JPH11184119A - Electrophotographic photoreceptor, process cartridge having the same and electrophotographic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the electrophotographic photoreceptor having improved sensitivity characteristics and stable potential characteristics at the time of repeated uses by incorporating as a charge generating material a hydroxygalium phthalocyanine pigment and as a charge transfer maternal a specified compound in a photosensitive layer. SOLUTION: This electrophotographic photoreceptor is provided on a conductive substrate with the photosensitive layer containing as the charge generating material the hydroxygalium phthalocyanine pigment and as the charge transfer material at least one of the compounds represented by formulae I and II in which each of Ar1 -Ar5 is an aryl group; each of R1 and R2 is an H or halogen atom or an alkyl, aralkyl, or aryl group; R3 is an H or halogen atom or an alkyl or alkyl, or aryl group; each of R4 and R5 is an H atom or an alkoxy or aralkyl or aryl group; and each of R6 and R7 is an H or halogen atom or an alkyl or alkoxy or aryl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

[0002]

2. Description of the Related Art Electrophotography is disclosed in U.S. Pat. No. 2,297,691.
As disclosed in the specification, a photoconductive material is used in which the electrical resistance changes according to the amount of irradiation received during image exposure, and in a dark place, a support coated with an insulating substance is used. . The basic characteristics required of an electrophotographic photoreceptor using this photoconductive material include (1) being able to be charged to an appropriate potential in a dark place, (2) having little charge dissipation in a dark place, and ( 3) The charge can be quickly dissipated by light irradiation.

[0003] Conventionally, selenium,
Inorganic photoreceptors having a photosensitive layer mainly containing an inorganic photoconductive compound such as cadmium sulfide and zinc oxide have been widely used. However, they satisfy the above conditions (1) to (3), but do not always satisfy thermal stability, moisture resistance, durability, productivity, and the like. For example, when selenium is crystallized, its characteristics as a photoreceptor deteriorate, making it difficult to manufacture. In addition, heat, fingerprints, and the like cause crystallization, which causes crystallization to deteriorate the performance as a photoreceptor. Cadmium sulfide has problems in moisture resistance and durability, and zinc oxide has problems in smoothness, hardness and friction resistance. Furthermore, the photosensitive wavelength region of many inorganic photosensitive members is limited. For example, the photosensitive wavelength region of selenium is the blue region, and the red region has little sensitivity.

Therefore, various methods have been proposed to extend the photosensitivity to the long wavelength region, but there are many restrictions on the selection of the photosensitive wavelength region. Even when zinc oxide or cadmium sulfide is used as a photoreceptor, the photosensitive wavelength range of the photoreceptor itself is narrow, and it is necessary to add various sensitizers. In order to overcome the disadvantages of these inorganic photoconductors, electrophotographic photoconductors containing various organic photoconductive compounds as main components have been actively developed in recent years. For example, U.S. Pat. No. 3,838,851 discloses a photoreceptor having a charge transporting layer containing triallylpyrazoline, and U.S. Pat. No. 3,871,882 discloses a charge generating layer comprising a derivative of a perylene pigment and a mixture of 3-propylene and formaldehyde. A photoreceptor comprising a charge transport layer comprising a condensate is already known. Further, as a photoreceptor using a bisazo pigment or a trisazo pigment as a charge generating material, JP-A-59-33445, JP-A-56-46237.
And Japanese Patent Application Laid-Open No. Sho 60-111249 are already known.

Further, the photosensitive wavelength range of the electrophotographic photosensitive member can be freely selected depending on the organic photoconductive compound. For example, azo organic pigments are disclosed in JP-A-61-272754 and JP-A-56-167.
The substance disclosed in Japanese Patent No. 759 has high sensitivity in the visible region, and the substance disclosed in Japanese Patent Application Laid-Open Nos. 57-195767 and 61-228453 has a sensitivity up to the infrared region. Some have.

Among these materials, those having sensitivity in the infrared region are laser beam printers, which have been remarkably advanced in recent years.
(Hereinafter abbreviated as LBP), LED printers, and the like, and the demand frequency is increasing.

Conventionally, copper phthalocyanine having sensitivity in the infrared region (JP-A-50-38543)
Phthalocyanine compounds such as oxytitanium phthalocyanine disclosed in Japanese Patent Application No. 3-128973 and Japanese Patent Application Laid-Open No. 5-263007 are recently disclosed as materials having high sensitivity in the infrared region. Are attracting attention, such as hydroxygallium phthalocyanine.

An organic photoreceptor using an organic photoconductive compound can be a function-separated type photoreceptor which is separated into a charge-generating substance for generating electric charge and a charge-transporting substance for transporting electric charge. The material selection range of the charge generation material and the charge transport material is wide, and an electrophotographic photoreceptor having arbitrary characteristics can be relatively easily produced.

Regarding the charge transporting substance, for example, a pyrazoline compound disclosed in Japanese Patent Publication No. 52-4188,
Hydrazone compounds disclosed in JP-A-42380 and JP-A-55-52063, JP-B-58-32372, JP-A-61-132950, and JP-A-62-20
8054, JP-A-3-78756, JP-A-7-72639, triphenylamine compounds, JP-A-54-151955 and JP-A-58-198.
No. 043 is known.

A photoreceptor having high sensitivity and durability in the infrared region has also been prepared by combining these various charge generating substances and charge transporting substances. Is desired.

The present inventors have repeatedly studied various combinations of a charge generating substance and a charge transporting substance. As a result, when the charge generating substance having a specific structure was combined with a charge transporting substance, particularly excellent sensitivity and potential were obtained. It has been found that a photoreceptor exhibiting the stability of the above can be produced, and the present invention has been achieved.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member having improved sensitivity characteristics and a stable potential characteristic during repeated use, and a process card provided with the electrophotographic photosensitive member. To provide a cartridge as well as an electrophotographic device.

[0013]

According to the present invention, there is provided an electrophotographic photoreceptor comprising a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a hydroxygallium phthalocyanine pigment as a charge generating substance, and has a charge transport property. A compound represented by the following general formula (1) as a substance;

Embedded image (Wherein, Ar ₁ represents an aryl group which may have a substituent, and R ₁ and R _{2 each} represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, An aralkyl group or an aryl group which may have a substituent,
R ₃ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. R ₁ and R ₂ may form a ring together. ) And a compound represented by the following general formula (2):

Embedded image (Wherein, Ar ₂ , Ar ₃ , Ar ₄ and Ar _{5 each} represent an aryl group which may have a substituent, and R ₄ and R _{5 each} represent a hydrogen atom or an alkyl group which may have a substituent. An aralkyl group which may have a substituent or an ant which may have a substituent
R ₆ and R ₇ represent a hydrogen atom, a halogen atom,
It represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. R ₄ and R ₅ may form a ring together. ), Which comprises at least one of the following:

According to the present invention, there is further provided an electrophotographic photoreceptor of the present invention, and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means, integrally supported on the electrophotographic apparatus main body. It is composed of a process cartridge characterized by being detachable.

Further, the present invention comprises an electrophotographic apparatus comprising the electrophotographic photoreceptor of the present invention, a charging unit, an image exposing unit, a developing unit and a transferring unit.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formulas (1) and (2), a halogen atom is a fluorine atom, a chlorine atom,
A bromine atom and an iodine atom are exemplified, and the alkyl group is exemplified by groups such as methyl, ethyl, propyl and butyl.
Examples of the aralkyl group include groups such as benzyl and phenethyl; examples of the aryl group include groups such as phenyl, diphenyl, naphthyl, anthryl and pyrenyl; examples of the alkoxy group include groups such as methoxy, ethoxy, and propoxy. Can be Further, as a substituent which may have,
Alkyl groups such as methyl, ethyl and propyl, methoxy,
Alkoxy groups such as ethoxy and propoxy, fluorine atoms,
Examples include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, a nitro group, a hydroxyl group and a cyano group. And substituted amino groups such as dimethylamino and diphenylamino.

The hydroxygallium phthalocyanine pigment includes, for example, hydroxygallium phthalocyanine having the following crystal form.

Bragg angle 2 in X-ray diffraction of CuKα
θ ± 0.2 ° is 7.4 °, 9.9 °, 25.0 ° and 2
Hydroxygallium phthalocyanine pigment having a crystal form having a strong peak at 8.2 °

Bragg angle 2 in X-ray diffraction of CuKα
Hydroxygallium phthalocyanine pigment having a crystal form having a strong peak at ±± 0.2 ° of 6.8 °, 13.6 °, 16.5 ° and 26.3 °

Bragg angle 2 in X-ray diffraction of CuKα
θ ± 0.2 ° is 7.0 °, 7.5 °, 10.5 °, 1
1.7 °, 12.7 °, 17.3 °, 18.1 °, 2
Hydroxygallium phthalocyanine pigment having a crystalline form with strong peaks at 4.5 °, 26.2 ° and 27.1 °

Bragg angle 2 in X-ray diffraction of CuKα
Hydroxygallium phthalocyanine pigment having a crystal form having a strong peak at θ ± 0.2 ° of 7.9 °, 16.5 °, 24.4 ° and 27.6 °

Bragg angle 2 in X-ray diffraction of CuKα
Hydroxygallium phthalocyanine pigment having a crystal form having a strong peak at ±± 0.2 ° of 7.7 °, 16.5 °, 25.1 ° and 26.6 °

Bragg angle 2 in X-ray diffraction of CuKα
θ ± 0.2 ° is 7.5 °, 9.9 °, 12.5 °, 1
Hydroxygallium phthalocyanine pigment having a crystalline form with strong peaks at 6.3 °, 18.6 °, 25.1 ° and 28.3 °

Next, specific examples of the compounds represented by formulas (1) and (2) are shown in Tables 1 to 6. However, it is not limited to these specific examples.

[Table 1]

[Table 2]

[Table 3]

[0025]

[Table 4]

[Table 5]

[Table 6]

The constitution of the photosensitive layer of the electrophotographic photosensitive member of the present invention includes, for example, the following forms. (1) layer containing charge generating material / layer containing charge transporting material (lower / upper layer) (2) layer containing charge transporting material / layer containing charge generating material (lower / upper layer) (3) charge Layer containing generator and charge transport material

In the electrophotographic photoreceptor of the present invention, the charge generation layer contains as much hydroxygallium phthalocyanine pigment as possible to obtain a sufficient absorbance, and
A thin film layer to shorten the range of generated charge carriers,
It is desirable that the thin film layer has a thickness of 5 μm or less, preferably 0.01 to 1 μm.

The charge generation layer can be formed by dispersing a hydroxygallium phthalocyanine pigment in a suitable binder and coating the dispersion on a conductive support.

The binder used when forming by coating can be selected from a wide range of insulating resins, and can be selected from organic photoconductive polymers such as poly-N-vinyl carbazole, polyvinyl anthracene, and polyvinyl pyrene. it can. Preferably, polyvinyl butyral, polyarylate (condensed polymer of bisphenol A and phthalic acid),
Polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide, polyamide, polyvinyl pyridine, cellulose resin, polyurethane, epoxy resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone, etc. . The amount of the resin contained in the charge generation layer is suitably 80% by weight or less, preferably 40% by weight or less.

The solvent for dissolving these resins differs depending on the type of the resin, and is preferably selected from those which do not dissolve the charge transport layer or the undercoat layer. Specifically, alcohols such as methanol, ethanol and isopropanol are used.
, Acetone, methyl ethyl ketone, ketones such as cyclohexane, N, N-dimethylformamide, N, N
Amides such as dimethylacetamide, sulfoxides such as dimethylsulfoxide, ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, chloroform, methylene chloride, and dichloroethylene. And aromatic halogenated hydrocarbons such as carbon tetrachloride and trichloroethylene, and aromatic compounds such as benzene, toluene, xylene, ligroin, chlorobenzene and dichlorobenzene.

As a coating method, a dipping coating method,
Spray coating method, spinner coating method,
Bead coating method, myr bar coating method,
A method such as a blade coating method, a roller coating method, and a curtain coating method can be employed. Drying is preferably performed by touch drying at room temperature and then heating and drying. Heat drying in the range of 30 to 200 ° C for 5 minutes to 2
Perform static or under blast over a time range.

The charge transport layer can be formed by dissolving a compound having a specific fluorene structure represented by the general formulas (1) and (2) together with a suitable binder, and applying the resulting solution.

Examples of the binder resin include acrylic resin, polyarylate, polyester, polycarbonate and the like.
Insulating resin such as polystyrene, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulfone, polyacrylamide, polyamide, chlorinated rubber, or poly-N-vinyl carbazole ,
Organic photoconductive polymers such as polyvinyl anthracene and polyvinyl pyrene are exemplified.

The charge transport layer has a limit of transporting charge carriers and cannot be made thicker than necessary, but has a thickness of 3 to 50 μm, preferably 8 to 30 μm. When forming the charge transport layer by coating, the above-mentioned appropriate coating method can be adopted.

An electrophotographic photosensitive member having a laminated structure of a charge generation layer and a charge transport layer is provided on a conductive support.

As the conductive support, a support having conductivity itself, for example, a metal or an alloy such as aluminum or an aluminum alloy is used.
An aluminum alloy, indium oxide, tin oxide, an indium oxide-tin oxide alloy, or the like, a plastic having a layer formed by a vacuum deposition method, conductive particles (for example, carbon black, silver particles, etc.) and a suitable binder. In addition, a plastic or a conductive support coated on the metal support, a conductive support in which conductive particles are impregnated in plastic or paper, a plastic having a conductive polymer, or the like is used.

A barrier is provided between the conductive support and the photosensitive layer.
An undercoat layer having a function and an adhesive function can be provided. The undercoat layer is made of casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylate copolymer, polyamide (nylon 6, nylon 66, nylon 61).
0, copolymerized nylon, alkoxylated nylon, etc.), polyurethane, gelatin, aluminum oxide and the like. The thickness of the undercoat layer is 0.1 to 5 μm, preferably 0.5 to 3 μm.

Further, the electrophotographic photosensitive member of the present invention may be provided with a surface protective layer as required.

The electrophotographic photosensitive member of the present invention can be used not only for an electrophotographic copying machine but also for a laser beam printer,
ED printer, CRT printer, LCD printer,
It can be widely applied to electrophotographic applications such as laser plate making and facsimile.

According to the present invention, the electrophotographic photoreceptor of the present invention and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means are integrally supported and attached to and detached from an electrophotographic apparatus main body. It is composed of a process cartridge characterized by being flexible.

Further, the present invention comprises an electrophotographic apparatus comprising the electrophotographic photoreceptor of the present invention, a charging unit, an image exposing unit, a developing unit and a transferring unit.

FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member according to the present invention. In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around an axis 2 at a predetermined peripheral speed in the direction of an arrow. In the rotation process, the photosensitive member 1 is uniformly charged at a predetermined positive or negative potential on the peripheral surface thereof by the primary charging means 3, and then the image exposure means (such as a slit exposure or a laser beam scanning exposure) is used. (See FIG. 1). Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 1.

The formed electrostatic latent image is then transferred to developing means 5
Is transferred to the transfer material 6 from the paper supply unit (not shown) and fed between the photosensitive member 1 and the transfer means 6 in synchronization with the rotation of the photosensitive member 1. Are sequentially transferred by the transfer means 6. The transfer material 7 having undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing, thereby being printed out as a copy (copy) outside the apparatus. The surface of the photoreceptor 1 after the image transfer is cleaned and cleaned by removing the transfer residual toner by the cleaning means 9, and further subjected to a static elimination process by the pre-exposure light 10 from the pre-exposure means (not shown). After that, it is repeatedly used for image formation. When the primary charging means 3 is a contact charging means using a charging roller or the like, pre-exposure is not necessarily required.

In the present invention, a plurality of components such as the photoreceptor 1, the primary charging means 3, the developing means 5 and the cleaning means 9 are integrally connected as a process cartridge. Alternatively, the process cartridge may be configured to be detachable from a main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. For example, at least one of the primary charging means 3, the developing means 5 and the cleaning means 9 is integrally supported together with the photoreceptor 1 to form a cartridge, and the apparatus main body is guided by a guide means such as the rail 12 of the apparatus main body. The process cartridge 11 can be detachably mounted on the cartridge. When the electrophotographic apparatus is a copier or a printer, the image exposure light 4 uses reflected light or transmitted light from the original, or reads the original with a sensor and converts it into a signal. This is light emitted by scanning of the laser beam, driving of the LED array, driving of the liquid crystal shutter array, and the like.

[0045]

EXAMPLES Table 7 shows examples of hydroxygallium phthalocyanine crystal forms which are charge generating substances used in the following examples.

[Table 7]

Table 8 shows examples of the charge generation materials used in the following comparative examples.

[Table 8]

Embodiment 1

Example 1 An undercoat layer of 0.4 μm vinyl chloride-maleic anhydride-vinyl acetate copolymer was formed on an aluminum plate.

Next, 4 parts of hydroxygallium phthalocyanine in the crystalline form of Pigment Example P-1 and polyvinyl butyral (butyralization degree: 65 mol%, number average molecular weight: 35,000)
0) 2 parts were added to 90 parts of cyclohexanone, dispersed by a sand mill for 3 hours, and diluted with 60 parts of ethyl acetate. A charge generation layer having a thickness of 0.3 μm after drying the prepared coating liquid on the undercoat layer was formed.

Next, Compound Example A-
5 parts of compound 2 and bisphenol Z-type polycarbonate
5 parts (viscosity average molecular weight 50,000) were dissolved in 38 parts of chlorobenzene. The prepared coating solution was applied onto the charge generating layer with a Myr bar so that the film thickness after drying was 18 μm to form a charge transporting layer, thereby preparing an electrophotographic photoreceptor. It is referred to as photoreceptor 1.

Comparative Example 1 A phthalocyanine pigment of Pigment Example Q-1 was used in place of Pigment Example P-1 of Example 1 as a charge generating substance.
An electrophotographic photosensitive member was prepared in the same manner as in Example 1. This is referred to as Comparative Photoconductor 1.

Comparative Example 2 A phthalocyanine pigment of Pigment Example Q-2 was used in place of Pigment Example P-1 of Example 1 as a charge generating substance.
An electrophotographic photosensitive member was prepared in the same manner as in Example 1. This is referred to as comparative photoreceptor 2.

Comparative Example 3 A phthalocyanine pigment of Pigment Example Q-3 was used in place of Pigment Example P-1 of Example 1 as the charge generating substance.
An electrophotographic photosensitive member was prepared in the same manner as in Example 1. This is referred to as Comparative Photoconductor 3.

Comparative Example 4 A phthalocyanine pigment of Pigment Example Q-4 was used in place of Pigment Example P-1 of Example 1 as a charge generating substance.
An electrophotographic photosensitive member was prepared in the same manner as in Example 1. This is referred to as Comparative Photoconductor 4.

The photosensitive member 1 and the comparative photosensitive members 1 to 4 were
A beam printer (trade name: LBP-SX, manufactured by Canon Inc.) was attached to a cylinder of a remodeled machine and charged so that the dark area potential became -700 V.
m laser light to reduce the potential of -700 V to -100.
The amount of light required to lower the voltage to V was measured and defined as sensitivity. Further, a potential when a light amount of 20 μJ / cm ² was irradiated was measured as a residual potential Vr. Table 9 shows the results.

[Table 9]

Next, these five types of photoreceptors were subjected to a humidity of 10%.
%, Air temperature 5 ° C., humidity 50%, air temperature 18 ° C., humidity 80%, and air temperature 35 ° C., in three environments, dark area potential −700, respectively.
V, 3,000 continuous with the bright part potential set to -100 V
A paper endurance test was performed on 0 sheets to measure the dark part potential and the light part potential after the durability test, and to evaluate the image.

The photoreceptor 1 obtained a good image equivalent to the initial one even after endurance in any environment, but the comparative photoreceptors 1 to 4 produced fog on a white background in any environment. In particular, in an environment with a humidity of 80% and an air temperature of 35 ° C., the comparative photoreceptor 4 provided an image which was not particularly good. In the comparative photoreceptors 1 to 4, the density was adjusted by a density adjustment lever to remove background fog.
The density of the black background became insufficient.

As described above, the electrophotographic photosensitive member of the present invention is
It is known that stable and high sensitivity characteristics are exhibited in a long wavelength region around 0 to 810 nm.

Examples 2 to 16 Combinations of hydroxygallium phthalocyanine in various crystal forms shown in Table 7 and some of the exemplified compounds represented by the general formulas (1) and (2) were combined with the charge-generating substance of the first embodiment. An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the charge transporting material was replaced. Photoconductors 2-16.

Each of the photoconductors 2 to 16 is attached to a cylinder of a remodeled laser beam printer (described above) in the same manner as in the first embodiment, and is charged so that the dark area potential becomes -700 V. and, this wavelength 802nm Les - the - it was measured quantity Ideruta ₆₀₀ required to lower the potential of being irradiated with light -700V as -100V. Further, the potential when the light amount of 20 μJ / cm ² was irradiated was measured as the residual potential Vr.
Table 10 shows the results.

After the photoconductors 2 to 16 were reset to have a dark area potential of -700 V and a light area potential of -200 V, 3,000 sheets of paper were continuously passed. Variation ΔV of dark area potential and bright area potential after endurance of sheets
It was measured _D and [Delta] V _L. Table 10 shows the results.

[0062]

[Table 10]

Comparative Examples 5 to 20 Examples 2 to 1 were repeated except that various phthalocyanine pigments shown in Table 8 were used in place of the charge generating substances in Examples 2 to 16.
Electrophotographic photoreceptor (Comparative photoreceptors 5 to 20) in the same manner as in 6.
Was prepared and evaluated in the same manner. Table 11 shows the results.

[0064]

[Table 11]

Comparative Examples 21 to 26 Compounds H-1, H-2, H-3 having the following structural formulas in place of the respective charge transporting substances in Examples 2 to 16 were prepared.
Electrophotographic photoreceptors (comparative photoreceptors 21 to 26) were prepared and evaluated in the same manner as in Examples 2 to 16, except that the compounds of H-4, H-5 and H-6 were used. . Table 12 shows the results.

Embedded image

[0066]

[Table 12]

As is clear from the results shown in Tables 10, 11 and 12, it is known that the electrophotographic photosensitive member of the present invention is extremely excellent in sensitivity, residual potential and repetition characteristics.

Example 17 An undercoat layer similar to that of Example 1 was formed on a 50 μm-thick aluminum sheet support, and a charge transport layer similar to that of Example 1 was formed to a thickness of 20 μm.

Next, bisphenol Z-type polycarbonate
5.5 parts were dissolved in 66 parts of cyclohexanone, 3 parts of Pigment Example P-1 was mixed with the solution, and the mixture was dispersed in a sand mill for 1 hour, and then mixed with 5 parts of bisphenol Z-type polycarbonate. Dissolve 10 parts of the charge transport material used in Example 1,
Further, 40 parts of tetrahydrofuran and 40 parts of dichloromethane were added and diluted to prepare a coating solution. This coating solution was applied onto the charge transport layer by a spray coating method, and dried to form a 6 μm-thick charge generation layer, thereby producing an electrophotographic photoreceptor. This is referred to as a photoconductor 12.

Comparative Example 27 An electrophotographic photosensitive member was prepared in the same manner as in Example 17 except that the compound of Q-1 was used as the charge generating material. This is referred to as a comparative photoconductor 27.

Comparative Example 28 An electrophotographic photosensitive member was prepared in the same manner as in Example 17, except that the compound of Q-2 was used as the charge generating material. This is referred to as a comparative photoconductor 28.

Comparative Example 29 An electrophotographic photosensitive member was prepared in the same manner as in Example 17, except that the compound of Q-3 was used as the charge generating material. This is referred to as a comparative photoconductor 29.

Comparative Example 30 An electrophotographic photosensitive member was prepared in the same manner as in Example 17 except that the compound of Q-4 was used as the charge generating material. This is referred to as a comparative photoconductor 30.

The photosensitive member 17 and the comparative photosensitive members 27, 28, 2
Each of the electrophotographic photosensitive members 9 and 30 was evaluated using an electrostatic tester (trade name: EPA-8100, manufactured by Kawaguchi Electric Co., Ltd.). The evaluation was carried out in such a way that the surface potential was 7
The sensitivity was determined by measuring the amount of light when the surface potential was lowered to 200 V by exposing with monochromatic light of 802 nm separated by a monochrome meter. Table 13 shows the results.

[0075]

[Table 13]

Example 18 On an aluminum support, 4.5 parts of an N-methoxymethylated 6 nylon resin (weight average molecular weight 45,000) and an alcohol-soluble copolymerized nylon resin (weight average molecular weight 5
A solution prepared by dissolving 9 parts of (0,000) in 95 parts of methanol was applied with a Myer bar to form an undercoat layer having a thickness of 0.8 μm after drying.

Next, 12 parts of the compound of P-1 and polyvinyl butyral (butyralization ratio 65%, weight average molecular weight 4
(5,000) and 200 parts of cyclohexanone were dispersed in a ball mill for 24 hours. This dispersion was applied on the undercoat layer by a blade coating method to form a charge generation layer having a thickness of 0.15 μm after drying.

Next, 4 parts of the compound A-5 and 4 parts of the compound B-11 were dissolved in 10 parts of bisphenol Z-type polycarbonate (weight average molecular weight: 45,000) in 70 parts of monochlorobenzene. The obtained solution was applied on the charge generation layer by a blade coating method, and the film thickness after drying was 18
An electrophotographic photosensitive member was formed by forming a μm charge transport layer. This is referred to as a photoconductor 18.

The photoconductor 18 thus produced was subjected to a corona discharge of -5 KV. At this time, the surface potential (initial potential V ₀ ) was measured. Further, the surface potential of this photoconductor after leaving it in a dark place for 1 second was measured. The potential V ₁ of the following sensitivity was dark decay 1
Exposure required to attenuate to / 6 (E _1/6 : μJ / cm
² ) was evaluated by measuring. At this time, a quaternary semiconductor laser of indium / gallium / aluminum / phosphorus (output: 5 mW: oscillation wavelength 680 n) was used as a light source.
m) was used. The results are shown. V ₀ : -695 V, V ₁ : -690 V, E _1/6 : 0.3
9 μJ / cm ²

Next, a laser beam printer, which is an electrophotographic printer of the reversal development type equipped with the semiconductor laser of the above, is used.
The actual image forming test was performed by attaching the photoconductor 18 to the printer (described above). The conditions are as follows. Surface potential after primary charging: -700 V Surface potential after image exposure: -150 V (exposure 2.0 μJ /
cm ² ) Transfer potential: +700 V Development polarity: negative polarity Process speed: 50 mm / sec Development condition (development bias): -450 V Scanning method after image exposure: image scan Exposure before primary charging: 50 lux · sec red overall exposure The image was formed by line scanning the laser beam in accordance with the character signal and the image signal, and good prints were obtained for both the character and the image.

Further, when 5,000 images were continuously output, stable prints from the initial stage to 5,000 sheets were obtained.

[0082]

According to the electrophotographic photoreceptor of the present invention, a specific hydroxygallium phthalocyanine is used as a charge generating material, and a charge transporting substance having a specific fluorene structure is used in combination. It has high sensitivity in such a long wavelength region, shows stable image characteristics in an electrophotographic process, and has a remarkable effect of being excellent in potential stability. Further, the same effects can be obtained in a process cartridge and an electrophotographic apparatus in which the electrophotographic photosensitive member of the present invention is combined.

[Brief description of the drawings]

FIG. 1 is a process car having an electrophotographic photoreceptor of the present invention.
FIG. 2 is a diagram illustrating a schematic configuration of an electrophotographic apparatus having a cartridge.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 electrophotographic photosensitive member of the present invention 2 axis 3 primary charging means 4 image exposure light 5 developing means 6 transfer means 7 transfer material 8 image fixing means 9 cleaning means 10 pre-exposure light 11 process cartridge 12 rail

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Mitsuhiro Kunieda 3- 30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Tetsuro Kanamaru 3- 30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside the corporation

Claims (9)

[Claims] 1. An electrophotographic photoreceptor comprising a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a hydroxygallium phthalocyanine pigment as a charge-generating substance, and has the following general formula (1) as a charge-transporting substance. A compound represented by the formula: (Wherein, Ar ₁ represents an aryl group which may have a substituent; R ₁ and R _{2 each} represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, An aralkyl group or an aryl group which may have a substituent,
R ₃ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. R ₁ and R ₂ may form a ring together. ) And a compound represented by the following general formula (2): (Wherein, Ar ₂ , Ar ₃ , Ar ₄ and Ar _{5 each} represent an aryl group which may have a substituent, and R ₄ and R _{5 each} represent a hydrogen atom or an alkyl group which may have a substituent. An aralkyl group which may have a substituent or an ant which may have a substituent
R ₆ and R ₇ represent a hydrogen atom, a halogen atom,
It represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. R ₄ and R ₅ may form a ring together. An electrophotographic photosensitive member comprising at least one of the following. 2. The method according to claim 1, wherein the hydroxygallium phthalocyanine crystal has a Bragg angle 2θ ± in X-ray diffraction of CuKα.
0.2 ° is 7.4 °, 9.9 °, 25.0 ° and 28.
2. The electrophotographic photosensitive member according to claim 1, which has a crystal form having a strong peak at 2 [deg.]. 3. The method according to claim 1, wherein the hydroxygallium phthalocyanine crystal has a Bragg angle 2θ ± in X-ray diffraction of CuKα.
0.2 ° is 6.8 °, 13.6 °, 16.5 ° and 2
2. The electrophotographic photosensitive member according to claim 1, which has a crystal form having a strong peak at 6.3 [deg.]. 4. The method according to claim 1, wherein the hydroxygallium phthalocyanine crystal has a Bragg angle of 2θ ± in X-ray diffraction of CuKα.
0.2 ° is 7.0 °, 7.5 °, 10.5 °, 11.7
°, 12.7 °, 17.3 °, 18.1 °, 24.5
2. The electrophotographic photoreceptor according to claim 1, wherein said electrophotographic photoreceptor has a crystal form having strong peaks at angles of 26.2 DEG and 27.1 DEG. 5. The method according to claim 1, wherein the hydroxygallium phthalocyanine crystal has a Bragg angle 2θ ± in X-ray diffraction of CuKα.
0.2 ° is 7.9 °, 16.5 °, 24.4 ° and 2
2. The electrophotographic photoreceptor according to claim 1, which has a crystal form having a strong peak at 7.6 [deg.]. 6. The method according to claim 1, wherein the hydroxygallium phthalocyanine crystal has a Bragg angle 2θ ± in X-ray diffraction of CuKα.
0.2 ° is 7.7 °, 16.5 °, 25.1 ° and 2
2. The electrophotographic photosensitive member according to claim 1, which has a crystal form having a strong peak at 6.6 [deg.]. 7. The method according to claim 7, wherein the hydroxygallium phthalocyanine crystal has a Bragg angle 2θ ± in X-ray diffraction of CuKα.
0.2 ° is 7.5 °, 9.9 °, 12.5 °, 16.3
°, 18.6 °, 25.1 ° and 28.3 °
2. The electrophotographic photoreceptor according to claim 1, which has a crystal form having cracks. 8. The electrophotographic photoreceptor according to claim 1, and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means are integrally supported, and are detachably attached to an electrophotographic apparatus main body. A process cartridge characterized by the following. 9. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposing unit, a developing unit, and a transferring unit.