JP2001066804A - Electrophotographic photoreceptor, process cartridge with the same, and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To supply an image free from image defects while retaining high sensitivity characteristics in the wavelength range of semiconductor laser light by forming a photosensitive layer containing a phthalocyanine pigment and a specified azotized calix [n] arene compound. SOLUTION: The electrophotographic photoreceptor has a photosensitive layer containing a phthalocyanine pigment and an azotized calix [n] arene compound of the formula, wherein (n) is an integer of 4-8, R1-R3 are each H or an alkyl and Ar is an aromatic hydrocarbon ring which may have a substituent optionally bonded through a bonding group or a heterocycle which may have a substituent. The phthalocyanine pigment may be any phthalocyanine which may have a substituent, e.g. a metal-free phthalocyanine or a metallophthalocyanine which may have a ligand and oxy-titanium phthalocyanine or gallium phthalocyanine, in particular crystal form oxy-titanium phthalocyanine is preferably used.

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 provided with the electrophotographic photosensitive member, and an electrophotographic apparatus.

[0002]

2. Description of the Related Art Inorganic photoconductive materials such as selenium, cadmium sulfide and zinc oxide have been conventionally used as photoconductive materials for electrophotographic photosensitive members. Organic photoconductive materials such as polyvinyl carbazole, oxadiazole, azo pigment, and phthalocyanine have advantages such as non-pollution and high productivity compared to inorganic photoconductive materials, but have low sensitivity and are difficult to commercialize. Met. For this reason, several sensitization methods have been proposed, but as an effective method, use of a function-separated type photoreceptor in which a charge generation layer and a charge transport layer are laminated has become mainstream and has been put to practical use. It has become.

On the other hand, in recent years, non-impact printers to which electrophotographic technology is applied have been widely used as terminal printers instead of conventional impact printers. These are mainly laser beam printers that use laser light as a light source, and a semiconductor laser is used as the light source in terms of cost, size of the apparatus, and the like. Currently, mainly used semiconductor lasers have an oscillation wavelength of 650 to 820 nm, which is a long wavelength. Therefore, development of an electrophotographic photoreceptor having sufficient sensitivity to such long wavelength light has been advanced.

[0004] Phthalocyanine compounds are extremely effective as charge generating materials having sensitivity up to such a long wavelength region. In particular, oxytitanium phthalocyanine and gallium phthalocyanine have excellent sensitivity characteristics as compared with conventional phthalocyanine compounds. By the time,
-239248, JP-A-61-217050, JP-A-62-67094, JP-A-63-21
Various crystal forms are disclosed in JP-A-8768, JP-A-64-17066, JP-A-5-98181, JP-A-5-263007 and JP-A-10-67946. Further, Japanese Patent Application Laid-Open Nos. 7-12888 and 9-34149 disclose a combination with a specific azo compound in order to improve the problem of the phthalocyanine compound, but while maintaining higher sensitivity characteristics. There has been a demand for a photoreceptor that provides an image with less image defects.

Electrophotographic photoreceptors using phthalocyanine have the above-mentioned excellent sensitivity characteristics, but have the disadvantage that the generated photocarriers are liable to remain in the photosensitive layer and are liable to cause potential fluctuation as a kind of memory. there were. Although not confirmed in principle, the electrons left in the charge generation layer may, for some reason, be at the interface between the charge generation layer and the charge transport layer or between the charge generation layer and the undercoat layer or between the undercoat layer and the conductive layer. It is thought that it moves to the interface and raises or lowers the barrier property of hole injection near the interface.

A phenomenon that appears when an electrophotographic photoreceptor is actually used is that when electrons stay at the interface between the charge transport layer and the charge generation layer, they appear as a decrease in the light potential or residual potential during continuous printing. For example, when used in a development process (a so-called reversal development system) in which a dark potential portion and a light potential portion, which are commonly used in a printer, are used as a development portion, the sensitivity at the location where light was applied during the previous printing is used. When a front white image is taken at the next printing, a so-called ghost phenomenon (hereinafter, abbreviated as a positive ghost) in which a previous printing portion appears to be black appears remarkably.

[0007] When electrons stay at the interface between the charge generation layer and the undercoat layer or between the undercoat layer and the conductive layer, the increase in the light portion potential during printing appears. When used in a reversal development system, the sensitivity at the place where light hit during the previous print becomes slow, and when the front black image is taken at the next print, the previous print part appears white, so-called ghost phenomenon (hereinafter abbreviated as negative ghost). Appears remarkably.

Of these phenomena, a negative ghost often appears at the beginning of printing and a positive ghost often appears during continuous printing. This phenomenon is particularly remarkable in a photoreceptor using an undercoat layer or the like as an adhesive layer of the charge generation layer. There is a drawback that the generation layer is easily filled and a ghost phenomenon is easily generated.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photoreceptor for supplying an image free from image defects while maintaining high sensitivity, particularly high sensitivity characteristics in a semiconductor laser wavelength region. An object of the present invention is to provide a process cartridge having an electrophotographic photosensitive member and an electrophotographic apparatus.

[0010]

According to the present invention, there is provided an electrophotographic photoreceptor having a photosensitive layer on a support, wherein the photosensitive layer contains a phthalocyanine pigment and has the following formula (1): [N] An electrophotographic photosensitive member containing an arene compound. Equation (1)

Embedded image (Wherein, n represents an integer of 4 to 8, and R ₁ , R ₂ and R
₃ represents a hydrogen atom or an alkyl group, and Ar represents an aromatic hydrocarbon ring which may have a substituent which may be bonded through a bonding group or a heterocyclic ring which may have a substituent. )

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 are detachably mountable to an electrophotographic apparatus main body. And a process cartridge.

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

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION As the phthalocyanine pigment used in the electrophotographic photoreceptor of the present invention, a metal-free phthalocyanine, a metal phthalocyanine which may have an axial ligand, and any phthalocyanine can be used. However, oxytitanium phthalocyanine and gallium phthalocyanine are particularly preferred. Further, any crystal form may be used. Among them, the Bragg angle 2θ of 7.4 ° ± 0.2 °, 28.2 ° ± 2 in CuKα characteristic X-ray diffraction is preferable.
Crystalline hydroxygallium phthalocyanine having a strong peak at 0.2 °, a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction of 7.4 °, 16.6 °,
Chlorogallium phthalocyanine in a crystalline form having strong peaks at 5.5 ° and 28.3 °, and oxytitanium in a crystalline form having a strong peak at 27.2 ° ± 0.2 ° of Bragg angle 2θ in CuKα characteristic X-ray diffraction Phthalocyanine is preferred because it has excellent sensitivity characteristics. Furthermore, CuKα
7.4 ° ± 0.2 of Bragg angle 2θ in characteristic X-ray diffraction.
Crystalline hydroxygallium phthalocyanine having strong peaks at 2 ° and 28.2 ° ± 0.2 °, 27.2 ° ± 0.2 of Bragg angle 2θ in CuKα characteristic X-ray diffraction
Oxytitanium phthalocyanine in a crystalline form having a strong peak at ° is preferred. Among them, particularly, CuKα
6. Bragg angle 2θ ± 0.2 ° in characteristic X-ray diffraction.
Hydroxygallium phthalocyanine in a crystalline form having strong peaks at 3 °, 24.9 ° and 28.1 °, 7.5 with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction
°, 9.9 °, 16.3 °, 18.6 °, 25.1 °,
Crystalline form of hydroxygallium phthalocyanine having a strong peak at 28.3 °, 9.0 °, 14.2 °, 2 ° at Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction.
Crystalline oxytitanium phthalocyanine having strong peaks at 3.9 ° and 27.1 °, 9.5 ° and 9.7 at Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction
°, 11.7 °, 15.0 °, 23.5 °, 24.1
Crystalline oxytitanium phthalocyanine having strong peaks at ° and 27.3 ° is preferred.

The azide calix [n] arene compound used in the electrophotographic photoreceptor of the present invention is described in, for example,
It is also described in -80779 and the like, and is represented by the following formula (1). Equation (1)

Embedded image (Wherein, n represents an integer of 4 to 8, and R ₁ , R ₂ and R
₃ represents a hydrogen atom or an alkyl group, and Ar represents an aromatic hydrocarbon ring which may have a substituent which may be bonded through a bonding group or a carbon ring which may have a substituent. )

Examples of the alkyl group in the above expression include groups such as methyl, ethyl and propyl, and R ₁ , R ₂ and R ₃ are particularly preferably hydrogen atoms.

The aromatic hydrocarbon ring which may have a substituent and the hetero ring which may have a substituent may be benzene, naphthalene, fluorene,
Hydrocarbon-based aromatic rings such as phenanthrene, anthracene, fluoranthene and pyrene, furan, thiophene, pyridine, indole, benzothiazole, carbazole,
Heterocycles such as benzocarbazole, acridone, dibenzothiophene, benzoxazole, benzotriazole, oxathiazole, thiazole, phenazine, cinnoline, benzocinnoline, and the above aromatic hydrocarbon ring or heterocycle are directly or aromatic groups or non-aromatic groups. Those linked by aromatic groups, such as triphenylamine,
Diphenylamine, N-methyldiphenylamine, biphenyl, terphenyl, binaphthyl, fluorenone, phenanthrenequinone, anthraquinone, benzuanthrone, diphenyloxazole, phenylbenzoxazole, diphenylmethane, diphenylsulfone, diphenylether, benzophenone, stilbene, distyrylbenzene, tetra Phenyl-p-phenylenediamine, tetraphenylbenzidine and the like.

Examples of the substituent which may be present on the aromatic hydrocarbon ring or the heterocyclic ring which may be bonded via the above-mentioned bonding group include alkyl groups such as methyl, ethyl, propyl and butyl, and methoxy and ethoxy. Examples include an alkoxy group, a dialkylamino group such as dimethylamino and diethylamino, an azoaryl group such as azophenyl, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a hydroxy group, a nitro group, a cyano group, and a halomethyl group.

Ar is particularly preferably a group in which a cyano group, a nitro group, an azophenyl group or a halogen atom having an electron-withdrawing property is bonded to a benzene ring.

Next, Tables 1 to 5 show examples of azoxy calix [n] arene compounds used in the electrophotographic photoreceptor of the present invention, but the present invention is not limited to these compounds.

[0020]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

Among these, exemplified compounds 1, 2, 3,
7, 15, and 21 are preferred, and Exemplified Compounds 1, 2, and 21 are particularly preferred.

The layer constitution of the electrophotographic photoreceptor of the present invention comprises a single layer containing a phthalocyanine pigment, an azoxy calix [n] arene compound represented by the formula (1) and a charge transport material simultaneously on a support. A charge generating layer containing a phthalocyanine pigment and an azogenated calix [n] arene compound represented by the formula (1) on a support, and a charge transport material on the charge generating layer There is a layer configuration having a photosensitive layer on which a charge transport layer is laminated. The stacking relationship between the charge generation layer and the charge transport layer may be reversed.

The support may be any conductive material, and examples thereof include metals such as aluminum and stainless steel, metals provided with a conductive layer, plastics, and paper. Examples of the shape include a cylindrical shape and a film shape. No.

An undercoat layer having a barrier function and an adhesive function can be provided between the support and the photosensitive layer. Examples of the material of the undercoat layer include polyvinyl alcohol, polyethylene oxide, ethyl cellulose, methyl cellulose, casein, polyamide, glue, gelatin and the like.
These materials are dissolved in a suitable solvent and coated on a support. Its thickness is 0.2 to 3.0 μm.

Further, it is preferable to provide a conductive layer between the support and the undercoat layer for the purpose of covering unevenness and defects of the support and preventing interference fringes. The conductive layer is formed using a liquid in which conductive powder such as carbon black, metal particles, and metal oxide is dispersed in a binder resin. The thickness of the conductive layer is 5 to 40 μm, preferably 10 to 30 μm.

The photosensitive layer composed of a single layer is prepared by mixing a phthalocyanine pigment, a specific azoxy calix [n] arene compound and a charge transport material in an appropriate binder resin solution, and coating the mixture on a support. And dried.

When forming a photosensitive layer having a laminated structure,
The charge generation layer may be formed by dispersing a phthalocyanine pigment and a specific azoxy calix [n] arene compound together with a suitable binder resin solution, applying the dispersion, and drying the dispersion. The charge transport layer is formed by applying a coating solution in which a charge transport material and a binder resin are dissolved in a solvent and drying the coating solution.

Examples of the charge transport material include various triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, triallylmethane compounds and the like. As the charge transporting material to be combined with the phthalocyanine pigment and the specific azoxy calix [n] arene compound, a triphenylamine-based compound is preferable.

Examples of the binder resin used for each layer include polyester, acrylic resin, polyvinyl carbazole, phenoxy resin, polycarbonate, polyvinyl butyral, polystyrene, polyvinyl acetate, polysulfone, polyarylate, vinylidene chloride,
Resins such as an acrylonitrile copolymer and polyvinyl benzal are exemplified. As the resin for dispersing the phthalocyanine pigment and the specific azoxy calix [n] arene compound of the present invention, polyvinyl butyral and polyvinyl benzal are preferred.

The coating method of the photosensitive layer includes dipping, spray coating, spinner coating, bead coating, blade coating, and the like.
An application method such as a beam coating method may be used.

When the photosensitive layer is a single layer, the thickness is 5 to 40 μm.
m, particularly preferably 10 to 30 μm. In the case of a laminated structure, the thickness of the charge generation layer is preferably from 0.01 to 10 μm, particularly preferably from 0.0 to 10 μm.
The thickness is preferably 5 to 5 μm, and the thickness of the charge transport layer is preferably 5 to 40 μm, particularly 10 to 30 μm.
m is preferable.

When the photosensitive layer is a single layer, the content of the phthalocyanine pigment is preferably 3 to 30% by mass based on the photosensitive layer. The content of the specific azoxy calix [n] arene compound is preferably from 0.1 to 10% by mass. The content of the charge transporting material is preferably from 30 to 70% by mass based on the photosensitive layer.
In the case of a laminated structure, the content of the phthalocyanine pigment is 30 to 90% by mass, and more preferably 50 to 80% by mass based on the charge generation layer.
% By mass is preferred. The content of the specific azoxy calix [n] arene compound is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass. The content of the charge transporting material is from 20 to 80% by mass, and
0-70 mass% is preferable. In each case,
The content of the specific azotized calix [n] arene compound is preferably from 0.3 to 10% by mass, more preferably from 0.5 to 5% by mass, based on the phthalocyanine pigment.

A protective layer may be provided on the photosensitive layer if necessary. The protective layer is made of a resin such as polyvinyl butyral, polyester, polycarbonate (polycarbonate Z, modified polycarbonate, etc.), nylon, polyimide, polyarylate, polyurethane, styrene-butadiene copolymer, ethylene-acrylic acid copolymer, styrene-acrylonitrile copolymer, etc. , And is formed by coating and drying on the photosensitive layer.
The thickness of the protective layer is preferably 0.05 to 20 μm. Also,
The protective layer may contain conductive particles, an ultraviolet absorber, and the like. As the conductive particles, for example, metal oxides such as tin oxide particles are preferable.

Next, an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention will be described. FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of 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 on its peripheral surface with a predetermined positive or negative potential by the primary charging means 3, and then exposed light 4 from exposure means (not shown) such as slit exposure or laser beam scanning exposure. Receive. 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
The toner-developed image developed by the above-described process is transferred to a transfer material 7 fed from a paper supply unit (not shown) between the photoconductor 1 and the transfer unit 6 in synchronization with the rotation of the photoconductor 1. The image is sequentially transferred by the transfer unit 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 of the apparatus as a copy. The surface of the photoreceptor 1 after the image transfer is cleaned by removing the untransferred toner by the cleaning unit 9, and is further cleaned by a pre-exposure unit (not shown).
After being subjected to static elimination processing by the pre-exposure light 10 from, it is repeatedly used for image formation. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not necessarily required.

In the present invention, a plurality of components, such as the photosensitive member 1, the primary charging unit 3, the developing unit 5, and the cleaning unit 9 described above, are integrally connected as a process cartridge. The 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 unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photoreceptor 1 to form a cartridge, and the process cartridge is detachable from the apparatus main body using a guide unit such as a rail 12 of the apparatus main body. It can be 11. When the electrophotographic apparatus is a copier or a printer, the 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. , The light emitted by the driving of the LED array, the driving of the liquid crystal shutter array, and the like.

[0037]

EXAMPLES "%" and "parts" described in the following Examples
Means "% by mass" and "parts by mass", respectively.

Example 1 50 parts of titanium oxide powder coated with tin oxide containing 10% of antimony oxide, resol type phenol resin 25
Part, methyl cellosolve 20 parts, methanol 5 parts and silicone oil (polydimethylsiloxane / polyoxyalkylene copolymer, average molecular weight 3000) 0.002
The portion was dispersed for 2 hours by a sand mill using glass beads of 1 mm in diameter to prepare a coating for the conductive layer. This coating material was dip-coated on an aluminum cylinder (diameter 30 mm × length 260.5 mm) and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.

A solution prepared by dissolving 5 parts of a 6-66-610-12 quaternary polyamide copolymer resin in a mixed solvent of 70 parts of methanol and 25 parts of butanol was dip-coated thereon.
An undercoat layer having a thickness of μm was formed.

Next, in the CuKα characteristic X-ray diffraction, the Bragg angles 2θ ± 0.2 ° of 7.5 °, 9.9 °, and 16.
10 parts of a crystalline form of hydroxygallium phthalocyanine having strong peaks at 3 °, 18.6 °, 25.1 ° and 28.3 °, 0.2 part of the above-mentioned compound 1 and polyvinyl butyral resin (trade name: Slek BX- 1, Sekisui Chemical Co., Ltd.) (5 parts) was added to 250 parts of cyclohexanone, dispersed for 1 hour by a sand mill using 1 mm diameter glass beads, and diluted with 250 parts of ethyl acetate. This paint is dip-coated on the undercoat layer,
Drying was performed at 10 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.16 μm.

Next, 10 parts of a charge transporting material having the following structural formula:

Embedded image Polycarbonate resin (trade name Iupilon Z-200,
10 parts of monochlorobenzene 7
A solution dissolved in 0 parts was prepared, dip-coated on the charge generation layer, and dried at 110 ° C. for 1 hour to form a 25 μm-thick charge transport layer, thereby producing an electrophotographic photoreceptor.

Example 2 An electrophotographic photosensitive member of Example 2 was prepared in exactly the same manner as in Example 1 except that the amount of Exemplified Compound 1 was changed to 0.1 part.

Example 3 An electrophotographic photosensitive member of Example 3 was prepared in exactly the same manner as in Example 1 except that the amount of Exemplified Compound 1 was changed to 1 part.

Example 4 An electrophotographic photosensitive member of Example 4 was prepared in exactly the same manner as in Example 1 except that Exemplified Compound 1 was replaced with Exemplified Compound 2.

Example 5 An electrophotographic photosensitive member of Example 5 was prepared in exactly the same manner as in Example 1 except that Exemplified Compound 1 was replaced with Exemplified Compound 3.

Example 6 Example 1 was repeated except that Exemplified Compound 1 was replaced with Exemplified Compound 21.
An electrophotographic photoreceptor of Example 6 was prepared in exactly the same manner as in Example 1.

Example 7 In the CuKα characteristic X-ray diffraction used in Example 1, a Bragg angle of 2θ ± 0.2 ° of 7.5 °, 9.9 °, 16.3 was used.
Crystalline hydroxygallium phthalocyanine having strong peaks at 0 °, 18.6 °, 25.1 °, and 28.3 ° was converted to a Bragg angle 2θ ± 0.2 in CuKα characteristic X-ray diffraction.
Of Example 7, except that the crystalline form of oxytitanium phthalocyanine having strong peaks at 9.0 °, 14.2 °, 23.9 °, and 27.1 ° was substituted. An electrophotographic photoreceptor was prepared.

Example 8 In the same manner as in Example 1, the layers up to the charge generation layer were formed. Next, 10 parts of a charge transport material having the following structural formula,

Embedded image Polycarbonate resin (trade name Iupilon Z-400,
10 parts monochlorobenzene 1
A solution dissolved in 00 parts was prepared, dip-coated on the charge generation layer, and dried at 150 ° C. for 30 minutes to form a 15 μm-thick charge transport layer, thereby producing an electrophotographic photoreceptor.

Example 9 The procedure up to Example 1 was repeated up to the formation of the charge generation layer. Next, 7 parts of a charge transport material having the following structural formula,

Embedded image 3 parts of a charge transport material having the following structural formula

Embedded image And polycarbonate resin (trade name Iupilon Z-2)
00, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was prepared by dissolving 10 parts in 70 parts of monochlorobenzene, dip-coated on the charge generation layer, and dried at 110 ° C. for 1 hour to form a charge transport layer having a thickness of 32 μm. Was formed to prepare an electrophotographic photosensitive member.

Comparative Example 1 For comparison, an electrophotographic photoreceptor of Comparative Example 1 was prepared in exactly the same manner as in Example 1 except that Exemplified Compound 1 used in Example 1 was not added.

Comparative Example 2 Except that the exemplified compound 1 used in Example 7 was not added,
An electrophotographic photosensitive member of Comparative Example 2 was prepared in exactly the same manner as in Example 7.

Comparative Example 3 The electrophotographic photoreceptor of Comparative Example 3 was prepared in the same manner as in Example 7 except that 3 parts of a bisazo pigment having the following structural formula was added instead of Exemplified Compound 1 used in Example 7. Created.

Embedded image

Using each of the prepared electrophotographic photosensitive members, the measurement of the light portion potential and the evaluation of the ghost image were performed. Evaluation was performed using a laser beam printer (trade name: Laser Jet 400)
0, manufactured by Hewlett-Packard Company). First, the initial bright portion potential was measured and the ghost image was evaluated in an environment of 23 ° C. and 55% RH. Then, a durability test was performed on 1,000 sheets under the same environment.
Five hours later, the measurement of the light portion potential and the evaluation of the ghost image were performed.

Next, each of the produced electrophotographic photosensitive members was left for 3 days at 15 ° C. and 10% RH at a low temperature and a low humidity (L / L) together with an evaluator, and then the measurement of the light portion potential and the evaluation of the ghost image were performed. Was done.

The above conditions for paper passing durability were set to an intermittent mode of printing four sheets per minute, and a durability pattern was performed in a mode in which lines having a width of about 0.5 mm were printed every 10 mm in length.

The ghost image evaluation method was as follows. The ghost image was formed by printing a black square pattern of 5 mm square by an arbitrary number for one round of the drum, and thereafter, a full-halftone image (an image having a dot density of one dot and one space) or an entire white image. Ghost image samples were sampled at the development volume of the machine, F5 (center value) and F9 (light density). The evaluation was made visually, and the degree of ghost was ranked as follows. Rank 1 is "a level at which a ghost is not visible at all in any mode". Rank 2 is "a level at which a ghost is slightly visible in a specific mode". Rank 3 is "a level at which a ghost is slightly visible in any mode." But you can see ghosts. ''

Table 6 shows the above results.

[Table 6]

[0058]

The electrophotographic photosensitive member of the present invention has a remarkable effect that an image free from image defects can be provided while maintaining high sensitivity, particularly high sensitivity characteristics in a semiconductor laser wavelength region. Further, in the process cartridge and the electrophotographic apparatus having the electrophotographic photosensitive member, the same effects can be obtained.

[Brief description of the drawings]

FIG. 1 is a view showing a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 electrophotographic photoreceptor of the present invention 2 axis 3 primary charging means 4 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

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Miki Tanabe 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H068 AA14 AA19 AA21 AA34 AA35 BA12 BA39 FA13 FA19 FA27

Claims (16)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a support, wherein the photosensitive layer contains a phthalocyanine pigment,
And azoxy calix [n] represented by the following formula (1)
An electrophotographic photosensitive member comprising an arene compound. Formula (1) (Wherein, n represents an integer of 4 to 8, and R ₁ , R ₂ and R
₃ represents a hydrogen atom or an alkyl group, and Ar represents an aromatic hydrocarbon ring which may have a substituent which may be bonded through a bonding group or a heterocyclic ring which may have a substituent. ) 2. The electrophotographic photosensitive member according to claim 1, wherein the phthalocyanine pigment is oxytitanium phthalocyanine. 3. The oxytitanium phthalocyanine having a Bragg angle 2θ of 27.27 in CuKα characteristic X-ray diffraction.
3. The electrophotographic photoreceptor according to claim 2, which is a crystalline oxytitanium phthalocyanine having a strong peak at 2 ° ± 0.2 °. 4. The method according to claim 1, wherein said oxytitanium phthalocyanine has a Bragg angle of 2 ± 0.2 in CuKα characteristic X-ray diffraction.
The electrophotographic photoreceptor according to claim 3, which is a crystalline oxytitanium phthalocyanine having strong peaks at 9.0 °, 14.2 °, 23.9 °, and 27.1 °. 5. The method according to claim 1, wherein the oxytitanium phthalocyanine has a Bragg angle of 2θ ± 0.2 in CuKα characteristic X-ray diffraction.
9.5 °, 9.7 °, 11.7 °, 15.0 °, 2 °
The electrophotographic photoreceptor according to claim 3, which is a crystalline form of oxytitanium phthalocyanine having strong peaks at 3.5 °, 24.1 °, and 27.3 °. 6. The electrophotographic photoconductor according to claim 1, wherein the phthalocyanine pigment is gallium phthalocyanine. 7. The electrophotographic photoreceptor according to claim 6, wherein said gallium phthalocyanine is hydroxygallium phthalocyanine. 8. The method according to claim 7, wherein said hydroxygallium phthalocyanine has a Bragg angle of 2θ in CuKα characteristic X-ray diffraction.
8. The electrophotographic photoreceptor according to claim 7, which is hydroxygallium phthalocyanine in a crystalline form having strong peaks at 4 ° ± 0.2 ° and 28.2 ± 0.2 °. 9. The method according to claim 8, wherein the hydroxygallium phthalocyanine has a Bragg angle of 2 ± 0.1 in CuKα characteristic X-ray diffraction.
The electrophotographic photoreceptor according to claim 8, which is hydroxygallium phthalocyanine in a crystalline form having strong peaks at 2 ° of 7.3 °, 24.9 °, and 28.1 °. 10. The method according to claim 1, wherein the hydroxygallium phthalocyanine has a Bragg angle 2θ ± in CuKα characteristic X-ray diffraction.
7.5 °, 9.9 °, 16.3 °, 18.6 of 0.2 °
9. A crystalline form of hydroxygallium phthalocyanine having strong peaks at angles of 25.1 °, 25.1 ° and 28.3 °.
2. The electrophotographic photoreceptor of claim 1. 11. The method according to claim 1, wherein said Ar is a group in which at least one group selected from the group consisting of a cyano group, a nitro group, an azophenol group, and a halogen atom is bonded to a benzene ring. Electrophotographic photoreceptor. 12. The electrophotographic photoreceptor according to claim ₁ , wherein said R ₁ , R ₂ and R ₃ are all hydrogen atoms, and said Ar is a 3,5-dinitrophenyl group. 13. The content of the azoxy calix [n] arene compound is from 0.3 to 0.3 with respect to the phthalocyanine pigment.
The electrophotographic photoreceptor according to claim 1, wherein the content is 10% by mass. 14. A charge-transporting layer comprising at least two charge-generating layers and a charge-transporting layer containing the phthalocyanine pigment and the azoxy calix [n] arene compound.
The electrophotographic photosensitive member according to any one of the above. 15. An electrophotographic apparatus main body, wherein the electrophotographic photosensitive member according to claim 1 and at least one unit selected from the group consisting of a charging unit, a developing unit and a cleaning unit are integrally supported. A process cartridge which is detachably mounted on a process cartridge. 16. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an exposing unit, a developing unit, and a transferring unit.