JP3083049B2 - Electrophotographic photoreceptor, process cartridge having the electrophotographic photoreceptor, and electrophotographic apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member, and more particularly, to an electrophotographic photosensitive member having an intermediate layer containing a resin having a specific structure. Also, the present invention
The present invention relates to a process cartridge having the electrophotographic photosensitive member and an electrophotographic apparatus.

[0002]

2. Description of the Related Art An electrophotographic photoreceptor usually has a photosensitive layer on a conductive support, but the photosensitive layer is generally a very thin layer. May become non-uniform. The tendency is that the current mainstream photosensitive layer is 0.5 μm
This is particularly remarkable in a so-called function-separated type photosensitive layer having a charge generation layer and a charge transport layer having extremely small thicknesses.

If the film thickness of the photosensitive layer is non-uniform, unevenness of potential and sensitivity will naturally occur, so the photosensitive layer must be formed as uniformly as possible.

[0004] An important characteristic required for an electrophotographic photosensitive member is stability of a light portion potential and a dark portion potential during repeated use.

[0005] If these potentials are not stable, the image density will not be stable or the image will be fogged.

Accordingly, a function of covering a defect on the surface of the support between the support and the photosensitive layer, improving the adhesion between the support and the photosensitive layer, and preventing injection of carriers from the support into the photosensitive layer. It has been proposed to provide an intermediate layer having

Conventionally, as a resin used for the intermediate layer,
Polyamides (JP-A-48-47344 and JP-A-52-25638) and polyesters (JP-A-52-25638)
JP-A-2020836 and JP-A-54-26738), polyurethane (JP-A-53-89435 and JP-A-2-115858), and a quaternary ammonium salt-containing acrylic polymer (JP-A-51-1984). -126149
And casein (Japanese Patent Laid-Open No. 55-103556) are known.

[0008]

However, in an electrophotographic photoreceptor using the above-mentioned material as an intermediate layer, the electric resistance of the intermediate layer easily changes in accordance with the change in temperature and humidity. It has been difficult to produce an electrophotographic photoreceptor that has excellent potential characteristics stably in all the following environments and can form excellent images.

For example, when the photoconductor is repeatedly used under low temperature and low humidity where the electric resistance of the intermediate layer tends to increase,
Electric charges are likely to remain in the intermediate layer, and the bright portion potential and the residual potential increase. As a result, there has been a problem that a copy image is fogged in the normal development and an image becomes thin in the reversal development, so that an image having a predetermined image quality cannot be obtained continuously.

On the other hand, under high temperature and high humidity where the electric resistance of the intermediate layer tends to decrease, the barrier function of the intermediate layer decreases, carrier injection from the support increases, and the dark area potential decreases. As a result, the image may become thin in the normal development, and black spot-like defects (black spots) and fog may occur in the image in the reversal development.

In addition, the provision of the intermediate layer often lowers the sensitivity of the photoreceptor itself even if the potential stability under low temperature and low humidity and the black spot defect on the image under high temperature and high humidity are improved. Was.

Accordingly, an object of the present invention is to provide an electron which can stably exhibit excellent potential characteristics and continuously form an excellent initial image in all environments from low temperature and low humidity to high temperature and high humidity. A photographic photoreceptor is provided.

Another object of the present invention is to provide an intermediate layer having excellent adhesion to a support and excellent film forming properties.
An object of the present invention is to provide a high-sensitivity electrophotographic photoreceptor which forms a good image without defects and has high sensitivity.

It is a further object of the present invention to provide a process cartridge and an electrophotographic apparatus having the above-described electrophotographic photosensitive member.

[0015]

That is, the present invention relates to an electrophotographic photoreceptor having a photosensitive layer on a conductive support via an intermediate layer, wherein the intermediate layer has the following formula (1):

[0016]

[Outside 2] (Wherein A represents a divalent organic group, and R ₁ and R ₂ are the same or different and each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a cyano group. R ₃ and R ₄ are the same or different and each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxyalkyl group and a substituted or unsubstituted aralkyl group.) An electrophotographic photoreceptor comprising a resin having at least one of a polyamic acid structure and a polyamic acid ester structure.

Further, the present invention is a process cartridge and an electrophotographic apparatus having the above electrophotographic photosensitive member.

As the divalent organic group represented by A, various ones may be mentioned as described later, and among them, the following formula (2)
Or a group represented by (3) is particularly preferred.

Formula -Ar _1- (2) (In the formula, Ar ₁ represents a substituted or unsubstituted aromatic hydrocarbon ring group and a substituted or unsubstituted aromatic heterocyclic group.) Formula -Ar ₂ -X —Ar ₃ — (3) (wherein, Ar ₂ and Ar ₃ are the same or different and represent a substituted or unsubstituted aromatic hydrocarbon ring group and a substituted or unsubstituted aromatic heterocyclic group, and X represents oxygen Atom, sulfur atom, substituted or unsubstituted alkylene group, carbonyl group and sulfonyl group.) Ar ₁ , Ar ₂ and Ar
₃ of the aromatic hydrocarbon ring as the group a phenylene group, such as biphenylene group and naphthylene group, and the like as the aromatic heterocyclic group pyridinediyl group and thiophenediyl group. Examples of the alkylene group X, methylene Groups, ethylene groups, propylene groups and isopropylene groups. Examples of the substituent which these groups may have include alkyl groups such as methyl, ethyl and propyl; halogen atoms such as fluorine, chlorine and bromine; halomethyl groups such as trifluoromethyl; methoxy, ethoxy and propoxy. An alkylamino group such as dimethylamino and diethylamino; an acyl group such as acetyl and benzoyl; and a cyano group.

Preferred examples of the divalent organic group represented by A include the following, but are not limited thereto.

[0021]

[Outside 3]

[0022]

[Outside 4] Of these, the following are particularly preferred.

[0023]

[Outside 5] Among them, the following are preferable.

[0024]

[Outside 6]

In the formula (1), R _{1 to} R ₄ are a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; an alkyl group such as methyl, ethyl and propyl;
An alkoxy group such as ethoxy and pyropoxy; and a cyano group. R _{1 to} R ₄ may be the same or different and may have a substituent such as a halogen atom.

In the formula (1), R ₅ and R _{6 each} represent a hydrogen atom; an alkyl group such as methyl, ethyl and propyl; an alkoxyalkyl group such as methoxyethyl; and an aralkyl group such as benzyl. R ₅ and R ₆ may be the same or different and may have a substituent such as a halogen atom.

The number average molecular weight of the resin used in the present invention is preferably from 500 to 100,000, and particularly preferably from 10,000 to 50,000.

In the present invention, the amide portion of the polyamic acid or polyamic acid ester structure and the acid or acid ester portion may be dehydrated or de-alcoholized depending on the drying conditions in the drying step usually performed in the production of an electrophotographic photoreceptor. The reaction may form a polyimide structure. In the present invention, the repeating unit having an amic acid structure and the repeating unit having an amic acid ester structure are preferably present in an amount of 20 to 80 mol% of the entire resin, and particularly preferably 40 to 60 mol%.
Preferably it is present. I'm not sure why,
The polyamic acid or polyamic acid ester structure prevents holes from being injected from the conductive support, facilitates the dissociation of carriers generated by the action of the charge generating substance and the injection of electrons into the intermediate layer, and the polyimide structure. By taking dense packing, dissociation of the carrier,
It is considered that the injection and movement of electrons were made smoother and less affected by moisture.

Preferred specific examples of the resin of the present invention are shown below, but the invention is not limited thereto.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

[Table 5]

[0035]

[Table 6]

Among these compounds, Compound No. 1 is particularly preferred because it is more excellent in environmental stability of the electrophotographic photoreceptor, stability of the material itself, easiness of synthesis of the material and economical efficiency.
1,2,3,4,10,11,12,26,27,2
8, 34, 35 and 36 are preferable, and the exemplified compound No. 1, 3, 10, 27 and 34 are preferred.

The resin having a polyamic acid structure having a repeating unit represented by the formula (1) is synthesized by a ring-opening polyaddition reaction of tetracarboxylic dianhydride and diamine in an organic polar solvent. Such organic polar solvents include:
Amide solvents such as N, N-dimethylacetamide, N, N-dimethylformamide and N-methylpyrrolidone; phenol solvents such as cresol and chlorophenol; ether solvents such as diethylene glycol dimethyl ether, and mixtures thereof. . In order to control the molecular weight of the resin, the reaction can be carried out by containing 5% or less of water. The reaction temperature is 2
The temperature is preferably from 0 to 120 ° C, particularly preferably from 20 to 40 ° C.
C. is preferred.

The resin having a polyamic acid ester structure having a repeating unit represented by the formula (1) can be synthesized by esterifying the above polyamic acid and alcohol in the presence of a suitable catalyst. Such catalysts include mineral acids such as sulfuric acid and hydrochloric acid and organic acids such as p-toluenesulfonic acid. It can also be synthesized by reacting a half-esterified tetracarboxylic acid with a diamine.

The above-mentioned polyimide can be synthesized by heat-treating the above-mentioned polyamic acid or polyamic acid ester. The processing temperature is preferably from 50 to 400 ° C., and the processing time is preferably from 5 minutes to 4 hours. The processing temperature and the processing time greatly affect the ratio of the amount of the polyamic acid or polyamic acid ester having the repeating unit represented by the formula (1) to the amount of the polyimide structure.
This quantitative ratio is determined by measuring the infrared absorption spectrum of the sample,
The absorbance at 1500 cm ^-1 which is specific to the naphthylene group and the 1770-1 which is specific to the imide group
It can be obtained by determining the ratio of the absorbance at 780 cm ^-1 or by measuring the H ¹ -NMR spectrum of the sample to determine the amount of protons of the carboxylic acid and carboxylic ester groups.

Hereinafter, examples of the synthesis of the resin used in the present invention will be described.

(Synthesis Example) 13.5 g (0.05 mol) of 1,4,5,8-naphthalenetetracarboxylic dianhydride while sending dry nitrogen gas to a 500 ml four-necked flask
And 160 g of N, N-dimethylacetamide.
This is stirred vigorously at 25 ° C., taking 1-2 minutes,
4'-diaminodiphenyl ether 10.0 g (0.0
5 mol) was added. When stirring was continued for 2 hours while supplying nitrogen, the reaction solution became a viscous pale yellow liquid. 160 g of N, N-dimethylacetamide was further added to the reaction solution to form a homogeneous solution, which was dropped into 5 l of vigorously stirred methanol, and the precipitated polyamic acid was collected by filtration. This product is dissolved in 250 g of N, N-dimethylacetamide,
The insoluble material was separated by filtration, and the filtrate was dropped into 5 l of methanol to precipitate a polymer. The precipitated polymer was collected by filtration, dispersed and washed with 2 l of methanol, dried and dried. 19.1 g of polyamic acid 3 was obtained.

Other resins used in the present invention can be synthesized in the same manner as described above.

The intermediate layer in the present invention may be composed of only one layer, or may be composed of a plurality of layers, at least one of which contains the resin of the present invention. When the intermediate layer is composed of a plurality of layers, examples of the resin other than the resin of the present invention include polyamide, polyester, and phenol resin.

Further, the intermediate layer of the present invention may contain other resins, additives, conductive materials, and the like, if necessary, in an amount within a range in which the effects of the present invention can be obtained. Other resins include polyamides, polyesters and phenolic resins, and additives include acceptor compounds such as 2,5,7-trinitrofluorenone and benzoquinone. Powders (eg, aluminum, copper, nickel, silver, etc.), short metal fibers, carbon fibers, conductive powders (eg, carbon black, titanium black, graphite, metal oxides and metal sulfides (eg, antimony oxide, indium oxide, Tin oxide, titanium oxide, zinc oxide, potassium titanate, barium titanate, magnesium titanate,
Zinc sulfide, copper sulfide, magnesium oxide, aluminum oxide, etc.), and those metal oxides and metal sulfides that have been surface-treated with a conductive substance, those that have been surface-treated with a silane coupling agent or titanium coupling agent, and Which has been subjected to reduction treatment].

In each case, the content of the resin of the present invention in the intermediate layer of the present invention is based on the total weight of the contained intermediate layer.
It is preferably from 10 to 90% by weight, especially from 30 to 90% by weight.
Preferably, it is 70% by weight.

The thickness of the intermediate layer of the present invention can be appropriately set in consideration of electrophotographic characteristics, defects on the support, etc., and is preferably 0.1 to 50 μm, and particularly preferably 0 to 50 μm. It is preferably from 0.5 to 30 μm.

The photosensitive layer of the electrophotographic photoreceptor of the present invention comprises a so-called single layer type in which a charge generating substance and a charge transporting substance are contained in the same layer, and a charge generating layer containing a charge generating substance and a charge transporting substance. It is roughly classified into a so-called laminated type having a charge transport layer contained therein. The laminated type is further classified into a type having a conductive support, a charge generation layer and a charge transport layer in this order, and a type having a conductive support, a charge transport layer and a charge generation layer in this order. In the present invention, it is preferable to use a laminate type, particularly a type in which a charge transport layer is laminated on a charge generation layer.

The charge generation layer is made of azo pigments such as monoazo, bisazo and trisazo; phthalocyanine pigments such as metal phthalocyanine and non-metal phthalocyanine; indigo pigments such as indigo and thioindigo; polycyclic quinone pigments such as anthrone and pyrenequinone. A perylene pigment such as perylene anhydride and perylene imide; a squarylium pigment; pyrylium and thiapyrylium salts; and a charge generating substance such as a triphenylmethane pigment using a suitable solvent to form a binder resin (binder resin). For example, it is formed by applying and drying a solution dispersed in a resin such as polyvinyl acetal, polystyrene, polyester, polyvinyl acetate, methacrylic resin, acrylic resin, polyvinylpyrrolidone, and cellulosic resin. Can. The thickness of the charge generation layer is usually preferably 5 μm or less, particularly preferably 0.05 to 2 μm.
μm is preferred.

The charge transport layer is formed by applying a solution in which the following charge transport substance is dissolved to a solution of a resin having film forming properties,
It is formed by drying. Charge transport materials are broadly classified into electron transport materials and hole transport materials. Electron transporting materials include 2,4,7-trinitrofluorenone,
Electron-accepting substances such as 4,5,7-tetranitrofluorenone, chloranil, and tetracyanoquinodimethane, and those obtained by polymerizing these substances. Examples of the hole transport material include polycyclic aromatic compounds such as pyrene and anthracene; carbazole, indole, imidazole, oxazole, thiazole, oxadiazole, pyrazole,
Heterocyclic compounds such as pyrazoline, thiadiazole and triazole; p-diethylaminobenzaldehyde-N,
Hydrazone-based compounds such as N-diphenylhydrazone and N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole; α-phenyl-4′-N, N-
Styryl compounds such as diaminostilbene and 5- [4- (di-p-tolylamino) benzylidene] -5H-dibenzo [a, d] dicycloheptene; benzidine compounds; triarylamine compounds; triphenylamine or these compounds (For example, poly-N-vinyl carbazole, polyvinyl anthracene, etc.) having a group consisting of Examples of the resin having a film forming property include polyester, polycarbonate, polymethacrylate, and polystyrene. The thickness of the charge transport layer is preferably from 5 to 40 μm, and particularly preferably from 10 to 30 μm.

In the case of a single layer type, it can be formed by applying and drying a solution in which the above-mentioned charge generating substance and charge transporting substance are dispersed and dissolved in a binder resin. In the case of a single layer type, the thickness of the photosensitive layer is 5 to 40.
μm, particularly preferably 10 to 30 μm.

Further, in the present invention, an organic photoconductive polymer layer such as polyvinyl carbazole and polyvinyl anthracene, a vapor deposition layer of the above-described charge generating substance, a selenium vapor deposition layer,
A selenium-tellurium vapor-deposited layer, an amorphous silicon layer and the like can also be used as the photosensitive layer.

The conductive support used in the present invention includes, for example, aluminum, aluminum alloy, copper, zinc, stainless steel, titanium, nickel, indium, gold and platinum. In addition, such metals and alloys,
Plastics (for example, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resin, etc.) formed as a film by a vacuum deposition method, or plastics such as those described above containing conductive particles (for example, carbon black and silver particles) together with a suitable binder resin. A support coated on a metal or alloy support or a support in which conductive particles are impregnated in plastic or paper can be used. Examples of the shape of the support include a drum shape, a sheet shape, and a belt shape, and it is preferable that the shape is most suitable for the applied electrophotographic photosensitive member.

Further, in the present invention, a resin layer or a resin layer containing conductive particles can be laminated on the photosensitive layer as a protective layer.

Examples of the method for applying the various layers described above include a dip coating method, a spray coating method, a beam coating method, a spinner coating method, a roller coating method, a Meyer bar coating method and a plated coating method.

The electrophotographic photoreceptor of the present invention can be applied to general electrophotographic devices such as copiers, laser printers, LED printers, and liquid crystal shutter printers.
Furthermore, the present invention can be widely applied to devices such as display, recording, light printing, plate making, and facsimile to which electrophotographic technology is applied.

FIG. 1 shows a schematic configuration of an electrophotographic apparatus using 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 1a in a direction of an arrow at a predetermined peripheral speed. The photosensitive member 1 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by a charging means 2 in the course of rotation, and then the exposure section 3 is subjected to slit exposure or laser beam scanning by an image exposure means (not shown). It receives light image exposure L such as exposure. In this way, an electrostatic latent image corresponding to the exposure image is sequentially formed on the peripheral surface of the photoconductor.

The formed electrostatic latent image is then transferred to developing means 4
The toner developed image is transferred from a paper supply unit (not shown) to the transfer material P fed between the photoconductor 1 and the transfer unit 5 in synchronization with the rotation of the photoconductor 1 by a transfer unit. 5 are sequentially transferred.

The transfer material P having undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing, and is printed out of the apparatus as a copy.

After the transfer of the image, the surface of the photoreceptor 1 is cleaned by a cleaning unit 6 to remove the untransferred toner, and is further subjected to a static elimination process by a pre-exposure unit 7, and then used repeatedly for image formation. .

In the present invention, of the above-mentioned components such as the electrophotographic photosensitive member 1, the developing means 4 and the cleaning means 6, a plurality of components are integrally connected as a process cartridge, and this process cartridge is copied. It may be configured to be detachable from the main body of an image forming apparatus such as a printer or a laser beam printer. For example, at least one of the charging unit 2, the developing unit 4, and the cleaning unit 6
One is supported together with the photoreceptor 1 to form a cartridge,
The process cartridge may be detachable from the apparatus main body by using a guide means such as a rail of the apparatus main body.

In the case where the electrophotographic apparatus is used as a copying machine or a printer, the light image exposure L involves irradiating the photosensitive member with reflected light or transmitted light from the original, or reading the original with a sensor. The signal is converted into a signal, and scanning of a laser beam, driving of an LED array, driving of a liquid crystal shutter array, and the like are performed in accordance with the signal to irradiate the photosensitive member with light.

On the other hand, when used as a facsimile printer, the light image exposure L is an exposure for printing received data. FIG. 2 is a block diagram showing an example of this case.

The controller 11 controls the image reading section 10 and the printer 19. The whole controller 11 is CP
It is controlled by U17. The read data from the image reading unit is transmitted to the partner station through the transmission circuit 13. Data received from the partner station is sent to the printer 19 through the receiving circuit 12. Predetermined image data is stored in the image memory. The printer controller 18 is the printer 1
9 is controlled. 14 is a telephone.

The image received from the line 15 (image information from a remote terminal connected via the line) is demodulated by the receiving circuit 12 and then decoded by the CPU 17 and sequentially stored in the image memory 16. Is stored. When the image of at least one page is stored in the memory 16, the image of the page is recorded. The CPU 17 is a memory 1
6, one page of image information is read out, and the decoded one page of image information is sent to the printer controller 18. The printer controller 18 receives 1
When the image information of the page is received, the printer 19 is controlled to record the image information of the page. CPU17
Is receiving the next page during recording by the printer 19.

In this way, the image is received and recorded.

Hereinafter, the present invention will be described in more detail by way of examples.

[0068]

【Example】

Example 1 Exemplified Compound No. 1 was placed on an aluminum plate. A solution prepared by dissolving 5 parts (parts by weight, hereinafter the same) of a polyamic acid represented by 3 in 95 parts of N, N-dimethylacetamide is applied by a Meyer bar, and dried at 140 ° C. for 10 minutes to obtain a film having a thickness of 1 μm. An intermediate layer was formed.

Next, the following equation

[0070]

[Outside 7] Is added to 5 parts of a bisazo pigment represented by
And dispersed with a sand mill for 20 hours. To this solution was added a solution prepared by dissolving 2.5 parts of butyral resin (BLS, manufactured by Sekisui Chemical Co., Ltd.) in 20 parts of tetrahydrofuran.
Time dispersed. A solution obtained by adding 100 parts of cyclohexanone and 100 parts of tetrahydrofuran to this dispersion and diluting the dispersion was applied to the intermediate layer formed above with a Meyer bar,
By drying, a charge generation layer having a thickness of 0.2 μm was formed.

Then, the following equation

[0072]

[Outside 8] A solution prepared by dissolving 5 parts of a triarylamine represented by the following formula and 5 parts of a polycarbonate resin (Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in 40 parts of monochlorobenzene is applied to the charge generating layer with a Mayer bar, and dried. As a result, a charge transport layer having a thickness of 20 μm was formed.

The obtained electrophotographic photosensitive member was subjected to an electrostatic copying machine tester (Model SP-428, Kawaguchi Electric Co., Ltd.)
Negatively charged with a −5 KV corona discharge using
After leaving in a dark place for 10 seconds, illuminance 10
The substrate was exposed to lux light, and the charging characteristics were evaluated. As the charging characteristics, the surface potential (V _O ), the amount of exposure necessary for the V _O to attenuate to 1/2, ie, the sensitivity (E1 / 2), and the potential after pre-exposure, ie, the residual potential (Vr) are measured. did.

The results are shown in Table 1.

Examples 2 to 10 Exemplified Compound Nos. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that the polyamic acid or polyamic acid ester shown in Table 1 was used instead of the polyamic acid of No. 3.

The results are shown in Table 1.

Comparative Example 1 The intermediate layer was prepared by mixing 5 parts of alcohol-soluble copolymerized nylon (Amilan CM-8000, manufactured by Toray Industries, Inc.) with methanol 95
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that the electrophotographic photoreceptor was formed using a solution dissolved in a part.

The results are shown in Table 1.

Comparative Example 2 The intermediate layer was dried at 100 ° C. for 60 minutes, and further dried at 250 ° C.
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the intermediate layer was formed by heat-treating for 3 hours. Table 1 shows the results of analysis by infrared absorption spectrum, in which the acid amide structure in the resin used for the intermediate layer was all imidized.

[0080]

[Table 7]

Example 11 Using an aluminum cylinder (outside diameter 30 mm × length 360 mm) instead of an aluminum plate, the intermediate layer was dried at 140 ° C. for 30 minutes, and the thickness of the intermediate layer was set to 2.0 μm.
An electrophotographic photosensitive member was prepared in the same manner as in Example 1, except that The application of each layer was performed by a dip coating method.

The obtained electrophotographic photosensitive member was charged, exposed and exposed.
It is installed in a regular development type plain paper copying machine in which a development-transfer-cleaning process is performed in a cycle of 0.8 seconds, and is continuously used in a low temperature and low humidity environment (15 ° C., 15% RH) for 10,000 hours.
A zero-image endurance test was performed. The evaluation was performed by measuring the dark potential (V _D ) at the initial stage, measuring the bright potential (V _L ) at the initial stage and after the durability test, and visually evaluating the obtained image. Further, a substrate peel test (based on the method described in JIS K5400 “General Test Method for Paints”) was performed on the intermediate layer prepared up to the intermediate layer in the same manner as described above.

The results are shown in Table 2.

Examples 12 to 20 An electrophotographic photosensitive member was prepared in the same manner as in Example 11 except that the solution for an intermediate layer used in Examples 2 to 10 was used.
evaluated.

The results are shown in Table 2.

Comparative Example 3 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 11, except that the intermediate layer solution used in Comparative Example 1 was used.

The results are shown in Table 2.

Comparative Example 4 An intermediate layer was formed of a polyester polyol (Nipporan 12
5, Nippon Polyurethane Industry Co., Ltd.) 14 parts, 2,6-
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 11, except that the electrophotographic photosensitive member was formed using a solution obtained by mixing 6 parts of tolylene diisocyanate, 0.02 part of dibutyltin dilaurate and 80 parts of methyl ethyl ketone.

The results are shown in Table 2.

Comparative Example 5 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 11, except that the intermediate layer solution used in Comparative Example 2 was used.

The results are shown in Table 2.

[0092]

[Table 8]

Example 21 Exemplified Compound No. 25 parts of polyamic acid, 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide, and N, N-dimethylacetamide 2
The first intermediate layer solution was obtained by dispersing 5 parts of the mixture by a sand mill for 20 hours. This solution was applied on an aluminum plate with a Meyer bar, and dried at 140 ° C. for 1 hour to form a first intermediate layer having a thickness of 13 μm.

Next, an intermediate layer (hereinafter, referred to as a second intermediate layer), a charge generation layer, and a charge transport layer were provided on the first intermediate layer in the same manner as in Example 1. However, the thickness of the second intermediate layer was 0.5 μm.

The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 1.

The results are shown in Table 3.

Examples 22 to 30 Exemplified Compound Nos. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 21, except that the polyamic acid or polyamic acid ester shown in Table 3 was used instead of the polyamic acid of No. 3.

The results are shown in Table 3.

Comparative Example 6 Conductive oxidation in which the first intermediate layer was coated with 25 parts of a resol type phenol resin (Plyofen J-325, manufactured by Dainippon Ink Co., Ltd.) and tin oxide containing 10% of antimony oxide A mixture obtained by dispersing a mixture of 50 parts of titanium powder, 25 parts of methyl cellosolve and 5 parts of methanol in a sand mill for 20 hours was used, and the second intermediate layer was formed of an alcohol-soluble copolymerized nylon (Amilan CM-8000, Toray Industries, Inc.) An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 21 except that 5 parts were prepared using a solution in which 95 parts of methanol was dissolved in 95 parts of methanol.

The results are shown in Table 3.

[0101]

[Table 9]

Examples 31 to 32 Electrophotographic photosensitive members were prepared in the same manner as in Examples 21 and 26 except that an aluminum cylinder (outer diameter 30 mm × length 360 mm) was used instead of the aluminum plate.
However, each layer was applied by a dip coating method.

The obtained electrophotographic photosensitive member was evaluated in the same manner as in Example 11. However, the base line peeling test was not performed.

The results are shown in Table 4.

[0105]

[Table 10]

Examples 33 and 34 In the same manner as in Examples 21 and 26, a first intermediate layer and a second intermediate layer were formed on an aluminum cylinder.

Next, 4 parts of an oxytitanium phthalocyanine pigment were added to a solution of 2 parts of polyvinyl butyral (BX-1, manufactured by Sekisui Chemical Co., Ltd.) in 34 parts of cyclohexanone, and dispersed by a sand mill for 8 hours. The solution for the charge generation layer was obtained by further adding and diluting 60 parts of tetrahydrofuran. This solution is applied on the middle layer,
By drying, a charge generation layer having a thickness of 0.2 μm was formed.

Next, a charge transport layer was formed in the same manner as in Example 11.

The obtained electrophotographic photosensitive member was charged, exposed, and exposed.
Attached to a reversal development type laser beam printer that performs the development-transfer-cleaning process in a cycle of 6 seconds, and performed a continuous 5,000 image endurance test in a high temperature and high humidity environment (30 ° C., 85% RH). Done. Evaluation,
The measurement was performed by measuring the dark portion potential (V _D ) at the initial stage, measuring the bright portion potential (V _L ) at the initial stage and after the durability test, and visually evaluating the obtained image.

Table 5 shows the results.

Comparative Example 7 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 33 except that the first intermediate layer and the second intermediate layer were formed in the same manner as in Comparative Example 6. However, the first intermediate layer and the second intermediate layer were applied by a dip coating method.

Table 5 shows the results.

[0113]

[Table 11]

[0114]

As described above, according to the present invention, in all environments from low temperature and low humidity to high temperature and high humidity, it has a stable high sensitivity and excellent potential characteristics, and is excellent even when used repeatedly. An electrophotographic photosensitive member capable of continuously forming an image, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus can be provided.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having an electrophotographic photosensitive member of the present invention.

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor of the present invention 1a shaft 2 Charging means 3 Exposure unit 4 Developing means 5 Transfer means 6 Cleaning means 7 Pre-exposure means 8 Image fixing means L Optical image exposure P Transfer material 10 Image reading unit 11 Controller 12 Receiving circuit 13 Transmission circuit 14 Telephone 15 Line 16 Image memory 17 CPU 18 Printer controller 19 Printer

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Kazuma Sato 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-58-59440 (JP, A) JP-A Sho 58-58540 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 5/14 G03G 5/05 101

Claims (7)

(57) [Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a conductive support via an intermediate layer, wherein the intermediate layer has the following formula (1): (In the formula, A represents a divalent organic group, and R _{1 to} R ₄ are the same or different and each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a cyano group. And R ₅ and R ₆ are the same or different and are each a hydrogen atom, a substituted or unsubstituted alkyl group,
It represents a substituted or unsubstituted alkoxyalkyl group and a substituted or unsubstituted aralkyl group. An electrophotographic photosensitive member comprising a resin having at least one of a polyamic acid structure and a polyamic acid ester structure having a repeating unit represented by the formula (1). 2. A compound represented by the following formula (2) or (3): -Ar _1- (2) wherein Ar ₁ is a substituted or unsubstituted aromatic hydrocarbon ring group and a substituted or unsubstituted aromatic group. Represents an aromatic heterocyclic group.) Formula -Ar ₂ -X-Ar _3- (3) (wherein, Ar ₂ and Ar ₃ are the same or different, and each represents a substituted or unsubstituted aromatic hydrocarbon ring group and a substituted or unsubstituted aromatic hydrocarbon ring group. The electrophotographic photoreceptor according to claim 1, wherein an unsubstituted aromatic heterocyclic group is represented, and X represents an oxygen atom, a sulfur atom, a substituted or unsubstituted alkylene group, a carbonyl group and a sulfonyl group. 3. The electrophotographic photosensitive member according to claim 2, wherein said A is represented by the formula (3). 4. The resin according to claim 1, wherein the proportion of the repeating unit having an amide acid structure and the repeating unit having an amide ester structure in the resin is 20 to 80 mol% based on all the repeating units of the resin. Or the electrophotographic photosensitive member according to 2. 5. The electrophotographic photoreceptor according to claim 4, wherein said proportion is 40 to 60 mol%. 6. 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 an electrophotographic apparatus main body. A process cartridge, comprising: 7. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposing unit, a developing unit, and a transfer unit.