JPH0441816B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to electrophotographic photoreceptors, and more particularly to electrophotographic photoreceptors having a low molecular weight organic photoconductor that provides improved electrophotographic properties. Conventionally, inorganic photoconductive materials such as selenium, cadmium sulfide, and zinc oxide are known as photoconductive materials used in electrophotographic photoreceptors. These photoconductive materials have a number of advantages, such as being able to be charged to an appropriate potential in the dark, having little charge dissipation in the dark, or quickly dissipating the charge when irradiated with light. However, it also has various drawbacks. For example, selenium-based photoreceptors easily crystallize due to factors such as temperature, humidity, dust, and pressure. Especially when the ambient temperature exceeds 40°C, crystallization becomes significant, resulting in decreased charging performance and white spots on images. There is a drawback when this occurs. Cadmium sulfide photoreceptors do not provide stable sensitivity in humid environments, and zinc oxide photoreceptors require the sensitizing effect of sensitizing dyes such as rose bengal. Since the sensitive dye deteriorates due to corona charging and undergoes photobleaching due to exposure light, it has the disadvantage that it cannot provide stable images over a long period of time. On the other hand, various organic photoconductive polymers including polyvinylcarbazole have been proposed, but these polymers are superior in terms of film formability and lightness compared to the inorganic photoconductive materials mentioned above. Despite this, it has been difficult to put it into practical use to date because sufficient film formation properties have not yet been achieved, and inorganic photoconductive materials have been lacking in terms of sensitivity, durability, and stability against environmental changes. This was because they were inferior in comparison. In addition, hydrazone compounds disclosed in U.S. Pat. No. 4,150,987, triarylpyrazoline compounds described in U.S. Pat. Low molecule organic photoconductors have been proposed, such as the 9-steryl anthracene compounds described. By appropriately selecting the binder used, such low-molecular-weight organic photoconductors can overcome the film-forming problems that had been a problem in the field of organic photoconductive polymers. However, it cannot be said to be sufficient in terms of sensitivity. For these reasons, a laminated structure in which the photosensitive layer is functionally separated into a charge generation layer and a charge transport layer has been proposed in recent years. Electrophotographic photoreceptors using this laminated structure as a photosensitive layer can now be improved in terms of sensitivity to visible light, charge retention, surface strength, and the like. Such an electrophotographic photoreceptor is disclosed in, for example, US Pat. No. 3,837,851;
This is disclosed in Publication No. 3871882, etc. However, electrophotographic photoreceptors that use conventional low-molecular-weight organic photoconductors in the charge transport layer have not yet achieved sufficient sensitivity, and when repeatedly charged and exposed, the bright area potential There are some points that need to be greatly improved, such as fluctuations in the dark potential. SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photoreceptor that eliminates the above-mentioned drawbacks or disadvantages. Another object of the invention is to provide a new organic photoconductor. Another object of the present invention is to provide a novel charge transport material in a laminated photosensitive layer in which a charge generation layer and a charge transport layer are functionally separated. This object of the present invention is achieved by an electrophotographic photoreceptor having a layer containing a hydrazone compound represented by the following general formula (1). In the formula, R ₁ represents an alkyl group that may have a substituent such as halogen, or an aralkyl group that may have a substituent such as halogen or alkyl, and R ₂ represents a hydrogen atom, halogen, alkyl group, or alkoxy R ₃ represents an alkyl group that may have a substituent such as halogen, an aralkyl group that may have a substituent such as halogen, alkyl, or alkoxy, or an aryl group. R ₄ and R ₅ represent an alkyl group, an aralkyl group, or a phenyl group, and these may be substituted with halogen, alkoxy, or the like. Further, R ₄ and R ₅ represent residues that together with the N atom form a 5- to 6-membered ring group such as a pyrrolidino group, a piperidino group, or a morpholino group. Ar represents an aryl group such as phenyl or naphthyl, which may be substituted with halogen, alkyl, alkoxy, or the like. Representative examples of the compound represented by general formula (1) are listed below. Next, a method for synthesizing the above compound will be illustrated. Dissolve 0.3 mol of the corresponding secondary amine in 350 ml of glacial acetic acid to obtain 22.4
G of sodium nitrite was gradually added to nitrosate, and after adding 350 ml of methanol, zinc powder was added as it was.
67.5g will be returned. Reduction should not exceed 35°C. Add 0.24 mol of aldehyde to a solution of hydrazine from which zinc dust has been filtered and stirred at room temperature with glacial acetic acid.
If the solution dissolved in 200ml is added dropwise, yellow hydrazone will precipitate out. It was purified by recrystallization from a mixed solvent of MEK/methanol (1/1) and subjected to sampling. Note that the above-mentioned secondary amine is synthesized by alkylating, aralkylating, and arylating a 3-aminocarbazole derivative. Alkylation and aralkylation are carried out by heating and reacting 2 times the mole of the 3-aminoalbazole derivative with an alkyl chloride or aralkyl chloride, followed by benzene treatment, and arylation is carried out by reacting 2 times the mole of the 3-aminocarbazole derivative with a carboxyl group at the adjacent position. This is achieved by heating decarboxylation of a chloro-substituted aryl at 150°C in the presence of a copper catalyst and potassium carbonate. All of these methods are known methods. In a preferred embodiment of the present invention, a hydrazone compound represented by the general formula (1) can be used as a charge transporting substance in an electrophotographic photoreceptor in which a photosensitive layer is functionally separated into a charge generation layer and a charge transport layer. The charge transport layer according to the present invention is preferably formed by applying a solution prepared by dissolving a hydrazone compound represented by the above general formula and a binder in a suitable solvent and drying the solution. Examples of the binder used here include polyarylate resin,
Polysulfone resin, polyamide resin, acrylic resin, acrylonitrile resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, phenolic resin, epoxy resin, polyester resin, alkyd resin, polycarbonate, polyurethane, or two or more repeating units of these resins For example, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, etc. can be mentioned. In addition to such insulating polymers, organic photoconductive polymers such as polyvinylcarbazole, polyvinylanthracene, and polyvinylpyrene can also be used. The blending ratio of this binder and the hydrazone compound is 10 parts by weight of the hydrazone compound per 100 parts by weight of the binder.
It is preferable to set it to 500 weight. The charge transport layer is electrically connected to the charge generation layer described below, and has the function of receiving charge carriers injected from the charge generation layer in the presence of an electric field and transporting these charge carriers to the surface. are doing. At this time, this charge transport layer may be laminated on or under the charge generation layer. However, it is desirable that the charge transport layer is laminated on the charge generation layer.
Since this charge transport layer has a limit in its ability to transport charge carriers, it cannot be made thicker than necessary. Typically it is between 5 microns and 30 microns, with a preferred range between 8 microns and 20 microns. The organic solvent used when forming such a charge transport layer varies depending on the type of binder used.
Alternatively, it is preferable to select a material that does not dissolve the charge generation layer or the subbing layer described below. Specific organic solvents include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone;
Amides such as N,N-dimethylformamide and N,N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane, and ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, chloroform, Aliphatic halogenated hydrocarbons such as methylene chloride, dichloroethylene, carbon tetrachloride, and trichlorethylene, or aromatics such as benzene, toluene, xylene, ligroin, monochlorobenzene, and dichlorobenzene can be used. Coating can be carried out using coating methods such as dip coating, spray coating, spinner coating, bead coating, Meyer bar coating, blade coating, roller coating, and curtain coating. For drying, it is preferable to dry to the touch at room temperature and then heat dry. Heat drying at a temperature of 30℃ to 200℃ for 5 minutes to 2
It can be carried out stationary or under blown air for a period of time within a range of hours. The charge transport layer of the present invention can contain various additives. Such additives include diphenyl, diphenyl chloride, o-terphenyl,
p-terphenyl, dibutyl phthalate, dimethyl glycol phthalate, dioctyl phthalate, triphenyl phosphoric acid, methylnaphthalene, benzophenone, chlorinated paraffin, dilaurylthiopropionate, 3,5-dinitrosalicylic acid,
Examples include various fluorocarbons. The charge generation layer used in the present invention includes selenium, selenium-tellurium, pyrylium, thiopyrylium dyes,
Phthalocyanine pigments, anthorone pigments,
dibenzpyrenequinone pigment, pyranthrone pigment,
Separately deposited layers or resins selected from charge-generating materials such as trisazo pigments, disazo pigments, azo pigments, indigo pigments, quinacridone pigments, asymmetric quinocyanines, quinocyanines, or amorphous silicon as described in JP-A-54-143645. A dispersion layer can be used. Examples of the charge generating substance used in the electrophotographic photoreceptor of the present invention include the following inorganic compounds and organic compounds. Charge generating substances (1) Amorphous silicon (2) Selenium-tellurium (3) Selenium-arsenic (4) Cadmium sulfide (58) Methine squarate dye (59) Indigo dye (CI No. 78000) (60) Thioindigo dye (CI No. 78800) 〓61) β-type copper phthalocyanine The charge-generating layer can be formed by dispersing the above-mentioned charge-generating substance in a suitable binder and coating it on the substrate, or by forming a vapor-deposited film using a vacuum evaporator. Obtainable. Binders that can be used to form the charge generating layer by coating can be selected from a wide range of insulating resins, and organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, and polyvinylpyrene. You can choose. Preferably, polyvinyl butyral, polyarylate (condensation polymer of bisphenol A and phthalic acid, etc.), polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide resin, polyamide, polyvinylpyridine, cellulose resin, urethane Examples include insulating resins such as resin, epoxy resin, casein, polyvinyl alcohol, and polyvinylpyrrolidone. The resin contained in the charge generation layer is suitably 80% by weight or less, preferably 40% by weight or less. Examples of organic solvents used during coating include alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, N,N-dimethylformamide,
Amides such as N,N-dimethylacetamide,
Sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane, and ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, aliphatic halogens such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, and trichloroethylene. Carbonized hydrocarbons or aromatics such as benzene, toluene, xylene, ligroin, monochlorobenzene, dichlorunzene, etc. can be used. Coating can be carried out using coating methods such as dip coating, spray coating, spinner coating, bead coating, Meyer bar coating, blade coating, roller coating, and curtain coating. The charge generation layer contains as much of the organic photoconductor as possible in order to obtain sufficient absorbance and is preferably a thin film layer, for example less than 5 microns, in order to shorten the range of the generated charge carriers. teeth
A thin film layer having a thickness of 0.01 micron to 1 micron is preferable. This means that most of the incident light is absorbed by the charge generation layer and generates a large number of charge carriers, and that the generated charge carriers are not deactivated by recombination or trapping, and the charge transport layer This is due to the need to inject. A photosensitive layer having such a laminated structure of a charge generation layer and a charge transport layer is provided on a substrate having a conductive layer. As the substrate having the conductive layer, materials that are themselves conductive can be used, such as aluminum, aluminum alloy, copper, zinc, stainless steel, vanadium, molybdenum, chromium, titanium, nickel, indium, gold, and platinum. In addition, plastics (e.g., polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resin, polyethylene fluoride, etc.), conductive particles (e.g. carbon black,
A substrate coated on plastic with a suitable binder (silver particles, etc.), a substrate made of plastic or paper impregnated with conductive particles, a plastic containing a conductive polymer, etc. can be used. A subbing layer having barrier and adhesive functions can also be provided between the conductive layer and the photosensitive layer. The subbing layer is made of casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide (nylon 6, nylon 66, nylon
610, copolymerized nylon, alkoxymethylene nylon, etc.), polyurethane, gelatin, aluminum oxide, etc. The thickness of the undercoat layer is 0.1 micron to 5 micron.
Preferably, 0.5 micron to 3 micron is appropriate. When using a photoreceptor in which a conductive layer, a charge generation layer, and a charge transport layer are laminated in this order, the hydrazone compound has hole transport properties, so the surface of the charge transport layer must be negatively charged, and when exposed to light after charging, In the exposed area, holes generated in the charge generation layer are injected into the charge transport layer, and then reach the surface to neutralize the negative charges, resulting in attenuation of the surface potential and an electrostatic contrast between the layer and the unexposed area. During development, it is necessary to use a positively charged toner, contrary to the case where a charge transport material is used. In another embodiment of the present invention, the aforementioned disazo pigments or
Pigments having photoconductivity such as pyrylium dyes, thiapyrylium dyes, selenapyrylium dyes, benzopyrylium dyes, benzothiapyryllium dyes, naphthopyryllium dyes, and naphthothiapyrylium dyes disclosed in the same publication No. 3586500, etc. Dyes can also be used as hydrazone sensitizers. In another specific example, a eutectic complex of a pyrylium dye and an electrically insulating polymer having an alkylidene diarylene moiety as disclosed in US Pat. No. 3,684,502 and the like can be used as a hydrazone sensitizer. This eutectic complex is, for example, 4-[4-bis-(2-chloroethyl)aminophenyl]-2,6
- diphenylthiapyrylium perchlorate and poly(4,4'-isoprolidene diphenylene carbonate) in a halogenated hydrocarbon solvent (e.g.
dichloromethane, chloroform, carbon tetrachloride,
1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, bromobenzene, 1,2-dichlorobenzene) and then dissolved in a non-polar solvent (e.g.
It is obtained as a particulate eutectic complex by adding hexane, octane, decane, 2,2,4-trimethylbenzene, and ligroin. The electrophotographic photoreceptor in this specific example includes styrene-butadiene copolymer, silicone resin, vinyl resin, vinylidene chloride-acrylonitrile copolymer, styrene-acrylonitrile copolymer, vinyl acetate-vinyl chloride copolymer, polyvinyl butyral, polymethyl methacrylate, poly-N −
Binders such as butyl methacrylate, polyesters, cellulose esters, etc. can be included with the hydrazone and eutectic complex. The electrophotographic photoreceptor of the present invention can be used not only for electrophotographic copying machines, but also for laser printers,
It can also be widely used in electrophotographic applications such as CRT printers and electrophotographic plate making systems. According to the present invention, it is possible to provide a highly sensitive electrophotographic photoreceptor, and the variation in bright area potential and dark area potential when repeatedly charging and exposing is small, and photomemory properties can be effectively improved. It has advantages. Hereinafter, the present invention will be explained according to examples. Example 1 7g of pigment purified by purifying β-type copper phthalocyanine (trade name: Lionol Blue NCB Toner) manufactured by Toyo Ink Mfg. Co., Ltd. after sequentially refluxing water in ethanol and benzene: "Trade name: "Lionol Blue NCB Toner" manufactured by DuPont : Polyester adhesive 49000 (solid content 20%)” 14
A coating solution was prepared by mixing 35 g of toluene and 35 g of dioxane and dispersing the mixture in a ball mill for 6 hours. This coating solution was applied onto an aluminum sheet using a Mayer bar to a dry film thickness of 0.5 microns to form a charge generation layer. Next, the above-mentioned exemplary compound H is used as a charge transport compound.
7g of -1 and polycarbonate resin (Teijin Kasei Ltd.)
A solution obtained by stirring and dissolving 7 g of Panlite K-1300 (trade name: Panlite K-1300) in a mixed solvent of 35 g of tetrahydrofuran and 35 g of chlorobenzene was placed on top of the charge generation layer, and the dry film thickness was 11 cm using a Mayer bar. An electrophotographic photoreceptor having a photosensitive layer having a two-layer structure was prepared by coating in a micron-thickness layer. The electrophotographic photoreceptor thus prepared was statically charged with corona at -5kV using an electrostatic copying paper tester Model-SP-428 manufactured by Kawaguchi Electric Co., Ltd., and held in a dark place for 1 second. The charging characteristics were investigated by exposing to light at an illuminance of 5 lux. As for chargeability, the surface potential (V ₀ ) and the exposure amount (E1/2) required to attenuate the potential (V ₁ ) by 1/2 when dark decayed for 1 second were measured. Furthermore, in order to measure the fluctuations in bright area potential and dark area potential during repeated use, the photoreceptor fabricated in this example was charged with a -5.6kV corona charger, and the exposure amount was
10lux.sec exposure optical system, developer, transfer charger,
It was attached to the cylinder of an electrophotographic copying machine equipped with a static elimination exposure optical system and a cleaner. This copying machine is configured to produce an image on transfer paper as a cylinder is driven. Using this copying machine, the initial bright area potential (V _L ), dark area potential (V _D ) and
The light potential (V _L ) and dark potential (V _D ) were measured after 5000 uses. The results are shown below. V ₀ : -560 volts V ₁ : -540 volts E1/2: 4.3lux.sec Initial V _D : -590 volts V _L : -30 volts After 5000 cycles V _D : -565 volts V _L : -40 volts Examples 2 to 16 In each of these Examples, exemplified compounds H-2, H-3, H-4, H-5,
H-6, H-7, H-8, H-9, H-10, H-
An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that No. 11, H-12, H-13, H-14, H-15, and H-16 were used. The electrophotographic properties of each photoreceptor were measured in the same manner as in Example 1. The results are shown below.

[Table] Example 17 4-(4-dimethylaminophenyl)-2,6-
3 g of diphenylthiapyrylium perchlorate and 5 g of the exemplified hydrazone compound H-2 were mixed with toluene (50)-dioxane (50) of polyester (Polyester Adhesive 49000: manufactured by DuPont).
The mixture was mixed with 100 ml of solution and dispersed in a ball mill for 6 hours. This dispersion was applied onto an aluminum sheet using a Mayer bar so that the film thickness after drying was 15 microns. The electrophotographic properties of the photoreceptor thus prepared were measured in the same manner as in Example 1. The results are shown below. V ₀ : -550 volts V ₁ : -545 volts E1/2: 4.0lux.sec Initial V _D : -570 volts V _L : -35 volts After 5000 cycles V _D : -560 volts V _L : -40 volts Example 18 Ammonia aqueous solution of casein (11.2 g of casein, 1 g of 28% ammonia water, 222 ml of water) on an aluminum plate.
was coated with a Mayer bar and dried to form an adhesive layer with a thickness of 1 micron. Next, 5 g of a disazo pigment having the following structure, Butyral resin (degree of butyralization 63 mol%) 2g
was dispersed with a solution dissolved in 95 ml of ethanol, and then coated on the adhesive layer to form a charge generation layer having a thickness of 0.4 microns after drying. Next, the above-mentioned hydrazone compound H-7 was added to 5
g and poly-4,4'-dioxydiphenyl-2,2
-Propane carbonate (viscosity average molecular weight 30000)
An electrophotographic photoreceptor was prepared by dissolving 5 g of the solution in 150 ml of dichloromethane and coating it on the charge generation layer and drying it to form a charge transport layer with a thickness of 11 microns. The electrophotographic properties of the electrophotographic photoreceptor thus prepared were measured in the same manner as in Example 1. V ₀ : -565 volts V ₁ : -555 volts E1/2: 4.6lux.sec Initial V _D : -590 volts V _L : -40 volts After 5000 cycles V _D : -585 volts V _L : -45 volts Example 19 A 0.2 mm thick molybdenum plate (substrate) whose surface was cleaned was fixed at a predetermined position in a glow discharge deposition tank. Next, the inside of the tank was evacuated to a vacuum level of approximately 5×10 ⁻⁶ torr. After that, the input voltage of the heater was increased to stabilize the molybdenum substrate temperature at 150℃. After that, hydrogen gas and silane gas (15% by volume relative to hydrogen gas) were introduced into the tank and stabilized at 0.5 torr by adjusting the gas flow rate and the main valve of the deposition tank. Next, 5MHz high-frequency power was applied to the induction coil to generate a glow discharge inside the coin in the tank, resulting in an input power of 30W. An amorphous silicon film was grown on the substrate under the above conditions, and the same conditions were maintained until the film thickness reached 2 μm, after which glow discharge was discontinued. Then the heating heater,
The high frequency power supply was turned off, and after waiting for the substrate temperature to reach 100°C, the hydrogen gas and silane gas outflow valves were closed, and after the inside of the tank was once lowered to below 10 ^-5 torr, the pressure was returned to atmospheric pressure, and the substrate was taken out. Next, a charge transport layer was formed on this amorphous silicon layer in exactly the same manner as in Example 1 except that Exemplified Compound H-14 was used as the charge transport compound. The photoreceptor thus obtained was placed in a charging exposure experimental device, charged with corona at 6 kV, and immediately irradiated with a light image. The light image was illuminated through a transmission test chart using a tungsten lamp light source. Thereafter, a good toner image was obtained on the photoreceptor surface by immediately cascading a charged developer (including toner and carrier) onto the photoreceptor surface. Example 20 4-(4-dimethylaminophenyl)-2,6-
After fully dissolving 3 g of diphenylthiapyrylium perchlorate and 3 g of poly(4,4'-isopropylidene diphenyllene carbonate) in 200 ml of dichloromethane, 100 ml of toluene was added to precipitate a eutectic complex. After separating this precipitate, dichloromethane was added to redissolve it, and then 100 ml of n-hexane was added to this solution to obtain a precipitate of a eutectic complex. 5g of this eutectic complex and 2g of polyvinyl butyral
The mixture was added to 95 ml of a methanol solution containing 100 ml of methanol, and dispersed in a ball mill for 6 hours. This dispersion was applied onto an aluminum plate having a casein layer using a Mayer bar so that the film thickness after drying was 0.4 microns to form a charge generation layer. Next, exemplified compound H- is applied on this charge generation layer.
A cover layer of a charge transport layer was formed in the same manner as in Example 1 except that No. 4 was used. The electrophotographic properties of the photoreceptor thus prepared were measured in the same manner as in Example 1. The results are shown below. V ₀ : -590 volts V ₁ : -575 volts E1/2: 4.0lux.sec Initial V _D : -580 volts V _L : -40 volts After 5000 cycles V _D : -570 volts V _L : -45 volts Example 21 5 g of the same eutectic complex used in Example 20 and 17.5 g of the above-exemplified hydrazone compound H-1 were added to 150 ml of a tetrahydrofuran solution of polyester (Polyester Adhesive 49000, manufactured by Dupont) and sufficiently mixed. Mix and stir. The film thickness after drying this liquid using a Mayer bar on an aluminum sheet is 15 μm.
It was applied so that The electrophotographic properties of this photoreceptor were measured in the same manner as in Example 1. The results are shown below. V ₀ : -605 volts V ₁ : -590 volts E1/2: 4.4lux.sec Initial V _D : -615 volts V _L : -45 volts After 5000 cycles V _D : -600 volts V _L : -50 volts .

Claims (1)

[Claims] 1. An electrophotographic photoreceptor containing a hydrazone compound represented by the following general formula: However, in the formula, R ₁ is an alkyl group or aralkyl group that may have a substituent, R ₂ is a hydrogen atom, halogen, an alkyl group, or an alkoxy group, and R ₃ is an alkyl group or an aralkyl group that may have a substituent. group or aryl group, R ₄ and R ₅ are alkyl groups, aralkyl groups, phenyl groups that may have substituents, or residues forming a 5- to 6-membered ring together with N atom, Ar has a substituent Indicates an aryl group that may be