JP2000250238A - Electrophotographic photoreceptor, process cartridge and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photoreceptor which has excellent sensitivity characteristics even in the wavelength region of 380-500 nm and is good in environmental characteristics by using a charge generating material having a specific structure, and to obtain an electrophotographic device and a process cartridge by which a practical and stable output image with high quality image can be obtained. SOLUTION: The charge generating material used in the electrophotographic photoreceptor contains both of a phthalocyanine pigment and an azo compound of formula I, wherein Ar is an aromatic hydrocarbon group or heterocyclic group, which may bond directly or through a bonding group and may have a substituent, Cp is a coupler residue having a phenolic hydroxy group and expressed by formula II. In the formulas I and II, n is an integer of 1-3; X is a residue necessary for forming a polycyclic aromatic ring or heterocyclic ring by condensing with benzene ring; R1 and R2 are each hydrogen atom, alkyl group which may have a substituent, or the like; Z is oxygen or sulfur; m is 0 or 1.

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. The present invention relates to a photoconductor, a process cartridge having the electrophotographic photoconductor, and an electrophotographic apparatus.

[0002]

2. Description of the Related Art At present, as a laser used in an electrophotographic apparatus using a laser as a light source, such as a laser printer, a semiconductor laser having an oscillation wavelength around 800 nm or around 680 nm is mainly used. In recent years, there has been an increasing need for higher image quality of output images, and various approaches to higher resolution have been made. The wavelength of the laser is also deeply involved in this high resolution, and as described in Japanese Patent Application Laid-Open No. 9-240051, the shorter the oscillation wavelength of the laser, the smaller the spot diameter of the laser becomes. A high-resolution latent image can be formed.

There are several techniques for shortening the laser oscillation wavelength. One is to use a nonlinear optical material and reduce the wavelength of the laser beam to half by using second harmonic generation (SHG) (Japanese Patent Laid-Open No. 9-27524).
No. 2, Japanese Unexamined Patent Application Publication No. 9-189930, Japanese Unexamined Patent Application Publication No.
No. 313033). This system, as the primary light source,
GaAs LDs and YAGs that have already established technology and can output high power
Since a laser can be used, long life and high output can be achieved.

The other is to use a wide gap semiconductor, and it is possible to reduce the size of the device as compared with a device using SHG. ZnSe-based semiconductor (Japanese Patent Laid-Open No. 7-3214)
09, JP-A-6-334272, etc.) and G
aN-based semiconductor (JP-A-8-88441, JP-A-7-88441)
An LD using the above-mentioned method has been a subject of much research because of its high luminous efficiency.

However, it is difficult to optimize the device structure, crystal growth conditions, electrodes and the like of these LDs, and it is difficult to perform long-term oscillation at room temperature, which is essential for practical use, due to defects in the crystals. However, technological innovations such as infrastructure progressed,
In October, Nichia Chemical Co., Ltd.
D is reported to be about 1150 hours continuous oscillation (50 ° C. condition), and practical use is imminent.

On the other hand, in a conventional electrophotographic photosensitive member used in an electrophotographic apparatus using a laser, 700 to 800 n
The electrophotographic photosensitive member used in an electrophotographic apparatus using white light in the visible to infrared wavelength range around 500 m
Although it has a large absorption band in the visible wavelength region near nm and can exhibit practical sensitivity characteristics, sufficient sensitivity cannot be obtained in the short wavelength region.

In addition, when a conventionally known charge generating material is used alone, even if it has a sensitivity around 380 to 500 nm, the sensitivity is largely environment-dependent and wavelength-dependent around this. It turned out that there was. For this reason, there has been a problem that the sensitivity varies due to a change in the surrounding environment such as humidity and temperature and the input laser wavelength, and an appropriate output cannot be obtained.

[0008]

SUMMARY OF THE INVENTION The object of the present invention is to
Providing an electrophotographic photoreceptor having high and flat sensitivity characteristics in the wavelength range of 0 to 500 nm and having a small environmental dependency of sensitivity, and using this photoreceptor and a short-wavelength laser, it is practical and stable. An object of the present invention is to provide an electrophotographic apparatus and a process cartridge capable of obtaining a high-quality output image.

[0009]

According to the present invention, in an electrophotographic photosensitive member used as an exposure light source having an oscillation wavelength of a semiconductor laser in a range of 380 to 500 nm, a charge generating material used for the electrophotographic photosensitive member is as follows. An electrophotographic photoreceptor containing both an azo compound represented by the general formula and a phthalocyanine compound represented by the following general formula (7), a process cartridge having the electrophotographic photoreceptor, and an electrophotographic apparatus are provided.

[0010]

Embedded image

In the formula, Ar represents an aromatic hydrocarbon group or a heterocyclic group which may be bonded directly or via a bonding group and may have a substituent, and Cp has a phenolic hydroxyl group. Represents a coupler residue, and at least one of Cp is a coupler residue represented by the following general formula (2) or (4). n represents an integer of 1 to 3. Where -N
= N-Cp does not bind to the same benzene ring more than once.

[0012]

Embedded image

[0013] In the formula, X is represents a residue necessary to form a naphthalene ring condensed with a benzene ring, a polycyclic aromatic ring or a carbazole ring such as anthracene ring, a heterocyclic ring such as benzimidazole carbazole ring, R ¹ And R ² represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group, or a heterocyclic group. Further, R ¹ and R ² may form a cyclic amino group via a nitrogen atom. Z represents an oxygen atom or a sulfur atom, and m represents 0 or 1.

[0014]

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In the formula, Y represents a divalent aromatic hydrocarbon group or a heterocyclic ring which may have a substituent.

Specifically, Ar is benzene, naphthalene, fluorene, phenanthrene, anthracene,
Aromatic hydrocarbon rings such as pyrene, furan, thiophene, pyridine, indole, benzothiazole, carbazole, acridone, dibenzothiophene, benzoxazole, oxadiazole, aromatic heterocycles such as thiazole, and the above aromatic ring directly or Bonded with an aromatic or non-aromatic group, for example, triphenylamine, diphenylamine, N-methyldiphenylamine,
Biphenyl, terphenyl, binaphthyl, fluorenone, phenanthrenequinone, anthraquinone, benzanthrone, diphenyloxadiazole, phenylbenzoxazole, diphenylmethane, diphenylsulfone, diphenylether, benzophenone, stilbene, distyrylbenzene, tetraphenyl-p-phenylene Organic groups derived from diamine, azobenzene, azoxybenzene, tetraphenylbenzidine and the like can be mentioned.

Examples of the substituent which the aromatic hydrocarbon group or the aromatic hetero group which may be bonded through the above-mentioned bonding group may have include an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group. Alkoxy groups such as methoxy group, ethoxy group or propoxy group, dialkylamino groups such as dimethylamino group or diethylamino group, halogen atoms such as fluorine atom, chlorine atom or bromine atom, hydroxyl group, nitro group, cyano group, halomethyl group and the like. No.

In the general formula (2), the alkyl group of R ¹ and R ^{2 is} a group such as a methyl group, an ethyl group or a propyl group;
Aryl groups such as phenyl, naphthyl and anthryl groups, aralkyl groups such as benzyl group and phenethyl group, and heterocyclic groups such as pyridyl group and thienyl group;
Carbazolyl group, benzimidazolyl group, benzothiazolyl group and other groups, as a cyclic amino group containing a nitrogen atom in the ring, pyrrole group, pyrroline group, pyrrolidine group, pyrrolidone group, indole group, indoline group, carbazole group,
Examples include an imidazole group, a pyrazole group, a pyrizolin group, an oxazine group, and a phenoxazine group.

Examples of the substituent include an alkyl group such as a methyl group, an ethyl group or a propyl group, an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and dimethyl. Examples include a dialkylamino group such as an amino group or a diethylamino group, a phenylcarbamoyl group, a nitro group, a cyano group, and a halomethyl group such as trifluoromethyl.

Among them, ^one of R ^{1 and} R ² is preferably a hydrogen atom, and the other is preferably a phenyl group which may have a substituent in terms of sensitivity. Further, the substituent on the phenyl is preferably an alkyl group, A halogen atom and a phenylcarbamoyl group are preferred. The phenylcarbamoyl group may further have a substituent as described above on phenyl.

The phthalocyanine compound is represented by the following general formula (7).

[0022]

Embedded image

In the formula, X ^{9 to} X ¹² represent chlorine or bromine;
w, x, y, and z each represent an integer of 0-4. M represents a hydrogen atom or an arbitrary divalent group.

M may be two hydrogen atoms or any divalent group, and any crystalline phthalocyanine may be used. Among them, M = H ₂ , Cu, TiO,
HOGa and ClGa are preferred.

Among them, more preferred phthalocyanine compounds are χ-type metal-free phthalocyanine, ε-type copper phthalocyanine, and CuKα having a Bragg angle (2θ ± 0.2 °) of 9.3 °, 10.3 ° in characteristic X-ray diffraction. 6 °, 1
Crystalline oxytitanium phthalocyanine having strong peaks at 3.2 °, 15.1 °, 26.3 ° (for example,
It is described in JP-A-62-67094; FIG.
7.6 °, 10.2 °, 22.5 °, 25.3 °, 2
Crystalline oxytitanium phthalocyanine having a strong peak at 8.6 ° (for example, JP-A-61-239248).
FIG. 6), 9.0 °, 14.2 °,
Crystalline oxytitanium phthalocyanine having strong peaks at 23.9 ° and 27.1 ° (see, for example,
No. 12897; FIG. 7 of the drawings), 9.5 °,
Crystalline oxytitanium phthalocyanine having strong peaks at 9.7 °, 15.0 °, 24.1 ° and 27.3 ° (for example, described in JP-A-1-17066; FIG. 8 of the drawings), 7 Hydroxygallium phthalocyanine in crystalline form having strong peaks at 0.4 ° and 28.2 ° (for example,
It is described in JP-A-5-263007; FIG.
It is a crystalline chlorogallium phthalocyanine having strong peaks at 7.4 °, 16.6 °, 25.5 ° and 28.2 ° (for example, described in JP-A-5-98181; FIG. 10 of the drawings). .

In particular, the Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα is 9.0 °,
Crystalline oxytitanium phthalocyanine having strong peaks at 14.2 °, 23.9 ° and 27.1 °, 9.5
°, 9.7 °, 15.0 °, 24.1 °, crystal form oxytitanium phthalocyanine having strong peaks at 27.3 °, and crystal form having strong peaks at 7.4 °, 28.2 ° Hydroxygallium phthalocyanine is preferred.

[0027]

Embodiments of the present invention will be described below in detail.

Specific examples of the charge generating material used in the present invention are listed below. In the structural formula, only the portions corresponding to Ar and Cp in the general formulas (1) and (3) are described. In the case where n is 2, 3 and Cp is different, the structure is shown as Cp1, Cp2, and Cp3.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

[Table 5]

[0034]

[Table 6]

[0035]

[Table 7]

[0036]

[Table 8]

[0037]

[Table 9]

Hereinafter, specific examples of the phthalocyanine compound used in the present invention will be listed.

CuK in a portion corresponding to M in the general formula (7)
Bragg angle (2θ ± 0.2) in characteristic X-ray diffraction of α
°).

[0040]

[Table 10]

In the present invention, the content ratio of the azo pigment to the phthalocyanine pigment is preferably from 50/1 to 1/50,
More preferably, it is in the range of 20/1 to 1/20.

Next, the electrophotographic photosensitive member of the present invention will be described in detail.

The structure of the photoreceptor may be any known structure as shown in FIGS. 1, 2 and 3.
Japanese Patent Application Laid-Open No. 9-240051 discloses that in a photoconductor in which a charge generation layer and a charge transport layer are laminated in this order on a conductive support as shown in FIG. 1, light of 380 to 500 nm is absorbed by the charge transport material, Although light does not reach the generation layer, there is no sensitivity in principle, but this is not always the case, and the charge transport material used in the charge transport layer is transparent to the laser oscillation wavelength. If the photoreceptor is used, a sufficient sensitivity can be obtained even with the photoreceptor of this configuration, and it can be used.

Hereinafter, a method for producing a function-separated type photoconductor in which a charge generation layer and a charge transport layer are laminated on a conductive support will be described.

The charge generation layer is prepared by coating a solution obtained by dispersing an azo compound represented by the general formula (1) or (3) together with a binder resin in a suitable solvent on a conductive support by a known method. And its film thickness is
Preferably 5 μm or less, more preferably 0.1 to 1 μm
It is.

The charge generation layer is formed by applying a liquid obtained by dispersing a charge generation material together with a binder resin in an appropriate solvent onto a conductive support by a known method,
The film thickness is preferably 5 μm or less, more preferably 0.1 to 1 μm.

In the present invention, a liquid in which the azo represented by the general formula (1) or (3) and the phthalocyanine pigment represented by the general formula (7) are dispersed together with a binder resin in a suitable solvent, or separately It may be a single layer obtained by applying a liquid obtained by mixing an azo pigment dispersion liquid and a phthalocyanine dispersion liquid dispersed in a liquid, or a plurality of layers obtained by applying the above-mentioned liquid a plurality of times. In the case of such a plurality of layers, the layer on the support side preferably contains an azo pigment.

The binder resin used at this time is selected from a wide range of insulating resins and organic photoconductive polymers, and includes polyvinyl butyral, polyvinyl benzal, polyarylate, polycarbonate, polyester, phenoxy resin, cellulose resin, Acrylic resins, polyurethanes, and the like are preferable, and these binder resins may have a substituent, and the substituent is preferably a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, a trifluoromethyl group, or the like. The amount of the binder resin used is preferably 80% by weight or less, more preferably 40% by weight or less, in terms of the content in the charge generation layer.

The solvent used is preferably selected from those which dissolve the binder resin and do not dissolve the charge transport layer and the undercoat layer described below. Specifically, tetrahydrofuran, ethers such as 1,4-dioxane,
Ketones such as cyclohexanone and methyl ethyl ketone,
Amines such as N, N-dimethylformamide, esters such as methyl acetate and ethyl acetate, toluene, xylene,
Examples include aromatics such as chlorobenzene, alcohols such as methanol, ethanol, and 2-propanol; and aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, and trichloroethylene.

The charge transport layer is stacked on or below the charge generation layer and has a function of receiving charge carriers from the charge generation layer in the presence of an electric field and transporting the carriers. The charge transporting layer is formed by applying a coating solution in which a charge transporting material is dissolved in a solvent together with an appropriate binder resin as necessary, and the thickness thereof is generally 5 to 40 μm, preferably 15 to 30 μm. Is more preferred.

As the charge transporting material, there are an electron transporting material and a hole transporting material.
2,4,7-trinitrofluorenone, 2,4,5,7
-Electron-withdrawing materials such as tetranitrofluorenone, chloranil, and tetracyanoquinodimethane; and polymerized materials of these electron-withdrawing materials.

As the hole transport material, for example, pyrene,
Polycyclic aromatic compounds such as anthracene, carbazoles,
Heterocyclic compounds such as indole, oxazole, thiazole, oxadiazole, pyrazole, pyrazoline, thiadiazole, and triazole compounds, hydrazone compounds, styryl compounds, benzidine compounds, triarylmethane compounds, Examples include triphenylamine-based compounds and polymers having a group consisting of these compounds in the main chain or side chain (for example, poly-N-vinylcarbazole, polyvinylanthracene, and the like).

These charge transporting materials may be used alone or in combination.
It can be used in combination of more than one kind. When the charge transport material does not have a film forming property, an appropriate binder resin can be used. Specifically, an insulating resin such as acrylic resin, polyarylate, polycarbonate, polyester, polystyrene, acrylonitrile-styrene copolymer, polyacrylamide, polyamide, chlorinated rubber or an organic photoconductive material such as poly-N-vinylcarbazole, polyvinylanthracene, etc. Polymer and the like.

However, when used for the photoreceptor having the structure shown in FIG. 1, it is necessary to select a charge transporting material or a binder resin which is transparent to the oscillation wavelength of the semiconductor laser used as described above.

Examples of the material of the conductive support include aluminum, aluminum alloy, copper, zinc, stainless steel, vanadium, molybdenum, chromium, titanium, nickel, indium, gold and platinum. Moreover, plastics (for example, polyethylene, polypropylene,
A support obtained by coating a support such as polyvinyl chloride, polyethylene terephthalate and an acrylic resin) or conductive particles (eg, carbon black, silver particles, etc.) on a plastic, metal or alloy as described above together with a suitable binder resin, or A support or the like in which conductive particles are impregnated in plastic or paper can be used. Examples of the shape include a drum shape, a sheet shape, and a belt shape.

An undercoat layer having a barrier function and an adhesive function can be provided between the conductive support and the photosensitive layer.
Further, a protective layer may be provided for the purpose of protecting the photosensitive layer from external mechanical and chemical adverse effects. Note that additives such as an antioxidant and an ultraviolet absorber may be used in the photosensitive layer as needed.

Next, the electrophotographic apparatus of the present invention will be described.

The electrophotographic apparatus of the present invention comprises the above-described electrophotographic photosensitive member and an image exposing means using a semiconductor laser having an oscillation wavelength of 380 to 500 nm, a charging means, a developing means, and a transferring means.

FIG. 4 shows a schematic configuration of an electrophotographic apparatus using a process cartridge having the electrophotographic photosensitive member of the present invention.

In FIG. 4, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around a shaft 2 in a direction of an arrow at a predetermined peripheral speed. The photoreceptor 1 receives a uniform charge of a predetermined positive or negative potential on its peripheral surface by the primary charging means 3 during the rotation process, and is then output from exposure means (not shown) such as slit exposure or laser beam scanning exposure. It receives exposure light 4 that has been enhanced and modulated in accordance with a time-series electrical digital image signal of desired image information. Thus, the photoconductor 1
An electrostatic latent image corresponding to the target image information is sequentially formed on the peripheral surface of the image.

The formed electrostatic latent image is then transferred to developing means 5
The toner image thus developed is transferred 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 to a transfer material 7 fed and fed. Then, the toner image formed and carried on the surface of the photoconductor 1 is sequentially transferred by the transfer unit 6.

The transfer material 7 to which the toner image has been transferred is separated from the surface of the photoreceptor, introduced into the image fixing means 8 and subjected to image fixing, thereby being printed out of the apparatus as an image formed product (print, copy). You.

After the transfer of the image, the surface of the photoreceptor 1 is cleaned by removing the untransferred toner by the cleaning means 9, and is further cleaned by a pre-exposure light 10 from a pre-exposure means (not shown).
Is used for image formation repeatedly after the charge removal processing. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, the pre-exposure is not necessarily required.

In the present invention, a plurality of components such as the above-described electrophotographic photosensitive member 1, primary charging means 3, developing means 5, and cleaning means 9 are integrally connected as a process cartridge. 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 unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photoreceptor 1 to form a cartridge, and is detachably attached to the apparatus main body using a guide unit such as a rail 12 of the apparatus main body. Process cartridge 1
It can be 1.

When the electrophotographic apparatus is a copier or a printer, the exposure light 4 is reflected light or transmitted light from the original, or the original is read by a sensor, converted into a signal, and a laser beam is emitted in accordance with the signal. Beam scanning, LED
Light emitted by driving the array, driving the liquid crystal shutter array, and the like.

[0066]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. In addition, "part" in an Example shows a weight part.

Example 1-1 A methoxymethylated nylon (weight average molecular weight: 3200) was coated on an aluminum support.
0) A solution prepared by dissolving 5 parts of 10 parts of alcohol-soluble copolymerized nylon (weight average molecular weight of 29000) in 95 parts of methanol was applied by a Meyer bar, and a dried undercoat layer having a thickness of 1 μm was formed.

Next, the azo pigment P ¹ -1 2 parts of a phthalocyanine pigment F-5 2 parts dissolved in 100 parts of cyclohexanone, a polyvinyl butyral resin (trade name: S-LEC BM-2, manufactured by Sekisui Chemical) is added to 4 parts of Then, the mixture was dispersed in a sand mill using 1 mmφ glass beads for 2 hours, 100 parts of methyl ethyl ketone was added thereto, and the mixture was diluted and collected. The solution was applied on a subbing layer with a Meyer bar, and heated at 80 ° C. By drying for 10 minutes, a charge generation layer having a thickness of 0.25 μm was formed.

Next, 5 parts of a charge transporting material represented by the following structural formula (8)

[0070]

Embedded image And polycarbonate Z resin (number average molecular weight 20,000)
A solution in which 5 parts were dissolved in 40 parts of monochlorobenzene was applied to the charge generation layer with a Meyer bar, and dried to form a charge transport layer having a thickness of 20 μm.

The electrophotographic photoreceptor thus prepared is
Electrostatic copying paper tester (Kawaguchi Electric: EPA-8100)
Was evaluated in the following manner. The results are shown in Table 1-1.

(Sensitivity) Under an environment of a temperature of 23 ° C. and a humidity of 50%, the photosensitive member was charged with a corona charger so that the surface potential became −700 V, and then separated with a monochromator.
Exposure was performed with monochromatic light of nm, and the amount of light required for the surface potential to attenuate to -350 V was measured to determine the sensitivity (E _1/2 ). Similarly, the sensitivities at 450 nm and 500 nm monochromatic light were measured.

(Environmental Dependency of Sensitivity) In a high temperature and high humidity environment (30 ° C./80%), and in a low temperature and low humidity environment (15 ° C./10
%), Sensitivity (E _1/2 ) was determined by irradiating monochromatic light of 400 nm in the same manner.

Examples 1-2 to 1-9 Electrophotography was performed in the same manner as in Example 1-1, except that the charge generating materials used in Example 1-1 were replaced with the pigments shown in Table 1-1. Create a photoconductor,
evaluated. The results are shown in Table 1-1.

[0075] (Example 1-10) The first charge generating film thickness 0.1μm was prepared in the same manner with a solution by adding an azo pigment P ¹ -4 4 parts in place of the charge-generating layer in Example 1-1 Example 1-1 except that a two-layered charge generation layer formed by laminating a 0.1 μm-thick second charge generation layer similarly prepared with a liquid containing phthalocyanine pigment F-54 parts was formed on the layer. An electrophotographic photoreceptor was prepared and evaluated in the same manner as described above. Table 1-1 shows the results.
Shown in

(Examples 1-11 and 12) Example 1-1
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-10, except that the pigment described in Table 1-1 was used instead of the charge generation layer in Example 1. The results are shown in Table 1-1.

[0077] (Example 1-13) in place of the mixed pigment of Example 1-1, azo pigments P ¹ -13 as a charge generating material
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1, except that a mixed pigment of 3.5 parts / 0.5 part of phthalocyanine pigment F-3 was used. The results are shown in Table 1-1.

(Example 1-14) The mixing ratio of the pigment was P ¹
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-13, except that -13 / F-3 was set to 0.5 / 3.5.
The results are shown in Table 1-1.

(Comparative Example 1-1) A charge generating material was used in Example 1.
Phthalocyanine pigment F-14 instead of the mixed pigment of
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1, except that parts were used. The results are shown in Table 1-1.

(Comparative Example 1-2) The charge generating material of Example 1 was used.
Phthalocyanine pigment F-24 instead of the mixed pigment of -1
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1, except that parts were used. The results are shown in Table 1-1.

(Example 2-1) Except that the charge generation material used in Example 1-1 was changed to 2 parts of azo pigment P ² -42 and phthalocyanine pigment F-5, the same procedure as in Example 1-1 was carried out. An electrophotographic photoreceptor was prepared and evaluated. The results are shown in Table 2-1.

(Examples 2-2 to 2-9) Electrophotography was performed in the same manner as in Example 2-1 except that the charge generating materials used in Example 2-1 were changed to the pigments shown in Table 2-1. Create a photoconductor,
evaluated. The results are shown in Table 2-1.

(Example 2-10) The first charge generation having a film thickness of 0.1 μm was prepared in the same manner as in Example 2-1 except that the charge generation layer was replaced with a solution containing 4 parts of azo pigment P ² -44. Example 2-1 except that a two-layered charge generation layer formed by laminating a 0.1 μm-thick second charge generation layer similarly formed with a liquid containing phthalocyanine pigment F-54 parts was formed on the layer. An electrophotographic photoreceptor was prepared and evaluated in the same manner as described above. Table 2-1 shows the results.
Shown in

(Examples 2-11 and 12) Example 2-1
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-10, except that the pigments shown in Table 2-1 were used instead of the charge generation layer in Example 1. The results are shown in Table 2-1.

[0085] Instead of mixing the pigment (Example 2-13) Example 2-1, azo pigments P ² -7 as a charge generating material
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-1 except that a mixed pigment of 3.5 parts / 0.5 part of phthalocyanine pigment F-3 was used. The results are shown in Table 2-1.

(Example 2-14) The mixing ratio of the pigment was P ²
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 2-13, except that -13 / F-3 was set to 0.5 / 3.5.
The results are shown in Table 2-1.

(Comparative Example 2-1) A charge generating material was used in Example 2.
Phthalocyanine pigment F-14 instead of the mixed pigment of
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-1 except that parts were used. The results are shown in Table 2-1.

(Comparative Example 2-2) A charge generating material was used in Example 2.
Phthalocyanine pigment F-24 instead of the mixed pigment of -1
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-1 except that parts were used. The results are shown in Table 2-1.

[0089]

[Table 11]

[0090]

[Table 12]

(Examples 1-15 to 1-28 and Comparative Example 1
-3, 4) Examples 1-1 to 1-14 and Comparative Example 1-1,
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1, except that the charge transport material used in No. 2 was changed to a compound of the following structural formula (9). Table 1-2 shows these results.
Shown in

(Examples 2-15 to 2-28 and Comparative Example 2
-3, 4) Examples 2-1 to 2-14 and Comparative Example 2-1,
An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 2-1 except that the charge transporting material used in No. 2 was replaced by the compound of the following structural formula (9), and evaluation was performed in the same manner. Table 2-2 shows these results.
Shown in

[0093]

Embedded image

[0094]

[Table 13]

[0095]

[Table 14]

(Examples 1-29 to 1-42 and Comparative Example 1)
-5, 6) Examples 1-1 to 1-14 and Comparative Example 1-1,
A photoconductor was prepared by reversing the configuration of the charge generation layer and the charge transport layer of the photoconductor prepared in 2, and the sensitivity was measured in the same manner as in Example 1-1. However, the charge transport material has the following structural formula (10)
And the charge polarity was positive. These results are shown in Table 1-3.

(Examples 2-29 to 2-42 and Comparative Example 2
-5, 6) Examples 2-1 to 2-14 and Comparative Example 2-1,
A photoreceptor was prepared by reversing the configuration of the charge generation layer and the charge transport layer of the photoreceptor prepared in 2, and the sensitivity was measured in the same manner as in Example 2-1. However, the charge transport material has the following structural formula (10)
And the charge polarity was positive. The results are shown in Table 2-3.

[0098]

Embedded image

[0099]

[Table 15]

[0100]

[Table 16]

From the above results, the electrophotographic photoreceptor used in the present invention has extremely excellent sensitivity in the oscillation wavelength region of the short-wavelength laser as compared with the photoreceptor of the comparative example, is flat, and has a low sensitivity to environmental changes. It can be seen that the fluctuation is small.

(Example 1-43) 50 parts of titanium oxide powder coated with tin oxide containing 10% antimony oxide,
Resol type phenolic resin 25 parts, Methyl cellosolve 2
0 parts, 5 parts of methanol and 0.002 parts of silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average molecular weight 3000) were dispersed in a sand mill using 1 mmφ glass beads for 2 hours to prepare a coating for a conductive layer. . The above-mentioned paint was applied by dip coating on an aluminum cylinder, and dried at 140 ° C. for 30 minutes.
m conductive layers were formed.

On this conductive layer, 6-66-610-12
A solution prepared by dissolving 5 parts of a quaternary polyamide copolymer resin in a mixed solvent of 70 parts of methanol / 25 parts of butanol was applied by a dipping method and dried to form an undercoat layer having a thickness of 1 μm.

Next, 2 parts of the azo pigment P ^{1-2 and} 2 parts of the phthalocyanine pigment F-5 were dissolved in 100 parts of cyclohexanone. Add polyvinyl butyral resin (trade name:
Esrec BM-S, manufactured by Sekisui Chemical Co., Ltd.) 4 parts, 1 m
Disperse for 2 hours in a sand mill using mφ glass beads, add 100 parts of methyl ethyl ketone, dilute, collect and apply this on the undercoat layer,
After drying at 80 ° C. for 10 minutes, a charge generation layer having a thickness of 0.15 μm was formed.

Next, a solution was prepared by dissolving 9 parts of a charge transport material represented by the following structural formula (11) and 10 parts of a bisphenol Z-type polycarbonate resin (number average molecular weight 20,000) in 60 parts of monochlorobenzene. It was applied on top by dipping. This was dried at a temperature of 110 ° C. for 1 hour to form a charge transporting layer having a thickness of 24 μm, thereby producing an electrophotographic photosensitive member.

[0106]

Embedded image

The electrophotographic photoreceptor thus prepared is
Canon printer L equipped with pulse modulator
BP-4000 remodeled machine (all solid blue SHG laser ICD-430 manufactured by Hitachi Metals, Ltd.
Equipped with 30nm. In addition, the reversal developing system is mounted on a Carlson type electrophotographic system including charging-exposure-development-transfer-cleaning capable of supporting an image input equivalent to 1200 dpi). At -200 V, a 1-dot 1-space image and a character (5 point) image were output, and the image was evaluated. The results are shown in Table 1-4.

(Examples 1-44 to 51) Examples 1-4 were as follows except that the pigments shown in Table 1-4 were used as charge generation materials.
An electrophotographic photoreceptor was prepared in the same manner as in Example 3, and the image was evaluated. The results are shown in Table 1-4.

(Comparative Examples 1-7 and 8) Electrophotography was performed in the same manner as in Example 1-43, except that the pigment shown in Table 1-4 was used instead of the mixed pigment of Example 1-43 as the charge generating material. A photoreceptor was prepared and image evaluation was performed. The results are shown in Table 1-4.

(Comparative Example 1-9) An electrophotographic photosensitive member was manufactured in the same manner as in Example 1-43, except that the light source of the evaluator used in Example 1-43 was changed to a GaAs semiconductor laser having an oscillation wavelength of 780 nm. Created and image evaluated. Table 1 shows the results.
It is shown in FIG.

Example 2-43 Examples 1-43 were the same as Example 1-43 except that the charge generating material used in Example 1-43 was replaced by 2 parts of azo pigment P ² -42 and 2 parts of phthalocyanine pigment F-5.
An electrophotographic photoreceptor was prepared in the same manner as described above, and image evaluation was performed in the same manner as in Example 1-43. The results are shown in Table 2-4.

(Examples 2-44 to 51) Examples 2 to 4 were repeated except that the pigments shown in Table 2-4 were used as the charge generation materials.
An electrophotographic photoreceptor was prepared in the same manner as in Example 3, and the image was evaluated. The results are shown in Table 2-4.

(Comparative Examples 2-7 and 8) Electrophotography was performed in the same manner as in Example 2-43, except that the pigment shown in Table 2-4 was used instead of the mixed pigment of Example 2-43 as the charge generating material. A photoreceptor was prepared and image evaluation was performed. The results are shown in Table 2-4.

Comparative Example 2-9 An electrophotographic photosensitive member was manufactured in the same manner as in Example 2-43, except that the light source of the evaluator used in Example 2-43 was changed to a GaAs semiconductor laser having an oscillation wavelength of 780 nm. Created and image evaluated. Table 2-
It is shown in FIG.

[0115]

[Table 17]

[0116]

[Table 18]

From these results, it can be seen that the electrophotographic apparatus of the present invention is excellent in dot reproducibility and character reproducibility and can obtain a high-resolution output image.

[0118]

As described above, according to the present invention, by using a charge generating material having a specific structure, excellent sensitivity characteristics can be obtained in an oscillation wavelength region of a semiconductor laser having a short wavelength of about 380 to 500 nm. And an electrophotographic photoreceptor with good environmental characteristics is provided, and by combining this electrophotographic photoreceptor with the semiconductor laser,
Provided are an electrophotographic apparatus and a process cartridge which can form a high-resolution image and can be stably used even when repeatedly used.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of a layer structure (a charge transport layer on a charge generation layer) of an electrophotographic photosensitive member used in an electrophotographic apparatus of the present invention.

FIG. 2 is a cross-sectional view illustrating an example of a layer structure (a charge generation layer on a charge transport layer) of an electrophotographic photosensitive member used in the electrophotographic apparatus of the present invention.

FIG. 3 is a cross-sectional view illustrating an example of a layer structure of an electrophotographic photosensitive member used in the electrophotographic apparatus of the present invention.

FIG. 4 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member according to the present invention.

FIG. 5 is a characteristic X-ray diffraction diagram of oxytitanium phthalocyanine used in the electrophotographic photoreceptor of the present invention.

FIG. 6 is a characteristic X-ray diffraction diagram of oxytitanium phthalocyanine used in the electrophotographic photoreceptor of the present invention.

FIG. 7 is a characteristic X-ray diffraction diagram of oxytitanium phthalocyanine used in the electrophotographic photoreceptor of the present invention.

FIG. 8 is a characteristic X-ray diffraction diagram of oxytitanium phthalocyanine used in the electrophotographic photoreceptor of the present invention.

FIG. 9 is a characteristic X-ray diffraction diagram of hydroxygallium phthalocyanine used in the electrophotographic photoreceptor of the present invention.

FIG. 10 is a characteristic X-ray diffraction diagram of chlorogallium phthalocyanine used in the electrophotographic photoreceptor of the present invention.

[Explanation of Symbols] a conductive support b photosensitive layer c charge generation layer d charge transport layer e charge generation material f binder resin g charge transport layer / binder resin 1 photoconductor 2 axis 3 charging means 4 exposure light 5 developing means 6 Transfer means 7 transfer material 8 fixing means 9 cleaning means 10 pre-exposure light 11 process cartridge 12 rail

Continued on the front page F term (reference) 2H068 AA19 AA34 AA35 AA37 BA38 BA39 BA42 BA43 BA45 BA51 BA53 FA01 FA14 FA27 FB07 2H076 AA58 AB05 EA00

Claims (17)

[Claims] An oscillation wavelength of a semiconductor laser is 380 to 5
An electrophotographic photoreceptor used with an exposure light source in the range of 00 nm, wherein the charge generation material used for the electrophotographic photoreceptor contains both a phthalocyanine pigment and an azo pigment represented by the following general formula (1). Electrophotographic photoreceptor. Embedded image (In the formula, Ar represents an aromatic hydrocarbon ring group or a heterocyclic group which may be bonded directly or via a bonding group and may have a substituent, and Cp represents a coupler residue having a phenolic hydroxyl group. And Cp is a coupler residue represented by the following general formula (2), and n is an integer of 1 to 3. However, it is possible that -N = N-Cp is bonded to the same benzene ring more than once. No) (Wherein, X represents a residue necessary for forming a polycyclic aromatic ring or a heterocyclic ring by condensing with a benzene ring, and R ¹ and R ² represent a hydrogen atom or an alkyl group which may have a substituent. , Aryl group,
Or a heterocyclic group. Further, R ¹ and R ² may form a cyclic amino group via a nitrogen atom. Z represents an oxygen atom or a sulfur atom, and m represents 0 or 1.) 2. An oscillation wavelength of a semiconductor laser is 380-5.
An electrophotographic photoreceptor used with an exposure light source in the range of 00 nm, wherein the charge generation material used for the electrophotographic photoreceptor contains both a phthalocyanine pigment and an azo pigment represented by the following general formula (3). Electrophotographic photoreceptor. Embedded image (In the formula, Ar represents an aromatic hydrocarbon ring group or a heterocyclic group which may be bonded directly or via a bonding group and may have a substituent, and Cp represents a coupler residue having a phenolic hydroxyl group. And Cp is a coupler residue represented by the following general formula (4), and n is an integer of 1 to 3. However, it is not possible that -N = N-Cp is bonded to the same benzene ring more than once. No) (Wherein, Y represents a divalent aromatic hydrocarbon group or a heterocyclic ring which may have a substituent) 3. An oscillation wavelength of the semiconductor laser is 400.
The electrophotographic photoreceptor according to claim 1, wherein the photoreceptor is in a range of from 450 to 450 nm. 4. The electrophotographic photoreceptor according to claim 1, wherein the phthalocyanine pigment is oxytitanium phthalocyanine represented by the following general formula (5). Embedded image (Wherein X ^{1 to} X ⁴ represent chlorine or bromine, and k, l, m,
n represents an integer of 0 to 4) 5. The electrophotographic photosensitive member according to claim 1, wherein the phthalocyanine pigment is gallium phthalocyanine represented by the following general formula (6). Embedded image (Wherein, X ^{5 to} X ⁸ represent chlorine or bromine, and q, r, s,
t shows the integer of 0-4. Z represents a hydroxyl group or chlorine) 6. The electron according to claim 4, wherein the phthalocyanine pigment is oxytitanium phthalocyanine having a strongest peak at 27.2 ° in Bragg angle (2θ ± 0.2 °) in characteristic X-ray diffraction of CuKα. Photoreceptor. 7. The phthalocyanine pigment is hydroxygallium phthalocyanine having strong peaks at 7.4 ° and 28.2 ° of Bragg angles (2θ ± 0.2 °) in characteristic X-ray diffraction of CuKα. 2. The electrophotographic photoreceptor of claim 1. 8. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive member has at least a charge generation layer and a charge transport layer laminated on a conductive support in this order. 9. An electrophotographic photoreceptor having a photosensitive layer on at least a conductive support and an electrophotographic apparatus having an exposure device using a laser beam as a light source, wherein the laser oscillation wavelength is in the range of 380 to 500 nm, And an electrophotographic apparatus, wherein the charge generation material of the photosensitive layer contains both a phthalocyanine pigment and an azo pigment represented by the following general formula (1). Embedded image (In the formula, Ar represents an aromatic hydrocarbon ring group or a heterocyclic group which may be bonded directly or via a bonding group and may have a substituent, and Cp represents a coupler residue having a phenolic hydroxyl group. And Cp is a coupler residue represented by the following general formula (2), and n is an integer of 1 to 3. However, it is possible that -N = N-Cp is bonded to the same benzene ring more than once. No) (In the formula, X represents a residue necessary for forming a polycyclic aromatic ring or a heterocyclic ring by condensing with a benzene ring, and R ¹ and R ² represent a hydrogen atom or an alkyl group which may have a substituent. , Aryl group,
Or a heterocyclic group. Further, R ¹ and R ² may form a cyclic amino group via a nitrogen atom. Z represents an oxygen atom or a sulfur atom, and m represents 0 or 1.) 10. An electrophotographic photoreceptor having a photosensitive layer on at least a conductive support, and an electrophotographic apparatus having an exposure device using a laser beam as a light source, wherein the laser oscillation wavelength is in the range of 380 to 500 nm, An electrophotographic apparatus, wherein the charge generation material of the photosensitive layer contains both a phthalocyanine pigment and a azo pigment represented by the following general formula (3). Embedded image (In the formula, Ar represents an aromatic hydrocarbon ring group or a heterocyclic group which may be bonded directly or via a bonding group and may have a substituent, and Cp represents a coupler residue having a phenolic hydroxyl group. And Cp is a coupler residue represented by the following general formula (4), and n is an integer of 1 to 3. However, it is not possible that -N = N-Cp is bonded to the same benzene ring more than once. No) (Wherein, Y represents a divalent aromatic hydrocarbon group or a heterocyclic ring which may have a substituent) 11. An oscillation wavelength of the semiconductor laser is 40.
The electrophotographic apparatus according to claim 9 or 10, wherein the electrophotographic apparatus is in a range of 0 to 450 nm. 12. The electrophotographic apparatus according to claim 9, wherein said phthalocyanine pigment is oxytitanium phthalocyanine represented by the following general formula (5). Embedded image (Wherein X ^{1 to} X ⁴ represent chlorine or bromine, and k, l, m,
n represents an integer of 0 to 4) 13. The electrophotographic apparatus according to claim 9, wherein the phthalocyanine pigment is gallium phthalocyanine represented by the following general formula (6). Embedded image (Wherein, X ^{5 to} X ⁸ represent chlorine or bromine, and q, r, s,
t shows the integer of 0-4. Z represents a hydroxyl group or chlorine) 14. The method according to claim 14, wherein the phthalocyanine pigment is CuKα.
Characteristic Bragg angle (2θ ± 0.2 °) in X-ray diffraction
The electrophotographic apparatus according to claim 12, which is oxytitanium phthalocyanine having the strongest peak at 27.2 °. 15. The method according to claim 15, wherein the phthalocyanine pigment is CuKα.
Bragg angle in characteristic X-ray diffraction (2θ ± 0.2 °)
The electrophotographic apparatus according to claim 13, which is hydroxygallium phthalocyanine having strong peaks at 7.4 ° and 28.2 °. 16. The electrophotographic apparatus according to claim 9, wherein the photosensitive member has at least a charge generation layer and a charge transport layer laminated on a conductive support in this order. 17. An electrophotographic photoreceptor according to claim 1, wherein said electrophotographic photoreceptor is charged with a charging means, and the electrophotographic photoreceptor on which an electrostatic latent image is formed is developed with toner. Developing means, and at least one means selected from the group consisting of a cleaning means for recovering toner remaining on the photoreceptor after the transfer step, are integrally supported together, and are detachably attached to the main body of the electrophotographic apparatus. Process cartridge.