JP2000105475A - Electrophotographic photoreceptor, process cartridge and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having high sensitivity even in the wavelength region of 380 to 500 nm and small potential changes by repeated use or by environment, and to provide a process cartridge and electrophotographic device from which a high-quality output image can be practically and stably obtd. when they are used in combination with the above photoreceptor and a short wavelength laser. SOLUTION: This electrophotographic photoreceptor has a photosensitive layer on a supporting body, and is irradiated with light from a semiconductor laser light having a wavelength of 380 to 500 nm. The photosensitive layer contains a charge transport material having the structure expressed by the formula. In the formula, Ar1-1 and Ar1-2 are aromatic cyclic groups which may have substituents, R1-1 to R1-4 are alkyl groups which may have substituents, aralkyl group which may have substituents, vinyl groups which may have substituents or aromatic cyclic groups which may have substituents, (however, at least two of R1-1 to R1-4 are aromatic cyclic groups which may have substituents), and R1-1 and R1-2, and R1-3 and R1-4 may be combined to form rings.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photoreceptor,
More particularly, the present invention relates to an electrophotographic photosensitive member suitable for a short-wavelength semiconductor laser capable of increasing the resolution of an image, a process cartridge, and an electrophotographic apparatus having a short-wavelength semiconductor laser as an exposure light source.

[0002]

2. Description of the Related Art At present, a semiconductor laser having an oscillation wavelength around 800 nm or around 680 nm is mainly used in an electrophotographic apparatus using a laser as a light source such as a laser printer. In recent years, various approaches for achieving higher resolution have been made due to a growing need for higher image quality of output images. 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 a laser beam to a half by using second harmonic generation (SHG) (Japanese Patent Laid-Open No. 9-275242,
JP-A-9-189930 and JP-A-5-3130
No. 33 publication). This system has already been established as a primary light source, and a GaAs semiconductor laser or Y
Since an AG laser can be used, a long life and a large output can be achieved.

The other uses a wide-gap semiconductor, and can reduce the size of the device as compared with a device using SHG. ZnSe based semiconductor laser (Japanese Unexamined Patent Publication No.
JP-A-321409 and JP-A-6-334272) and GaN-based semiconductor lasers (JP-A-8-0884).
No. 41 and JP-A-7-335975)
However, due to its high luminous efficiency, it has been the subject of much research for some time.

[0006] In these semiconductor lasers, it is difficult to optimize the element structure, crystal growth conditions, electrodes, and the like, and it is difficult to perform long-term oscillation at room temperature, which is essential for practical use, due to defects in the crystal.

[0007] However, technological innovations such as the base have progressed, and 19
In October 1997, GaN based semiconductor laser
Practical use is imminent, as reported by continuous time oscillation (50 ° C. condition).

[0008]

An electrophotographic photosensitive member used in a conventional laser-based electrophotographic apparatus is 700
It has been designed to exhibit practical sensitivity characteristics in a wavelength range of about 800 nm. However, even if these conventional electrophotographic photoreceptors are incorporated in an electrophotographic apparatus using a semiconductor laser having an oscillation wavelength of 400 to 500 nm, practical sensitivity characteristics cannot be obtained. The main reason is that charge generation substances used in conventional long-wavelength laser photoconductors, specifically, metal-free phthalocyanines, metal phthalocyanines such as copper phthalocyanine and oxytitanium phthalocyanine, and some azo pigments are ,
This is because there is no sufficient absorption band near 400 to 500 nm, and sufficient carriers are not generated in such a wavelength range.

Further, even when a charge generating substance having a sufficient absorption band around 400 to 500 nm is used, it is not always possible to obtain sufficient sensitivity characteristics. In recent years, electrophotographic photoreceptors, in which the function of generating charge carriers and the function of transferring charges are separately assigned to layers, a so-called stacked type (separated type) is advantageous for high sensitivity. Has become. In a photoreceptor in which a charge generation layer and a charge transport layer are laminated in this order on a conductive support, sensitivity is exhibited only when the laser beam passes through the charge transport layer and reaches the charge generation layer. However, a photoreceptor using a charge transport material having a large absorption coefficient of short-wave light in the vicinity of 400 to 500 nm does not sufficiently reach the charge generation layer, and therefore, a charge generation material having a large absorption of light of 400 to 500 nm is used. Does not show sufficient sensitivity.

Further, a photoreceptor using a charge generating substance having a sufficient absorption band around 400 to 500 nm is provided.
When the light source near nm is combined, compared with the case where the conventional long wavelength light source photoconductor and the long wavelength light source are combined,
The inventors of the present invention have clarified that the potential fluctuation of the photoreceptor is large when repeatedly used and image defects such as a ghost phenomenon easily occur in an image. One reason for this is that some of the excitons and charge carriers generated in the charge generation layer by irradiation with light of short wavelength and high energy are
It is conceivable to accumulate in the photosensitive layer without being consumed in the electrophotographic process, thereby changing the charging ability and sensitivity characteristics of the photoreceptor. The present inventors have found that such excitons and carriers can be suppressed from accumulating by an electron transfer reaction with a charge transport substance or another compound. In other words, there is an optimal charge transport material for suppressing potential fluctuations and memory phenomena during repeated use and obtaining a stable and high-quality image.

In recent years, printers and the like using electrophotographic photosensitive members have been used in various fields.
There is a more stringent demand for always providing stable images even in various environments.

An object of the present invention is to provide an electrophotographic photosensitive member having high sensitivity characteristics even in a wavelength range of 380 to 500 nm and having a small potential fluctuation upon repeated use. An object of the present invention is to provide an electrophotographic apparatus capable of stably obtaining a high-quality output image by using the same, and a process cartridge detachable from the apparatus.

[0013]

That is, the present invention relates to an electrophotographic photosensitive member having a photosensitive layer on a support, wherein the electrophotographic photosensitive member is irradiated with a semiconductor laser beam having a wavelength of 380 to 500 nm; The photosensitive layer has the following formula (1):
An electrophotographic photoreceptor containing the charge transporting material represented by (2) or (3).

According to the present invention, there is provided a process cartridge which integrally supports at least one means selected from an electrophotographic photosensitive member and a charging means, a developing means and a cleaning means and is detachable from an electrophotographic apparatus main body.
The electrophotographic photosensitive member has a photosensitive layer on a support,
A process cartridge which is irradiated with a laser beam having a wavelength of 500 nm, and the photosensitive layer contains a charge transporting material represented by the following formula (1), (2) or (3).

According to the present invention, there is provided an electrophotographic apparatus having an electrophotographic photosensitive member, a charging means, an exposing means, a developing means and a transferring means, wherein the exposing means comprises 380-5
A semiconductor laser having an oscillation wavelength of 00 nm, wherein the electrophotographic photosensitive member has a photosensitive layer on a support, and the photosensitive layer is a charge transporting compound represented by the following formula (1), (2) or (3): An electrophotographic apparatus characterized by containing a substance.

[0016]

[Outside 10]

In the formula, Ar _1-1 and Ar _1-2 each represent an aromatic ring group which may have a substituent. R _{1-1 to} R _1-4 each have an alkyl group which may have a substituent, an aralkyl group which may have a substituent, a vinyl group which may have a substituent, and a group which has a substituent. A good aromatic ring group is shown (provided that at least two of R _{1-1 to} R _1-4 are an aromatic ring group which may have a substituent). Incidentally, R _1-1 and R _1-2 and R _1-3 and R _1-4 is directly or _{-CH 2 -, - CH 2 CH} 2 -, - CH =
A ring may be formed via an organic group such as CH-, -O- and -S-.

[0018]

[Outside 11]

In the formula, Ar _2-1 represents an aromatic ring group which may have a substituent. R _{2-1 to} R _2-4 each have an alkyl group which may have a substituent, an aralkyl group which may have a substituent, a vinyl group which may have a substituent, and It shows a good aromatic ring group (provided that at least two of R _{2-1 to} R _2-4 are an aromatic ring group which may have a substituent). In addition,
R _2-1 and R _2-2 and R _2-3 and R _2-4 are directly _or-
CH ₂ —, —CH ₂ CH ₂ —, —CH ＝ CH—, —O—
And a ring may be formed via an organic group such as -S-.

[0020]

[Outside 12]

In the formula, Ar _3-1 and Ar _3-2 represent an aromatic ring group which may have a substituent. R _{3-1 to} R _3-4 each may have an alkyl group which may have a substituent, an aralkyl group which may have a substituent, a vinyl group which may have a substituent, and a substituent. It shows a good aromatic ring group (provided that at least two of R _{3-1 to} R _3-4 are an aromatic ring group which may have a substituent). Incidentally, R _3-1 and R _3-2 and R _3-3 and R _3-4 is directly or _{-CH 2 -, - CH 2 CH} 2 -, - CH =
A ring may be formed via an organic group such as CH-, -O- and -S-. X _3-1 represents a divalent organic group, preferably -CR ₁ R _2- (wherein R ₁ and R ₂ are hydrogen,
An alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aralkyl group which may have a substituent,
An aromatic ring group which may have a substituent and a heterocyclic group which may have a substituent, wherein R ₁ and R ₂ may form a ring), -O-, -S-,- CH ₂ —O—CH ₂ —, —O
—CH ₂ —O—, —NR ₃ — (wherein R ₃ represents an alkyl group which may have a substituent and an aromatic ring group which may have a substituent) and a substituent. Represents a good arylene group.

In the formulas (1) to (3), R _{1-1 to} R _1-4 ,
Examples of the aromatic ring group represented by R _{2-1 to} R _2-4 , R _{3-1 to} R _3-4 and R _{1 to} R ₃ include aromatic hydrocarbon groups such as phenyl, naphthyl, anthracenyl and pyrenyl, pyridyl and quinolyl. , Thienyl, furyl, carbazolyl, benzimidazolyl and benzothiazolyl. As the aromatic ring group of Ar _1-1 , Ar _1-2 , Ar _2-1 , Ar _3-1 and Ar _3-2 , benzene, naphthalene,
A divalent aromatic hydrocarbon group and an aromatic heterocyclic group in which two hydrogen atoms have been removed from an aromatic hydrocarbon ring such as anthracene and pyrene and an aromatic heterocycle such as pyridine, quinoline, thiophene and furan; Can be Alkyl groups include groups such as methyl, ethyl, propyl, butyl, and hexyl. Aralkyl groups include groups such as benzyl, phenethyl, naphthylmethyl, and furfuryl. Alkoxy groups include groups such as methoxy and ethoxy.

The substituents which these groups may have include alkyl groups such as methyl, ethyl, propyl, butyl and hexyl, alkoxy groups such as methoxy, ethoxy and butoxy, fluorine, chlorine, bromine and iodine. Such as halogen atoms, aromatic hydrocarbon groups such as phenyl and naphthyl, heterocyclic groups such as pyridyl, quinolyl, thienyl and furyl, acyl groups such as acetyl and benzyl, haloalkyl groups such as trifluoromethyl, cyano groups, and nitro groups Phenylcarbamoyl group, carboxy group and hydroxy group.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred examples of the charge transporting substances represented by the formulas (1), (2) and (3) are described below.
However, it is not limited to these compounds. Equation (2) represents the structural formula

[0025]

[Outside 13] Only the portions corresponding to A-Ar _2-1 -B, A and B when indicated by are described.

[0026]

[Outside 14]

[0027]

[Outside 15]

[0028]

[Outside 16]

[0029]

[Outside 17]

[0030]

[Outside 18]

[0031]

[Outside 19]

[0032]

[Outside 20]

[0033]

[Outside 21]

[0034]

[Outside 22]

[0035]

[Outside 23]

[0036]

[Outside 24]

[0037]

[Outside 25]

[0038]

[Outside 26]

[0039]

[Outside 27]

[0040]

[Outside 28]

[0041]

[Outside 29]

[0042]

[Outside 30]

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

As shown in FIGS. 1 to 6, the photoreceptor has a single-layer type in which a single photosensitive layer containing both a charge generating substance and a charge transporting substance is provided on a support. Any type such as a stacked type having a charge generation layer containing a substance and a charge transport layer containing a charge transport substance may be used. In addition, an undercoat layer having a barrier function and an adhesive function is provided between the support and the photosensitive layer (FIGS. 4 and 6), and the purpose is to protect the photosensitive layer from external mechanical and chemical adverse effects. Alternatively, a protective layer may be provided on the photosensitive layer (FIGS. 5 and 6). Among these configurations, a laminated type having a configuration in which at least a charge generation layer and a charge transport layer are laminated on a support in this order, for example, the configurations of FIGS. 1, 4, 5, and 6 are electrophotographic characteristics. This is particularly preferred in terms of In each figure, a represents a support, b represents a charge generation layer, c represents a charge transport layer, d represents a single-layer type photosensitive layer, e represents an undercoat layer, and f represents a protective layer.

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

The support in the present invention only needs to have conductivity, and examples thereof include the following forms.

(1) Aluminum, aluminum alloy,
Plates or drums made of metals such as stainless steel and copper.

(2) Aluminum, on a non-conductive support such as glass, resin and paper or the conductive support of the above (1).
Metals such as palladium, rhodium, gold and platinum are deposited or laminated.

(3) A conductive polymer on a non-conductive support such as glass, resin and paper or the conductive support of (1),
A layer formed by depositing or applying a layer containing a conductive compound such as tin oxide and indium oxide.

Examples of the effective charge generating substance used in the present invention include the following substances. These charge generating substances may be used alone or in combination of two or more.

(1) Azo pigments such as monoazo, bisazo and trisazo (2) Indigo pigments such as indigo and thioindigo (3) Phthalocyanine pigments such as metal phthalocyanine and nonmetal phthalocyanine (4) Perylene anhydride and perylene Perylene pigments such as acid imide (5) Polycyclic quinone pigments such as anthraquinone and pyrenequinone (6) Squarylium dyes (7) Pyrylium salts and thiopyrylium salts (8) Triphenylmethane dyes (9) Selenium and amorphous Inorganic substances such as silicon

The layer containing the charge generating substance, that is, the charge generating layer, can be formed by dispersing the above-described charge generating substance in a suitable binder and applying the resultant to a conductive support. it can. Further, it can be formed on a conductive support by a dry method such as evaporation, sputtering, and CVD.

The binder can be selected from a wide range of binder resins, for example, polycarbonate resin, polyester resin, polyarylate resin, butyral resin, polystyrene resin, polyvinyl acetal resin, diallyl phthalate resin, acrylic resin, methacrylic resin. , Vinyl acetate resin, phenolic resin, silicone resin, polysulfone resin, styrene-butadiene copolymer resin, alkyd resin, epoxy resin, urea resin and vinyl chloride-vinyl acetate copolymer resin, but are not limited thereto. Not something. These may be used alone or in combination of two or more as a copolymer.

The resin contained in the charge generation layer is preferably at most 80% by weight, particularly preferably at most 40% by weight.
The charge generation layer has a thickness of 5 μm or less, particularly 0.01 μm.
It is preferable to set the thickness to 2 μm. Various sensitizers may be added to the charge generation layer.

The layer containing the charge transporting material, ie, the charge transporting layer, is formed by combining at least the charge transporting material represented by the above formula (1), (2) or (3) with a suitable binder. Can be formed. Examples of the binder used in the charge transport layer include those used in the charge generation layer, and further include photoconductive polymers such as polyvinyl carbazole and polyvinyl anthracene.

The charge transporting substance includes an electron transporting substance and a hole transporting substance. Examples of the electron transporting substance include:
2,4,7-trinitrofluorenone, 2,4,5,7
-Electron-withdrawing substances such as tetranitrofluorenone, chloranil, and tetracyanoquinodimethane, and those obtained by polymerizing these electron-withdrawing materials.

As the hole transporting substance, the above formula (1)
In addition to the amine compounds represented by the formulas (2) and (3),
For example, polycyclic aromatic compounds such as pyrene and anthracene, carbazole, indole, oxazole,
Heterocyclic compounds such as thiazole, oxadiazole, pyrazole, pyrazoline, thiadiazole, and triazole compounds, hydrazone compounds, triarylmethane compounds, stilbene compounds, and groups composed of these compounds are mainly used. Polymers having a chain or a side chain (for example, poly-N-vinyl carbazole and polyvinyl anthracene) are included.

In the present invention, the amine compounds represented by formulas (1), (2) and (3) may be used alone or in combination of two or more. It may be used in combination with a charge transporting material having another structure as described above as long as the above effects can be obtained.

The mixing ratio of the binder and the charge transporting substance is preferably 10 to 500 parts by weight of the charge transporting substance per 100 parts by weight of the binder. The charge transport layer is electrically connected to the above-described charge generation layer, and has a function of receiving charge carriers injected from the charge generation layer in the presence of an electric field and transporting these charge carriers to the surface. ing. Since the charge transport layer has a limit for transporting charge carriers, the film thickness cannot be increased more than necessary, but the thickness is 5 μm to 40 μm, particularly 10 μm to 30 μm.
The range of m is preferred.

Further, an antioxidant, an ultraviolet absorber, a plasticizer and the like can be added to the charge transporting layer as required.

The undercoat layer can be formed of casein, polyvinyl alcohol, nitrocellulose, polyamide (nylon 6, nylon 66, nylon 610, copolymerized nylon and N-alkoxymethylated nylon, etc.), polyurethane, aluminum oxide and the like. . The film thickness is preferably from 0.1 to 10 μm, particularly preferably from 0.5 to 5 μm.

The protective layer is a resin layer or a resin layer containing conductive particles and the like.

These various layers can be formed using a suitable organic solvent by a coating method such as a dip coating method, a spray coating method, a spinner coating method, a roller coating method, a Meyer bar coating method and a blade coating method. .

The exposure means in the present invention only needs to have a semiconductor laser having an oscillation wavelength of 380 to 500 nm as an exposure light source, and other configurations are not particularly limited. Other configurations of the semiconductor laser are not particularly limited as long as the oscillation wavelength is within the above range. In the present invention, it is preferable that the oscillation wavelength of the semiconductor laser is 400 to 450 nm in view of the wide selection range of the charge transport material, cost, and electrophotographic characteristics.

The charging means, developing means, transfer means and cleaning means in the present invention are not particularly limited.

FIG. 7 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 in a direction of an arrow at a predetermined peripheral speed. The photoreceptor 1 rotates during the rotation process.
The peripheral surface is uniformly charged with a predetermined positive or negative potential by the primary charging means 3 and then receives exposure light 4 from exposure means (not shown) such as laser beam scanning exposure. 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 which has undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing to be printed out as a copy out of the apparatus.

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 the pre-exposure light 10 from the pre-exposure means (not shown).
Is used for image formation repeatedly after the charge removal processing. In the figure, since the primary charging means 3 is a contact charging means using a charging roller, 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, a process in which 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 can be attached to and detached from the apparatus main body by using a guide unit such as the rail 12 of the apparatus main body. The cartridge 11 can be used.

[0072]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the following examples, “parts” indicates “parts by weight”.

(Example 1) N on an aluminum support
-Methoxymethylated 6 nylon resin (weight average molecular weight 3
A solution prepared by dissolving 5.5 parts of (0000) and 8 parts of an alcohol-soluble copolymerized nylon resin (weight average molecular weight of 28,000) in a mixed solution of 30 parts of methanol / 89 parts of butanol is applied by a Meyer bar and dried. Thus, an undercoat layer having a thickness of about 1 μm was provided.

Next, an azo compound 2 represented by the following structural formula
0 parts and butyral resin (butyralization degree 65 mol%,
10 parts by weight (weight average molecular weight 30,000) was added to 400 parts of tetrahydrofuran, and dispersed by a sand mill using glass beads having a diameter of 1 mm for 20 hours. This dispersion was applied to the undercoat layer prepared above using a Meyer bar and dried to form a charge generation layer having a thickness of about 0.25 μm.

[0075]

[Outside 31]

Next, 7 parts of the exemplified compound 1-8 was added to a bisphenol Z-type polycarbonate (weight average molecular weight: 45.0
00) A charge transport layer solution was prepared by dissolving 10 parts in 65 parts of monochlorobenzene, this solution was applied on the charge generation layer by a Meyer bar, and dried at 100 ° C. for 1 hour to form a charge having a thickness of 22 μm. A transport layer was formed, and an electrophotographic photoreceptor was prepared.

The electrophotographic characteristics of the photoreceptor prepared as described above were measured using an electrostatic copying paper tester (made by Kawaguchi Electric: EPA-
8100) as follows.

(Initial Characteristics) The surface potential of the photosensitive member was set to -700.
V was charged with a corona charger, and then exposed to 450 nm monochromatic light separated by a monochromator, and the amount of light required for the surface potential to attenuate to -350 V was measured.
The half-life exposure sensitivity (E1 _{/ 2} ) was determined. Further, the residual surface potential (Vr) 30 seconds after the exposure was measured.

(Repeatability and environmental characteristics) Initial dark portion potential (V) under normal temperature and normal humidity (temperature 23 ° C., humidity 55% RH)
d) and the initial light portion potential (Vl) are -700 V, respectively.
Charging and exposure were repeated 5,000 times using a monochromatic light of 450 nm set at around -200 V, and the fluctuation amounts (ΔVd, ΔVl) of Vd and Vl were measured. Thereafter, the environment was changed to high temperature and high humidity (temperature of 33 ° C., humidity of 85% RH), and the fluctuation amount of Vl from under normal temperature and normal humidity was measured. A negative sign in the potential fluctuation indicates a decrease in the absolute value of the potential, and a positive sign indicates an increase in the absolute value of the potential.

(Optical Memory) Initial Vd of Photoconductor, 450
The initial Vl for monochromatic light of nm is -700 V and -2, respectively.
It was set near 00V. Next, a light intensity 2 is applied to a part of the photoconductor.
After irradiation with 0 μW / cm ² of 450 nm monochromatic light for 20 minutes, Vd and Vl of the photoreceptor were measured again. Was measured (ΔVl). A negative sign in the potential difference indicates that the irradiated part potential has a lower absolute value than the non-irradiated part, and a positive sign indicates the opposite.

Table 1 shows the results.

Examples 2 to 5 Electrophotographic photosensitive members were prepared and evaluated in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of the exemplified compounds 1-8. Table 1 shows the results
Shown in

Comparative Example 1 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that Comparative Compound 1 represented by the following structural formula was used instead of Exemplified Compound 1-8. Table 1 shows the results.

[0084]

[Outside 32]

Comparative Example 2 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that Comparative Compound 2 represented by the following structural formula was used instead of Exemplified Compound 1-8. Table 1 shows the results.

[0086]

[Outside 33]

[0087]

[Table 1]

Examples 6-9 Exemplified compounds 1-8 were prepared as shown in Table 2.
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that the compound shown in Table 1 was used. Table 2 shows the results.

[0089]

[Table 2]

Examples 10 to 13 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the compounds shown in Table 3 were used as exemplary compounds. Table 3 shows the results.

[0091]

[Table 3]

Examples 14 to 16 and Comparative Example 3 In the same manner as in Example 1 except that the azo compound was changed to a compound represented by the following structural formula, and the charge transporting material was changed to a compound shown in Table 4. An electrophotographic photosensitive member was prepared and evaluated. Table 4 shows the results.

[0093]

[Outside 34]

[0094]

[Table 4]

Examples 17 to 19 Electrophotographic photosensitive members were prepared and evaluated in the same manner as in Example 14 except that the exemplified compounds were changed to the compounds shown in Table 5. Table 5 shows the results.

[0096]

[Table 5]

Examples 20 to 22 Electrophotographic photosensitive members were prepared and evaluated in the same manner as in Example 14, except that the exemplified compounds were changed to the compounds shown in Table 6. Table 6 shows the results.

[0098]

[Table 6]

From these results, the electrophotographic photosensitive member using the compounds represented by the formulas (1) to (3) was incorporated in an electrophotographic apparatus having a short-wavelength exposure light source, as compared with the photosensitive member of the comparative example. In this case, it can be seen that a higher sensitivity is exhibited, the potential and the stability of the sensitivity during repeated use are more excellent, the environment dependency is smaller, and the optical memory for short wavelength light is smaller.

(Examples 23 to 31 and Comparative Example 4) A photosensitive member was prepared by reversing the vertical relationship between the charge generation layer and the charge transport layer of the photosensitive members prepared in Examples 14 to 22 and Comparative Example 3. The initial sensitivity was measured in the same manner as in Example 1. However, the charging polarity was positive. Table 7 shows the results.

[0101]

[Table 7]

From these results, the electrophotographic photoreceptor of the present invention can obtain practical sensitivity as a photoreceptor for short wavelength laser even in a so-called reverse layer configuration in which a charge transport layer and a charge generation layer are laminated in this order. It is understood that it can be done.

(Examples 32-34 and Comparative Example 5) 10%
50 parts of titanium oxide powder coated with tin oxide containing antimony oxide, 25 parts of resole type phenol resin, 20 parts of methyl cellosolve, 5 parts of methanol and silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average molecular weight 3, 000) 0.002 parts to 1 mm
The dispersion was dispersed for 2 hours with a sand mill using φ glass beads to prepare a coating for the conductive layer. This paint is dip-coated on an aluminum cylinder (30 mmφ × 261 mm),
By drying at 140 ° C. for 30 minutes, the film thickness becomes 20 μm.
m conductive layers were formed.

On this conductive layer, 5 parts of N-methoxymethylated nylon 6 resin (weight average molecular weight 52,000) and 10 parts of alcohol-soluble copolymerized nylon resin (weight average molecular weight 48,000) were added to 95 parts of methanol. By dip coating the dissolved liquid and drying, the film thickness becomes 0.8μ
m was formed.

20 parts of the azo compound used in Example 1 was added to a solution prepared by dissolving 10 parts of polyvinyl butyral (trade name: SREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) in 200 parts of cyclohexanone. The mixture was dispersed for 20 hours in a sand mill using, and further diluted by adding 200 parts of ethyl acetate. This solution was dip-coated on the undercoat layer and dried at 95 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.4 μm.

Next, 9 parts of the exemplified compounds shown in Table 8 and bisphenol Z-type polycarbonate (weight average molecular weight 4
(5,000) was dissolved in 65 parts of monochlorobenzene. This liquid was applied onto the charge generation layer by dip coating, and dried at 100 ° C. for 1 hour to form a charge transport layer having a thickness of 22 μm.

The electrophotographic photoreceptor thus prepared was converted to a Canon printer LBP-2000 remodeling machine equipped with a pulse modulator (Hitachi Metals, Ltd. as a light source).
Equipped with all solid blue SHG laser ICD-430 / oscillation wavelength 430nm. In addition, the reversal development system was modified to a Carlson-type electrophotographic system consisting of charging-exposure-development-transfer-cleaning, which can support image input equivalent to 600 dpi. ), And the following image evaluation was performed.

(Evaluation of Reproducibility of Dots and Characters) The dark portion potential Vd = -650 V and the bright portion potential Vl = -200 V were set, and one dot / one space image and a character (5 point) image were output. The obtained image was visually evaluated.
In Table 8, ◎ indicates excellent, は indicates good, Δ indicates acceptable, and × indicates inferior.

(Evaluation of Ghost) Under normal temperature and normal humidity (23 ° C.,
Initially, an appropriate character pattern was printed for one rotation of the drum at a humidity of 55% RH), and then an image sample was output to visually check whether or not a ghost phenomenon had occurred. Next, continuous printing of 5,000 sheets of a durable pattern was performed, an image sample was output after the endurance, and it was confirmed whether or not a ghost phenomenon occurred after the endurance. The durable pattern is a line having a width of about 2 mm printed every 7 mm in length and width. The image sample used was an image of black on the entire surface and a dot density of one dot per space, and the development volumes of the machine, F5 (center value) and F9
(Low concentration). The evaluation criteria are as follows: a ghost is not visible, rank 5; a sight that can be seen in one dot and one space F9 is rank 4, a sight that is seen in one dot and one space F5 is a rank 3, and a ghost that is entirely visible in F9 is rank 2. What was visible in F5 was designated as rank 1.

Table 8 shows the results.

Comparative Example 6 An electrophotographic photosensitive member was prepared in the same manner as in Example 32 except that the azo compound was replaced with a compound represented by the following structural formula.

[0112]

[Outside 35]

(Comparative Example 7) An electrophotographic photosensitive member was prepared in the same manner as in Comparative Example 6, except that the exemplified compound was replaced with Comparative Compound 1.

With respect to the photosensitive members prepared in Comparative Examples 6 and 7, the light source of the printer was changed to a G light having an oscillation wavelength of 780 nm.
Evaluation was performed in the same manner as in Example 32 except that the aAs-based semiconductor laser was used instead. Table 8 shows the results.

[0115]

[Table 8]

Examples 35 to 46 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 32 except that the exemplified compounds were changed to the exemplified compounds shown in Table 9. Table 9 shows the results.
Shown in

Comparative Example 8 An electrophotographic photosensitive member was prepared in the same manner as in Example 35 except that the azo compound was changed to the compound used in Comparative Example 6.

The prepared photoreceptor was evaluated in the same manner as in Example 35 except that the light source of the printer was changed to a GaAs semiconductor laser having an oscillation wavelength of 780 nm. Table 9 shows the results.

[0119]

[Table 9]

(Examples 38 to 40)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 32 except that the exemplified compounds shown in the above were replaced. Table 10 shows the results.

Comparative Example 9 An electrophotographic photosensitive member was prepared in the same manner as in Example 38 except that the azo compound was replaced with the compound used in Comparative Example 6.

The prepared photoreceptor was evaluated in the same manner as in Example 38 except that the light source of the printer was changed to a GaAs semiconductor laser having an oscillation wavelength of 780 nm. Table 10 shows the results.

[0123]

[Table 10]

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. In addition, it can be seen that a clear image without defects is stably obtained.

[0125]

As described above, the electrophotographic photoreceptor of the present invention has high sensitivity in the oscillation wavelength region of a semiconductor laser having a short wavelength of about 400 to 500 nm, and forms a continuous image by repeated charging and exposure. In addition, there is a remarkable effect that a change in the light portion potential and the dark portion potential is small when the environment changes, and a high-quality image can be stably obtained. Also,
By combining this electrophotographic photoreceptor with the above-mentioned semiconductor laser, a process cartridge and an electrophotographic apparatus which can form a high-resolution image and can be used stably even under repeated use and environmental changes are provided.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of a layer configuration of an electrophotographic photoreceptor of the present invention.

FIG. 2 is a cross-sectional view illustrating an example of a layer configuration of the electrophotographic photosensitive member of the present invention.

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

FIG. 4 is a cross-sectional view illustrating an example of a layer configuration of the electrophotographic photosensitive member of the present invention.

FIG. 5 is a cross-sectional view illustrating an example of a layer configuration of the electrophotographic photosensitive member of the present invention.

FIG. 6 is a cross-sectional view illustrating an example of a layer configuration of the electrophotographic photosensitive member of the present invention.

FIG. 7 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.

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

Claims (18)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a support, wherein the electrophotographic photosensitive member is irradiated with a semiconductor laser beam having a wavelength of 380 to 500 nm, and the photosensitive layer has the following formula (1): An electrophotographic photoreceptor containing the charge transporting material represented by (2) or (3). [Outside 1] (In the formula, Ar _1-1 and Ar _1-2 each represent an aromatic ring group which may have a substituent. R _{1-1 to} R _1-4 each represent an alkyl group which may have a substituent, An aralkyl group which may have a group, a vinyl group which may have a substituent, and an aromatic ring group which may have a substituent (provided that at least two of R _{1-1 to} R _1-4 are represented by Is an aromatic ring group which may have a substituent).
_1-1 and R _1-2 and R _1-3 and R _1-4 may combine to form a ring. [Outside 2] (Wherein, Ar _2-1 represents an aromatic ring group which may have a substituent. R _{2-1 to} R _2-4 each represent an alkyl group which may have a substituent, Aralkyl group, a vinyl group which may have a substituent, and an aromatic ring group which may have a substituent (provided that at least two of R _{2-1 to} R _2-4 represent a substituent. has also a good aromatic group) .R _2-1 and R _2-2
And R _2-3 and R _2-4 may combine to form a ring. [Outside 3] (In the formula, Ar _3-1 and Ar _3-2 represent an aromatic ring group which may have a substituent. R _{3-1 to} R _3-4 each represent an alkyl group which may have a substituent, An aralkyl group which may have a group, a vinyl group which may have a substituent, and an aromatic ring group which may have a substituent (provided that at least two of R _{3-1 to} R _3-4 are represented by Is an aromatic ring group which may have a substituent).
_3-1 and R _3-2 and R _3-3 and R _3-4 may combine to form a ring. X _3-1 represents a divalent organic group. ) 2. The electrophotographic photosensitive member according to claim 1, wherein the charge transporting material is represented by the formula (1). 3. The electrophotographic photosensitive member according to claim 1, wherein the charge transporting material is represented by the formula (2). 4. The electrophotographic photosensitive member according to claim 1, wherein the charge transporting material is represented by the formula (3). 5. The wavelength of a semiconductor laser beam is 400
The electrophotographic photoreceptor according to any one of claims 1 to 4, wherein the thickness is from 450 to 450 nm. 6. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer has a charge transport layer on the charge generation layer. 7. A process cartridge which integrally supports an electrophotographic photosensitive member and at least one means selected from a charging means, a developing means and a cleaning means and is detachable from an electrophotographic apparatus main body. The body has a photosensitive layer on the support,
A process cartridge, which is irradiated with a laser beam having a wavelength of 500 nm, and the photosensitive layer contains a charge transporting material represented by the following formula (1), (2) or (3). [Outside 4] (In the formula, Ar _1-1 and Ar _1-2 each represent an aromatic ring group which may have a substituent. R _{1-1 to} R _1-4 each represent an alkyl group which may have a substituent, An aralkyl group which may have a group, a vinyl group which may have a substituent, and an aromatic ring group which may have a substituent (provided that at least two of R _{1-1 to} R _1-4 are represented by Is an aromatic ring group which may have a substituent).
_1-1 and R _1-2 and R _1-3 and R _1-4 may combine to form a ring. [Outside 5] (Wherein, Ar _2-1 represents an aromatic ring group which may have a substituent. R _{2-1 to} R _2-4 each represent an alkyl group which may have a substituent, Aralkyl group, a vinyl group which may have a substituent, and an aromatic ring group which may have a substituent (provided that at least two of R _{2-1 to} R _2-4 represent a substituent. has also a good aromatic group) .R _2-1 and R _2-2
And R _2-3 and R _2-4 may combine to form a ring. [Outside 6] ( _Wherein , Ar _3-1 and Ar _3-2 represent an aromatic ring group which may have a substituent. R _{3-1 to} R _3-4 each represent an alkyl group which may have a substituent, An aralkyl group which may have a group, a vinyl group which may have a substituent, and an aromatic ring group which may have a substituent (provided that at least two of R _{3-1 to} R _3-4 are represented by Is an aromatic ring group which may have a substituent).
_3-1 and R _3-2 and R _3-3 and R _3-4 may combine to form a ring. X _3-1 represents a divalent organic group. ) 8. The process cartridge according to claim 7, wherein the charge transport material is represented by the formula (1). 9. The process cartridge according to claim 7, wherein the charge transport material is represented by the formula (2). 10. The process cartridge according to claim 7, wherein the charge transport material is represented by the formula (3). 11. A semiconductor laser beam having a wavelength of 40.
The process cartridge according to any one of claims 7 to 10, wherein the thickness is from 0 to 450 nm. 12. The process cartridge according to claim 7, wherein the photosensitive layer has a charge transport layer on the charge generation layer. 13. An electrophotographic apparatus having an electrophotographic photosensitive member, a charging unit, an exposing unit, a developing unit, and a transferring unit, wherein the exposing unit has a semiconductor laser having an oscillation wavelength of 380 to 500 nm as an exposure light source. An electrophotographic apparatus, wherein an electrophotographic photoreceptor has a photosensitive layer on a support, and the photosensitive layer contains a charge transporting material represented by the following formula (1), (2) or (3). [Outside 7] (In the formula, Ar _1-1 and Ar _1-2 each represent an aromatic ring group which may have a substituent. R _{1-1 to} R _1-4 each represent an alkyl group which may have a substituent, An aralkyl group which may have a group, a vinyl group which may have a substituent, and an aromatic ring group which may have a substituent (provided that at least two of R _{1-1 to} R _1-4 are represented by Is an aromatic ring group which may have a substituent).
_1-1 and R _1-2 and R _1-3 and R _1-4 may combine to form a ring. [Outside 8] (Wherein, Ar _2-1 represents an aromatic ring group which may have a substituent. R _{2-1 to} R _2-4 each represent an alkyl group which may have a substituent, Aralkyl group, a vinyl group which may have a substituent, and an aromatic ring group which may have a substituent (provided that at least two of R _{2-1 to} R _2-4 represent a substituent. has also a good aromatic group) .R _2-1 and R _2-2
And R _2-3 and R _2-4 may combine to form a ring. [Outside 9] (In the formula, Ar _3-1 and Ar _3-2 represent an aromatic ring group which may have a substituent. R _{3-1 to} R _3-4 each represent an alkyl group which may have a substituent, An aralkyl group which may have a group, a vinyl group which may have a substituent, and an aromatic ring group which may have a substituent (provided that at least two of R _{3-1 to} R _3-4 are represented by Is an aromatic ring group which may have a substituent).
_3-1 and R _3-2 and R _3-3 and R _3-4 may combine to form a ring. X _3-1 represents a divalent organic group. ) 14. The electrophotographic apparatus according to claim 13, wherein the charge transporting substance is represented by the formula (1). 15. The electrophotographic apparatus according to claim 13, wherein the charge transporting substance is represented by the formula (2). 16. The electrophotographic apparatus according to claim 13, wherein the charge transporting substance is represented by the formula (3). 17. The semiconductor laser beam has a wavelength of 40.
The electrophotographic apparatus according to any one of claims 13 to 16, wherein the thickness is from 0 to 450 nm. 18. The electrophotographic apparatus according to claim 13, wherein the photosensitive layer has a charge transport layer on the charge generation layer.