage was extremely high at 9V, and from this we could understand that it had sufficient charging performance. Furthermore, the Td was approximately 25 seconds, and from this it was understood that it had sufficient charge retention performance.

Moreover, E was 10.5 lux town seconds, and from this it was understood that although the sensitivity was slightly lower than that of Examples 1 to 5, it had a practically sufficient photosensitivity performance.

Furthermore, in the photoreceptors according to the present invention shown in Examples 1 to 5,
While almost no difference was observed between E and Eo, the Eo of the photoreceptor in this example was reduced to 20.6 lux·sec, which is within a range that poses no problem for practical use.
A decrease in sensitivity over time was observed.

From the above, the photoreceptor according to the present invention shown in this example has performance as a photoreceptor. Further, when an image was formed and transferred to this photoreceptor using a commonly used Carlson process, an image was obtained.

Comparative Example I A laminated film was produced in the same manner as in Example 1 except that the flow rate of lithium tertiary-butylade gas was 0.2 sec in the CTL process.

When CHN quantitative analysis was performed on the a-C film obtained here, the amount of hydrogen atoms contained was 53 at% with respect to the total amount of carbon atoms and hydrogen atoms, and roughly from Auger analysis, the amount of oxygen atoms was The amount was 1.2 at% based on the total constituent atoms. On the other hand, lithium atoms could not be detected and were less than 0.1 atomic %, which is the detection limit of the Auger analyzer. Also, a
The thickness of the -C film was 12.5 μm.

Characteristics: When the obtained laminated film was used in a commonly used Carlson process, Vmax was -700V, that is, since the total photoreceptor film thickness was 12.9 μm, C and A were 56. O
This is very similar to V, and from this it can be understood that it has sufficient charging performance. Furthermore, the Td was approximately 25 seconds, and from this it was understood that it had sufficient charge retention performance. But °, E is 16. The flux was relatively low at seconds, and the Vr was relatively high at -40V.

When we roughly measured ET, we found that the half potential was not reached even when using a white light intensity of 80 lux sec.
No measured value was obtained, and Vr' was as high as -350.

From the above, it was concluded that the laminated film shown in this example showed significant deterioration in sensitivity over time and did not have the performance as a practical photoreceptor. Furthermore, when images were formed and transferred using the commonly used Carlson process for this laminated film at a high exposure dose, only images with so-called fog were obtained, and after 3 months, no image was formed. It was not possible to obtain an image. From this, it can be understood that the effect of stabilizing sensitivity by adding alkali metal atoms in the present invention is understood.

Example 7 In the CTL process, the flow rate of nitrous oxide gas was set to 58cc.
A photoreceptor according to the present invention was produced in the same manner as in Example 5 except that m was used. CHN for the a-C film obtained here
Quantitative analysis revealed that the amount of hydrogen atoms contained was 50 at% based on the total amount of carbon atoms and hydrogen atoms, and Auger analysis revealed that the amount of alkali metal atoms, that is, lithium atoms, contained in the total composition was 50%. 0.3 atomic% to atoms
, the amount of oxygen atoms was 0.2 at.%. Also, a-C
The film thickness of the film was 9.3 μm.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, Vmax was -650, that is, since the total photoreceptor film thickness was 9.7 μm, C and A were 67 and OV
It was understood from this that it had sufficient charging performance. Furthermore, the Td was approximately 15 seconds, and from this it was understood that it had sufficient charge retention performance. Also, E is 2. The flux seconds and vr were good at -10V. On the other hand, Vmax' changed to -550 V, C3A, ° changed to 56.7, and Td' changed to 8 seconds, all of which showed a slight tendency for performance to deteriorate over time due to a decrease in the amount of oxygen atoms. It was just a non-issue.

From the above, the photoreceptor according to the present invention shown in this example.

has the performance as a photoreceptor. Further, when an image was formed and transferred to this photoreceptor using a commonly used Carlson process with a high charger output, an image was obtained.

Comparative Example 2 A Kinuta film was produced in the same manner as in Example 5, except that nitrous oxide gas was not introduced in the CTL process.

When CON quantitative analysis was performed on the a-C film obtained here, the amount of hydrogen atoms contained was 51 atomic% based on the total amount of carbon atoms and hydrogen atoms. The amount of metal atoms, ie, lithium atoms, was 0.3 atoms (96) with respect to all constituent atoms, and no oxygen atoms were detected. In addition, the thickness of the obtained a-C film is
It was 11.3 um.

Characteristics: When the obtained laminated film was used in a commonly used Carlson process, VmaX was -600 and it was stable. That is, since the total photoreceptor film thickness was 11.7 μm, C and A were 51.3.
V, which is extremely high, and from this fact it was concluded that it had sufficient charging performance. Furthermore, the Td was approximately 20 seconds, which indicates that it has sufficient charge retention performance. Further, E was 2.9 lux·sec, and Vr was -10 V, which were good. However, Vmax' is -300V, C.

A, ゛ was 25.6 V, Td' was 3 seconds, and in both cases, compared to Example 5, there was a marked tendency for charging performance to deteriorate over time due to the absence of oxygen atoms.

From the above, the laminated film shown in this example had poor stability as a photoreceptor, and was not practical. Moreover, even if an image is formed and transferred using a conventional Carlson process with a high charger output three months after its production, only an extremely low-density image can be obtained from this laminated film. It was understood that it could not be used as a practical photoreceptor.

From these facts, it is understood that in the present invention, the addition of oxygen atoms stabilizes the charging performance.

Immediately after implementation, a photoreceptor according to the present invention was manufactured using a manufacturing apparatus according to the present invention, in which a conductive substrate, a charge transport layer, and a charge generation layer were provided in this order, as shown in FIG.

CTL process: In the glow discharge decomposition apparatus shown in FIG.
08), hydrogen gas is released from the first tank (701),
and acetylene gas from the second tank (702) into the first and second flow rate controllers (713 and 714) under an output pressure of 1.0 Kg/cm2, respectively, and simultaneously through the seventh and eighth control valves. (725, and 726) and release the first container (
719) to the cyclohexanone gas from the first temperature controller (72
2) At a temperature of 85°C, lithium tertiary-butyrad gas is supplied from the second container (720) to the second temperature regulator (720).
23) Flowed into the eighth flow controller (729) at a temperature of 185°C. Adjust the scale of each flow controller,
The flow rate of hydrogen gas is set to 40 seconds, the flow rate of acetylene gas is set to 40 seconds, the flow rate of lithium tert-butylade gas is set to 5 sccrr+, and the flow rate of cyclohexanone gas is set to 20 seconds, and the flow rate is set to 40 seconds, and the flow rate of cyclohexanone gas is set to 20 seconds. (732) from the reaction chamber (73
3) It flowed into the interior. 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, a conductive substrate (75
For 2), use an aluminum board of 50 x 50 x 3 mm thick, heat it to 200°C in advance, and with the gas flow rate and pressure stable, connect the connection selection switch (
744) connected to the low frequency power supply (741>
and applied 200W to the power application electrode (736).
A plasma polymerization reaction was carried out for about 35 minutes by applying electric power at a frequency of 120 KH2 to form a 16 μm thick a-C film as a charge transport layer on the conductive substrate (752).

After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

Quantitative analysis of the a-CM'A Niki cHN obtained as described above revealed that the amount of hydrogen atoms contained was 40 at% based on the total amount of carbon atoms and hydrogen atoms, roughly based on Auger analysis. From the alkali metal atoms contained, i.e.
The amount of lithium atoms was 3.9 at% and the amount of oxygen atoms was 4.7 at% based on the total constituent atoms.

CGL process: Next, a charge generation layer was formed in the same manner as in Example 1.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, Vmax was -650 mm, that is, since the total photoreceptor film thickness was 16.4 μm, C and A were 39.6.
V, which is extremely high, and from this we can understand that it has sufficient charging performance. Furthermore, the Td was approximately 25 seconds, and from this it was understood that it had sufficient charge retention performance. In addition, E was 6.3 lux·sec, and it was understood that the film had suitable photosensitivity performance. In addition, Vr is low at -10V (
, I understand that it is good.

In the Carlson process commonly used for this photoreceptor,
When an image was created and transferred, a clear image was obtained.

A photoreceptor of the present invention was produced in the same manner as in Example 8, except that the flow rate of cyclohexanone gas during the application was 30 sec cm. When the obtained a-C film was subjected to CHN quantitative analysis, the amount of hydrogen atoms contained was 38 at% based on the total amount of carbon atoms and hydrogen atoms, and roughly Auger analysis revealed that the amount of contained alkali metal atoms was , that is, the amount of lithium atoms is 3.9 at% based on the total constituent atoms, and the amount of oxygen atoms is 7.
．． It was 0 atom%.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, Vmax was -850 mm, that is, since the total photoreceptor film thickness was 17.4 μm, C and A were 48.9.
It was understood from this figure that it had sufficient charging performance. Moreover, Td was about 30 seconds, which made it clear that it had sufficient charge retention performance. Furthermore, E was 10.2 lux·sec, which was understood to have a photosensitivity performance that, although slightly low, poses no problem in practical use. Further, Vr was -30V, which was understood to pose no practical problem. Furthermore, Eo was 13.6 lux·sec, which was understood to pose no practical problem.

In the Carlson process commonly used for this photoreceptor,
When an image was created and transferred, an image was obtained.

A laminated film was produced in the same manner as in Example 8, except that the flow rate of comparative cyclohexanone gas was 60 sec, and the temperature of the first temperature controller (722) was 90°C.

When CHN quantitative analysis was performed on the a-C film obtained here, the amount of hydrogen atoms contained was 37 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of metal atoms, i.e. lithium atoms, is 3.8 at% based on the total constituent atoms, and the amount of oxygen atoms - u
lo, 3 at.%. Moreover, the film thickness of the obtained a-C film was 18 μm.

Characteristics: When the obtained laminated film was used in a commonly used Carlson process, Vmax was -750V, that is, since the total film thickness was 18.4 μm, COA was extremely high at 40.8V. It was understood that it had sufficient charging performance. Furthermore, the Td was approximately 30 seconds, and from this it was understood that it had sufficient charge retention performance. but,
E is 35.4 lux·sec, and the sensitivity is very low.
Furthermore, Vr was as high as 1,100 square meters, and it was concluded that the laminated film obtained here did not have practical photoreceptor performance.

From these facts, it is understood that in the photoreceptor of the present invention, addition of excessive oxygen atoms is not necessarily suitable.

X journey example 1p Lithium tertiary-butyrad gas flow rate 8 seconds
A photoreceptor of the present invention was produced in the same manner as in Example 1, except that m was used. When CHN quantitative analysis was performed on the obtained a-C film, the amount of hydrogen atoms contained was 42 at% based on the total amount of carbon atoms and hydrogen atoms, and roughly Auger analysis revealed that the amount of contained alkali metal atoms was 42 at% based on the total amount of carbon atoms and hydrogen atoms. That is, the amount of lithium atoms is 5.5% relative to all constituent atoms. ○ atomic%, the amount of oxygen atoms was 1.6 atomic%.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, Vmax was -650 mm, that is, since the total photoreceptor film thickness was 11.2 μm, C and A were 58. O
V, which is extremely high, and from this we can understand that it has sufficient charging performance. Furthermore, the Td was approximately 15 seconds, and from this it was understood that it had sufficient charge retention performance. In addition, E was 1.1 lux·sec, and it was reasonable that the film had suitable photosensitivity performance. In addition, Vr is low at 15■,
It was understood that it was good.

In the Carlson process commonly used for this photoreceptor,
When an image was created and transferred, a clear image was obtained.

Daitabikai J1 Lithium tertiary-butyrad gas flow rate 15se
A photoreceptor of the present invention was produced in the same manner as in Example 1, except that the acetylene gas flow rate was 20 SC cm, and the a-C film formation time was 4 hours and 30 minutes. When the obtained a-C film was subjected to CHN quantitative analysis, the amount of hydrogen atoms contained was 43 at% based on the total amount of carbon atoms and hydrogen atoms, and roughly Auger analysis revealed that the amount of contained alkali metal atoms was 43 at% based on the total amount of carbon atoms and hydrogen atoms. , that is, the amount of lithium atoms is 1 for all constituent atoms.
The amount of oxygen atoms was 1.9 at%.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, Vmax was -450V, that is, since the total photoreceptor film thickness was 10.2 μm, C and A were 44. I
V, which is extremely high, and it was understood from this that it had sufficient charging performance. Furthermore, the Td was approximately 10 seconds, which indicates that the material has sufficient charge retention performance. In addition, E was 0.9 lux·sec, and it was understood that it had suitable photosensitivity performance. In addition, Vr was as low as -5V, which was understood to be good. On the other hand, VmaX゛ is -400
VSTd' was about 8 seconds, and although there was a tendency for the charging ability to decrease as the amount of alkali metal atoms increased, it was understood that there was no problem in practical use.

In the Carlson process commonly used for this photoreceptor,
When an image was created and transferred, an image was obtained.

A photoreceptor of the present invention was produced in the same manner as in Example 3, except that the CTL process and the CGL process were replaced. Quantitative CHN analysis of the resulting a-C film revealed that the amount of hydrogen atoms contained was 44 at% based on the total amount of carbon atoms and hydrogen atoms, and roughly Auger analysis revealed that the amount of alkali metal atoms contained was 44 at%. That is, the amount of lithium atoms was 1.3 at% and the amount of oxygen atoms was 1.4 at% based on all constituent atoms.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, Vmax was -650 μm, that is, although the total photoreceptor film thickness was 12.5 μm, C and A were 52. O
V, which is extremely high, and from this fact it was concluded that it had sufficient charging performance. Further, Td was about 20 seconds, which indicates that it has sufficient charge retention performance. In addition, E was 3.8 lux·sec, and it was understood that it had suitable photosensitivity performance. In addition, Vr is low at -20V,
It was understood that it was good.

In the Carlson process commonly used for this photoreceptor,
When an image was created and transferred, an image was obtained. From this, it is understood that the photoreceptor of the present invention can be manufactured even if the product N configuration is changed.

Example 2 except that potassium acrylate gas was used instead of lithium tert-butylade gas, the flow rate was 1 sec, and the temperature of the first temperature controller (722) was 230°C.
A photoreceptor of the present invention was produced in the same manner as described above. Obtained a −
Quantitative analysis of CHN on a C film revealed that the amount of hydrogen atoms contained was 3% compared to the total amount of carbon atoms and hydrogen atoms.
Further, Auger analysis revealed that the amount of alkali metal atoms contained, that is, potassium atoms, was 0.8 at%, and the amount of oxygen atoms was 1.4 at%, based on the total constituent atoms.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, VmaX was -650V, that is, since the total photoreceptor film thickness was 10.5 μm, C and A were 61.9.
V, which is extremely high, and it was understood from this that it had sufficient charging performance. Furthermore, the Td was approximately 15 seconds, and from this fact it was understood that it had sufficient charge retention performance. In addition, E was 2.5 lux·sec, and it was understood that it had suitable photosensitivity performance. In addition, ■r is low at -20V,
It was understood that it was good.

Furthermore, Vmax', C, A,', Td', ET, V
, l, values almost equivalent to these were obtained within the measurement error range.

In the Carlson process commonly used for this photoreceptor,
When an image was created and transferred, a clear image was obtained. From this, it is understood that the photoreceptor of the present invention can be produced regardless of the type of alkali metal atom.

Example 14 Using a photoreceptor manufacturing apparatus according to the present invention, a photoreceptor of the present invention having a conductive substrate, a charge generation layer, and a charge transport layer provided in this order as shown in FIG. 2 was manufactured, and the CGL process: A vapor-deposited film of aluminum chlorophthalocyanine chloride AlClPc (C1) was deposited using a conventional vacuum vapor deposition method under conditions of a boat temperature of 450 to 490°C, a vacuum degree of 5X10-5 to 1X10-' Torrs, and a deposition time of about 10 minutes using about 1,000 people. It was provided with a film thickness of . Roughly, solvent treatment was performed with THF vapor for 30 minutes.

CTL process: In the glow discharge decomposition apparatus shown in FIG. 70
8, and 710), hydrogen gas from the first tank (701), butadiene gas from the second tank (702),
Nitrous oxide gas was then flowed from the fourth tank (704) into the first, second, and fourth flow rate controllers (713, 714, and 716) under an output pressure of 1°0 Kg/am 2 . At the same time, lithium tertiary-butyrad gas is supplied from the first container (719) to the first temperature regulator (722) at a temperature of 180.
While sublimating from the solid at ℃, the 7th flow rate control device (
728).

Then, adjust the scales of each flow rate controller to set the hydrogen gas flow rate to 40 seconds and the butadiene gas flow rate to 40 seconds.
, the flow rate of lithium tertiary-butylade gas was 2.8
secm, and the flow rate of nitrous oxide gas is set to 40 sec, via an intermediate mixer (731),
It flowed into the reaction chamber (733) from the main pipe (732). After each flow rate became stable, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) was 0.5 Torr. On the other hand, as the conductive substrate (752), A
Fir 5OX horizontal 50 with vapor deposited film of lClPc (CI)
An aluminum substrate with a thickness of
41) and apply 120W to the power application electrode (736).
Applying a power of 11 at a frequency of 150KHz to approximately 15
A conductive substrate (752) is subjected to a plasma polymerization reaction for a minute.
Thick on top? An a-C film with r7.3 μm was formed as a charge transport layer. After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (733) was sufficiently evacuated.

CHN quantitative analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms contained was 42 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of alkali metal atoms, ie, lithium atoms, contained was 1.9 at.%, and the amount of oxygen atoms was 2.2 at.% based on the total constituent atoms.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, Vmax was -600V, that is, since the total photoreceptor film thickness was 7.4 μm, C and A were 81. IV
It was understood from this that it had sufficient charging performance. Furthermore, the Td was approximately 15 seconds, and from this it was understood that it had sufficient charge retention performance. Also, E is 1. flux seconds, and from this fact it was understood that it has sufficient photosensitivity performance. Also, Vr is -1
It was understood that the voltage was 0V, which was extremely good. Furthermore, using semiconductor data light with an emission wavelength of 780 nm as the exposure source,
When I measured the sensitivity in the same way as E, it was 6.2er.
g/am2, and was understood to have sufficient sensitivity even in the long wavelength range.

From the above, it is understood that the photoreceptor according to the present invention shown in this example has excellent performance and can be manufactured even if the type of charge generation layer is changed. In addition, when an image was formed and transferred on this photoreceptor using the commonly used Carlson process, it was found that the image was clear regardless of whether white light was used as the exposure source or semiconductor laser light was used as the exposure source. was gotten.

Once the X treatment is performed, as shown in FIG.
A photoreceptor of the present invention was prepared in which a conductive substrate, a charge transport layer, and a charge generation layer were provided in this order.

CTL process: In the glow discharge decomposition apparatus shown in FIG. ，
8o8, and 810), and the first tank (801)
hydrogen gas, acetylene gas from the second tank (802), and nitrous oxide gas from the fourth tank (804) at an output pressure of 1. .

It was allowed to flow into the first, second and fourth flow controllers (813, 814 and 816) under OKg/cm2. At the same time, while sublimating lithium tert-butylade gas from the solid from the first temperature controller (822) at a temperature of 180°C from the first container (819), the seventh flow rate controller (828)
It flowed inside.

Then, adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 200 sccrr+ and the acetylene gas flow rate to 120 sccrr+.
secm, the flow rate of lithium tert-butylade gas is 2.8 sccrr+1 and the flow rate of nitrous oxide gas is 4.
Set it so that it is 0 sec, and mixer (831
) into the reaction chamber (833) from the main pipe (832). After each flow rate stabilizes, the reaction chamber (833
) so that the pressure in ( ) becomes 0.5 Torr.
845) was adjusted. On the other hand, as the conductive substrate (852), a cylindrical aluminum substrate with a diameter of 80 mm and a length of 330 mm is used. It is heated to 180°C in advance, and the connection selection switch (852) is heated in advance to 180°C.
The high frequency power source (839) connected to the conductive substrate (44) is turned on, and a power of 250 Watts is applied to the power application electrode (836) at a frequency of 13.56 MHz to perform a plasma polymerization reaction for about 3 hours. 852), a 13.3 μm thick a-C film was formed thereon as a charge transport layer.

After the film formation was completed, power application was stopped, the control valve was closed, and the inside of the reaction chamber (833) was sufficiently evacuated.

CHN quantitative analysis was performed on the a-C film obtained as described above, and the amount of hydrogen atoms contained was 35 at% based on the total amount of carbon atoms and hydrogen atoms. The amount of alkali metal atoms, ie, lithium atoms, contained was 2.5 at.%, and the amount of oxygen atoms was 1.5 at.% based on the total constituent atoms.

CGL process: Next, the first control valve (807) and the fourth control valve (810
), and the sixth control valve (812) are released, and the first tank (
801), hydrogen gas from the fourth tank (804), nitrous oxide gas from the fourth tank (804), and sixth tank (804). Silane gas was flowed from the tank (806) into the first and sixth flow controllers (813, 816 and 818) under an output pressure of IKg/cm2. Adjust the scale of each flow rate controller to increase the hydrogen gas flow rate to 2.
00sec, nitrous oxide gas flow rate 1.0sec
, and the flow rate of silane gas were set to 101005e and allowed to flow into the reaction chamber (833). After each flow rate became stable, the pressure control valve (845) was adjusted so that the pressure inside the reaction chamber (833) was 1.0 Torr. On the other hand, a-
The conductive substrate (852) on which the C film is completely formed is 180
℃, and with the gas flow rate and pressure stable, a power of 200 Watt was applied to the power application electrode (836) at a frequency of 13.56 MHz from the high frequency power source (839) to generate a glow discharge. . This discharge was carried out for 15 minutes to form an a-Si:H charge generation layer having a thickness of 0.4 μm.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, Vmax was -650V, which was 2. That is, the total photoreceptor film thickness was 13.7 μm, so C and A were 47.
The voltage was extremely high at 4V, and from this it was understood that it had sufficient charging performance. Furthermore, the Td was approximately 10 seconds, and from this it was understood that the film had sufficient charge retention performance.

Moreover, E was 1.2 lux·sec, and from this it was understood that the film had sufficient photosensitivity performance. In addition, it was understood that ■r was -10V, which was extremely good.

From the above, it is clear that the photoreceptor according to the present invention shown in this example has excellent performance and can be manufactured even if the substrate shape is changed. Further, when this photoreceptor was mounted on a Minolta Camera Co., Ltd. EP6502 and an image was formed and transferred, a clear image was obtained.

[Brief explanation of the drawing]

1 to 6 are drawings showing the structure of a photoreceptor according to the present invention, and FIGS. 7 to 8 are drawings showing an apparatus for manufacturing a photoreceptor according to the present invention. Applicant: Minolta Camera Co., Ltd. Figure 1 Figure 3 Figure 5 Figure 2 Figure 4 Figure 6

Claims (1)

[Claims] In a photoreceptor having a charge generation layer and a charge transport layer, the charge transport layer is an amorphous solid formed by plasma polymerizing hydrocarbons in a gas phase and whose constituent atoms are carbon and hydrogen, and Contains at least an alkali metal atom and an oxygen atom as chemical modifiers, and the content thereof is 0.1 to 10 at% of alkali metal atoms and 7 at% or less of oxygen atoms based on all constituent atoms. photoreceptor.