JPH08320583A - Electrophotographic photoreceptor, process cartridge having the electrophotographic photoreceptor and electrophotographic device - Google Patents

Abstract

PURPOSE: To decrease fluctuation in the bright potential and in the dark poten tial when an image is continuously formed by repetition of electrification and exposure and to improve durability by incorporating a specified oxytitanium phthalocyanine and a specified compd. into a photosensitive layer. CONSTITUTION: This electrophotographic photoreceptor has a photosensitive layer on a conductive base body. The photosensitive layer contains such an oxytitanium phthalocyanine that the Cu-KαX-ray diffraction measurement shows intense peaks at the Bragg angle (2θ±0.2 deg.) of 9.0 deg., 14.2 deg., 23.9 deg., and 27.1 deg., and further contains a compd. having at least one fulvene structure expressed by formula. In formula, R1 -R5 are hydrogen atoms, substd. or unsubstd. alkyl groups, substd. or unsubstd. aryl groups, or substd. or unsubstd. aralkyl groups, and R2 and R3 , R4 and R5 may be bonded to form rings.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, selenium has been used as an electrophotographic photoreceptor.
Inorganic photoreceptors having a photosensitive layer containing zinc oxide, cadmium sulfide or the like as a main component have been widely used. Although these have some basic characteristics, they are difficult to form.
There are problems such as poor plasticity and high manufacturing cost. Furthermore,
Inorganic photoconductive materials are generally highly toxic and have great restrictions in production and handling.

Organic photoconductors containing an organic photoconductive compound as a main component have many advantages such as compensating for the above-mentioned drawbacks of inorganic photoconductors, and have attracted attention. Many proposals have been made so far. It has been put to practical use. As such an organic photoreceptor, a charge transfer complex formed of a photoconductive polymer represented by poly-N-vinylcarbazole and a Lewis acid such as 2,4,7-trinitro-9-fluorenone. An electrophotographic photosensitive member containing as a main component has been proposed. These organic photoconductive polymers are superior in lightness and film-forming property to the inorganic photoconductive materials, but are sensitive, durable, and
It is inferior to inorganic photoconductive materials in terms of stability due to environmental changes, and is not always satisfactory.

On the other hand, the electrophotographic photosensitive member, which is a function-separated type photosensitive member in which the charge generating function and the charge transporting function are shared by different substances, has the disadvantages of sensitivity and durability which have been the drawbacks of the organic photosensitive member. It brought a significant improvement. Such a function-separated type photoconductor has the advantages that the material selection range for the charge generation substance and the charge transport substance is wide, and that an electrophotographic photoconductor having arbitrary characteristics can be prepared relatively easily. .

As the charge generating substance, phthalocyanine pigments, azo pigments, polycyclic quinone pigments, squaric acid dyes, pyrylium salt dyes and the like are known. Particularly, phthalocyanine pigments have strong light resistance and charge generating ability. Many structures and crystal forms have been proposed in view of their large size and easy material synthesis.

As the charge transport material, for example, Japanese Examined Patent Publication No. 52
Pyrazoline compounds described in JP-A-4188, JP-B-5
Hydrazone compounds described in JP-A-5-42380 and JP-A-55-52063, and JP-B-58-32372.
JP-A-61-132955 and JP-A-3
Triphenylamine compounds described in JP-A-114058, JP-A-54-151955 and JP-A-58-
The stilbene compounds described in 198043 are known.

As the fulvene compound contained in the electrophotographic photosensitive member, for example, JP-A-52-128373, JP-A-54-110837 and JP-A-55-
No. 161247, JP-A-60-98437,
JP-A-60-174749, JP-A-62-120
The prior arts described in Japanese Patent Application Laid-Open No. 346, Japanese Patent Application Laid-Open No. 63-30851, Japanese Patent Application Laid-Open No. 4-287049 and the like are known.

What is required of the electrophotographic photosensitive member is that
(1) be stable to light and heat, (2) ozone generated by corona discharge, NO _X, it is stable to nitric acid, (3) to have high electrophotographic sensitivity,
(4) High compatibility with organic solvent and binder, (5)
It is easy to manufacture and inexpensive.

Further, as the durability is further improved, a protective layer is provided on the photosensitive layer for improving the durability, and the photoreceptor is stored for a long time in a copying machine, a laser beam printer or the like. As a result, cracks may occur in the charge transport layer, or the charge transport material may be crystallized or phase-separated, resulting in image defects.

Further, in a reversal development system compatible with digitalization, since the primary charging and the transfer charging have opposite polarities, a so-called transfer memory having different charging properties depending on the presence / absence of transfer is generated, which is extremely uneven in density on an image. It is easy to appear.

Further, in the electrophotographic photosensitive member having a high sensitivity, a so-called photo memory in which the chargeability of the bright portion and the dark portion is different due to external leakage light or the like is generated, which also causes uneven density on the image. It's very easy to appear.

Therefore, an electrophotographic photoreceptor satisfying all of the above problems and requirements at a higher level has been studied.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide various organic photoconductive compounds which have been provided in conventional electrophotographic photoreceptors by providing an organic photoconductive compound which sufficiently satisfies the characteristics required for the electrophotographic photoreceptors. The drawback is to be eliminated. That is,
(1) To provide an electrophotographic photosensitive member having a large sensitivity and capable of stably maintaining the potential during repeated use,
(2) Providing a protective layer on the photosensitive layer, or copying machine or laser
To provide an electrophotographic photosensitive member which does not cause cracks in the charge transporting layer or crystallization of the charge transporting substance even if the photosensitive member is stored for a long time in a beam printer or the like. To provide an electrophotographic photosensitive member that is less likely to cause a transfer memory, (4) To provide an electrophotographic photosensitive member that has light resistance and is less likely to cause a photo memory, and (5) Is easy to manufacture and inexpensive. It is to provide a novel electrophotographic additive or organic photoconductive compound that can be provided.

[0014]

The present invention provides an electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer has a Bragg angle (2θ ± 0.
2 °) of 9.0 °, 14.2 °, 23.9 ° and 27.
From an electrophotographic photoreceptor containing an oxytitanium phthalocyanine having a strong peak at 1 °, and a compound having at least one fulvene group represented by the following general formula (1): Composed. General formula (1)

Embedded image In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group, and , R ₂ and R ₃ and R ₄ and R ₅ may together form a ring.

In the present invention, the compound having at least one fulvene structure represented by the following general formula (1) is preferably the fulvene compound represented by the general formula (2). General formula (2)

[Chemical 4] In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, and , R ₂ and R ₃ and R ₄ and R ₅ may together form a ring. Ar represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. n is an integer of 1 to 3.

Further, in the present invention, Ar in the fulvene compound represented by the general formula (2) is more preferably a substituted or unsubstituted aryl group.

Further, in the present invention, it is more preferable that Ar in the fulvene compound represented by the general formula (2) is a substituted aryl group and that Ar has a substituted amino group.

In the general formulas (1) and (2),
Examples of the alkyl group include groups such as methyl, ethyl, propyl and butyl, examples of the aryl group include groups such as phenyl, diphenyl, naphthyl, anthryl and pyrenyl, and examples of the aralkyl group include groups such as benzyl and phenethyl. Is mentioned. Examples of the substituent include an alkyl group such as methyl, ethyl and propyl, an alkoxy group such as methoxy, ethoxy and propoxy, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a nitro group, a hydroxyl group and a cyano group.

Specific examples of the compound having at least one fulvene structure represented by the general formula (2) are shown in Tables 1 to 7.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

Examples of the constitution of the photosensitive layer of the electrophotographic photosensitive member of the present invention include the following forms. (1) Layer containing charge generating substance / layer containing charge transporting substance (lower layer / upper layer) (2) Layer containing charge transporting substance / layer containing charge generating substance (lower layer / upper layer) (3) Charge Layer containing generator and charge transport material

The compound having a fulvene structure-containing group represented by the general formula (1) of the present invention has the effect of improving various problems by adding it to the photosensitive layer. Can be used as
Further, in particular, the fulvene compound represented by the general formula (2) has a high capability of transporting holes, and therefore, as a material having both an effect of improving the problems in the photosensitive layer of the above-described form and an effect as a charge transport material. Can be used. Of these, a fulvene compound in which Ar is a substituted or unsubstituted aryl group and Ar has a substituted amino group is particularly preferable. When the form of the photosensitive layer is (1), the polarity of primary charging is preferably negative, when it is (2) it is positive, and when it is (3), it may be either positive or negative. Of course, the form of the photosensitive layer of the electrophotographic photosensitive member of the present invention is not limited to the above-mentioned basic structure.

Further, in the electrophotographic photoreceptor of the present invention, a protective layer is provided on the surface of the photosensitive layer or a layer between the photosensitive layer and the conductive support is provided in order to improve durability and adhesiveness or control charge injection. May be provided with an undercoat layer.

The form of the photosensitive layer of the electrophotographic photosensitive member of the present invention is particularly preferably the form (1) among the above constitutions, and the electrophotographic photosensitive member of this form will be described in more detail.

Examples of the conductive support in the present invention include the following materials. (1) Plate-shaped or drum-shaped metal or alloy such as aluminum, aluminum alloy, stainless steel and copper, (2) non-conductive support such as glass, resin and paper, and conductive support of the above (1) A thin layer formed by vapor-depositing or laminating a metal or alloy such as aluminum, aluminum alloy, palladium, gold and platinum on the body, (3) non-conductive support such as glass, resin and paper A layer formed by vapor-depositing or coating a layer containing a conductive polymer, a conductive compound such as tin oxide and indium oxide on the conductive support (1).

At least CuK is used as the charge generating substance.
Bragg angle in α characteristic X-ray diffraction (2θ ± 0.2 °)
Oxytitanium phthalocyanine having a strong peak at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° (for example, described in JP-A-3-128973), and further You may use the substance shown in 2 in combination of 2 or more types. (1) Azo pigments such as monoazo, disazo and trisazo, (2) phthalocyanine pigments such as metal phthalocyanine and non-metal phthalocyanine, (3) indigo pigments such as indigo and thioindigo, (4) perylene anhydride and perylene. Perylene pigments such as acid imides, (5) polycyclic quinone pigments such as anthraquinone and pyrenequinone,
(6) squarylium dye, (7) pyrylium salt and thiapyrylium salt, (8) triphenylmethane dye,
(9) Inorganic substances such as selenium and amorphous silicon.

The charge generation layer can be formed by dispersing the above-mentioned charge generation substance in a suitable binder and coating it on a conductive support. It can also be formed by forming a thin film on the conductive support by a dry method such as vapor deposition, sputtering or CVD. The fulvene compound according to the present invention may be contained in the charge generation layer.

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, phenol resin, silicone resin, polysulfone resin, styrene-butadiene copolymer resin, alkyd resin, epoxy resin, urea resin, vinyl chloride-vinyl acetate Examples thereof include copolymer resins, but the present invention is not limited to these. These may be used alone, as a mixture, or as a copolymer polymer, or may be used in combination of two or more kinds.

The proportion of the binder resin in the charge generation layer is preferably 80% by weight or less, particularly 40% by weight or less, based on the total weight of the layer. The thickness of the charge generation layer is 5 μm
In the following, it is particularly preferably 0.01 to 2 μm.

Various additives such as a sensitizer and a deterioration inhibitor can be added to the charge generation layer.

The charge-transporting layer can be formed by applying a solution containing a known charge-transporting substance, the fulvene compound specified in the present invention, and a suitable binder resin. The charge-transporting substance includes an electron-transporting substance and a hole-transporting substance, and the electron-transporting substance includes 2,4,7-trinitrofluorenone, 2,4,7-trinitrofluorenone.
Examples thereof include electron-withdrawing substances such as 5,7-tetranitrofluorenone, chloranil, and tetracyanoquinodimethane, and polymers obtained by polymerizing these electron-withdrawing substances.

Examples of the hole-transporting substance include polycyclic aromatic compounds such as pyrene and anthracene, carbazole-based compounds, and indole-based compounds.
-Based, oxazol-based, thiazole-based, oxadiazo-
Heterocyclic compounds such as phenol-based, pyrazol-based, pyrazoline-based, thiadiazole-based and triazol-based compounds, p-diethylaminobenzaldehyde-N, N-diphenylhydrazone, N, N-diphenylhydrazino-3-methylidene A hydrazone compound such as -9-ethylcarbazole,
Tri-p-tolylamine, 4- (di-p-tolylamino) -biphenyl, 2- (di-p-tolylamino)-
Triallylamine compounds such as 9,9′-dimethylfluorenone and 1-di-p-tolylaminopyrene, α-phenyl-4′-N, N-diphenylaminostilbene,
5- [4- (di-p-tolylamino) benzylidene]-
Styryl compounds such as 5H-dibenzo [a, d] cycloheptene, benzidine compounds, triarylmethane compounds, tri (p-tolyl) amine, 2- [di- (p-
Tolyl)]-aminobiphenyl, 1- [di- (p-tolyl)]-aminopyrene and other triarylamine compounds or polymers having groups of these compounds in the main chain or side chain (eg poly-N). -Vinylcarbazo-
And polyvinyl anthracene).

In addition to these organic charge transporting materials, inorganic materials such as selenium, selenium-tellurium, amorphous silicon, cadmium sulfide, etc. can be used.

These charge transport materials may be used alone or in combination.
A combination of two or more species can be used.

The binder resin used in the charge transport layer includes, in addition to the binder resin used in the charge generation layer, a photoconductive polymer compound such as polyvinylcarbazole resin and polyvinylanthracene resin. Is mentioned.

The compounding ratio of the binder resin and the charge transport material is 10 to 5 charge transport materials per 100 parts by weight of the binder resin.
00 parts by weight, particularly 50 to 200 parts by weight are preferred. When the charge transporting substance and the fulvene compound specified in the present invention are mixed and used, the compounding ratio is 0.01 to 400 parts by weight, particularly 0.1 to 100 parts by weight, per 100 parts by weight of the charge transporting substance. Parts are preferred.

Since the charge transport layer has a limit for transporting charge carriers, the film thickness cannot be increased more than necessary, but 5 to 40 μm, particularly 10 to 30 μm is preferable.

Further, in addition to the fulvene compound specified in the present invention, an antioxidant, an ultraviolet absorber, a plasticizer and the like can be added to the charge transport layer, if necessary.

As the coating method for forming the above-mentioned various layers by coating, a dip coating method, a spray coating method, a spinner coating method, a roller coating method, a Mayer bar. -Coating methods such as a coating method and a blade coating method can be mentioned.

The electrophotographic photosensitive member of the present invention is not used in an electrophotographic copying machine, but can be used in a laser beam printer,
It can be widely used in electrophotographic application fields such as CRT printers, LED printers, facsimiles and electrophotographic plate making systems.

The present invention integrally supports the electrophotographic photosensitive member of the present invention and at least one means selected from the group consisting of charging means, developing means and cleaning means, and is attachable to and detachable from the main body of the electrophotographic apparatus. It is composed of a process cartridge characterized by being flexible.

Further, the present invention comprises an electrophotographic apparatus having the electrophotographic photosensitive member of the present invention, a charging means, an image exposing means, a developing means and a transferring means.

FIG. 1 shows a schematic structure of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention. In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 in a direction of an arrow at a predetermined peripheral speed. In the course of rotation of the photoconductor 1, the peripheral surface of the photoconductor 1 is uniformly charged to a predetermined positive or negative potential by a primary charging means 3, and then an image exposure means (non-exposure means) such as slit exposure or laser beam scanning exposure is used. Image exposure light 4 from the drawing is received. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the photoconductor 1.

The formed electrostatic latent image is then developed by the developing means 5.
The toner-developed toner image developed and developed by the transfer material 7 is fed from a sheet feeding unit (not shown) between the photoconductor 1 and the transfer unit 6 in synchronization with the rotation of the photoconductor 1. Then, the image is sequentially transferred by the transfer means 6. The transfer material 7 that has received the image transfer is separated from the surface of the photoconductor and is introduced into the image fixing means 8 to undergo the image fixing, and is printed out as a copy (copy) to the outside of the apparatus. The surface of the photoreceptor 1 after the image transfer is cleaned by the cleaning means 9 after removal of the residual toner after transfer, and is further neutralized by the pre-exposure light 10 from the pre-exposure means (not shown). And then repeatedly used for image formation. The primary charging means 3 is a charging roller.
In the case of a contact charging means using a wire or the like, pre-exposure is not always necessary.

In the present invention, a plurality of constituent elements such as the photosensitive member 1, the primary charging means 3, the developing means 5 and the cleaning means 9 are integrally connected as a process cartridge. However, the process cartridge may be detachably attached to the main body of the electrophotographic apparatus such as a copying machine or a laser beam printer. For example, at least one of the primary charging means 3, the developing means 5 and the cleaning means 9 is integrally supported with the photoconductor 1 to form a cartridge, and a guide means such as a rail 12 of the apparatus main body is used. The process cartridge 11 can be attached to and detached from the main body. Further, when the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 uses reflected light or transmitted light from a document, or a document is read by a sensor,
It is the light emitted by the signalization and the scanning of the laser beam, the driving of the LED array, the driving of the liquid crystal shutter array, etc., performed according to this signal.

On the other hand, when used as a printer for a facsimile, the image exposure light 4 becomes exposure light for printing the reception data. FIG. 2 is a block diagram showing an example of this case. The controller 14 controls the image reading unit 13 and the printer 22. The entire controller 14 is controlled by the CPU 20. The read data from the image reading unit 13 is transmitted to the partner station through the transmission circuit 16. The data received from the partner station is sent to the printer 22 through the receiving circuit 15. Predetermined image data is stored in the image memory. The printer controller 21 controls the printer 22. 17 is a telephone. The image received from the line 18 (image information from the remote terminal connected via the line) is demodulated by the receiving circuit 15, and then the image information is decoded by the CPU 20 and sequentially stored in the image memory 19. To be done. Then, when at least one page of image is stored in the image memory 19, the image of that page is recorded. CPU20
Reads one page of image information from the image memory 19 and sends the decoded one page of image information to the printer controller -21. Printer controller
When the printer 21 receives the image information of one page from the CPU 20, the printer 21 prints the image information of the page.
22 is controlled. The CPU 20 receives the next page during recording by the printer 22. In this way, the image is received and recorded.

[0046]

【Example】

Example 1 4.5 g of N-methoxymethylated 6 nylon resin (weight average molecular weight 30,000) and alcohol-soluble copolymerized nylon resin (weight average molecular weight 250
A solution of 9.5 g of 00) dissolved in 90 g of methanol was applied with a Mayer bar to form an undercoat layer having a film thickness after drying of 0.5 μm.

Next, Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 9.0 °, 14.2 °, 2
Oxytitanium phthalocyanine pigment 4 g having a strong peak at 3.9 ° and 27.1 ° and polyvinyl butyra
2g of resin is added to 100g of cyclohexanone, and 1m
The dispersion was dispersed for 1 hour in a sand mill using mφ glass beads, and 50 g of ethyl acetate was added to dilute the dispersion to prepare a coating liquid. This coating solution was applied onto the undercoat layer with a Mayer bar so that the film thickness after drying would be 0.22 μm,
A charge generation layer was formed.

Then, 10 g of a compound having the following structural formula:

Embedded image A coating solution was prepared by dissolving 1 g of Compound Example 24 and 10 g of a polycarbonate resin (weight average molecular weight 20000) in 70 g of chlorobenzene. This solution was applied on the charge generation layer by a coater to form a charge transport layer having a film thickness after drying of 20 μm, and an electrophotographic photosensitive member having three laminated layers was prepared.

The electrophotographic photosensitive member was corona-charged at -5 KV by a static method using an electrostatic photocopy paper tester Model-SP-428 manufactured by Kawaguchi Electric Co., Ltd., and kept in the dark for 1 second, and then irradiated with light. Then, the charging characteristics were examined. The charging characteristics are as follows: the surface potential (V ₀ ) and the exposure amount (E) required to attenuate the potential (V ₁ ) when dark-decayed for 1 second to 1/5.
_1/5 ) was measured. At this time, as a light source, a gallium / aluminum / arsenic ternary semiconductor laser (output 5 mW,
An oscillation wavelength of 780 nm) was used.

Further, in order to evaluate the potential characteristics when it is repeatedly used in an actual machine, an aluminum cylinder (φ30 mm × 260.5 m) is used instead of the aluminum sheet.
m) is used and the coating method is an immersion coating method, and the electrophotographic photosensitive member prepared in the same manner as in the above example is provided with a reversal development type laser equipped with the same semiconductor laser as described above. -Equipped with a beam printer (a modified LBP-SX, manufactured by Canon Inc.) and evaluated repeatedly for potential characteristics. The conditions are as follows. V _D : -700
V, _VL : -150 V (exposure amount 0.7 μJ / cm ²⁾ , transfer potential: +700 V, developing polarity: negative polarity, process speed: 50 mm / sec, developing bias: -450 V,
Scanning method after image exposure: Image scanning, exposure before primary charging: 40 lux · sec full red exposure.

As a test for promoting the cracking of the photosensitive layer, finger grease was adhered to the surface of the electrophotographic photosensitive member prepared as described above, and the photosensitive layer was allowed to stand for 8 hours at room temperature and normal pressure to determine whether or not the photosensitive layer was cracked. I observed.

As a test for promoting crystallization of the charge transport material,
Finger grease was adhered to the surface of the electrophotographic photosensitive member prepared as described above, and the mixture was left at 75 ° C. for 1 week to observe whether or not crystallization occurred in the charge transport material.

As a measurement of the photo memory for white light, the initial surface potential (V _D ) when the electrophotographic photosensitive member prepared as described above was charged to −700 V by the same printer as above before light irradiation. And the potential after the whole image exposure (V ₁ )
Then, the photoconductor was masked so as to have a bright part and a dark part, and was irradiated with 3000 lux under a fluorescent lamp for 20 minutes, and then left for 5 minutes to change the initial potential (ΔV
_D) and the (ΔV _L) was measured.

Examples 2 to 9 and Comparative Examples 1 to 9 In this Example and Comparative Example, instead of the Exemplified Compound 24 used in Example 1, in the Examples, compounds of the compound examples shown in Table 9 below were used. Was added in the same manner as in Example 1 except that the composition of the photosensitive member shown in Table 8 below was used in Comparative Example.
An electrophotographic photosensitive member was prepared by the same method as described above. Then, the electrophotographic characteristics of this electrophotographic photosensitive member, the crack of the photosensitive layer, the crystallization of the charge transport material and the evaluation of the photo memory were evaluated by the same method as in Example 1. Examples 1-9
The results of Comparative Examples 1 to 9 are shown in Tables 9 and 10.
And 12 respectively. Comparative compound 1

[Chemical 6] Comparative compound 2

[Chemical 7] Azo pigment 1

Embedded image Azo pigment 2

[Chemical 9]

[0055]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

Example 10 5.5 g of N-methoxymethylated 6 nylon resin (weight average molecular weight: 35000) and an alcohol-soluble copolymerized nylon resin (weight average molecular weight: 300) on an aluminum sheet.
00) 10.5 g was dissolved in a mixed solvent of 60 g of methanol and 20 g of isopropyl alcohol to prepare a Mayer bar.
To form an undercoat layer having a thickness of 1.0 μm after drying.

Next, Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 9.0 °, 14.2 °, 2
4.2 g of an oxytitanium phthalocyanine pigment having a strong peak at 3.9 ° and 27.1 ° and 2 g of polyvinyl butyral resin were added to 110 g of cyclohexanone,
A sand mill using 1 mmφ glass beads was used for dispersion for 3 hours, and 20 g of ethyl acetate was added to the dispersion to dilute the solution to prepare a coating solution. This coating solution was applied onto the undercoat layer with a Mayer bar so that the film thickness after drying would be 0.2 μm,
A charge generation layer was formed.

Next, 9 g of a compound having the following structural formula was added:

[Chemical 10] A coating liquid was prepared by dissolving 1.2 g of Compound Example 36 and 10 g of a polycarbonate Z-type resin (weight average molecular weight of 60000) in 68 g of chlorobenzene. This solution was applied on the charge generation layer by a blade coating method to form a charge transport layer having a thickness of 23 μm after drying, and an electrophotographic photosensitive member having three laminated layers was prepared.

Corona discharge of -5 KV was applied to the electrophotographic photosensitive member, and the surface potential (V ₀ ) at this time was measured. Further, the surface potential of this photoconductor after leaving it in a dark place for 1 second was measured. The sensitivity was evaluated by measuring the exposure dose (E _1/6 : μJ / cm ² ) required to attenuate the potential (V ₁ ) after dark decay to _1/6 . At this time, a gallium / aluminum / arsenic ternary semiconductor laser (output 5 mW, oscillation wavelength 780 nm) was used as a light source.

Next, a reversal development type laser beam printer (LBP-) equipped with the same semiconductor laser as above.
An aluminum cylinder (φ30 mm × 260.5) with the above electrophotographic photosensitive member in a SX remodeling machine, manufactured by Canon Inc.
mm) and attached to the cylinder, and the transfer memory (V _DI −V _D2 ) is measured with the primary charging voltage when the transfer current is OFF as V _DI and the primary charging voltage when the transfer current is ON as V _D2. After that, an image forming test was performed. The conditions are as follows. Surface potential after primary charging: -700 V, surface potential after image exposure: -150 V (exposure amount 1.0 μJ / cm
² ), transfer potential: +700 V, development polarity: negative polarity, process speed: 47 mm / sec, development condition (development bias): -450 V, scan method after image exposure: image scan, exposure before primary charging: 8. Full red exposure of 0 lux · sec. Image formation was performed by line scanning the laser beam in accordance with the character signal and the image signal.
Good prints were obtained for both images.

Further, the crack of the photosensitive layer of the electrophotographic photosensitive member prepared in the same manner as described above, the crystallization of the charge transport material and the evaluation of the photomemory of the electrophotographic photosensitive member were evaluated in Example (1).
The same method was used. The results are shown in Table 12.

Examples 11 to 16 Corresponding to Examples 11 to 16 in the same manner as in Example 10 except that the compounds of the compound examples shown in Table 13 below were used instead of the compound example 36 used in Example 10. An electrophotographic photosensitive member was prepared. The electrophotographic characteristics of each electrophotographic photosensitive member, the transfer memory, the crack of the photosensitive layer, the crystallization of the charge transport material and the photomemory of the electrophotographic photosensitive member were evaluated in the same manner as in Example 10. The results are shown in Tables 13 and 14.

[0063]

[Table 13]

[Table 14]

Comparative Examples 10 to 18 In the electrophotographic photosensitive member prepared in Example 10,
The charge generating substance and the compound added to the charge transport layer are shown in Table 1 below.
Electrophotographic photoreceptors corresponding to Comparative Examples 10 to 18 were prepared in the same manner as in Example 10 except that the compound shown in FIG. Electrophotographic characteristics of each electrophotographic photoreceptor, transfer memory,
The cracking of the photosensitive layer, the crystallization of the charge transport material and the evaluation of the photo memory of the electrophotographic photosensitive member were performed by the same method as in Example 10. The results are shown in Tables 16 and 17. Comparative compound 3

[Chemical 11] Comparative compound 4

[Chemical 12] Azo pigment 3

[Chemical 13] Azo pigment 4

Embedded image

[0065]

[Table 15]

[Table 16]

[Table 17]

Example 17 Bragg angle (2θ ± 0.
2 °) of 9.0 °, 14.2 °, 23.9 ° and 27.
2.6 g of an oxytitanium phthalocyanine pigment having a strong peak at 1 ° and 4.8 g of a compound having the following structural formula

[Chemical 15] Then, 0.8 g of Compound Example 31 and 10.0 g of a copolyester resin (weight average molecular weight of 20,000) were mixed in a mixed solvent of 50 g of cyclohexanone and 50 g of toluene, and dispersed with a ball mill for 2 hours. This dispersion was applied onto an aluminum sheet with a Mayer bar and dried at 120 ° C. for 1 hour to prepare an electrophotographic photoreceptor having a film thickness after drying of 16 μm. The initial characteristics of the produced electrophotographic photosensitive member were measured by the same method as in Example 1. _{V 0: -700V, V 1:} -680V, E 1/5: 2.2
lux · sec, photo memory values were ΔV _D : 8V, ΔV _L : 3V. Further, when a test for promoting cracking of the photosensitive layer and crystallization of the charge-transporting substance was conducted in the same manner as in Example 1, 8 It was not observed at all even after a lapse of time, and the crystallization was 1
It was not recognized even after a week.

Example 18 A 30% methanol solution of an alcohol-soluble nylon resin (6-66-610-12 quaternary nylon copolymer, weight average molecular weight 30,000) on an aluminum sheet was applied to a Mayer bar. To form an undercoat layer having a thickness of 0.95 μm after coating and drying.

Next, Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 9.0 °, 14.2 °, 2
6 g of oxytitanium phthalocyanine pigment having a strong peak at 3.9 ° and 27.1 ° and 1 g of azo pigment having the following structural formula

Embedded image And 5 g of polyvinyl butyral resin to cyclohexanone 1
It was added to 100 g and dispersed in a sand mill using a glass bead of 1 mmφ for 1 hour, and 4,4′-thiobis (6
-Tert-butyl-m-cresol) was added, and
A coating liquid was prepared by adding 30 g of ethyl acetate for dilution.
This coating solution is applied on the undercoat layer so that the film thickness after drying is 0.25.
A charge generation layer was formed by coating with a Mayer bar so as to have a thickness of μm.

Next, the compound having the following structural formula was added to 5.2.
g and

[Chemical 17] 3.6 g of a compound having the following structural formula

Embedded image 1.2 g of Compound Example 28 and 11.5 g of a polycarbonate resin (weight average molecular weight of 20,000) were dissolved in 70 g of monochlorobenzene, and this solution was coated on a charge generation layer with a Mayer bar and dried. A charge transport layer having a film thickness of 25 μm was formed to prepare a three-layer electrophotographic photoreceptor. The initial characteristics of the produced electrophotographic photosensitive member were measured by the same method as in Example 1. _{V 0: -700V, V 1:} -695V, E 1/5: 0.5
2lux · sec, photo memory values were ΔV _D : 5 V, ΔV _L : 2 V. Further, when a test for promoting cracking of the photosensitive layer and crystallization of the charge-transporting substance was conducted in the same manner as in Example 1, it was found that the crack was 8 It was not observed at all even after a lapse of time, and the crystallization was 1
It was not recognized even after a week.

Example 19 A 35% methanol solution of an alcohol-soluble nylon resin (6-66-610-12 quaternary nylon copolymer, weight average molecular weight 30,000) on an aluminum sheet was used as a Mayer bar. To form an undercoat layer having a thickness of 1.1 μm after coating and drying.

Next, the Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 9.0 °, 14.2 °, 2
Oxytitanium phthalocyanine pigment 6.3 g having strong peaks at 3.9 ° and 27.1 ° and azo pigment 1 g having the following structural formula.

[Chemical 19] And 4.9 g of polyvinyl butyral resin were added to 90 g of cyclohexanone, and the mixture was dispersed in a sand mill using a glass bead of 1 mmφ for 2 hours, and 2,2′-methylenebis (4-methyl-6-tert-butylpheno) was added thereto. -G) was added, and 30 g of ethyl acetate was added for dilution to prepare a coating solution. This coating solution was applied onto the undercoat layer with a Mayer bar so that the film thickness after drying would be 0.2 μm to form a charge generation layer.

Next, Compound Example 30 was used as a charge-transporting substance, and 8.6 g of the compound was mixed with 11.5 g of a polycarbonate resin (weight average molecular weight of 40,000) and dissolved in 70 g of monochlorobenzene. The charge generation layer was coated with a Mayer bar to form a charge transport layer having a thickness of 22 μm after drying to prepare a three-layer electrophotographic photoreceptor. The initial characteristics of the produced electrophotographic photosensitive member were measured by the same method as in Example 1. V ₀ : -700V, V ₁ : -690V, E _1/5 : 0.5
4lux · sec, values of photo memory are ΔV _D : 4V, ΔV _L : 1V Further, when a crack promotion test of the photosensitive layer and the crystallization of the charge transport material was conducted in the same manner as in Example 1, it was found that the crack was 8 It was not observed at all even after a lapse of time, and the crystallization was 1
It was not recognized even after a week.

Example 20 On an aluminum support, 6.2 g of N-methoxymethylated 6 nylon resin (weight average molecular weight 25000) and alcohol-soluble copolymerized nylon resin (weight average molecular weight 200) were used.
00) 9.5 g of methanol 60 g and butanol 20 g
The solution dissolved in the mixed solvent of was applied with a Mayer bar to form an undercoat layer having a film thickness after drying of 0.75 μm.

Next, Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 9.0 °, 14.2 °, 2
5.8 g of oxytitanium phthalocyanine pigment having a strong peak at 3.9 ° and 27.1 ° and 2 g of azo pigment having the following structural formula

Embedded image 5 g of polyvinyl butyral resin was added to cyclohexanone 95
It was added to g and dispersed in a sand mill using a glass bead of 1 mmφ for 1 hour, and 20 g of ethyl acetate was added to this to dilute to prepare a coating liquid. This coating liquid was applied onto the undercoat layer so that the film thickness after drying was 4,4'-
Butylidene bis (6-tert-butyl-m-crezo-
1 g), and 30 g of ethyl acetate was added to dilute the solution to prepare a coating solution. This coating solution was applied onto the undercoat layer with a Mayer bar so that the film thickness after drying was 0.25 μm, to form a charge generation layer.

Next, 6.0 g of a compound having the following structural formula
When

[Chemical 21] 1.5 g of Compound Example 27, 1.5 g of Exemplified Compound 37, and polycarbonate resin (weight average molecular weight 20000) 1
After dissolving 1.5 g of monochlorobenzene in 74 g, this solution was applied on the charge generation layer with a Meyer bar to form a charge transport layer having a thickness of 22 μm after drying. Created. The initial characteristics of the produced electrophotographic photosensitive member were measured by the same method as in Example 1. V ₀ : -705V, V ₁ : -700V, E _1/5 : 0.5
4lux · sec, values of photo memory are ΔV _D : 6V, ΔV _L : 2V Further, when a crack test of the photosensitive layer and an accelerated crystallization test of the charge transport material were conducted in the same manner as in Example 1, it was 8 It was not observed at all even after a lapse of time, and the crystallization was 1
It was not recognized even after a week.

Example 21 A 38% methanol solution of an alcohol-soluble nylon resin (6-66-610-12 quaternary nylon copolymer, weight average molecular weight 18000) on an aluminum sheet was used as a Mayer bar. To form an undercoat layer having a thickness of 0.5 μm after coating and drying.

Next, the Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction are 9.0 °, 14.2 °, 2
Cyclohexanone 110 was obtained by adding 7.7 g of a crystalline oxytitanium phthalocyanine pigment having a strong peak at 3.9 ° and 27.1 ° and 5.2 g of polyvinyl butyral resin.
28 g to a ball mill and dispersed for 3 hours.
Ethyl acetate of was added to dilute to prepare a coating liquid. This coating solution is applied on the undercoat layer so that the film thickness after drying is 0.15 μm.
To form a charge generation layer.

Next, Compound Example 46 was used as a charge transport material, 7.5 g of which was used as a polycarbonate resin (weight average molecular weight 80,000) and 50 g of monochlorobenzene.
Dissolve in a mixed solvent of 20 g of dichloromethane and dichloromethane, and apply this solution on the charge generating layer by the blade coating method to form a charge transporting layer having a thickness of 18 μm after drying. It was created. The initial characteristics of the produced electrophotographic photosensitive member were measured by the same method as in Example 1. V ₀ : -705V, V ₁ : -700V, E _1/5 : 0.8
5lux · sec, photo memory values were ΔV _D : 9V, ΔV _L : 4V Further, when a cracking test of the photosensitive layer and a crystallization accelerating test of the charge transport material were conducted in the same manner as in Example 1, it was found that the cracking was 8 It was not observed at all even after a lapse of time, and the crystallization was 1
It was not recognized even after a week.

Example 22 A 35% methanol solution of an alcohol-soluble nylon resin (6-66-610-12 quaternary nylon copolymer, weight average molecular weight 30,000) on an aluminum sheet was used as a Mayer bar. To form an undercoat layer having a thickness of 1.9 μm after coating and drying.

Next, a compound having the following structural formula was added to 8.2.
g and

[Chemical formula 22] Compound Example 35 (0.8 g) and bisphenol A type poly
Bone resin (weight average molecular weight 28,000) 10 g was added to monochlorobenzene (60 parts by weight) -dichloromethane (2
(0 parts by weight) It was dissolved in 75 g of a mixed solvent, and this solution was coated on the undercoat layer with a Mayer bar to form a charge transport layer having a thickness of 20 μm after drying.

Next, the Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 9.0 °, 14.2 °, 2
4.2 g of an oxytitanium phthalocyanine pigment having a strong peak at 3.9 ° and 27.1 ° and 2.2 g of a butyral resin (butyralization degree: 55 mol%) were added to 65 g of cyclohexanone, and the mixture was sand-milled. Disperse for 1 hour, and deposit this dispersion on the charge transport layer to a film thickness of 1.2 μm
And a charge generation layer was formed by coating with a Mayer bar so that an electrophotographic photoreceptor was prepared. The initial characteristics of the produced electrophotographic photosensitive member were measured by the same method as in Example 1. However, the charging was positive. V ₀ : + 710V, V ₁ : + 705V, E _1/5 : 1.6
lux · sec, photo memory values are ΔV _D : 14V, ΔV _L : 6V

Example 23 5.2 g of N-methoxymethylated 6 nylon resin (weight average molecular weight 20000) and alcohol-soluble copolymerized nylon resin (weight average molecular weight 28000) on a glass support.
A solution prepared by dissolving 8.8 g in a mixed solvent of 34 g of methanol and 65 g of butanol was applied by dip coating, and the film thickness after drying was 1 μm.
To form an undercoat layer.

Next, 7 g of a compound having the following structural formula was added.

[Chemical formula 23] 3 g of Compound Example 41 and 10 g of bisphenol A-type polycarbonate resin (weight average molecular weight of 30,000) were dissolved in 70 g of monochlorobenzene, and this solution was applied on the undercoat layer with a Mayer bar and dried. A charge transport layer having a thickness of 18 μm was formed.

Next, 60 g of an acrylic monomer having the following structural formula was added.

[Chemical formula 24] 40 g of tin oxide ultrafine particles having an average particle diameter of 400 angstrom before dispersion, 3 g of 2-methylthioxanthone as a photoinitiator, and 280 g of methyl cellosolve were dispersed in a sand mill for 72 hours. Using this dispersion, a film was formed on the photosensitive layer by the beam coating method and dried, and then photocured with a high pressure mercury lamp at a light intensity of 8 mW / cm ² for 30 seconds to obtain a film having a thickness of 2.1 μm. A protective layer was formed. The obtained sample was observed with a transmission microscope while shining light from the back surface at an angle of 15 °, but cracks and crystallization of the charge transport material did not occur.

Comparative Example 19 A sample was prepared in the same manner as in Example 23 except that Compound Example 41 was not used in the charge transport layer formed in Example 23, and the sample was observed with a transmission microscope by the same method. As a result, cracks in the charge transport layer were found.

[0086]

The electrophotographic photoreceptor containing the fulvene compound specified in the present invention has excellent durability with little fluctuation in the light potential and the dark potential during continuous image formation by repeated charging and exposure. Further, even in the reversal developing system, the transfer memory is extremely small, and cracks in the photosensitive layer that cause image defects and crystallization of the charge transport material are extremely unlikely to occur, and a remarkable effect that a photo memory is hardly generated is exhibited. The same effect can be obtained in a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

[Brief description of drawings]

FIG. 1 is a process chart having an electrophotographic photoreceptor of the present invention.
It is a figure which shows schematic structure of the electrophotographic apparatus which has a triggle.

FIG. 2 is a diagram showing an example of a block of a facsimile having the electrophotographic photosensitive member of the present invention.

FIG. 3 is an X-ray diffraction diagram of oxytitanium phthalocyanine used in the present invention.

FIG. 4 is a diagram showing an IR chart of Compound Example 18.

[Explanation of symbols]

 1 Electrophotographic Photoreceptor of the Present Invention 2 Axis 3 Primary Charging Means 4 Image Exposure Light 5 Developing Means 6 Transfer Means 7 Transfer Material 8 Image Fixing Means 9 Cleaning Means 10 Pre-Exposure Light 11 Process Cartridge 12 Rails 13 Image reading unit 14 Controller 15 Receiver circuit 16 Transmitter circuit 17 Telephone 18 Line 19 Image memory 20 CPU 21 Printer-Controller 22 Printer-

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Norihiro Kikuchi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Mitsuhiro Kunieda 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Within the corporation

Claims (6)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the photosensitive layer has a Bragg angle (2θ ± 0.2 °) of 9.0 ° in CuKα characteristic X-ray diffraction.
Containing oxytitanium phthalocyanine having a strong peak at 4.2 °, 23.9 ° and 27.1 °, and
An electrophotographic photoreceptor comprising a compound having at least one fulvene group represented by the following general formula (1). General formula (1) In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group, and , R ₂ and R ₃ and R ₄ and R ₅ may be bonded to form a ring. 2. The electrophotographic photosensitive member according to claim 1, wherein the compound having at least one fulvene structure represented by the general formula (1) is a fulvene compound represented by the following general formula (2). General formula (2) In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, and , R ₂ and R ₃ and R ₄ and R ₅ may together form a ring. Ar represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. n is an integer of 1 to 3. 3. The electrophotographic photosensitive member according to claim 2, wherein Ar in the fulvene compound represented by the general formula (2) is a substituted or unsubstituted aryl group. 4. The electrophotographic photosensitive member according to claim 2, wherein Ar in the fulvene compound represented by the general formula (2) is a substituted aryl group, and Ar has a substituted amino group. 5. The electrophotographic photosensitive member according to claim 1, and at least one unit selected from the group consisting of a charging unit, a developing unit and a cleaning unit are integrally supported, and are detachably attached to the main body of the electrophotographic apparatus. A process cartridge characterized by the following. 6. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposing unit, a developing unit and a cleaning unit.