JPS63169655A - Photosensitive body - Google Patents

Abstract

PURPOSE:To improve the electric chargeability of an electric charge transfer layer and to stabilize the charge transferability thereof for a long period of time by using an amorphous solid which is formed by subjecting a hydrocarbon to a plasma polymn. in a vapor phase then to an acid treatment as the charge transfer layer. CONSTITUTION:The amorphous solid which is formed by subjecting the hydrocarbon to the plasma polymn. in the vapor phase then to the acid treatment and contains C and H as constituting atoms, is used as the charge transfer layer of a separated- function type photosensitive body. The charge transfer layer is formed by the following method. The inside of a reaction chamber 733 of a glow discharge device is first evacuated to a high vacuum, and the gaseous hydrogen from a 1st tank 701, the gaseous ethylene from the 2nd tank 702 and the styrene from a 1st vessel 719 are so set as to attain a prescribed flow rate and are admitted via a mixer 731 into the chamber 733. Electric power of a prescribed frequency is then impressed to an electric power impressing electrode 736 to execute the plasma polymn. so that the film of a desired thickness is deposited on an Al substrate 752. The above-mentioned film is then taken out of the chamber 733 and is subjected to the acid treatment to form the charge transfer layer. An electric charge generating layer is thereafter formed on the charge transfer layer.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a photoreceptor having a charge transport layer made of an amorphous carbon source.

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

The main problems with conventional photoreceptor materials include inorganic substances such as amorphous selenium, selenium arsenide, selenium tellurium, cadmium sulfide, zinc oxide, and amorphous silicon, polyvinyl carbazole, metal phthalocyanine, disazo pigments, and 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 binding material, and a laminated structure in which a charge generation layer and a charge transport layer are provided for each function. Can be mentioned.

However, each of the photoreceptor materials that have been used for some time has 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 a photoconductor 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 above-mentioned materials had poor durability and many unstable factors in terms of performance.

In order to eliminate these drawbacks, in recent years, amorphous silicon, which can be produced by a glow discharge method, has been increasingly applied to 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. Also, while it requires a large amount of silane gas,
Since the gas is expensive, 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, in recent years, it has been proposed to use a plasma organic polymer film as a photoreceptor.

Plasma organic polymerized films themselves have been known for a long time, such as diene ()LShen) and bell (A, T, Be1l).
) et al., Journal of Applied Polymer Science (1973)
plied Polymer 5ience) Vol.
American Chemical Society (America)
Plasma pol.
ymerization), its film formability has been discussed.

For example, JP-A-59-28161 discloses a photoreceptor in which a plasma-polymerized polymer layer having a mesh structure is provided on a substrate as a blocking layer and an adhesive layer, and an amorphous silicon layer is provided thereon. ing. Tokukai Showa 6
Publication No. 0-63541 discloses a photoreceptor in which a diamond-like carbon pattern 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 said that the film thickness is preferably 2 .mu.m or less in terms of resistance to cracking and residual charge.

Problems to be Solved and Solved by the Invention As mentioned above, plasma organic polymer films produced by conventional methods are used only for applications assuming insulation properties, that is, they are inferior to ordinary polyethylene films. Gotoku 1016Ωcm
It was considered to be an insulating film having a certain specific resistance, or at least was used with the recognition that it was such a film. 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. Therefore, it can only be used as an extremely thin film with a thickness of about 5 μm at most, and carriers either pass through the film by tunnel effect or
When a tunneling effect cannot be expected, only a thin film that does not pose a problem as a residual potential in practical use is used.

In the SLL type photoreceptor, the charge↑fl layer transport must have excellent carrier transport properties, and the carrier mobility must be at least 10'' [cm2/V/s eC].
The above value is required. In addition, in order to suitably use it in an electrophotographic system, it must have excellent charging performance, and a withstand voltage of at least 10 [V/μm] or more is required.
In order to roughly reduce the load on the charger, the relative dielectric constant ε is set to 6.
It is preferable to have the following values.

Means for Solving the Problems The present invention provides a functionally separated photoreceptor having a charge generation layer and a charge transport layer, in which the charge transport layer is formed by plasma polymerizing hydrocarbons in a gas phase and then acid treatment. The present invention relates to a functionally separated photoreceptor characterized by being an amorphous solid consisting of carbon and hydrogen as constituent atoms. Although the charge transport layer does not have clear photoconductivity with respect to visible light or light with a wavelength near semiconductor laser light, it stably provides suitable charge transport properties over a long period of time, and generally has charging ability, Because it has excellent photoreceptor performance such as durability, weather resistance, and environmental pollution resistance, and is also excellent in light transmission, it can be used especially when forming a laminated structure as a function-separated photoreceptor (indeed, it provides a high degree of freedom). It is something that can be done.

While considering the application of plasma organic polymer films to photoreceptors, the present inventors found that organic polymer films, which were originally thought to be insulating, were found to be difficult to apply after plasma polymerization of hydrocarbons in the gas phase. found that an amorphous carbon film made of carbon and hydrogen atoms formed by acid treatment has a low resistivity and can easily provide charge transport properties. There are many unclear points in the theoretical interpretation, and it is not possible for the present inventor to comment on it in detail. It is presumed that many electrons, unpaired electrons, residual free radicals, etc. exist in the structure and effectively contribute to charge transport properties. Generally speaking, a film that is simply plasma-polymerized is structurally unstable and prone to deterioration over time due to its electrostatic properties, but by adding acid treatment, this deterioration over time is eliminated and Irl electrical properties are stable over a long period of time. (Hereinafter, the charge !5+ layer transport layer according to the present invention will be referred to as an a-C film).

In the present invention, at least one type of hydrocarbon is used as an organic gas for forming the a-C film. The phase state of the hydrocarbon does not necessarily have to be a gas phase at normal 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, either liquid phase or solid phase can be used. As the hydrocarbons, saturated hydrocarbons, unsaturated hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons are used.

There are many types of hydrocarbon urea 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 noxacosane, pentacosane, octacosane, nonacosane, triacontane, todoriacontane, pentatriacontane, etc., as well as isobutane, isopentane, neopentane, isohexane, neohexane, 2,3-dimethylbutane, 2-methylhexane, 3-ethylpencune, 2,2-dimethylpentane,
2,4-dimethylpentane, 3,3-dimethylpentane, tributane, 2-methylhebutane, 3-methylhebutane, 2,2-dimethylhexane, 2,2.5-dimethylhexane, 2,2.3- ) dimethylpentane, 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, a-butene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, and 2-methyl. -Olefins such as 2-butene, 1-hexene, tetramethylethylene, 1-heptene, 1-octene, 1-nonene, 1-decene, and allene, methylalene, butadiene, pentadiene, hexadiene, cyclobutadiene, etc. diolefins, and triolefins such as ocimene, allocimene, myrcene, hexatriene, and acetylene,
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, cyclopentane, cyclohexane, cyclohebutane, cyclooctane, cyclononane, cyclodecane, cyclobuntecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, and cyclohexadecane. , cycloparaffins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, etc., as well as dichloroolefins such as limonene, tervirune, phelandrene, silvestrene,
Tsuen, caren, pinene, borniline, kanghuen, fuendien, cyclofenchen, tricyclene, pisabolin, zingiberine, curcumene, humulene, kajinensesesquivenichen, selinene, caryophyllene, santarene, cedrene, kamphorin, phylloclatene, podocarprene, mirin, etc. Terpenes, 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, terphenyl, diphenylmethane, triphenylmethane,
Dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, phenanthrene, etc. are used.

The a-C film in the present invention has carbon atoms and hydrogen atoms as its 11 constituent atoms, and the amount of hydrogen atoms contained is o, 1 to 67 at%, based on the total amount of carbon atoms and hydrogen atoms.
It is preferably 30 to 60 atomic %. The amount of hydrogen atoms is 0
．． If it is less than 1 atomic %, the transport performance deteriorates and suitable photosensitivity cannot be obtained. If the amount of hydrogen atoms is higher than 67 atomic %, 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. By increasing the pressure, lowering the pressure, lowering the dilution rate of the raw material hydrocarbon gas, 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, etc. It is possible to control.

The thickness of the a-C film as a charge transport layer in the present invention is suitably 5 to 50 μm, particularly 7 to 20 μm, and 5 μm if used in a normal electrophotographic process.
If it is thinner, the charging potential will be lower (t: sufficient copy image) 4
If it is thicker than 50 μm, it is impossible to obtain a
Unfavorable 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 and contribute to bright attenuation. is possible.

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. Furthermore, examples of acids used in the acid treatment of the a-C film include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, hydrochloric acid, and boric acid. Although it varies depending on the type of acid used, examples of acid treatment methods include:
Approximately 0.01N to 1ON aqueous solution at 50℃ to 150℃
Maintain the saturated vapor pressure state at around ℃, and add the a
-〇 The membrane may be left for about 5 minutes to 3 hours. or
It is sufficient to keep an aqueous solution of O, OIN to 1ON at a temperature of about 5° C. to 35° C. and immerse it for about 1 second to 1 hour.

The charge generating layer used in the photoreceptor according to the present invention is not particularly limited and includes, for example, amorphous selenium, selenium arsenide, selenium tellurium, cadmium sulfide, zinc oxide, and optionally different elements (for example, 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, azo 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, Pyrylium compounds, quinacridone compounds, indigo compounds, polycyclic quinone compounds, disbenzimidazole compounds, induthrone compounds, squarylium compounds, etc. (real substances 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.

Furthermore, the charge generation layer is not subject to any limitations in the manufacturing method; for example, the charge transport layer (a-
It may be formed by the same manufacturing method as for C film), or by electrodeposition in a liquid phase, coating 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, as this leads to reductions in manufacturing equipment costs and process labor.

Further, as long as the charge generation layer is not affected, the acid treatment according to the present invention may be performed with the charge generation m provided.

The photoreceptor in the present invention is a separable photoreceptor consisting of 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 selected as appropriate. be.

FIG. 1 shows, as one embodiment, a structure in which a charge transport layer (2) and a charge generation layer (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, as another embodiment, a charge transport layer (2), a charge generation layer (3), and a charge transport layer (2) on a conductive substrate (1).
This figure shows a structure in which these are sequentially laminated.

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). In FIG. 2, two electrons generated in the charge generation layer (3) travel to the photoreceptor surface in the charge transport layer (2), and in the third In the figure, the charge generation layer (3)
The holes generated in the charge transport layer (2) on the conductive substrate side travel toward the conductive substrate (1), and at the same time, the electrons generated in the charge generation layer (3) travel through the charge transport layer (2) on the surface side. (2)
The light travels through the photoreceptor surface to form 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 protection layer (3) as a rough form.
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 retaining Wk layer, but for example, when the photoreceptor is A surface protective layer may also be provided for the purpose of adjusting the integrity of various elements within the copying machine, such as preventing surface contamination.

FIG. 5 shows an intermediate layer (5), a charge generation layer (3), and a charge transport layer (2) on a conductive substrate (1) as a rough form.
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 preferred to provide an intermediate layer to ensure adhesion and injection blocking effect. In the case of the configurations shown in Figures 1 and 3,
Since the bonding surface with the conductive substrate is the charge G1 transport layer according to the present invention, which has excellent adhesiveness and injection blocking effect, there is no need to provide an intermediate layer. Note that an intermediate layer may be provided for the purpose of adjusting compatibility with the manufacturing process before the formation of the photosensitive layer.

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. That is, it corresponds to the form shown in FIG. 1 with an intermediate layer and a surface protective layer provided. The reason for providing the intermediate layer and the surface protective layer is the same as described above, and therefore, providing an intermediate layer and a surface protective layer in the configurations shown in FIGS. 2 and 3 can be an alternative form.

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, nλJ5 should be 5μ to prevent residual potential from occurring.
It is necessary to keep it below m.

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 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 d 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). (719) to (721) in the figure
) are first to third containers containing raw material compounds that are in a liquid phase or in-phase state at room temperature, and each container can be heated by first to third heaters (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 (725) to (727).
28) to (730). 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 are
Heat can be applied to the gas obtained by vaporizing the raw material compound, which is in a liquid phase or the same phase state at room temperature, by an appropriately arranged pipe heater (734) so as not to condense on the way. A grounded tffl (735) and a power application electrode (736) are installed facing each other in the reaction chamber, and each electrode can be heated by an electrode heater (737). A high frequency power matching device (738) is connected to the power application electrode (736).
high frequency power supply (739L low frequency power matching box (7
A low frequency power source (741) is connected through a low-frequency power source (741) and a DC power source (743) is connected through a low-pass filter (742), and power with different frequencies can be applied by a connection selection switch (744). The pressure in the reaction chamber (733) can be adjusted by a pressure control valve 1 (745),
The pressure inside the reaction chamber (733) is reduced using the exhaust system Hiko selection valve (746).
via the expansion 11 pump (747), oil rotary pump (748), cooling exclusion device (749), mechanical booster pump (750), oil rotary pump (748)
) is carried out. The exhaust gas is further rendered safe and harmless by an appropriate exclusion device (753) before being exhausted into the atmosphere. These exhaust system piping can also be heated by 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. has been done. reaction chamber (
733) can also be heated by the reaction chamber heater (751) for the same reason, and a conductive substrate (752) is installed on the electrode arranged inside. In FIG. 7, a conductive substrate (75
2) is fixed to the ground electrode (735),
It may be fixedly disposed on the power application electrode (736) or may be disposed 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 (733). be.

In FIG. 8, a cylindrical conductive substrate (752) that also serves as the ground electrode (735) in FIG. 7 is installed inside the reaction chamber (733), and an electrode heater (737) is installed inside the reaction chamber (733).
are arranged. Around the conductive substrate (7'S2), a similarly cylindrical power source ti (736) is arranged, and an electrode heater (737) is arranged outside. The conductive substrate (752) is rotatable using an external drive motor (754).

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"' Torr, and the degree of vacuum is checked and the gas adsorbed inside the device is desorbed. At the same time, an electrode heater is used to heat the electrode and the conductive material fixed to the electrode. The substrate is heated to a predetermined temperature.If necessary, an undercoat layer or charge generation layer is provided on the conductive substrate in advance in order to obtain a desired photoreceptor structure from among the above-mentioned photoreceptor structures. The undercoat layer or the charge generation layer may be placed using the water device or a separate device.Then, the first to sixth tanks and the first to third containers may be placed. A suitable gas consisting of hydrocarbons is introduced into the reaction chamber at a constant flow rate using the first to ninth flow rate controllers, and the inside of the reaction chamber is maintained at a constant reduced pressure state by the pressure control valve.The gas flow rate is stabilized. After that, select, for example, a high-frequency power supply using a connection selection switch and apply high-frequency power to the power application electrode.Discharge starts between both electrodes, and a solid phase film is formed on the substrate over time.Reaction The film thickness is controlled by time, and the discharge is stopped when a predetermined film thickness is reached.Then, the first to ninth control valves are closed and the reaction chamber is sufficiently evacuated.At this point, the desired photoreceptor configuration is obtained. If a charge generation layer or an overcoat layer is required in the desired photoreceptor configuration, the photoreceptor is taken out and treated with an acid in the same manner. A photoreceptor according to the present invention is obtained by applying these layers using another reactor or by transferring them to a separate apparatus.In this case, the acid treatment is carried out after the charge generation layer or overcoat layer is provided. It's okay.

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

X-twisting Using a manufacturing apparatus according to the present invention, a photoreceptor was produced in which a conductive substrate, a charge transport layer, and a charge generation layer were provided in this order, as shown in FIG.

Charge transport layer forming step (CTL step): In the glow discharge decomposition device shown in FIG. 7, first, the reaction device (733)
After creating a high vacuum of about 10-6 Torr inside the
The first and second control valves (707 and 708) are released, and hydrogen gas is supplied from the first tank (701) and ethylene gas is supplied from the second tank (702) at an output pressure of 1.0 kg/
Cm2 into the eleventh and second flow rate controllers (713 and 714), and at the same time, the seventh control valve (725) is released and the styrene is transferred from the first container (719) into the first heater (72).
2) Once vaporized at 25°C, the seventh flow controller (72
8) It was allowed to flow into the interior.

Then, adjust the scale of each flow rate controller to set the water ice-gas flow rate to 40 sec, and the ethylene gas flow rate to 30 sccm.
, and the flow rate of styrene gas is set to 18scam, and the main pipe (73
2) into the reaction chamber (733). After each flow rate stabilizes, the pressure in the reaction chamber (733) is 0.5
The pressure control valve (745) was adjusted so that the pressure was Torr. On the other hand, the conductive substrate (752) is 150X horizontal 5
Using an aluminum substrate with a thickness of 0 x 3 mm, 100
℃, and with the gas flow rate and pressure stable, turn on the low frequency power supply (741) that was previously connected using the connection selection switch (744), and connect the power application electrode (73).
In step 6), a power of 100 Wa 11 was applied under a frequency range of 30 KHz to carry out a plasma polymerization reaction for about 30 minutes, and a 10 um thick a-C film was formed 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.

When CHN quantitative analysis was performed on the a-C film obtained as described above, the amount of hydrogen atoms contained was 48 atomic % based on the total position of carbon atoms and hydrogen atoms.
.

Acid treatment step: The amC film was taken out from the reaction chamber and treated with 0. The mixture was left for 30 minutes in a closed container in which the saturated vapor pressure of IN diluted hydrochloric acid was maintained at 100°C. After the acid treatment in this manner, it was returned to the reaction chamber.

Charge generation layer forming step (CGL step): Next, the first control valve (707) and the sixth control valve (707) are formed.
12) and hydrogen gas from the first tank (701),
and silane gas from the sixth tank (706) at an output pressure of I
1st, 5th and 6th flow rate fI71 under Kg/am2
It was made to flow into the I controllers (713, 717 and 718).

Adjust the scale of each flow rate controller to set the hydrogen gas flow rate to 210.
secm, and the flow rate of silane gas to 90 sca
m, and do not allow it to flow into the reaction chamber (733). After each flow rate stabilizes, the pressure in the reaction chamber (733) decreases to 1.
The pressure control valve (745) was adjusted so that the pressure was 0 Torr. On the other hand, a conductive substrate (75
2) is heated to 100℃, and the gas flow rate and pressure are adjusted.
is stable, frequency 1 from high frequency Ehara (739)
Power applied under 3.56MHz 41 (736) to 50
Watt power was applied to generate glow discharge. This discharge was performed for 15 minutes, and a-3i with a thickness of 0.3 μm:
A H charge generation layer was formed.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, the highest charging potential was about -1000 V. That is, since the total photoreceptor film thickness was 10.3 μm, the charging ability per 1 μm was approximately The voltage was extremely high at 100V, which confirmed that it had sufficient charging performance. Further, the time required for the dark decay from 1,600 V to 1,550 V in the dark was about 35 seconds, which confirmed that it had sufficient charge retention performance. In addition, after initial charging to -500V, the brightness was attenuated to -150V using white light, and the amount of light required was approximately 2.1 lux seconds, which indicates that it has sufficient photosensitivity performance. was confirmed. In addition, 3 months after the production of this photoreceptor, the same (
When the white light sensitivity was measured as a child, it was confirmed that there was almost no deterioration over time at approximately 2.3 lux·sec.

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

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

CGL, CTL process: The CGL process and CTL process in Example 1 were performed in this order.

Acid treatment step: After the charge generation layer and charge transport layer were formed, the saturated vapor pressure of 0°IN diluted sulfuric acid was maintained at 100°C, and the sample was left in a closed container for 30 minutes for acid treatment.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, the highest charging potential was about -100V, that is, since the total photoreceptor film thickness was 10.3 μm, the charging ability per 1 μm was was extremely high at about 100 V, which confirmed that it had sufficient charging performance. Further, the time required for dark decay from -600V to -550V in the dark was about 40 seconds, which confirmed that it had sufficient charge retention performance. In addition, after initial charging to -5oOV, the amount of light required to attenuate to -150V using white light was approximately 4.6 lux seconds, which indicates that it has sufficient photosensitivity performance. This was confirmed. In addition, when the white light sensitivity was measured in the same manner 3 months after the photoconductor was prepared, the sensitivity was about 4. It was confirmed that there was almost no deterioration over time using flux seconds.

From the above, the photoreceptor according to the present invention shown in this example stably exhibits excellent performance as a photoreceptor. When the image was transferred, a clear image was obtained.

Using the manufacturing apparatus according to the present invention, a photoreceptor was produced 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.
68), hydrogen gas is released from the first tank (701),
Propane gas is supplied 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, and simultaneously into the seventh control valve (714).
25) and vaporizes benzene from the first container ('719) at the temperature of the first heater (722) at 60°C.
The liquid was allowed to flow into the flow rate controller (728).

Then, adjust the scales of each flow rate controller to set the hydrogen gas flow rate to 40 seconds and the propane gas flow rate to 50 seconds.
And the m'FA of benzene gas is set to 20 sec, and the main pipe (
732) into the reaction chamber (733). After each flow rate stabilizes, the pressure inside the reaction chamber (733) is 0.7
The pressure control valve (745) was adjusted so that the pressure was Torr. On the other hand, as a conductive substrate (752), 50 fir x 5 horizontal
Using an aluminum substrate with a thickness of 0 x 3 mm, 100
℃, and with the gas flow rate and pressure stable, turn on the low frequency power supply (741) that was previously connected using the connection selection switch (744), and connect the power application electrode (73).
6), a plasma polymerization reaction was carried out for about 30 minutes by applying electricity of 100 Wa 11 at a frequency of 30 KHz, and a 15 μm thick a-C film was formed as a charge transport layer on the conductive substrate (752). After completing the film formation, stop applying power and
The control valve was closed and the inside of the reaction chamber (733) was sufficiently evacuated.

When CHN quantitative analysis was performed on the a-C film obtained as described above, the amount of hydrogen atoms contained was 40 at % based on the total amount of carbon atoms and hydrogen atoms.

Acid treatment step: Next, the vacuum was broken, the sample was taken out, and the sample was immersed in 0°2N diluted nitric acid at 30°C for 2 seconds for acid treatment.

CGL process: Next, the sample was transferred to another vacuum evaporator, and A s 2 S e 3 was applied as a 1 μm charge generation layer by a resistance heating method.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, the maximum charging potential exceeded -1,000 V, and it was confirmed that it had sufficient charging performance. Also, in the dark
The time required for dark decay from 00V to -550V was approximately 25 seconds, which confirmed that it had sufficient charge retention performance. In addition, using white light initially charged to -500V, the brightness was attenuated to -150V. However, the amount of light required was approximately 1.8 lux.
seconds, and from this, it was confirmed that the film had sufficient photosensitivity performance. In addition, 3 months after the production of this photoreceptor,
When white light sensitivity was measured in the same way, the result was approximately 1.8.
It was confirmed that there was no deterioration over time at all in Lux/second.

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

Carrier l A photoreceptor was produced in the same manner as in Example 1 except that the acid treatment step was omitted.

Characteristics: When the obtained photoreceptor was used in a commonly used Carlson process, the highest charging potential was about -1000 V. That is, since the total photoreceptor film thickness was 10.3 μm, the charging ability per 1 μm was approximately 1oov (approximately high), which confirms that it has sufficient (1f) electric performance.
The time required for dark decay from 1,600 V to 1,550 V in the dark was about 35 seconds, and this confirmed that it had sufficient charge retention performance. Also, -500
After initial charging to V, the light intensity required to attenuate to -150 cm using white light was approximately 1.9 lux·sec, which indicates that it has sufficient photosensitivity performance. confirmed.

However, when we similarly measured the white light sensitivity of this photoreceptor three months after its manufacture, we found that approximately 60 lux·sec of photoelectricity was required, confirming that extremely severe deterioration over time had occurred. .

This comparative example confirmed that the photoreceptor produced according to the present invention and subjected to the acid treatment step stably exhibits excellent performance as a photoreceptor.

Comparative Example 2 A photoreceptor was produced in the same manner as in Example 3, except that the acid treatment step was omitted.

Characteristics: When the obtained photoreceptor was used in a conventional Carlson process, the highest charging potential exceeded -1,000 V, which confirmed that it had sufficient charging performance. Further, the time required for dark decay from -600V to -550V in the dark was about 30 seconds, which confirmed that it had sufficient charge retention performance. Also, -50
After initial charging to 0V, the light intensity was attenuated to -150μ using white light, and the amount of light required was approximately 1.6 lux·sec, which indicates that it has sufficient photosensitivity performance. It was approved.

However, when we similarly measured the white light sensitivity of this photoreceptor three months after its manufacture, we found that a light intensity of approximately 73 lux·sec was required, which confirmed that extremely severe deterioration occurred over time. Ta.

From this comparative example, it was confirmed that the photoreceptor produced according to the present invention and subjected to the acid treatment step stably exhibits excellent performance as a photoreceptor.

[Brief explanation of the drawing]

Applicant: Minolta Camera Co., Ltd. Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6

Claims (1)

[Claims] In a functionally separated photoreceptor having a charge generation layer and a charge transport layer, the charge transport layer is formed by plasma polymerizing hydrocarbons in a gas phase and then treating them with an acid. A photoreceptor characterized by being a crystalline solid.