JP2636261B2 - Photoconductor - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photoconductor provided with a surface protective layer.

2. Description of the Related Art Amorphous selenium photoreceptor is well known as an electrophotographic photoreceptor, and its disadvantages in heat resistance, spectral sensitivity, dark decay and the like are described below. Improvements have been made by adopting a laminated structure provided with a selentellurium alloy layer.

The selenium-arsenic alloy photoreceptor is more sensitive than all other photoreceptors in the relative luminosity range required by ordinary copiers, and the length required by printers using semiconductor laser light as a light source. In the wavelength sensitivity region, it is known that a photosensitive member having a laminated structure in which selenium and a selenium-tellurium alloy are provided in this order is one of the photosensitive members having the highest sensitivity.

However, repeated use of such a photoreceptor causes problems such as image defects and white stripes. This is because selenium arsenide and selenium tellurium alloy are as soft as about H in pencil hardness of JIS-K-5400 standard, and the photoreceptor surface is scraped or scratched due to abrasion with transfer paper, cleaning member, developer, etc. in repeated use. It is to stick. Severe surface contact caused by manual operation at the time of paper jam and recovery from paper jam also contributes to this.

In addition, since selenium metal is toxic, there is a concern that the metal such as selenium or arsenic that has been scraped off, or selenium or arsenic vaporized by heat in a copying machine may affect the human body.

Therefore, an attempt to solve the above problem by providing a protective layer on the surface of the photoreceptor has been proposed, but what is fundamentally important for the surface protective layer is that the provision of the surface protective layer reduces the deterioration of the photoreceptor characteristics. The use does not cause peeling of the film.

The technique described in Japanese Patent Application Laid-Open No. Sho 60-61761 discloses a photoreceptor in which the surface of a photosensitive active layer is coated with a diamond-like carbon film.

However, the photoreceptor described above has poor surface potential stability,
There is a disadvantage that the image density tends to decrease. Further, the above publication discloses that amorphous silicon is used as a photosensitive active layer, and there is a drawback that when it is applied to a selenium-based photosensitive layer, charging ability and adhesiveness are reduced.

The techniques described in JP-A-53-23636 and JP-A-53-111734 disclose a photoreceptor in which a specific silicon compound is coated on a selenium-based photosensitive layer and cured to form an insulating layer. ing.

However, the above-described photoreceptor has a disadvantage that the surface of the photoreceptor is easily damaged due to low surface hardness.

The technique described in JP-A-59-58437 discloses a photoconductor in which a protective layer mainly composed of a compound of Si and N or Si and O is provided on a photosensitive layer containing selenium. However, the above-described photoreceptor has a drawback that it has poor moisture resistance and easily causes image deletion.

Therefore, the photoreceptor having a single-layer structure of a selenium-arsenic alloy or a laminated structure in which selenium and a selenium-tellurium alloy are provided in this order has a soft surface and is easily scratched. Also, there is no effective protective film that does not cause image deletion or the like.

Therefore, a first object of the present invention is to provide a surface protective layer that does not cause film peeling.

Another object of the present invention is to provide a photoreceptor that does not damage the surface of the photoreceptor even when used repeatedly and has excellent surface potential stability.

It is a further object of the present invention to provide a photoreceptor having a protective film without lowering the charging ability and the adhesiveness.

Means for Solving the Problems The present invention relates to a photoreceptor having a single layer of a selenium-arsenic alloy or a laminated structure in which selenium and a selenium tellurium alloy are provided in this order on a conductive substrate. And a photoreceptor characterized by having a surface protective layer composed of two outermost layers composed of an amorphous hydrocarbon film (a-C film) formed by a glow discharge plasma polymerization method on the resin layer. .

FIG. 1 shows an example of the structure of the photoreceptor of the present invention, in which a photosensitive layer (2) and a resin layer (1) are formed on a conductive substrate (3).
b) and a surface protective layer (4) composed of an outermost surface layer (1a) composed of an amorphous hydrocarbon film (hereinafter referred to as "a-C film")
Are sequentially laminated.

The conductive substrate (3) may be a material having at least the outermost surface having conductivity, and may have any shape such as a cylindrical shape, a flexible belt shape, and a flat plate shape.

The photosensitive layer (2) is a single layer of selenium arsenide or a selenium layer and a selentellurium alloy known per se, which are sequentially laminated on a substrate (3).

The resin layer (1b) serves to improve the adhesiveness between the conductive substrate (3) and the a-C film, and is made of a known resin such as a thermoplastic resin, a thermosetting resin, a photocurable resin, or a photoconductive resin. Etc. can be used.

As such a resin, for example, polyester resin, polyamide resin, polybutadiene, acrylic resin, ethylene-
Thermoplastic resins such as vinyl acetate copolymer, ion exchange olefin copolymer (ionomer), styrene-butadiene block copolymer, polycarbonate, vinyl chloride-vinyl acetate copolymer, cellulose ester, and polyimide; epoxy resin, urethane resin Thermosetting resins such as silicone resins, phenolic resins, melamine resins, xylene resins, alkyd resins, thermosetting acrylic resins; photocurable resins; photocurable resins such as poly-N-vinylcarbazole, polyvinylpyrene and polyvinylanthracene Examples of the resin include a silicone resin, an acrylic resin, a melamine resin, a polycarbonate resin, a polybutadiene, and an epoxy resin.

It is desirable that these resins have a volume resistance of 1 × 10 ¹⁴ Ω · cm or more.

The resin layer (1b) has a thickness of about 0.05 to 5 after a solution obtained by dissolving the above resin in an appropriate solvent is dried on the surface of the photosensitive layer (2).
μm, preferably 0.05-2 μm, more preferably 0.1-
It is formed by coating and drying to a thickness of 1 μm. When the thickness of the resin layer (1b) is less than 0.01 μm, the adhesiveness decreases, and when the thickness is more than 5 μm, the light transmittance decreases. As a coating method, a known spray method, dipping method, ring coating method, or the like can be applied. In addition to these coating methods, it is also possible to provide a resin by vacuum evaporation or a sputtering method.

Solvents that can be used in the coating solution for forming the adhesive layer may be appropriately selected according to the selected resin, but those that are easy to dry are preferable. Examples of such solvents include gasoline, petroleum, benzine, and mineral spirits. , Petroleum naphtha, VM & P. Naphtha, decalin, tetralin, aliphatic hydrocarbons such as P-cymene or hexane, aromatic hydrocarbons such as benzene, toluene, xylene, trichloroethylene, perchlorethylene, chloroform, carbon tetrachloride, Halogenated hydrocarbons such as ethylene trichloride, benzene monochloride, benzene monobromide, and benzene dichloride, amyl alcohol, ethyl alcohol, isopropyl alcohol, 2-ethylbutyl alcohol, 2-ethylhexyl alcohol, cyclohexanol, methyl alcohol, Methyl amyl alcohol , Benzyl alcohol, alcohols such as butyl alcohol, acetone, acetonylacetone, diisobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, methyl butyl ketone, methyl cyclohexanone, methyl dipropyl ketone, methyl ethyl ketone, methyl orthohexyl ketone, Ketones such as methyl isobutyl ketone, methyl propyl ketone, and mesityl oxide; esters such as acetates, butyrate, propionate, and formate; butyl lactate, isopropyl lactate, ethyl lactate, and ethyl oxypropionate , Alcohol esters such as diethyl maleate, ethyl acetoacetate, ethyl pyruvate, isopropyl ether, ethyl ether, diethyl carbitol, diethyl cellosolve, butyrate Ethers such as ethers, ketone alcohols such as acetonymethanol, diacetone alcohol, dihydroxylacetone, pyrivir alcohol, isopropyl cellosolve, carbitol, glycidol, cellosolve, glycol ether, benzyl cellosolve, butyl carbitol, butyl cellosolve, methyl car Bitol, methyl cellosolve, ether alcohols such as triethylene glycol monoethyl ether, ketone ethers such as acetal ethyl ether, acetonyl methanol ethyl ether, methyl ethoxyethyl ether, butyl carbitol acetate, butyl cellosolve acetate, carbitol acetate, Ester ethers such as cellosolve acetate, 3-methoxybutyl acetate, methyl carbitol acetate, and methyl cellosolve acetate Etc., or a mixed solvent thereof can be mentioned, in particular ethyl acetate, butyl acetate, hexane, toluene, methyl isobutyl ketone, cellosolve acetate, or a mixed solvent thereof are preferred.

The amount of the resin used in the coating solution for forming the adhesive layer is 0.4 to 20.0% by weight, preferably 0.9 to 6.0% by weight, more preferably 1.0 to 5.0% by weight based on the coating solution. If the amount is less than 0.4% by weight, it is necessary to repeat a number of coating and drying steps in order to obtain a desired film thickness. On the other hand, if it exceeds 20% by weight, the viscosity of the solution becomes too high, causing problems such as uneven coating and difficulty in controlling the film thickness.

The outermost surface layer (1a) composed of an aC film is a film having a suitable chargeability itself, excellent translucency, and a high hardness of about 4H, which is hard to be damaged. If the photosensitive layer is directly provided on a photosensitive layer having a laminated structure in which selenium and a selenium-tellurium alloy are provided in this order, film peeling is likely to occur during actual use. However, according to the present invention, by providing the resin between the photosensitive layer and the a-C layer, it is possible to maintain the advantages of the a-C layer, such as favorable charging ability, light transmissivity, and hardness, and to remove the film. Can be prevented.

Although the amount of hydrogen atoms contained in the aC film is not particularly limited, it is inevitably limited by the structure of the surface protective layer and the manufacturing aspect of glow discharge, and the amount is generally 5 to 60 atomic.
% (Hereinafter abbreviated as "atm.%").

The amounts of carbon atoms and hydrogen atoms contained in the a-C film are as follows:
It can be known by means such as organic element analysis, Auger analysis, and SIMS analysis.

The outermost layer (1a) of the present invention has a thickness of 0.01 to 5 μm, preferably 0.05 to 2 μm, and more preferably 0.1 to 1 μm.
It is formed to a thickness of μm.

When the thickness is less than 0.01 μm, the film strength is reduced, and the film is easily scratched. On the other hand, when the thickness is more than 5 μm, the light transmittance decreases, and the irradiation light cannot be effectively guided into the photosensitive layer, resulting in a decrease in sensitivity.

The outermost surface layer (1a) is formed by a glow discharge method. The outermost layer (1a) discharges molecules containing at least carbon atoms and hydrogen atoms in the gaseous phase under reduced pressure, diffuses active neutral or charged species contained in the generated plasma atmosphere onto the substrate, Alternatively, it can be formed as an aC film by a so-called plasma reaction (hereinafter, referred to as a P-CVD reaction), which is induced by a porcelain force or the like and deposited as a solid phase by a recombination reaction on the substrate.

Each of the above molecules does not necessarily need to be in a gaseous phase at normal temperature and normal pressure, and any liquid or solid phase can be used as long as it can be vaporized through melting, evaporation, sublimation or the like by heating or decompression.

As a molecule containing at least a carbon atom and a hydrogen atom, a hydrocarbon, for example, a saturated hydrocarbon, an unsaturated hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, or the like can be used.

As the saturated hydrocarbon, for example, methane, ethane, propane, butane, pentane, hexane, heptane, octane, isobutane, isopentane, neopentane, isohexane, neohexane, dimethylbutane, methylhexane, ethylpentane, dimethylpentane, triptan, methyl Heptane, dimethylhexane, trimethylpentane, isonanone, and the like can be used.

Examples of unsaturated hydrocarbons include, for example, ethylene, propylene, isobutylene, butene, pentene, methylbutene, hexene, tetramethylethylene, heptene, octene, arene, methylarene, butadiene, pentadiene, hexadiene, cyclopentadiene, ocimene, allocimene, myrcene. , Exatriene, acetylene, methylacetylene, butyne, pentine, hexine, heptin, octin, butadiyne and the like can be used.

As the alicyclic hydrocarbon, for example, cyclopropane,
Cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, limonene, tervinolene, ferrandrene, silvestren, tsuen, karen, pinene, bornylene, camphene, fenchen, Cyclofenchen, tricyclene, pisabolene, zingiberene, curcumen, humulene, casinensesquibenichen,
Selinene, caryophyllene, santalen, cedren, kampholen, phyllocladene, podocarprene, millen, and the like can be used.

Examples of aromatic hydrocarbons include, for example, benzene, toluene, xylene, hemimelitene, pseudocumene, mesitylene, prenitene, isodurene, durene, pentamethylbenzene, hexamethylbenzene, ethylbenzene, propylbenzene, cumene, styrene, biphenyl, terphenyl, diphenylmethane , Triphenylmethane, dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, phenanthrene and the like can be used.

In particular, a compound having an unsaturated bond is preferable in terms of forming a high-quality film because of its high reactivity. Among them, film-forming properties,
Butadiene and propylene are particularly preferred in terms of gas handling easiness and cost.

The amount of hydrogen atoms contained in the aC film varies depending on the form of the film forming apparatus and the conditions during film formation, and when the amount of hydrogen decreases, for example, increasing the substrate temperature, decreasing the pressure, Lowering the dilution rate of the raw hydrocarbon gas, using a raw gas gas with a low hydrogen content, increasing the applied power, lowering the frequency of the alternating electric field, increasing the DC electric field intensity superimposed on the alternating electric field, etc. There are cases.

2 and 3 are views showing an example of a glow discharge decomposition apparatus for forming the outermost surface layer of the present invention. FIG. 2 shows a parallel plate type P-CVD device, and FIG. 3 shows a cylindrical type P-CVD device.

 First, a description will be given with reference to FIG.

In FIG. 2, reference numerals (701) to (706) denote first to sixth tanks in which a raw material compound and a carrier gas which are in a gaseous state at ordinary temperature are sealed, and each tank has first to sixth control valves (707) to (707). (712) and the first to sixth flow controllers (713)
To (718).

As a carrier gas, hydrogen gas, argon gas, helium gas, or the like can be used.

In the figure, reference numerals (719) to (721) denote first to third containers enclosing a raw material compound in a liquid phase or a solid state at ordinary temperature. Each of the first to third heaters (722) is used for vaporization. ) To (724), and the respective containers are connected to seventh to ninth control valves (725) to (727) and seventh to ninth flow controllers (728) to (730). ing.

After these gases are mixed in the mixer (731), they are sent to the reaction chamber (733) via the main pipe (732).

The piping in the middle is a gas which is a vaporized gas of the raw material compound which was in a liquid phase or a solid phase at normal temperature, and can be heated by a suitably arranged piping heater (734) so as not to condense on the way. .

Ground electrode (735) and power application electrode (736) in the reaction chamber
Are placed facing each other, and each electrode is an electrode heater (737)
Can be heated.

The power application electrode (736) has a matching device for high-frequency power (73
8) through the high-frequency power supply (739), through the low-frequency power matching device (740), through the low-frequency power supply (741), and through the low-pass filter (742) to the DC power supply (743). By the selection switch (744), power having different frequencies, for example, high-frequency power having a frequency of 1 KHz to 13.56 MHz can be applied. Furthermore, it is also possible to superimpose DC power.

The thickness in the reaction chamber (733) can be adjusted by the pressure control valve (745), and the pressure in the reaction chamber (733) can be reduced via the exhaust system selection valve (746), the diffusion pump (747), and the oil. This is performed by a rotary pump (748) or a cooling exclusion device (749), a mechanical clutch booster pump (750), and an oil rotary pump (748).

The exhaust gas is further rendered safe and harmless by an appropriate exclusion device (753) and then exhausted to the atmosphere.

These exhaust pipes are also provided with pipe heaters (73) that are appropriately arranged so that the gas in which the raw material compound in the liquid or solid state at room temperature does not condense on the way.
According to 4), heating is possible.

Reaction chamber heater (751) for reaction chamber (733) for the same reason
, And the substrate (752) is placed on the electrodes arranged inside.

These heaters may be selected according to the nature of the raw material gas to be used or not. In particular, an organic compound having a boiling point of -20 ° C to + 70 ° C under normal pressure is used as the raw material gas. When used, it is often unnecessary, and the manufacturing apparatus can be simplified, which is preferable.

In general, when an organic compound having a boiling point lower than −20 ° C. is used as a raw material gas, an organic compound having a boiling point higher than + 70 ° C. is used in order to prevent the generation of a fine powdery polymer inside the reaction chamber (733). When used as a raw material gas, it is desirable to provide various heaters as described above in order to prevent condensation in various pipes.

In FIG. 2, the substrate (752) is fixed to the ground electrode (735). However, the substrate (752) may be fixed to the power applying electrode (736), or may be fixed to both.

The apparatus shown in FIG. 3 is basically the same as the apparatus shown in FIG. 2, and the configuration in the reaction chamber (733) is changed according to the fact that the substrate (752) is cylindrical. Things.
The substrate (752) also serves as a ground electrode (735), and both the power application electrode (736) and the electrode heater (737) have a cylindrical shape. Further, the conductive substrate (752) can be rotated on its own by using a drive motor (not shown) from the outside.

In the above configuration, the reaction chamber used for photoconductor production is
The pressure is previously reduced to about 10 ^-4 to 10 ^-6 Torr by a diffusion pump, and the degree of vacuum is checked and the gas adsorbed inside the apparatus is desorbed.

At the same time, the electrodes and the substrate fixed to the electrodes are heated to a predetermined temperature by the electrode heater.

As the substrate, a photosensitive member having a single layer of a known selenium arsenic alloy or a laminated structure in which a selenium, a selenium tellurium alloy, and a resin layer are provided in this order on a conductive substrate is used.

Next, the first to sixth tanks and the first to third tanks
The raw material gas is introduced from the container into the reaction chamber at a constant flow rate using the first to ninth flow controllers, and the pressure in the reaction chamber is maintained at a reduced pressure of about 0.05 Torr to 5.0 Torr by a pressure regulating valve.

After the gas flow is stabilized, the connection selection switch
For example, a low-frequency power source is selected, and low-frequency power is supplied to the power application electrode.

Discharge is started between the two electrodes, and a solid-phase amorphous hydrocarbon film is formed on the substrate with time.

When a predetermined thickness is reached, the discharge is stopped to obtain a photoreceptor having the aC film according to the present invention as the outermost surface layer.

In the outermost surface layer a-C film of the present invention, carbon, hetero atoms other than hydrogen, for example, halogen atoms such as fluorine, chlorine, bromine or iodine, oxygen atoms, nitrogen atoms, and the periodic table as a conductive controlling substance. Group III elements (Ba, Al, Ga, In,
Etc.) and a V element of the periodic table (P, AS, Sb, etc.).

The introduction of a halogen atom can improve the surface slipperiness and improve the filming resistance of the surface protective layer.
Such an effect is particularly large when a fluorine atom is introduced.

The introduction of oxygen or nitrogen atoms causes each atom to forcibly break a weak bond during the reaction, filling in between,
It is considered that strong bond dissociation between nitrogen / oxygen atoms and between oxygen / carbon atoms is eliminated, and as a result, adhesion of moisture is prevented.

The group V element is introduced so that the surface side becomes relatively N-type. By doing so, a reverse bias effect can be provided, and an improvement in charging ability, a reduction in dark decay, an improvement in sensitivity, and the like are achieved.

The addition of a group IV element increases the hardness, so that the photoconductor is less likely to be damaged, and is effective in improving moisture resistance.

A plurality of these hetero atoms may be used, may be mixed only at a specific position in the aC outermost surface layer depending on the purpose, or may have a concentration distribution.

Halogen atom, oxygen atom, nitrogen atom, Periodic Table III
A heteroatom such as a group V element or a group V element of the periodic table
In order to mix them into the -C film, an appropriate gaseous compound containing these elements may be formed in a plasma state together with a hydrocarbon gas.

Examples of the molecule containing at least a halogen atom include, for example, F ₂ , HF, HCl, CF ₄ , CCl ₄ , C ₃ F ₈ , C ₃ F ₆ , CF ₂ CH ₂ , CF
HCFH or the like can be used.

Examples of a molecule containing at least one of an oxygen atom and a nitrogen atom include, for example, O ₂ , H ₂ O, N ₂ , NH ₃ , N ₂ O, N
O, CO, CO ₂ , NH ₂ NH ₂ , CH ₃ OH, CH ₃ COCH ₃ , CH ₃ OCH ₃ , HCOO
H, HCHO, CH ₃ NH ₂ , (CH ₃ ) ₃ N, and the like can be used. A plurality of these molecules may be used.

Examples of molecules containing at least a Group III element of the periodic table include B ₂ H ₆ , BCl ₃ , BBr ₃ , BF ₃ , B (OC ₂ H ₅ ) ₃ ,
_{AlCl 3, Al (CH 3)} 3, Al (Oi-C 3 H 7) 3, Ga (C
_{2 H 5) 3, In (} C 2 H 5) can be used ₃ or the like.

As a molecule containing at least a Group V element of the periodic table,
For _{example, PH 3, PF 3, PF} 5, PCl 2 F, PCl 2 F 3, PCl 3, PBr 3,
PO (OCH ₃ ) ₃ , P (C ₂ H ₅ ) ₃ , POCl ₃ , AsH ₃ , AsCl ₃ , As
_{Br 3, AsF 3, AsF 5} , AsCl 3, SbH 3, SbF 3, SbCl 3, Sb (OC 2
H _{5) 3,} or the like can be used.

The amount of the heteroatom contained in the aC film can be adjusted by increasing or decreasing the amount of the heteroatom-containing molecule used in the plasma CVD reaction. In order to distribute the amount of hetero atoms contained in the aC film non-uniformly in the depth direction of the aC film, it is necessary to increase or decrease the amount of molecules containing hetero atoms during the plasma CVD reaction. I just need. Here, the effect appears when the addition of a hetero atom is 0.1 atm.% Or more. The upper limit is not particularly limited, and is inevitably determined by the raw materials to be used and the production method called the glow discharge method.

The content of the hetero atom can be determined by means such as Auger analysis and elemental analysis.

Example 1 A silicone resin (KR21) was placed on an aluminum conductive cylindrical substrate (80 mm in diameter × 330 mm in length) provided with a 50 μm-thick selenium arsenide alloy single-layer photosensitive layer using a vacuum deposition apparatus according to a conventional method.
4: Shin-Etsu Chemical Co., Ltd.) Spray-coat a solution prepared from 2.5% by weight and 97.5% by weight of ethyl acetate so that the film thickness after drying becomes 0.15 μm, and dry at 85 ° C. for 1 hour to form a silicone resin layer. Formed.

Next, an outermost surface layer made of an aC film was formed on the silicone resin layer obtained as described above, using a glow discharge decomposition apparatus shown in FIG.

First, after the inside of the reactor (733) is evacuated to a high vacuum of about 10 ^-6 Torr, the first and second control valves (707, 708) are opened,
Hydrogen gas from the first tank (701) and butadiene gas from the second tank (702) flow into the first and second flow controllers (713) and (714) at an output pressure of 1.0 kg / cm ² , respectively. I let it.
Then, the scale of each flow controller is adjusted so that the flow rate of the hydrogen gas is set to 100 sccm and the flow rate of the butadiene gas is set to 60 sccm, and the main pipe (731) is passed through the intermediate mixer (731).
From 2), it flowed into the reaction chamber (733).

After each flow rate was stabilized, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) became 0.5 Torr.

On the other hand, as the substrate (752), a substrate obtained by providing a silicone resin layer on the aluminum conductive cylindrical substrate having the selenium arsenic alloy single layer structure was used. The substrate (752)
The temperature was raised from room temperature to 50 ° C. over about 15 minutes before gas introduction.

With the gas flow rate and pressure stabilized, a low-frequency power source (74
1) is input, a power of 130 Watt is applied to the power application electrode (736) at a frequency of 150 KHz, a plasma polymerization reaction is performed for about 2 minutes, and an aC film having a thickness of 0.15 μm is formed on the substrate (752). It was formed as the outermost surface layer.

After the film formation is completed, stop applying power, close the control valves other than hydrogen gas, flow only 200 sccm of hydrogen gas into the reaction chamber (733), maintain the pressure at 10 Torr, and lower the temperature to 30 ° C in about 15 minutes. did.

Thereafter, the control valve for hydrogen gas was closed, the inside of the reaction chamber (733) was sufficiently evacuated, the vacuum in the reaction chamber (733) was broken, and the photoconductor having the surface protective layer according to the present invention was taken out.

Organic quantitative analysis and Auger analysis of the aC film obtained as described above revealed that the amount of contained hydrogen atoms was 43 atm.% Based on all constituent atoms.

Evaluation of characteristics of photoreceptor: The pencil hardness of the obtained photoreceptor surface was JIS-K
It was about 6H when measured based on the -5400 standard, and it was understood that the photoreceptor was hardened by the surface protective layer.

Further, the adhesiveness was determined by a matrix test based on the JIS-K-5400 standard and found to be 10 points, indicating that the surface protective layer of the photoreceptor according to the present invention was excellent in adhesiveness. .

In addition, the charger output +6 in the normal Carlson method.
The photoreceptor obtained under 7 mkV was charged to +600 V, and the white light sensitivity of the photoreceptor obtained in this example was measured. The half-exposure amount was about 0.97 lux · sec. Since the value measured before was about 0.91luxsec,
It was confirmed that the surface protective layer of the photoreceptor according to the present invention did not impair the sensitivity inherent in the photoreceptor having a single-layer structure of selenium-arsenic alloy.

The obtained photoconductor was left for 6 hours in an environment in which a low-temperature and low-humidity atmosphere at a temperature of 10 ° C and a relative humidity of 30% and a high-temperature and high-humidity atmosphere at a temperature of 50 ° C and a relative humidity of 90% were alternately repeated every 30 minutes. As a result, no peeling or cracking of the surface protective layer was observed, and the surface protective layer of the photoreceptor of the present invention was a film having excellent practical adhesion to the photoreceptor having a single-layer structure of selenium arsenic alloy. It was confirmed that there was.

When the photoreceptor obtained in this example was mounted on a copying machine EP650Z manufactured by Minolta Camera Co., and a real image was obtained, a clear image was obtained. In addition, a real image was obtained under an environment of a temperature of 35 ° C. and a relative humidity of 85%. No image deletion was observed. Also, no peeling of the surface protective layer was observed in contact with the developer, the transfer paper, and the cleaning member in the copying machine.

When 250,000 real shots were taken in a normal room, clear images were obtained until the end. In addition, when the composition of the surface was analyzed by Auger analysis after actually photographing 250,000 sheets, selenium or arsenic was not detected.

From the above, the surface protective layer of the photoreceptor according to the present invention,
It was confirmed that the improvement in durability and the harmfulness were achieved without impairing the image quality.

Example 2 Except for using an aluminum conductive cylindrical substrate (diameter 80 × length 330 mm) provided with a 50 μm-thick photosensitive layer having a laminated structure in which selenium and a selenium-tellurium alloy were provided in this order using a vacuum deposition apparatus according to a conventional method. Was performed in the same manner as in Example 1.

Characteristics: The obtained photoreceptor has the same characteristics as in Example 1. In addition, selenium, tellurium, arsenic and the like were not detected from the cleaning blade and the waste toner which were constantly used during the printing durability test. From this, it was confirmed that the surface protective layer of the photoreceptor according to the present invention achieves improvement in durability and harmfulness without deteriorating image quality.

Example 3 2.0% by weight of an acrylic polyol (Acridic A808: manufactured by Dainippon Ink Co., Ltd.) in a mixed solvent of 76.1% by weight of methyl ethyl ketone and 20% by weight of Isopar H (manufactured by Esso Chemical Co.) 1.9% by weight), and the mixture was stirred for 1 hour. The coating solution prepared was dipped and coated to a thickness of about 0.2 μm after drying, and dried to form a resin layer. A photoconductor was produced in the same manner as in Example 1.

Characteristics: The obtained photoreceptor has the same characteristics as in Example 1. In addition, selenium, tellurium, arsenic and the like were not detected from the cleaning blade and the waste toner which were constantly used during the printing durability test. From this, it was confirmed that the surface protective layer of the photoreceptor according to the present invention achieves improvement in durability and harmfulness without deteriorating image quality.

Example 4 Except for using an aluminum conductive cylindrical substrate (diameter 80 × length 330 mm) provided with a 50 μm-thick photosensitive layer having a laminated structure in which selenium and a selenium-tellurium alloy were provided in this order according to a conventional method using a vacuum deposition apparatus. Was performed in the same manner as in Example 3.

Characteristics: The obtained photoreceptor has the same characteristics as in Example 1. In addition, selenium, tellurium, arsenic and the like were not detected from the cleaning blade and the waste toner which were constantly used during the printing durability test. From this, it was confirmed that the surface protective layer of the photoreceptor according to the present invention achieves improvement in durability and harmfulness without deteriorating image quality.

Example 5 A photoconductor was prepared in the same manner as in Example 1 except that the fourth control valve (710) was opened, and a phosphine gas diluted to 10% with hydrogen was introduced from the fourth tank (704) at 100 sccm. Produced.

Organic quantitative analysis and Auger analysis of the aC film on the outermost surface layer of the photoreceptor obtained in the present example showed that the amount of hydrogen atoms contained was 42 atm.
The amount of phosphorus atoms was 1.0 atm.% As the maximum value in the depth direction in the film with respect to all the constituent atoms.

The obtained photoreceptor is increased by +60 in a normal Carlson method.
When charged to 0 V, the charger output required +5.2 kV. From this, it can be understood that the charging ability was improved because the addition of a Group V element of the periodic table, ie, phosphorus, enabled charging to a surface potential of +600 V with a smaller charger output.
With respect to other characteristics, characteristics similar to those of Example 1 were obtained.

Example 6 Except for using an aluminum conductive cylindrical substrate (diameter 80 × length 330 mm) provided with a 50 μm-thick photosensitive layer having a laminated structure in which selenium and a selenium-tellurium alloy were provided in this order according to a conventional method using a vacuum deposition apparatus. Was performed in the same manner as in Example 5.

The obtained photoreceptor had the same characteristics as in Example 5.

Example 7 Acrylic polyol (Acridic A808: manufactured by Dainippon Ink) 2.0% by weight of an isocyanate compound (Bernock DN950: Dainippon Isocyanate) in a mixed solvent of 76.1% by weight of methyl ethyl ketone and 20% by weight of Isopar H (manufactured by Esso Chemical) 1.9%), and the resulting mixture was stirred for 1 hour. The coating solution prepared was dipped and coated to a thickness of about 0.2 μm after drying, and dried to form a resin layer. In the same manner as in No. 7, a photoconductor was prepared.

The obtained photoreceptor had the same characteristics as in Example 5.

Example 8 Except for using an aluminum conductive cylindrical substrate (diameter 80 × length 330 mm) provided with a 50 μm-thick photosensitive layer having a laminated structure in which selenium and a selenium-tellurium alloy were provided in this order according to a conventional method using a vacuum deposition apparatus. Was performed in the same manner as in Example 7.

The obtained photoreceptor had the same characteristics as in Example 5.

Example 9 An epoxy resin (Epiclon 1050: Dainippon Japan) was provided on an aluminum conductive cylindrical substrate (80 mm in diameter × 330 mm in length) provided with a photosensitive layer of a 50 μm-thick selenium arsenide alloy single layer structure by a vacuum deposition apparatus according to a conventional method. 3.5% by weight, toluene 9
After drying the coating solution consisting of 6.5% by weight, the film thickness is about 0.2μm
And dried at 80 ° C. for 1 hour to form an epoxy resin layer.

Next, on the epoxy resin layer obtained as described above,
Using the glow discharge decomposition apparatus shown in the figure, an outermost surface layer composed of an aC film was formed.

First, after the inside of the reactor (733) is evacuated to a high vacuum of about 10 ^-6 Torr, the first and second control valves (707, 708) are opened,
Hydrogen gas from the first tank (701) and propylene gas from the second tank (702) flow into the first and second flow controllers (713) and (714) at an output pressure of 1.0 kg / cm ² , respectively. I let it.
Then, the scale of each flow controller is adjusted so that the flow rate of the hydrogen gas is set to 250 sccm and the flow rate of the propylene gas is set to 60 sccm, and the main pipe (731) is passed through the intermediate mixer (731).
From 2), it flowed into the reaction chamber (733).

After each flow rate was stabilized, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) became 2.0 Torr.

On the other hand, as the substrate (752), a substrate provided with an epoxy resin layer on the aluminum conductive cylindrical substrate having the selenium arsenic alloy single layer structure was used. The substrate (752) was heated from room temperature to 70 ° C. over about 15 minutes before gas introduction.

With the gas flow rate and pressure stabilized, a low-frequency power source (74
1) is input, a power of 100 Watt is applied to the power application electrode (736) at a frequency of 150 KHz to perform a plasma polymerization reaction for about 1 minute and 30 seconds, and an a-C layer having a thickness of 0.15 μm is formed on the substrate (752).
The film was formed as the outermost layer.

After the film formation is completed, stop applying power, close the control valves other than hydrogen gas, flow only 200 sccm of hydrogen gas into the reaction chamber (733), maintain the pressure at 10 Torr, and lower the temperature to 30 ° C in about 15 minutes. did.

Thereafter, the control valve for hydrogen gas was closed, the inside of the reaction chamber (733) was sufficiently evacuated, the vacuum in the reaction chamber (733) was broken, and the photoconductor having the surface protective layer according to the present invention was taken out.

Organic quantitative analysis and Auger analysis of the aC film obtained as described above revealed that the amount of contained hydrogen atoms was 43 atm.% Based on all constituent atoms.

Characteristics: The obtained photoreceptor has the same characteristics as in Example 1. In addition, selenium, tellurium, arsenic and the like were not detected from the cleaning blade and the waste toner which were constantly used during the printing durability test. From this, it was confirmed that the surface protective layer of the photoreceptor according to the present invention achieves improvement in durability and harmfulness without deteriorating image quality.

Example 10 Except for using an aluminum conductive cylindrical substrate (diameter 80 × length 330 mm) provided with a 50 μm-thick photosensitive layer having a laminated structure in which selenium and a selenium-tellurium alloy were provided in this order using a vacuum deposition apparatus according to a conventional method. Was performed in the same manner as in Example 9.

Characteristics: The obtained photoreceptor had the same characteristics as in Example 5. In addition, selenium, tellurium, arsenic and the like were not detected from the cleaning blade and the waste toner used constantly during the printing durability test. From this, it was confirmed that the surface protective layer of the photoreceptor according to the present invention achieves improvement in durability and harmfulness without deteriorating image quality.

Example 11 Thermosetting acrylic resin (HR620: manufactured by Mitsubishi Rayon Co.) 2.
8% by weight, melamine resin (Uban 20HS: manufactured by Mitsui Toatsu)
A coating solution prepared by adding a mixed solution of 0.7% by weight and methyl isobutyl ketone: cellosolve acetate (1: 1) and stirring is applied by dipping so that the film thickness after drying is about 0.15 μm, and the temperature is 80 ° C. A photoconductor was prepared by the same way as that of Example 9 except that the resin layer was formed by drying for 1 hour.

Characteristics: The obtained photoreceptor had the same characteristics as in Example 1. In addition, selenium, tellurium, arsenic and the like were not detected from the cleaning blade and the waste toner used constantly during the printing durability test. From this, it was confirmed that the surface protective layer of the photoreceptor according to the present invention achieves improvement in durability and harmfulness without deteriorating image quality.

Example 12 Except for using an aluminum conductive cylindrical substrate (diameter 80 × length 330 mm) provided with a 50 μm-thick photosensitive layer having a laminated structure in which selenium and a selenium-tellurium alloy were provided in this order using a vacuum deposition apparatus according to a conventional method. Was performed in the same manner as in Example 9.

Characteristics: The obtained photoreceptor had the same characteristics as in Example 1. In addition, selenium, tellurium, arsenic and the like were not detected from the cleaning blade and the waste toner used constantly during the printing durability test. From this, it was confirmed that the surface protective layer of the photoreceptor according to the present invention achieves improvement in durability and harmfulness without deteriorating image quality.

Example 13 An epoxy resin (Epiclon 1050: Dainippon Japan) was provided on an aluminum conductive cylindrical substrate (80 mm in diameter × 330 mm in length) provided with a photosensitive layer of a 50 μm-thick selenium arsenide alloy single layer structure according to a conventional method using a vacuum evaporation apparatus. 3.5% by weight, toluene 9
After drying the coating solution consisting of 6.5% by weight, the film thickness is about 0.2μm
And dried at 80 ° C. for 1 hour to form an epoxy resin layer.

Next, on the epoxy resin layer obtained as described above,
Using the glow discharge decomposition apparatus shown in the figure, an outermost surface layer composed of an aC film was formed.

First, after the inside of the reactor (733) is evacuated to a high vacuum of about 10 ^-6 Torr, the first, second and third control valves (707, 708,
709) and release hydrogen gas and second gas from the first tank (701).
Butadiene gas from tank (702), third tank (703)
The first, second, and third flow controllers (713), (714), respectively, under an output pressure of 1.0 kg / cm ² ,
(715). Then, by adjusting the scale of each flow controller, the flow rate of the hydrogen gas was set at 100 sccm, the flow rate of the butadiene gas was set at 60 sccm, and the flow rate of the carbon tetrafluoride gas was set at 120 sccm.
Through the mixer (731) on the way,
It flowed into the reaction chamber (733) from the main pipe (732).

After each flow rate was stabilized, the pressure control valve (745) was adjusted so that the pressure in the reaction chamber (733) became 0.5 Torr.

On the other hand, as the substrate (752), a substrate provided with an epoxy resin layer on the aluminum conductive cylindrical substrate having the selenium arsenic alloy single layer structure was used. The substrate (752) was heated from room temperature to 50 ° C. over about 15 minutes before gas introduction.

With the gas flow rate and pressure stabilized, a low-frequency power source (74
1) is applied, a power of 150 Watt is applied to the power application electrode (736) at a frequency of 100 KHz to perform a plasma polymerization reaction for about 1 minute, and an aC film having a thickness of 0.10 μm is formed on the substrate (752). It was formed as the outermost surface layer.

After the film formation is completed, stop applying power, close the control valves other than hydrogen gas, flow only 200 sccm of hydrogen gas into the reaction chamber (733), maintain the pressure at 10 Torr, and lower the temperature to 30 ° C in about 15 minutes. did.

Thereafter, the control valve for hydrogen gas was closed, the inside of the reaction chamber (733) was sufficiently evacuated, the vacuum in the reaction chamber (733) was broken, and the photoconductor having the surface protective layer according to the present invention was taken out.

When an organic quantitative analysis was performed on the amorphous hydrocarbon film obtained as described above, the amount of hydrogen atoms contained was 40 atm.% Based on all constituent atoms, and halogen atoms, that is,
The amount of fluorine atoms was 3.7 atm.% Based on all constituent atoms.

Evaluation of characteristics of photoreceptor: The pencil hardness of the obtained photoreceptor surface was JIS-K
It was about 6H when measured based on the -5400 standard, and it was understood that the photoreceptor was hardened by the surface protective layer.

Further, the adhesiveness was determined by a matrix test based on the JIS-K-5400 standard and found to be 10 points, indicating that the surface protective layer of the photoreceptor according to the present invention was excellent in adhesiveness. .

In addition, the charger output +6 in the normal Carlson method.
The photoreceptor obtained under 8 kV was charged to +600 V, and the white light sensitivity of the photoreceptor obtained in this example was measured. The half-exposure amount was about 0.96 lux · sec. Since the value measured before was about 0.90 lxsec,
It has been confirmed that the surface protective layer of the photoreceptor according to the present invention does not impair the inherent sensitivity of the photoreceptor having a selenium arsenic alloy single layer structure.

Further, the obtained photoreceptor was left for 6 hours in an environment in which a low-temperature and low-humidity atmosphere at a temperature of 10 ° C. and a relative humidity of 30% and a high-temperature and high-humidity atmosphere at a temperature of 50 ° C. and a relative humidity of 90% were alternately repeated every 30 minutes. However, no peeling or cracking of the surface protective layer was observed, and the surface protective layer of the photoreceptor of the present invention is a film having excellent practical adhesion to the photoreceptor having a single-layer structure of selenium arsenic alloy. It was confirmed that.

The photoreceptor obtained in this example was mounted on a copying machine EP650Z manufactured by Minolta Camera Co., and a real image was obtained, and a clear image was obtained. No image deletion was observed. Also, no peeling of the surface protective layer was observed in contact with the developer, the transfer paper, and the cleaning member in the copying machine.

When 250,000 real shots were taken in a normal room, clear images were obtained until the end. In addition, when the composition of the surface was analyzed by Auger analysis after actually photographing 250,000 sheets, selenium or arsenic was not detected.

Furthermore, no filming occurs on the photoconductor surface,
It was understood that the surface slipperiness was good.

From the above, it was confirmed that the surface protective layer of the present invention achieves improvement in durability and harmfulness without deteriorating image quality.

Comparative Examples 1 and 2 In the same manner as in Example 1 except that the resin layer was not provided, a photosensitive layer having a single-layer structure of selenium-arsenic alloy (Comparative Example 1) and a photosensitive layer having a laminated structure in which selenium and selenium were provided in this order ( Comparative Example 2) An outermost surface layer of an aC film was formed thereon to prepare a photoconductor.

Adhesion of the surface of the obtained photoreceptor was determined by JIS-K-540.
As judged by a grid test based on the 0 standard, it was 2 points, and it was confirmed that the adhesiveness was improved by the present invention.

Effect of the Invention According to the present invention, the surface protective layer of the photosensitive member having a single layer of selenium arsenide alloy or a laminated structure in which selenium and selenium tellurium are provided in this order is replaced with a resin layer and an outermost surface protective layer composed of an aC film. By adopting the layer structure, the inherent properties of the photoreceptor are not impaired, and the surface protective layer has excellent peeling resistance and durability.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of the photoconductor. 2 and 3 show an example of an apparatus for producing the outermost surface layer of the photoreceptor according to the present invention. The symbols in the figure are as follows. (1a): outermost layer (1b): resin layer (2): photosensitive layer (3): conductive substrate (4): surface protective layer (701) to (706): tank (707) )-(712) ... Control valve (713)-(718) ... Flow controller (728)-(730) ... Flow controller (719)-(721) ... Container (722)-(724) … Heating device (731)… Mixer (732)… Main tube (733)… Reaction chamber (734)… Piping heater (736)… Electrical electrode (737)… Electrode heater (738) ) Matching device for high-frequency power (739) Matching device for high-frequency power (740) Matching device for low-frequency power (741) Low-frequency power supply (742) Low-pass filter (743) DC power supply (744) ) Connection selection switch (745) Pressure control valve (746) Exhaust system selection valve (747) Diffusion pump (748) Oil rotary pump (749) Cooling exclusion device (750) … Mechanical booster Pump (751) .... reaction chamber heater (752) ... substrate (753) ... removal systems

 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Kenji Masaki 2-30 Azuchicho, Higashi-ku, Osaka-shi, Osaka Inside Osaka International Building Minolta Camera Co., Ltd. (56) References JP-A-60-61761 (JP, A) Kaisho 60-225163 (JP, A)

Claims (1)

(57) [Claims] 1. A photoreceptor having a single layer of selenium-arsenic alloy or a laminated structure in which selenium and a selenium-tellurium alloy are provided in this order on a conductive substrate, a resin layer on the surface of the photoreceptor and a glow discharge on the resin layer. A photoreceptor comprising a surface protective layer composed of two outermost layers composed of an amorphous hydrocarbon film (a-C film) formed by a plasma polymerization method.