JP2002107984A - Electrophotographic photoreceptor, method for manufacturing the same, electrophotographic device, electrophotographic process and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor in which satisfactory image can be obtained even when the photoreceptor is repeatedly used under a high temperature and high humidity or low temperature and low humidity condition. SOLUTION: The electrophotographic photoreceptor has a conductive supporting body 1, intermediate layer 2 and photoconductive layer 3 in this order. The intermediate layer 2 consists of a crosslinked material of N-alkoxy methylated polyamide and contains an inorganic pigment. The intermediate layer 2 has low moisture absorption, which decreases the environmental dependence of the photosensitive characteristics of the photoreceptor and suppresses increase in the residual potential. By using the above electrophotographic photoreceptor, preferable images can be obtained even when the photoreceptor is repeatedly used under a high temperature and high humidity or a low temperature and low humidity condition.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member used for a laser beam printer, a facsimile, a digital copy, etc., a method of manufacturing the same, an electrophotographic apparatus, a process cartridge, and an electrophotographic process.

[0001]

2. Description of the Related Art The basic constitution of an electrophotographic photosensitive member is to form a photoconductive layer containing a photosensitive material on a conductive support.
In addition to this configuration, improved adhesion of the photoconductive layer, improved coating properties, improved charging properties, prevention of unnecessary charge injection from the support,
It is known to provide an intermediate layer between the support and the photoconductive layer, for example for covering defects on the support.

As the intermediate layer, methoxymethylated polyamide is known as a material having a good balance of various properties. However, N-alkoxymethylated polyamides typified by methoxymethylated polyamides have very high hygroscopicity due to their structures containing alkoxy groups. Due to the water content, the photoreceptor provided with an intermediate layer using N-alkoxymethylated polyamide has remarkably fluctuated photoreceptor characteristics when repeatedly used at high temperature, high humidity or low temperature and low humidity. Therefore, when an electrophotograph is produced using such a photoconductor,
There is a problem that an abnormal image such as a black spot or a decrease in density is caused.

[0003] There is known a photoreceptor in which an intermediate layer is formed using only a crosslinked methoxymethylated polyamide. (JP-A-2-108064, JP-A-10-
(See, for example, Japanese Patent No. 268543, Japanese Patent No. 2817421, and Japanese Patent No. 2785282.) However, crosslinking was insufficient, and the photoreceptor characteristics still depended on the environment. further,
In this case, if the thickness of the intermediate layer is increased, the following problem occurs. The surface of the photoreceptor is first charged and exposed, and the electric charge moves because the exposed portion becomes conductive, whereby information of an image is written as an electrostatic latent image.
When the thickness of the intermediate layer is large and exceeds 1.0 μm,
There is a problem that charges remain after image exposure and the residual potential increases when the photoreceptor is used repeatedly. The increase in the residual potential is, in other words, the deterioration of the photoconductor, and an abnormality occurs in the image to be produced. To avoid this problem, when using methoxymethylated polyamide alone in the intermediate layer,
The thickness had to be 1.0 μm or less. When the thickness of the intermediate layer is reduced, the effect of sufficiently hiding defects such as scratches and irregularities on the surface of the conductive support is lost. Therefore, in order to control the surface state of the conductive support, steps such as cutting and polishing of the surface are required, and the production cost of the photoconductor has been increased. Furthermore, when an electrophotographic apparatus provided with a contact charging device is mounted with a photoconductor provided with a thin intermediate layer, the intermediate layer is thin, so that the photoconductor is destroyed by discharge, and as a result, an abnormal image is likely to occur. Particularly, in the reversal development process, the influence of the discharge destruction appears as a large black spot on the image, which has been a serious problem.

On the other hand, it has been proposed to add a thermosetting resin such as a melamine resin in order to improve the problem due to the hygroscopicity of the methoxymethylated polyamide (JP-A-3-33).
No. 7861, Japanese Patent No. 2861557). But,
In an intermediate layer to which only a melamine resin is simply added, even though the hygroscopicity is improved, there remains a problem that various properties of the methoxymethylated polyamide greatly depend on temperature and humidity. Therefore, the electrophotographic photoreceptor provided with the photoconductive layer on the intermediate layer still has a large dependence of the photoreceptor characteristics on temperature and humidity. Therefore, when an image is formed by repeatedly using the photoreceptor at a high temperature and a high humidity or at a low temperature and a low humidity, an abnormal image such as a black spot and a decrease in density is caused as described above.

The undercoat layer corresponding to the intermediate layer is made of a thermoplastic resin and a thermosetting resin, and the thermoplastic resin is a modified polyamide resin mainly composed of modified polyamide 6 or a copolymerized polyamide containing polyamide 6. An electrophotographic photosensitive member has been disclosed (Japanese Patent Application Laid-Open No. 5-150535, Japanese Patent No. 2861557). However, when this photoreceptor is used under low temperature and low humidity, the light portion potential (V
L) greatly fluctuated, which also resulted in an abnormal image.

Meanwhile, in order to enhance the effect of hiding defects on the conductive support and to enhance the effect of scattering incident light such as coherent light (eg, laser light) to suppress the generation of interference fringes. It is well known to disperse an inorganic pigment such as titanium oxide in the resin (Japanese Patent Application Laid-Open Nos. 61-204462 and 62-280864). A photoreceptor provided with an intermediate layer in which such an inorganic pigment is dispersed does not cause any particular problem at the initial stage, but when mounted on an electrophotographic apparatus and used for a long time, background image, white spots, etc. The defect that a defect becomes gradually remarkable arises.

As described above, it is proposed to provide a second layer having no filler between an intermediate layer in which an inorganic pigment is dispersed and a conductive support, in order to improve the problem that occurs during long-term use. (JP-A-63-2895)
54, JP-A-64-031163). However, the improvement was not sufficient, and an abnormal image was generated when such a layer configuration was used for a long time.

It has also been proposed to form an undercoat layer (intermediate layer) with a non-conductive titanium oxide and a polyamide resin dissolved and dispersed in a mixed solvent of an alcohol and a specific organic solvent (Japanese Patent Laid-Open No. Hei 6-1994). 202366, Patent No. 2885609
issue). However, the hygroscopicity of the intermediate layer is large, and the characteristics of the photoreceptor greatly depend on the environment. Therefore, as described above, repeated use at high temperature and high humidity or low temperature and low humidity causes an abnormal image of black spots and density reduction.

On the other hand, there has been disclosed a photoreceptor in which an intermediate layer made of only a resin is provided between a photoconductive layer and a layer in which titanium oxide coated with SnO ₂ containing Sb ₂ O ₃ is dispersed (see Japanese Patent Application Laid-Open (JP-A) no. 61
-036755). However, the chargeability, sensitivity, image quality and the like are not totally satisfied. A photoreceptor in which a polyamide resin intermediate layer is provided between a thermosetting resin layer in which an inorganic pigment is dispersed and a photoconductive layer is also disclosed (Japanese Patent Application Laid-Open No. 9-288367). In the photoreceptor provided with the intermediate layer of the polyamide resin, although there is an effect of suppressing an abnormal image after long-time use, there is a large problem that the light portion potential in the actual device at a low temperature and a low humidity rises greatly. The rise in the light portion potential occurs with the rise in the residual potential of the photoconductor, and the two show the same rising trend with the deterioration of the photoconductor.

In order to crosslink the N-alkoxymethylated polyamide and the melamine resin at a practical temperature, a solution in which both are dissolved in a solvent must be acidified and heated. When titanium oxide is dispersed in a resin solution to which an acidic catalyst has been added, the dispersion does not have sufficient stability, and the pot life of the dispersion is short. In the dispersion having a short pot life, the storage period becomes longer and the aggregation of the inorganic pigment occurs to increase the number of coarse particles in the solution. When the number of coarse particles increases, the surface of the intermediate layer formed using this solution does not become uniform, the effect of covering defects of the conductive support decreases, and the photoconductive layer laminated on the intermediate layer becomes uniform. It cannot be formed. For this reason, the photoreceptor characteristics of the obtained photoreceptor are not uniform, and when this photoreceptor is used, abnormal images such as density unevenness and black spots occur. For this reason, at the time of manufacturing the photoreceptor, it is necessary to frequently change the coating solution (acidic resin solution) for forming the intermediate layer, which causes a problem that the manufacturing cost increases.

Therefore, an intermediate layer in which a surface-treated titanium oxide is dispersed in a crosslinked product of a methoxymethylated polyamide resin and a melamine resin has been proposed (JP-A-9-269).
606). In this intermediate layer, surface-treated titanium oxide is used in order to improve the dispersion stability of titanium oxide in the resin solution. However, when the surface-treated titanium oxide is used, the photoreceptor including the intermediate layer is liable to cause a residual potential increase due to repeated use due to the influence of the surface treatment. Therefore, the intermediate layer had to be provided in a considerably thin film. As described above, when the intermediate layer is a thin film, there has been a problem that a step of controlling the surface of the conductive support is required, or a discharge breakdown occurs to generate an abnormal image. Further, due to the influence of the surface treatment of titanium oxide, the environmental dependency of the photoreceptor has been increased.

[0012]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a highly durable electrophotographic apparatus capable of obtaining a good image even when repeatedly used in a high-temperature, high-humidity or low-temperature, low-humidity environment. Photoconductor and manufacturing method thereof, electrophotographic apparatus and process cartridge including electrophotographic photoconductor, and
An object of the present invention is to provide an electrophotographic process using the electrophotographic photosensitive member.

Another object is to provide an electrophotographic photosensitive member capable of obtaining a good image without discharge breakdown and no increase in residual potential, a method of manufacturing the same, an electrophotographic apparatus having the electrophotographic photosensitive member, and Process cartridges, and
An object of the present invention is to provide an electrophotographic process using the electrophotographic photosensitive member.

Still another object is to provide a method for producing an electrophotographic photoreceptor using a coating solution for an intermediate layer, which is inexpensive and has extremely excellent dispersion stability.

[0015]

According to a first aspect of the present invention, there is provided an electrophotographic photosensitive member, comprising: a conductive support; an intermediate layer provided on the conductive support; An intermediate layer containing an inorganic pigment and a binder resin, wherein the binder resin is cross-linked with N-alkoxymethylated polyamide or N-alkoxymethylated polyamide and melamine. An electrophotographic photosensitive member characterized by being a crosslinked product with a resin is provided.

The electrophotographic photoreceptor of the present invention uses a crosslinked N-alkoxymethylated polyamide or a crosslinked product of an N-alkoxymethylated polyamide and a melamine resin as a binder resin for the intermediate layer. It is known that N-alkoxymethylated polyamide undergoes a crosslinking reaction by heating. As an example, the crosslinking reaction of a methoxymethylated polyamide is shown in the following formula. As shown in the equation below,
The methoxy group is reduced by demethoxylation accompanying the crosslinking reaction, and the crosslinked product of methoxymethylated polyamide has a three-dimensional structure. The crosslinked N-alkoxymethylated polyamide has reduced hygroscopicity due to reduced alkoxy groups, and if this is used for the intermediate layer, it is possible to produce a photoreceptor whose photoreceptor characteristics are less dependent on temperature and humidity. Further, the crosslinked product of the N-alkoxymethylated polyamide and the melamine resin also has a three-dimensional structure similarly to the methoxymethylated polyamide, and by using this in the intermediate layer, the photosensitive member has a small temperature-humidity dependency. Body can be manufactured.

[0017]

Embedded image

If the intermediate layer having a certain thickness is formed only of the crosslinked N-alkoxymethylated polyamide, the residual potential of the photosensitive member after image exposure is increased as described above, which causes an abnormal image. In order to solve this problem, the electrophotographic photoreceptor of the present invention has an inorganic pigment dispersed in an intermediate layer composed of a crosslinked product. Due to the presence of the inorganic pigment, an increase in the residual potential is suppressed, and the thickness of the intermediate layer can be increased. Therefore, the photoreceptor provided with the intermediate layer is hardly deteriorated even when used repeatedly. Further, by increasing the thickness of the intermediate layer, the discharge breakdown of the intermediate layer can be suppressed when the photoconductor is charged using the contact charging method. Abnormalities such as spots can be reduced. Further, by increasing the thickness of the intermediate layer, even if there are scratches and irregularities on the support surface, they can be sufficiently concealed, so that steps such as cutting and polishing, which have been conventionally performed for controlling the support surface, become unnecessary. .
In addition, even when a low-cost support having a poor surface condition (many defects) is used, defects of the support are sufficiently hidden by the intermediate layer, and a thin charge generation layer is coated on the intermediate layer. In this case, this intermediate layer is also excellent in coatability of the charge generation layer. Therefore, when the obtained electrophotographic photosensitive member is mounted on a contact charging type electrophotographic apparatus and used, no discharge breakdown occurs.

The N-alkoxymethylated polyamide used in the present invention is an N-alkoxymethylated polyamide having an alkoxy group having 1 to 10 carbon atoms.
-The alkoxymethylated polyamide has a good solubility in a solvent for preparing a coating solution, and thus can be suitably used. N- having an alkoxy group having 1 to 10 carbon atoms
Examples of the alkoxymethylated polyamide include methoxymethylated polyamide, ethoxymethylated polyamide, and butoxymethylated polyamide.

The substitution rate of the alkoxymethyl group of the N-alkoxymethylated polyamide used in the present invention is not particularly limited, but the alkoxymethylation rate (substitution rate) is 15 mol.
% Or more of N-alkoxymethylated polyamide is more preferred. When the alkoxymethylation rate is high, the solubility in the solvent used for the coating solution for the intermediate layer is improved. Therefore, a uniform intermediate layer can be formed, and the coating property of the photoconductive layer provided on the intermediate layer is improved. If an electrophotographic photosensitive member having such an intermediate layer is used, discharge breakdown is unlikely to occur even in a contact charging type electrophotographic apparatus. Further, the N-alkoxymethylated polyamide having an alkoxymethylation ratio (substitution ratio) of 15 mol% or more has good dispersibility with inorganic pigments, and a uniform intermediate layer can be obtained even when inorganic pigments are dispersed. In particular, according to the study of the present inventors, when an N-alkoxymethylated polyamide having an alkoxymethylation ratio (substitution ratio) of 15 mol% or more is used, the dispersibility with a surface-untreated titanium oxide described below becomes very good, It was found that the dispersion stability was improved, and the pot life of the coating solution for the intermediate layer was significantly increased. Furthermore, it was found that the adhesion between the photoconductive layer and the support was also improved.

Of the above N-alkoxymethylated polyamides, methoxymethylated polyamides are preferred because they are easily available. The methoxymethylated polyamide used in the present invention may be polyamide 6, polyamide 12, or a copolymer polyamide containing these as a component, for example, T.I. L.
Cairns (J. Am. Chem. Soc. 71.P
651 (1949)). The methoxymethylated polyamide is obtained by replacing the hydrogen of the amide bond of the original polyamide with a methoxymethyl group. This substitution ratio can be selected in a wide range depending on the denaturing conditions.

The inorganic pigment used for the intermediate layer may be a commonly used pigment, but a white color having almost no absorption in visible light and near-infrared light or a color close thereto is desirable in consideration of increasing the sensitivity of the photoreceptor. . For example, white pigments such as titanium oxide, zinc white, zinc sulfate, lead white, and lithopone, and extenders such as aluminum oxide, silica, calcium carbonate, barium sulfate, and the like can be given.

The ratio P / R of the inorganic pigment (P) to the binder resin (R) is preferably in the range of 0.1 / 1 to 5.0 / 1 by volume.

Among the above-mentioned inorganic pigments, titanium oxide is more preferred. This is because titanium oxide has a higher refractive index than other white pigments, is chemically and physically stable, has a large hiding power, and has a high whiteness. Titanium oxide includes rutile type and anatase type, and any of them can be used. The aluminum oxide may be a commonly used aluminum oxide.

Among the above-mentioned inorganic pigments, a mixture of titanium oxide and aluminum oxide is also preferable as in the case of titanium oxide. The present inventors have found that the use of an intermediate layer of titanium oxide and aluminum oxide as the intermediate layer of the photoreceptor reduces the fluctuation of the photoreceptor characteristics due to the environment. This is presumably because the dispersion state of the inorganic pigment with the resin is improved by using a mixture of titanium oxide and aluminum oxide, and the intermediate layer has an optimum resistance value.
The mixing method of titanium oxide and aluminum oxide may be such that both powders are mixed and dispersed, and the mixing method is not specified. The particle size of titanium oxide and aluminum oxide is 0.1 to
10 μm is preferred, and among them, those having a particle diameter of 0.3 to 1 μm are particularly preferably used because the use thereof increases dispersibility with a resin component and improves electrophotographic properties.

Further, it is preferable to use titanium oxide whose surface is untreated. Titanium oxide is commercially available which has been subjected to an inorganic treatment such as an alumina treatment or a silica treatment in order to improve dispersibility, weather resistance, discoloration resistance and the like. However, it has been found that when the surface-treated titanium oxide is contained in the intermediate layer, the characteristics of the photoreceptor deteriorate at high temperature and high humidity or at low temperature and low humidity due to the effect of the treatment. In order to reduce the deterioration of the photoreceptor characteristics, it is preferable to use titanium oxide which has not been subjected to a surface treatment.

The purity of titanium oxide is preferably 99.5% by weight or more. As impurities of the inorganic pigment, Na ₂ O, K ₂
Some are hygroscopic, such as O. Although such impurities are minute amounts, their hygroscopicity makes the properties of titanium oxide environmentally dependent. As a result, the photoreceptor containing titanium oxide containing such impurities in the intermediate layer has environmental characteristics of the photoreceptor characteristics. Therefore, by setting the purity of titanium oxide to 99.5% by weight or more, it is possible to further reduce the environmental fluctuation of the photoconductor characteristics.

The melamine resin constituting the crosslinked product with the N-alkoxymethylated polyamide may be a commercially available melamine resin. However, it can be seen that the dispersibility with the surface-untreated titanium oxide becomes very good, especially by using the butylated melamine resin, the dispersion stability is improved, and the pot life of the coating solution for the intermediate layer is significantly increased. Was.

The intermediate layer of the photoreceptor of the present invention further comprises a first
The structure may be divided into two layers, an intermediate layer and a second intermediate layer. In this case, the first intermediate layer formed on the conductive support is made of a thermosetting resin in which an inorganic pigment is dispersed. Next, the second intermediate layer formed on the first intermediate layer is composed of N-alkoxymethylated polyamide or a crosslinked product of N-alkoxymethylated polyamide and melamine resin.
Also in this case, since the hygroscopicity of the N-alkoxymethylated polyamide can be suppressed, the environmental dependency of the photosensitive characteristics can be reduced. Furthermore, an increase in the residual potential can be suppressed by the presence of the inorganic pigment contained in the first intermediate layer, and the entire intermediate layer can be made thicker, so that an abnormal image due to discharge breakdown can be suppressed. As for the N-alkoxymethylated polyamide and the inorganic pigment, the same pigments as in the case where the above-mentioned intermediate layer is a single layer can be used.

As the thermosetting resin constituting the first intermediate layer, for example, a thermosetting resin obtained by thermally polymerizing an oil-free alkyd resin and an amino resin such as a butylated melamine resin can be used.

The thickness of the second intermediate layer is preferably from 0.01 to 1 μm. If it is too thin, the effect of suppressing abnormal images is small, and if it is too thick, the residual potential tends to increase.

According to a second aspect of the present invention, there is provided a method for producing an electrophotographic photoreceptor, wherein a conductive support is provided; and the conductive support contains an inorganic pigment and a binder resin. A coating film is formed by applying a coating liquid for forming an intermediate layer, and the binder resin is a crosslinked N-alkoxymethylated polyamide or a crosslinked product of an N-alkoxymethylated polyamide and a melamine resin; To form an intermediate layer; and providing a photoconductive layer on the intermediate layer.

The method for forming an intermediate layer according to the production method of the present invention is as follows.
The alkoxymethylated polyamide and the melamine resin are dissolved in a lower aliphatic alcohol such as methanol, ethanol, and propanol. At this time, in order to enhance the stability of the solution, a chlorinated hydrocarbon such as trichloroethane, trichloroethylene, dichloroethane, dichloromethane and chloroform may be mixed.

Next, an inorganic pigment is dispersed in the above solution. As a method for dispersing the inorganic pigment, a conventional method such as a ball mill, a roll mill, a sand mill, and an attritor can be applied. Thus, a coating liquid for an intermediate layer is prepared.

The coating solution for the intermediate layer is coated on a conductive support by a coating method such as blade coating, knife coating, spray coating, or dip coating, and then dried. An intermediate layer is formed. The thickness of the intermediate layer is 0.5 to 5
0.0 μm is preferred.

The intermediate layer has a temperature of 85 to 18 which is a temperature sufficient for the crosslinking reaction of the N-alkoxymethylated polyamide to proceed.
Drying is performed at 5 ° C, preferably 100 to 180 ° C, more preferably 100 to 135 ° C. Below 85 ° C,
In the drying step, crosslinking of the N-alkoxymethylated polyamide does not proceed sufficiently, and the residual alkoxy groups increase. As a result, when a photoreceptor is manufactured, the photoreceptor is highly dependent on the environment. On the other hand, if the drying is performed at a temperature exceeding 185 ° C., a photosensitive member having deteriorated photosensitive characteristics may be obtained.

In preparing the coating solution for the intermediate layer, a mixed solvent of alcohols and ketones can be used.
By using such a mixed solvent, when the surface-untreated titanium oxide is dispersed, the dispersion stability of the coating solution for the intermediate layer is improved, and the pot life of the coating solution for the intermediate layer is significantly increased. I understood. In this case, the method for preparing the coating solution for the intermediate layer is as follows. First, an N-alkoxymethylated polyamide and a melamine resin are mixed with alcohols such as methanol, ethanol, and propanol, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diethyl ketone. In a mixed solvent of The mixing ratio of the alcohol and the ketone is selected so that both the N-alkoxymethylated polyamide and the melamine resin are completely dissolved.

In this case, in order to evaluate the dispersibility of the inorganic pigment in the coating solution for the intermediate layer, the particle size distribution of the inorganic pigment in the coating solution may be measured as used in Examples described later.
As a measuring method, a weight sedimentation method or a light transmission type particle size distribution measuring method is used, and further, it may be directly observed with a microscope.
Particles of an inorganic pigment such as titanium oxide are 1.0% in the coating solution.
μm or less is preferred. Dispersion liquid with a long pot life has few coarse particles of 1.0 μm or more from the initial stage of coating liquid preparation,
In addition, there is little change in the particle size distribution even after long-term storage. On the other hand, the dispersion liquid having a short pot life has a long storage period and causes aggregation of the inorganic pigment, so that coarse particles increase in the coating liquid.

To efficiently crosslink the N-alkoxymethylated polyamide and the N-alkoxymethylated polyamide with the melamine resin and at a practical temperature, add an acid catalyst to the coating solution for the intermediate layer. Then, the coating liquid can be heated after being made acidic. In order to make the coating solution for the intermediate layer acidic, an organic acid such as maleic acid, citric acid, tartaric acid, and succinic acid and an inorganic acid such as boric acid and hypophosphorous acid may be added. The addition amount may be from 0.1% by weight to 10% by weight based on the N-alkoxymethylated polyamide.

According to a third aspect of the present invention, there is provided a method for producing an electrophotographic photoreceptor, wherein a conductive support is provided; a thermosetting resin having an inorganic pigment dispersed on the conductive support. Forming a first intermediate layer consisting of: on the first intermediate layer,
A coating solution for forming a second intermediate layer containing a binder resin is applied to form a coating film, and the binder resin is a crosslinked N-alkoxymethylated polyamide or N-alkoxymethylated polyamide and a melamine resin. A method for producing an electrophotographic photoreceptor in which the coating film is heated to form a second intermediate layer; and a photoconductive layer is provided on the second intermediate layer.

According to a third aspect of the present invention, the intermediate layer is provided with the first layer.
An intermediate layer and a second intermediate layer are formed separately. To form the first intermediate layer, first, a thermosetting resin is dissolved in an organic solvent. Next, the inorganic pigment is dispersed in the solution. As a method for dispersing the inorganic pigment, a conventional method such as a ball mill, a roll mill, a sand mill, and an attritor can be applied. The coating liquid in which the inorganic pigment is dispersed is applied to a conductive support using a coating method such as blade coating, knife coating, spray coating, or dip coating, and then dried to be cured. An intermediate layer is formed. The thickness of the first intermediate layer is usually 0.01 to 100 μm, preferably 2 to 50 μm. When the photoreceptor is manufactured, if the thickness of the first intermediate layer is too small, the effect of defects in the conductive support appears on the image, and if the thickness is too large, the residual potential tends to increase.

On this first intermediate layer, (a) cross-linked N
A second intermediate layer comprising a crosslinked product of an alkoxymethylated polyamide or (b) an N-alkoxymethylated polyamide and a melamine resin. In the case of the latter crosslinked product (b), the proportion of the N-alkoxymethylated polyamide and the melamine resin is usually 0.01 to 100 parts by weight of the melamine resin per 1 part by weight of the N-alkoxymethylated polyamide. Is fine.

The method for forming the second intermediate layer is as follows.
Dissolving the alkoxymethylated polyamide or N-alkoxymethylated polyamide and the melamine resin in a lower aliphatic alcohol such as methanol, ethanol, or propanol to prepare a second intermediate layer coating solution. At this time, chlorinated hydrocarbons such as trichloroethane, trichloroethylene, dichloroethane, dichloromethane and chloroform may be mixed in order to enhance the stability of the coating solution.

At this time, in order to promote crosslinking, the second
It is desirable to make the coating solution for the intermediate layer acidic. For this purpose, an organic acid such as maleic acid, citric acid, tartaric acid, and succinic acid, and an inorganic acid such as boric acid and hypophosphorous acid may be added to the coating solution. The amount of these acidic catalysts added is (a) 0.1% to 10% based on the weight of the N-alkoxymethylated polyamide, or (b) based on the total weight of the N-alkoxymethylated polyamide and the melamine resin. 0.1% to 1
0%.

This second intermediate layer coating solution is coated with a blade,
Coating and drying are performed on the first intermediate layer using a coating method such as knife coating, spray coating, or dip coating. The thickness of the second intermediate layer is preferably from 0.01 μm to 1.0 μm. If it is too thin, the effect of suppressing abnormal images is small, and if it is too thick, the residual potential tends to increase. Further, the drying temperature is preferably a temperature sufficient for the crosslinking of the coating liquid to proceed, that is, 85 ° C. or higher. Drying temperature is 8
When the temperature is lower than 5 ° C., the crosslinking does not proceed completely, the residual alkoxy group increases, and an electrophotographic photoreceptor having high environmental dependency is obtained. The upper limit of the drying temperature is usually about 185 ° C.

According to a fourth aspect of the present invention, there is provided an electrophotographic apparatus comprising the electrophotographic photoreceptor according to the first aspect of the present invention; charging means; and developing means. Is done.

Since the electrophotographic apparatus of the present invention is equipped with the electrophotographic photosensitive member of the present invention, a good image can be provided even when repeatedly used under high temperature, high humidity and low temperature and low humidity.

In recent years, as a charging method for an electrophotographic apparatus, an apparatus using a contact charging system instead of general corona charging has been put to practical use. This charging method has advantages such as simplification of the apparatus and reduction of ozone generated by corona discharge. Conventionally, in the contact charging method, there was a problem that an abnormal image was generated due to discharge destruction of the photoreceptor. However, when the photoreceptor of the present invention is used, the intermediate layer can be made thicker, thereby suppressing the discharge destruction. . Therefore,
An electrophotographic apparatus capable of contact-charging the surface of the photoreceptor with an electric potential of 600 V or more in absolute value and capable of obtaining a good image even when used repeatedly can be provided.

According to a fifth aspect of the present invention, there is provided a process cartridge, which is selected from the electrophotographic photosensitive member according to the first aspect of the present invention, and charging means, image exposing means, developing means and transfer means. A process cartridge comprising at least one means; and being detachable from the main body of the electrophotographic apparatus.

Since the process cartridge of the present invention is equipped with the electrophotographic photosensitive member of the present invention, it can provide a good image even when mounted on an electrophotographic apparatus and repeatedly used under high temperature, high humidity, and low temperature and low humidity.

According to a sixth aspect of the present invention, an electrostatic latent image is formed on the surface of the electrophotographic photosensitive member according to the first aspect of the present invention; and the electrostatic latent image is reversely developed. An electrophotographic process is provided.

In the electrophotographic process of the present invention, since the electrophotographic photosensitive member of the present invention is used, no abnormal image is generated, and a good image can be provided under high temperature, high humidity and low temperature and low humidity.

In the reversal development process, it is better to take a sufficient difference between the dark portion potential corresponding to the charging potential by the charging means and the bright portion potential corresponding to the state where the surface charge has disappeared by exposing the image, to obtain the potential due to environmental changes. There is room for fluctuations, and a good image can be provided. As one of the means, there is a method of increasing the charging potential of the photoreceptor. On the contrary, the higher the charging potential on the surface of the photoreceptor, the higher the rate of occurrence of discharge breakdown. However, the electrophotographic process of the present invention is an electrophotographic process in which an electrostatic latent image having a dark portion potential of 600 V or more in absolute value is formed on the surface of an electrophotographic photoreceptor, and the formed electrostatic latent image is reversely developed. However, large black spots due to discharge breakdown do not occur in the obtained image, and a good image can be provided.

[0054]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The photoreceptor of the present invention and a method for manufacturing the same will be described in detail with reference to the drawings and embodiments. First, the layer configuration of the photoreceptor of the present invention will be described with reference to the drawings.

(1) Layer Configuration of Electrophotographic Photoreceptor FIG. 1 shows an intermediate layer 2 and a photoconductive layer 3 on a conductive support 1.
FIG. 1 is a configuration diagram of an electrophotographic photosensitive member according to the present invention in which are laminated in this order. FIG. 2 is a block diagram of another electrophotographic photoreceptor according to the present invention, in which a first intermediate layer 2a containing an inorganic pigment, a crosslinked N-alkoxymethylated polyamide or N-alkoxy This is a configuration in which a second intermediate layer 2b composed of a crosslinked product of a methylated polyamide and a melamine resin, and a photoconductive layer 3 are provided in this order. FIGS. 3 and 4 are configuration diagrams of a function-separated type electrophotographic photosensitive member in which the photoconductive layer 3 is composed of the charge generation layer 3a and the charge transport layer 3b. The electrophotographic photoreceptor of the present invention is provided on a conductive support 1.
As long as it has one intermediate layer 2, or two layers of the first intermediate layer 2a and the second intermediate layer 2b, and the photoconductive layer 3, it may have other layers other than those described above. The type and configuration of the layers are not restricted at all.

(2) Conductive Support The conductive support 1 may be any conductive support conventionally used in the field of electrophotographic photosensitive members.

(3) Structure of Photoconductive Layer On the intermediate layer 2 or the second intermediate layer 2b formed on the conductive support 1 as described in the section of the means for solving the above problems. According to a conventional method, a photoconductive layer 3 (single-layer type) as shown in FIGS. 1 and 2 or a photoconductive layer (lamination) as shown in FIGS. 3 and 4 comprising a charge generation layer 3a and a charge transport layer 3b Mold). The photoconductive layer included in the photoreceptor of the present invention may be a single layer type or a laminated type. Here, the laminated type will be described first.

(4) Structure of Charge Generating Layer First, the charge generating layer 3a will be described. The charge generation layer 3a is a layer containing a charge generation substance as a main component, and may use a binder resin as needed. As the charge generation substance, an inorganic material and an organic material can be used.

(5) Charge-generating substance used for the charge-generating layer Crystalline selenium, amorphous selenium,
Selenium-tellurium, selenium-tellurium-halogen, selenium-
An arsenic compound, amorphous silicon, or the like can be given. In the case of amorphous silicon, a material obtained by terminating a dangling bond with a hydrogen atom or a halogen atom, or a material obtained by doping a boron atom, a phosphorus atom or the like is preferably used.

On the other hand, known materials can be used as the organic material. For example, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azulhenium salt pigment, methine squaric acid pigment, azo pigment having a carbazole skeleton, azo pigment having a triphenylamine skeleton, azo pigment having a diphenylamine skeleton, dibenzo Azo pigment having a thiophene skeleton, azo pigment having a fluorenone skeleton, azo pigment having an oxadiazol skeleton, azo pigment having a bisstilbene skeleton, azo pigment having a distyryl oxadiazol skeleton, distyryl carbazole skeleton Azo pigments, perylene pigments, anthraquinone pigments or polycyclic quinone pigments, quinone imine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, Jigoido pigments, bisbenzimidazo - such as Le based pigments. These charge generating substances can be used alone or as a mixture of two or more. A phthalocyanine pigment having a phthalocyanine skeleton is preferable from the viewpoint of deterioration due to erosion of various discharge products (such as ozone and NOx products) generated in an actual machine and photosensitivity characteristics. Among metal phthalocyanines, titanyl phthalocyanine is preferred.

Further, if necessary, a low-molecular charge transport material may be added. The low-molecular charge transport material that can be used in combination with the charge generation layer includes a hole transport material and an electron transport material.

Examples of the electron transporting substance include chloranil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone,
2,4,8-trinitrothioxanthone, 2,6,8-
Examples thereof include electron accepting substances such as trinitro-4H-indeno [1,2-b] thiophen-4one and 1,3,7-trinitrodibenzothiophene-5,5-dioxide. These electron transport materials can be used alone or as a mixture of two or more.

As the hole transporting material, the following electron donating materials can be used, and are preferably used. For example, oxazole derivatives, oxadiazol derivatives, imidazole derivatives, triphenylamine derivatives, 9-
(P-diethylaminostyrylanthracene), 1,1
-Bis- (4-dibenzylaminophenyl) propane,
Styryl anthracene, styryl pyrazoline, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives,
Examples include acridine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives. These hole transporting substances can be used alone or as a mixture of two or more kinds.

(5) Binder Resin Used for Charge Generating Layer The binder resin optionally used for the charge generating layer 3a includes polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, and the like.
Acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-
Vinyl carbazole, polyacrylamide and the like are used. These binder resins can be used alone or as a mixture of two or more.

In addition to the above-mentioned binder resin as the binder resin for the charge generation layer, the following general formula (1):
The polymer charge transporting substances of (6), (14), (16), (18) and (20) are preferably used, and the other polymer charge transporting substances include the following. (A) a polymer having a carbazole ring in the main chain and / or the side chain, for example, poly-N-vinyl carbazole,
Compounds described in JP-A-82056, JP-A-54-9632, JP-A-54-11737, and JP-A-4-183719 are exemplified. (B) Polymer having a hydrazone structure in the main chain and / or side chain For example, JP-A-57-78402, JP-A-3-5
Compounds described in JP-A-0555 / 2005 are exemplified. (C) Polysilylene polymer For example, JP-A-63-285552,
Compounds described in JP-A-194497 and JP-A-5-70595 are exemplified. (D) Polymer having a tertiary amine structure in the main chain and / or side chain For example, N-bis (4-methylphenyl) -4-aminopolystyrene, JP-A-1-13061, JP-A-1-13061
-19049, JP-A-1-1728, JP-A-1-105260, JP-A-2-167335, JP-A-5-66598, JP-A-5-403
Compounds described in Japanese Patent Publication No. 50 are exemplified. (E) Other polymers For example, a condensation polymer of formaldehyde of nitropyrene, JP-A-51-73888, JP-A-56-15074
Compounds described in JP-A No. 9 are exemplified.

The polymer having an electron donating group used for the charge generating layer 3a is not limited to the above polymer, but may be a copolymer of a known monomer, a block polymer, a graft polymer, or a star polymer. Alternatively, for example, a crosslinked polymer having an electron donating group as disclosed in JP-A-3-109406 can be used.

(6) Method of Forming Charge Generating Layer The method of forming the charge generating layer includes a vacuum thin film forming method and a casting method from a solution dispersion system.
For the former method, a vacuum evaporation method, a glow discharge polymerization method, an ion plating method, a sputtering method, a reactive sputtering method, a CVD method, or the like is used, and charge generation is performed using the above-mentioned inorganic or organic material. A layer can be formed well. Further, in order to provide a charge generation layer by a casting method described below, the above-mentioned inorganic or organic charge generation material is used together with a binder resin, if necessary, using a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, butanone or the like. -Dispersion with a mill, an attritor, a sand mill, or the like, and the dispersion is appropriately diluted and applied. The coating can be performed by a dip coating method, a spray coating method, a bead coating method, or the like.

The charge generation layer 3 provided as described above
The thickness of a is suitably about 0.01 to 5 μm, and preferably 0.05 to 2 μm.

(7) Structure of the charge transport layer The purpose of the charge transport layer 3b is to hold the charge, and to transfer the charge generated and separated in the charge generation layer 3a by exposure to combine with the charge held. It is a layer to be. High electrical resistance is required to achieve the purpose of retaining the charged charge, and in order to achieve the purpose of obtaining a high surface potential with the retained charged charge, the dielectric constant is low and the charge mobility is low. Good things are required. In addition, good wear characteristics are required for mechanical loads such as contact members, toner development, paper contact, and cleaning using a brush or blade in an actual machine.

The charge transport layer 3b for satisfying these requirements is composed of a charge transport material and a binder resin used as needed. More preferably, it is composed of a polymer charge transport material. The charge transport material and the binder resin can be formed by dissolving or dispersing in a suitable solvent, and then applying and drying the solution. If necessary, a plasticizer, an antioxidant, a leveling agent and the like can be added in an appropriate amount in addition to the charge transport material and the binder resin.

(8) Charge Transport Material Used for Charge Transport Layer The charge transport material includes a hole transport material and an electron transport material. Examples of the electron transporting substance include chloranil, bromanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,
4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophene-4
ON, 1,3,7-trinitrodibenzothiophene-
Electron accepting substances such as 5,5-dioxide are exemplified. These electron transport materials can be used alone or as a mixture of two or more.

Examples of the hole transporting substance include the following electron donating substances, and are preferably used. For example, oxazole derivatives, oxadiazol derivatives, imidazole derivatives, triphenylamine derivatives, 9-
(P-diethylaminostyrylanthracene), 1,1
-Bis- (4-dibenzylaminophenyl) propane,
Styryl anthracene, styryl pyrazoline, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives,
Examples include acridine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives. These hole transporting substances can be used alone or as a mixture of two or more kinds.

(9) Binder Resin Used for Charge Transporting Layer The binder resin used if necessary includes polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, and styrene-maleic anhydride copolymer. Coalescence, polyethylene, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyacrylate resin, methacrylic resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl Formal, polyacrylamide, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, alkyd resin, etc. A thermoplastic resin or a thermosetting resin is used.

(10) Binder resin used as a charge transporting material for use in the charge transporting layer In addition, a polymer charge transporting material having both a function as a charge transporting material and a function as a binder resin is preferably used in the charge transporting layer. Is done. The charge transport layer composed of these polymeric charge transport materials has excellent abrasion resistance. The following general polymer substances can be used. (A) Polymer having a carbazole ring For example, poly-N-vinyl carbazole,
No. 82056, JP-A-54-9632, JP-A-54-11737, JP-A-4-175337, JP-A-4-183719, JP-A-6-23
Compounds described in JP-A-4841 are exemplified. (B) Polymer having a hydrazone structure For example, JP-A-57-78402, JP-A-61-78402
JP-A-20953, JP-A-61-296358,
JP-A-1-134456, JP-A-1-17916
No. 4, JP-A-3-180851, JP-A-3-180851
180852, JP-A-3-50555, JP-A-5-310904, JP-A-6-234840
And the like. (C) Polysilylene polymer For example, JP-A-63-285552,
88461, JP-A-4-264130, JP-A-4-26
4131, JP-A-4-264132, JP-A-4-264
133 and the compounds described in JP-A-4-289867. (D) Polymer having a triarylamine structure For example, N-bis (4-methylphenyl) -4-aminopolystyrene, JP-A-1-134457, JP-A-2-282264, JP-A-2-304456 Gazette, JP-A-4-1330065, JP-A-4-133
066, JP-A-5-40350, JP-A-5-500
Compounds described in JP-A-202135 are exemplified. (E) Other polymers For example, a condensation polymer of formaldehyde of nitropyrene, JP-A-51-73888, JP-A-56-15074
9, JP-A-6-234836 and JP-A-6-34836.
Compounds described in JP-A-234837 are exemplified.

The polymer having an electron donating group used for the charge transporting layer is not limited to the above polymer, but may be a copolymer of a known monomer, a block polymer, a graft polymer, a star polymer, or the like. It is also possible to use, for example, a crosslinked polymer having an electron donating group as disclosed in JP-A-3-109406.

Further, polycarbonates, polyurethanes, polyesters, and the like having a triarylmine structure, which are more useful as a polymer charge transporting material used in the charge transporting layer,
Examples of the polyether include the compounds described below. For example, Japanese Patent Application Laid-Open No.
-13061, JP-A-64-19049,
JP-A-4-11627, JP-A-4-225014
JP, JP-A-4-230767, JP-A-4-3767
20420, JP-A-5-232727, JP-A-7-56374, JP-A-9-127713, JP-A-9-222740, JP-A-9-26
No. 5197, Japanese Unexamined Patent Application Publication No. 9-211877, Japanese Unexamined Patent Application Publication No. 9-304956, and the like.

(11) Polycarbonate used for charge transport layer: General formula (1)

Further, examples of the polycarbonate having a branched chain having a triarylamine structure, which is more useful as a polymer charge transport material used in the charge transport layer, include the following. The polycarbonate having a triarylamine structure in a branched chain refers to a polymer structure in which one aryl group of the triarylamine structure is branched from the main chain of the polycarbonate via a bonding group or not. As the polymer charge transporting material used in the present invention, the following general formulas (1), (6), (14),
Polycarbonates having a triarylamine structure represented by (16), (18) or (20) in a branched chain are effectively used. The following general formulas (1), (6), (14),
The polymer charge transport materials represented by (16), (18) and (20) are exemplified below, and specific examples are shown.

Formula (1)

Embedded image In the formula, R ₁ , R ₂ and R ₃ are each independently a substituted or unsubstituted alkyl group or a halogen atom, R ₄ is a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₅ and R ₆ are substituted or unsubstituted. The substituted aryl group, o, p, and q are each independently, an integer of 0 to 4, k, j represents a composition,
0.1 ≦ k ≦ 1, 0 <j ≦ 0.9, n represents the number of repeating units and is an integer of 5 to 5000. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula (2).

Embedded image In the formula, R ₁₀₁ and R ₁₀₂ each independently represent a substituted or unsubstituted alkyl group, aryl group or halogen atom.
l and m are integers from 0 to 4, Y is a single bond, and has 1 to 1 carbon atoms.
2 linear, branched or cyclic alkylene group, -O
-, - S -, - SO -, - SO 2 -, - CO -, - CO
—O—Z—O—CO— (wherein, Z represents an aliphatic divalent group) or the following general formula (3)

Embedded image (In the formula, a represents an integer of 1 to 20, b represents an integer of 1 to 2000, and R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or aryl group.) Here, R ₁₀₁ and R ₁₀₂ and R ₁₀₃ and R ₁₀₄ may be the same or different.

Specific Examples of General Formula (1) R ₁ , R ₂ , and R ₃ each independently represent a substituted or unsubstituted alkyl group or a halogen atom. Specific examples thereof include the following. Yes, they can be the same or different.

The alkyl group is preferably C ₁ -C ₁₂
In particular, it is a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group (representing 1 to 12 carbon atoms), and these alkyl groups are furthermore a fluorine atom, a hydroxyl group,
Cyano group, C ₁ -C ₄ alkoxy group, phenyl group, or halogen atom, C ₁ -C ₄ alkyl group or C ₁ -C ₄
It may contain a phenyl group substituted by a C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl,
n-butyl group, i-butyl group, trifluoromethyl group,
2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group,
4-chlorobenzyl, 4-methylbenzyl, 4-methoxybenzyl, 4-phenylbenzyl and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

R ₄ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and specific examples of the alkyl group are the same as those described above for R ₁ , R ₂ and R ₃ . R ₅ ,
R ₆ represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] cycloheptenylidenephenyl group, and a non-fused polycyclic group such as a biphenylyl group and a terphenylyl group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The above aryl group may have the following groups as substituents. (A) a halogen atom, a trifluoromethyl group, a cyano group, or a nitro group; (B) Examples of the alkyl group include the same groups as those described above for R ₁ , R ₂ and R ₃ . (C) As the alkoxy group (-OR ₁₀₅ ), R ₁₀₅ represents the alkyl group defined in (b). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like. (D) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. This is C ₁ -C ₄
Or a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be (E) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (F) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (b). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N-dibenzylamino group. (G) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X in the general formula (1) represents the following general formula (4)
When a diol compound having a triarylamino group is polymerized by a phosgene method, a transesterification method, or the like, the diol compound is introduced into the main chain by using a diol compound represented by the following general formula (5) in combination. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group represented by the following general formula (4) and a bischloroformate derived from the following general formula (5). In this case, the polycarbonate produced is an alternating copolymer.

[0088]

Embedded image

[0089]

Embedded image

The following are specific examples of the diol compound of the general formula (5). 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1,
3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, diethylene glycol, triethylene glycol,
Examples thereof include aliphatic diols such as polyethylene glycol and polytetramethylene ether glycol, and cyclic aliphatic diols such as 1,4-cyclohexanediol, 1,3-cyclohexanediol, and cyclohexane-1,4-dimethanol.

The diol having an aromatic ring includes
4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2 -Bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-
Bis (4-hydroxyphenyl) cyclopentane, 2,
2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylsulfone,
4,4′-dihydroxydiphenylsulfoxide, 4,
4′-dihydroxydiphenyl sulfide, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl oxide, 2,
2-bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) xanthene, ethylene glycol-bis (4-hydroxybenzoate), Examples thereof include diethylene glycol-bis (4-hydroxybenzoate), triethylene glycol-bis (4-hydroxybenzoate) 1,3-bis (4-hydroxyphenyl) -tetramethyldisiloxane, and phenol-modified silicone oil.

(12) Polycarbonate used for charge transport layer: General formula (6) General formula (6)

Embedded image In the formula, R ₇ and R ₈ are a substituted or unsubstituted aryl group,
Ar ₁ , Ar ₂ and Ar ₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula (1).

Specific examples of the general formula (6) Specific examples of R ₇ and R ₈ include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] cycloheptenylidenephenyl group, biphenylyl group, terphenylyl group as a non-fused polycyclic group, or the following general formula (7).

Embedded image Here, W is -O -, - S -, - SO -, - SO 2 -,
—CO— and a divalent group represented by the following structural formulas (8) to (11).

Embedded image

Embedded image

Embedded image

Embedded image

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₁ , Ar ₂ and Ar ₃ include the divalent groups of the aryl groups represented by R ₇ and R ₈ , which may be the same or different.

The above aryl group and arylene group may have the following groups as substituents. Further, these substituents are represented as specific examples of R ₁₀₆ , R ₁₀₇ and R _{108 in} the above general formula. (A) a halogen atom, a trifluoromethyl group, a cyano group, or a nitro group; (B) The alkyl group is preferably a C ₁ -C _12, particularly a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are furthermore preferably fluorine atoms. atom, a hydroxyl group, a cyano group, an alkoxy group of C ₁ -C _4, containing a phenyl group or a halogen atom, C ₁ -C phenyl group substituted by ₄ alkyl or alkoxy group of C ₁ -C _4, Is also good. Specifically, methyl, ethyl, n-propyl, i-propyl, t-
Butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl group,
2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4
-Methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like. The (c) an alkoxy group (-OR _109), R ₁₀₉ represents an alkyl group as defined (b). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like. (D) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. This is C ₁ -C ₄
Or a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be (E) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (F) a substituent represented by the following general formula (12).

Embedded image In the formula, R ₁₁₀ and R ₁₁₁ each independently represent an alkyl group or an aryl group defined in (b), and examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group, and these are C _{1 to} C ₄ alkoxy groups, C ₁ -C ₄
May be contained as a substituent. Further, a ring may be formed together with a carbon atom on the aryl group. Specifically, a diethylamino group, N-
Examples include a methyl-N-phenylamino group, an N-diphenylamino group, an N-di (p-tolyl) amino group, a dibenzylamino group, a piperidino group, a morpholino group, and a uroridyl group. (G) An alkylenedioxy group or an alkylenedithio group such as a methylenedioxy group or a methylenedithio group.

X in the general formula (6) is represented by the following general formula (1)
When the diol compound having a triarylamino group of 3) is polymerized by a phosgene method, a transesterification method or the like, the diol compound is introduced into the main chain by using a diol compound of the following general formula (5) in combination. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. X is a diol compound having a triarylamino group represented by the following general formula (13) and a diol compound represented by the following general formula (5)
Is also introduced into the repeating unit by a polymerization reaction with bischloroformate derived from In this case, the polycarbonate produced is an alternating copolymer.

Embedded image X in the diol compound of the general formula (5) is the same as in the general formula (1).

(13) Polycarbonate used for charge transport layer: General formula (14) General formula (14)

Embedded image In the formula, R ₉ and R ₁₀ are a substituted or unsubstituted aryl group,
Ar ₄ , Ar ₅ and Ar ₆ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula (1).

Specific examples of the general formula (14) Specific examples of R ₉ and R ₁₀ include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] cycloheptenylidenephenyl group, and a non-fused polycyclic group such as a biphenylyl group and a terphenylyl group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₄ , Ar ₅ and Ar ₆ include the divalent groups of the aryl groups represented by R ₉ and R ₁₀ , which may be the same or different. The above-mentioned aryl group and arylene group may have the following groups as substituents. (A) a halogen atom, a trifluoromethyl group, a cyano group, or a nitro group; (B) The alkyl group is preferably a C ₁ -C _12, particularly a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are furthermore preferably fluorine atoms. atom, a hydroxyl group, a cyano group, an alkoxy group of C ₁ -C _4, containing a phenyl group or a halogen atom, C ₁ -C phenyl group substituted by ₄ alkyl or alkoxy group of C ₁ -C _4, Is also good. Specifically, methyl, ethyl, N-propyl, i-propyl, t-
Butyl group, s-butyl group, N-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl group,
2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4
-Methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like. (C) As the alkoxy group (-OR ₁₁₂ ), R ₁₁₂ represents the alkyl group defined in (b). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like. (D) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. This is C ₁ -C ₄
Or a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group and the like can be mentioned. Can be (E) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (F) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (b). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N-dibenzylamino group. (G) Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X in the general formula (14) represents the following general formula (1)
When the diol compound having a triarylamino group of 5) is polymerized by a phosgene method, a transesterification method, or the like, the diol compound is introduced into the main chain by using the diol compound of the following general formula (5) in combination. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. Alternatively, the diol compound having a triarylamino group represented by the following general formula (15) is introduced into the repeating unit by a polymerization reaction with a bischloroformate derived from the following general formula (5). In this case, the polycarbonate produced is an alternating copolymer.

[0105]

Embedded image X in the diol compound of the general formula (5) is the same as in the general formula (1).

(14) Polycarbonate used for charge transport layer: General formula (16) General formula (16)

Embedded image In the formula, R ₁₁ and R ₁₂ are a substituted or unsubstituted aryl group,
Ar ₇ , Ar ₈ , and Ar ₉ are the same or different arylene groups, and s represents an integer of 1 to 5. X, k, j and n are the same as in the case of the general formula (1).

Specific examples of the general formula (16) R ₁₁ and R _{12 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different. Good.

Examples of the aromatic hydrocarbon group include a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] cycloheptenylidenephenyl group, and a non-fused polycyclic group such as a biphenylyl group and a terphenylyl group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₇ , Ar ₈ and Ar ₉ include the divalent groups of the aryl groups represented by R ₁₁ and R ₁₂ , which may be the same or different.

The above aryl group and arylene group are represented by (a) to (g) described in the description of the above general formula (14).
May be present as a substituent.

X in the general formula (16) represents the following general formula (1)
When the diol compound having a triarylamino group 7) is polymerized by a phosgene method, a transesterification method, or the like, the diol compound is introduced into the main chain by using the diol compound of the following general formula (5) in combination. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. X is a diol compound having a triarylamino group represented by the following general formula (17) and a diol compound represented by the following general formula (5)
Is also introduced into the repeating unit by a polymerization reaction with bischloroformate derived from In this case, the polycarbonate produced is an alternating copolymer.

[0113]

Embedded image X in the diol compound of the general formula (5) is the same as in the general formula (1).

(15) Polycarbonate used for charge transport layer: General formula (18) General formula (18)

Embedded image In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are a substituted or unsubstituted aryl group, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆ are the same or different arylene groups, Y ₁ , Y ₂ and Y ₃ are A single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, and a vinylene group may be the same or different. X, k, j and n are
This is the same as in the case of the general formula (1).

Specific examples of the general formula (18) Specific examples of R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] cycloheptenylidenephenyl group, and a non-fused polycyclic group such as a biphenylyl group and a terphenylyl group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

Further, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆
Examples of the arylene group represented by are the divalent groups of the above aryl groups represented by R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ ;
They may be the same or different.

The above aryl group and arylene group are represented by (a) to (d) described in the description of the above general formula (14).
May be present as a substituent.

Y ₁ , Y ₂ and Y ₃ are a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, a vinylene group, And may be the same or different.

Examples of the alkylene group include those represented by the above general formula (1)
It represents a divalent group derived from the alkyl group shown in (b) described in the description of 4). Specifically, methylene group, ethylene group, 1,3-propylene group, 1,4-butylene group, 2-methyl-1,3-propylene group, difluoromethylene group, hydroxyethylene group, cyanoethylene group,
Methoxyethylene group, phenylmethylene group, 4-methylphenylmethylene group, 2,2-propylene group, 2,2-
Examples thereof include a butylene group and a diphenylmethylene group.

Examples of the cycloalkylene group include a 1,1-cyclopentylene group, a 1,1-cyclohexylene group,
Examples thereof include a 1-cyclooctylene group.

Examples of the alkylene ether group include a dimethylene ether group, a diethylene ether group, an ethylene methylene ether group, a bis (triethylene) ether group, and a polytetramethylene ether group.

X in the general formula (18) represents the following general formula (1)
When the diol compound having a triarylamino group of 9) is polymerized by a phosgene method, a transesterification method, or the like, the diol compound is introduced into the main chain by using a diol compound of the following general formula (5) in combination. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. X represents a diol compound having a triarylamino group represented by the following general formula (19) and a diol compound represented by the following general formula (5)
Is also introduced into the repeating unit by a polymerization reaction with bischloroformate derived from In this case, the polycarbonate produced is an alternating copolymer.

[0125]

Embedded image X in the diol compound of the general formula (5) is the same as in the general formula (1).

(15) Polycarbonate used for charge transport layer: General formula (20) General formula (20)

Embedded image In the formula, R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅ are a substituted or unsubstituted aryl group, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ , Ar ₂₈
Represents the same or different arylene groups. X, k, j and n are the same as in the case of the general formula (1).

Specific examples of the general formula (20) R ₂₂ , R ₂₃ , R ₂₄ and R _{25 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following. May or may not be.

Examples of the aromatic hydrocarbon group include a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] cycloheptenylidenephenyl group, and a non-fused polycyclic group such as a biphenylyl group and a terphenylyl group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ and Ar ₂₈ include R ₂₂ ,
The divalent groups of the above-mentioned aryl groups represented by R ₂₃ , R ₂₄ and R ₂₅ are mentioned, and may be the same or different.

The above aryl group and arylene group are represented by (a) to (g) described in the description of the above formula (14).
May be present as a substituent.

X in the general formula (20) represents the following general formula (2)
When the diol compound having a triarylamino group of 1) is polymerized by a phosgene method, a transesterification method, or the like, the diol compound is introduced into the main chain by using the diol compound of the following general formula (5) in combination. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. X represents a diol compound having a triarylamino group represented by the following general formula (21) and a diol compound represented by the following general formula (5)
Is also introduced into the repeating unit by a polymerization reaction with bischloroformate derived from In this case, the polycarbonate produced is an alternating copolymer.

[0133]

Embedded image

Embedded image X in the diol compound of the general formula (5) is the same as in the general formula (1).

Other polycarbonates having a triarylamine structure in the branched chain include those described in JP-A-6-234.
JP-A-838, JP-A-6-234839, JP-A-6-295077, JP-A-7-325409, JP-A-9-297419, JP-A-9-807
No. 83, JP-A-9-80784, JP-A-9-80784
Compounds described in 80772, JP-A-9-265201 and the like are exemplified.

(16) Solvents and Additives Used for Charge Transport Layer As the solvent for preparing the coating solution for the charge transport layer, tetrahydrofuran, dioxane, toluene, monochlorobenzene, dichloroethane, methylene chloride and the like are used.

It is appropriate that the thickness of the charge transport layer 3b is about 5 to 100 μm. However, when the thickness is 10 μm to 22 μm, image characteristics such as reproducibility of fine lines and fine dots are further improved. Further, a plasticizer, an antioxidant, a leveling agent, a low-μ imparting agent, and the like may be added to the charge transport layer.

As the plasticizer, those used as general plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount of the plasticizer is suitably about 0 to 30% by weight based on the binder resin. is there.

Antioxidants include phenol-based, quinone-based,
Those used as antioxidants for general resins such as amine-based, sulfur-based, and phosphorus-based antioxidants can be used as they are, and the amount used is 0 to 30 with respect to the binder resin.
A suitable amount is about weight%.

As the leveling agent, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain are used. About 5% by weight is appropriate.

As the low μ imparting agent, those used as lubricants for general resins such as silicone oil, fluorine resin, natural wax, metal soap and the like used in the above-mentioned leveling agent can be used as they are. Is suitably about 0 to 30% by weight based on the binder resin.

(17) Photoconductive Layer of Single Layer Structure Next, the case where the photoconductive layer 3 has a single layer structure will be described. When a single-layer photoconductive layer is provided by a casting method, it can be formed by dissolving or dispersing a charge-generating substance, a low-molecular-weight substance, a high-molecular charge-transporting substance, and silicone oil in an appropriate solvent, and applying and drying this. The aforementioned materials can be used for the charge generating substance and the charge transporting substance.

Further, a plasticizer can be added as required. Further, as the binder resin that can be used as needed, in addition to using the binder resin described above for the charge transport layer 3b as it is, a mixture of the binder resin described for the charge generation layer 3a and using it Is also good. The thickness of the single-layer photoreceptor is suitably about 5 to 100 μm, and preferably about 10 to 22 μm.

(18) Protective Layer For the purpose of protecting the photoconductive layer, the electrophotographic photoreceptor of the present invention has
A protective layer may be provided on the photosensitive layer. Materials used for the protective layer include ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether,
Allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallyl sulfone, polybutylene, polybutylene terephthalate, polycarbonate, polyether sulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylbenten, polypropylene, polyphenylene oxide , Polysulfone, polystyrene,
Examples include resins such as AS resin, butadiene-styrene copolymer, polyurethane, polyvinyl chloride, polyvinylidene chloride, and epoxy resin. Other protective layers include fluororesins such as polytetrafluoroethylene, silicone resins, and inorganic materials such as titanium oxide, tin oxide, and potassium titanate dispersed in these resins for the purpose of improving abrasion resistance. Can be added. As a method for forming the protective layer, a normal coating method is employed. The thickness of the protective layer is suitably about 0.1 to 10 μm. In addition to the above, known materials such as aC and a-SiC formed by a vacuum thin film forming method can be used as the protective layer.

(19) Charging Conductive Member Used for Charging Means The charging conductive member used in the electrophotographic apparatus of the present invention includes:
It is arranged in contact with the surface of the photoreceptor, applies an external voltage directly and uniformly to the photoreceptor, and charges the surface of the photoreceptor to a predetermined potential. As such a charging conductive member,
Metals such as aluminum, iron, and copper; conductive polymer materials such as polyacetylene, polypyrrole, and polythiophene;
Use rubber or artificial fiber obtained by dispersing conductive particles such as carbon black or metal in an insulating resin such as polycarbonate, polyvinyl, or polyethylene, or use an insulating resin whose surface is coated with a conductive substance. be able to. Rollers,
Any shape such as a brush, a blade, and a belt may be used. The voltage applied to the charging conductive member may be DC, AC, or DC + AC. The application method may be applied instantaneously, or the applied voltage may be increased stepwise.

(20) Examples and Comparative Examples Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples. Example 1 First, an intermediate layer was formed as follows. Methoxymethylated polyamide (methoxymethylation rate 30 mol%) 73
A part by weight was dissolved in 1000 parts by weight of methanol, and 281.3 parts by weight of surface-untreated rutile-type titanium oxide was added thereto, followed by performing ball mill dispersion for 72 hours. Thereafter, tartaric acid (solid content 10%) dissolved in methanol was added to 36.5.
A coating solution for an intermediate layer was prepared by adding parts by weight. This is applied to an aluminum drum having a diameter of 30 mm and a length of 340 mm,
After drying at 130 ° C. for 20 minutes, an intermediate layer having a thickness of 3.5 μm was formed.

Next, a charge generation layer was formed as follows. Butyral resin SREC BMS (manufactured by Sekisui Chemical) 5
Parts by weight were dissolved in 150 parts by weight of cyclohexanone, and 15 parts by weight of a trisazo pigment represented by the following structural formula (22) was added thereto, followed by dispersion in a ball mill for 72 hours. Further, 210 parts by weight of cyclohexanone was added and dispersed for 5 hours.
This was diluted with cyclohexanone while stirring so that the solid content became 1.0% by weight. The coating solution for the charge generation layer obtained in this way is dip-coated on the intermediate layer,
After drying at 120 ° C. for 10 minutes, a charge generation layer having a thickness of about 0.2 μm was formed.

Next, a charge transport layer was formed as follows. 8.5 parts by weight of a charge transport material of the following structural formula (23),
10 parts by weight of polycarbonate resin Panlite C-1400 (manufactured by Teijin Chemicals) and 0.002 parts by weight of silicone oil KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 85 parts by weight of methylene chloride. The thus-obtained charge transport layer coating solution was dip-coated on the above-mentioned charge generation layer.
After drying for 25 minutes, a charge transport layer having a thickness of 25 μm was formed, and an electrophotographic photosensitive member was produced.

[0148]

Embedded image

The photoreceptor obtained as described above was mounted on a copier Imagio MF-2200 (manufactured by Ricoh Co., Ltd.), and after repeated use in different environments, the obtained image was evaluated. Evaluation environment: 22 ° C / 50% RH, 10 ° C / 15%
RH and 30 ° C./90% RH. Measure the dark area potential (hereinafter referred to as VD) corresponding to the charging potential and the light area potential (hereinafter referred to as VL) corresponding to the potential after image exposure after initial and 10,000 copies (A4 landscape) in each environment. Then, the obtained image was visually evaluated. The measured values and evaluation results are shown in Table 1 described below. The MF-2200 sets the initial VD and the initial VL to -90 when the photoconductor is mounted.
It adjusted so that it might be set to 0V and -200V. It should be noted that the IMAGEO MF-2200 employs a contact type charging means using a roller and a reversal developing method.

Example 2 A photoconductor was prepared in the same manner as in Example 1, except that the pigment to be dispersed in the intermediate layer was changed to 281.3 parts by weight of untreated surface-type titanium oxide and 2 parts by weight of aluminum oxide. Produced. After producing the photoreceptor, the results of environmental tests performed in the same manner as in Example 1 are shown in Table 1 below.

Example 3 A photoconductor was prepared by the same way as that of Example 2 except that A-type titanyl phthalocyanine was used instead of the trisazo pigment of structural formula (22). After producing the photoreceptor, the results of environmental tests performed in the same manner as in Example 1 are shown in Table 1 below.

Comparative Example 1 A photoconductor was prepared in the same manner as in Example 1, except that tartaric acid was not added, the drying temperature was 80 ° C., and the methoxymethylated polyamide was not crosslinked. After producing the photoreceptor, the results of the same environmental tests as in Example 1 are shown in Table 1 below.

[0153]

[Table 1]

In Examples 1 to 3 using the photoreceptor of the present invention, in any environment, images after repeated use were good or had no problem in practical use.
On the other hand, in the photoreceptor of Comparative Example 1 in which the methoxymethylated polyamide was not crosslinked, the image density decreased after repeated use. Further, comparing the VLs after 10,000 copies, it can be seen that in the first to third embodiments, the VL stays at -260 to -285 V, whereas in the first comparative example, the VL greatly varies from -400 to -600 V. Was. Therefore, it can be seen that the photoreceptor of the present invention has reduced environmental dependence and can suppress an increase in the absolute value of the light portion potential due to repeated use, that is, the deterioration of the photoreceptor.

Example 4 First, an intermediate layer was formed as follows. Methoxymethylated polyamide (methoxymethylation rate 13 mol%) 73
Parts by weight of 665 parts by weight of methanol and 285 parts by weight of n
-Butanol, and 560 parts by weight of a surface-untreated rutile-type titanium oxide was added thereto, followed by ball mill dispersion for 90 hours. Thereafter, 22 parts by weight of hypophosphorous acid (solid content: 10%) dissolved in methanol was added to prepare an intermediate layer coating solution. This was applied to an aluminum drum having a diameter of 80 mm and a length of 360 mm, and dried at 125 ° C for 30 minutes to form an intermediate layer having a thickness of 7.0 µm.

Next, a charge generation layer was formed as follows. Butyral resin SREC BMS (manufactured by Sekisui Chemical) 5
Parts by weight were dissolved in 150 parts by weight of cyclohexanone, and 15 parts by weight of the trisazo pigment of the above structural formula (22) was added thereto, followed by dispersion in a ball mill for 72 hours. Further, 210 weight of cyclohexanone was added and dispersed for 5 hours. This was diluted with cyclohexanone while stirring so that the solid content became 1.0% by weight. The coating solution for a charge generation layer obtained in this manner was dip-coated on the intermediate layer,
Drying was performed at 10 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.2 μm.

Further, a charge transport layer was formed as follows. 9.5 parts by weight of a charge transport material of the following structural formula (24),
10 parts by weight of polycarbonate resin Panlite L-1250 (manufactured by Teijin Chemicals) and 0.002 parts by weight of silicone oil KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 85 parts by weight of methylene chloride. The coating solution for a charge transport layer obtained in this manner is applied onto the charge generation layer by dip coating, and dried at 130 ° C. for 20 minutes to form a 20 μm-thick charge transport layer, thereby producing an electrophotographic photoreceptor. did.

[0158]

Embedded image

A photocopier Imagio 420V (manufactured by Ricoh) obtained by modifying the photoreceptor obtained as described above as follows.
And the initial image and 3 in an environment of 20 ° C / 52% RH.
The image after copying 000 sheets (A4 landscape) was visually evaluated. The results are shown in Table 2 below. Details of modification Charging method: Contact charging method using a roller Initial VD: -700 V Initial VL: -150 V Developing bias: -500 V Developing method: Reversal developing method

Example 5 A methoxymethylated polyamide having a methoxymethylation rate of 2
A photoconductor was prepared in the same manner as in Example 4 except that the composition was changed to 0 mol%. After producing the photoreceptor, the result of performing the same image evaluation as in Example 4 is shown in Table 2 below.

Example 6 A photoconductor was prepared in the same manner as in Example 5, except that the drying temperature of the intermediate layer was changed to 95 ° C. After producing the photoreceptor, the result of performing the same image evaluation as in Example 4 is shown in Table 2 below.
It was shown to.

Comparative Example 2 In Example 4, no hypophosphorous acid was added and the drying temperature was 95
A photoreceptor was prepared in exactly the same manner as in Example 4 except that the temperature was set to 0 ° C and the methoxymethylated polyamide was not crosslinked. After producing the photoconductor, the same image evaluation as in Example 4 was performed. The results are shown in Table 2 below.

[0163]

[Table 2]

As is clear from the results in Table 2, Example 4
The photoreceptors of Nos. 1 to 6 of the present invention provided good or practically acceptable images even after repeated use. On the other hand, in the photoreceptor of Comparative Example 2 in which the methoxymethylated polyamide was not crosslinked, the image density was reduced when repeatedly used.
Therefore, it was found that the photoreceptor of the present invention hardly deteriorated even when it was repeatedly used.

Example 7 In Example 5, the support was 30 mm in diameter × 340 m in length.
m aluminum drum and charge transport layer thickness 15 μm
A photoreceptor was produced in exactly the same manner as in Example 5, except that

The photoreceptor obtained as described above was mounted on a copier Imagio MF-250M (manufactured by Ricoh) and charged at 20 ° C./5
In an environment of 2% RH, the images at the initial stage and after 1000 copies (A4 landscape) were visually evaluated. The results of the evaluation are shown in Table 3 below. The MF-250M has an initial VD and an initial VL of -600 when the photoconductor is mounted.
V and −100 V, and the developing bias was further adjusted to −450 V. The MF-250 employs a contact charging means using a roller and a reversal developing method.

Comparative Example 3 The same procedure as in Example 7 was carried out except that no hypophosphorous acid was added and the drying temperature was 90
° C and the methoxymethylated polyamide was not crosslinked. Except for this, the photoconductor was manufactured in the same manner as in Example 7. After producing the photoreceptor, the results of image evaluation performed in the same manner as in Example 7 are shown in Table 3 below.

Comparative Example 4 The same procedure as in Example 7 was carried out except that no hypophosphorous acid was added and the drying temperature was 90.
° C and the methoxymethylated polyamide was not crosslinked. Except for this, the photoconductor was manufactured in the same manner as in Example 7. After producing the photoreceptor, the results of image evaluation performed in the same manner as in Example 7 are shown in Table 3 below.

Comparative Example 5 In Example 7, a coating solution for an intermediate layer was prepared as follows without adding titanium oxide, and the thickness of the intermediate layer was set to 0.3 μm.
A photoconductor was prepared in the same manner as in Example 7 except that 73 parts by weight of methoxymethylated polyamide (methoxymethylation rate: 20 mol%) was dissolved in 154 parts by weight of methanol and 66 parts by weight of n-butanol, and then hypophosphorous acid (solid content: 10% by weight) dissolved in methanol. Was added to obtain a coating liquid for an intermediate layer. After producing the photoreceptor, the results of image evaluation performed in the same manner as in Example 7 are shown in Table 3 below.

Comparative Example 6 An intermediate layer having a thickness of 2.8 μm was formed in the same manner as in Comparative Example 5 without adding titanium oxide. Example 7 except for the intermediate layer
A photoreceptor was produced in the same manner as described above. After producing the photoreceptor, the results of image evaluation performed in the same manner as in Example 7 are shown in Table 3 below.

[0171]

[Table 3]

From the results shown in Table 3, in Example 7 using the photoreceptor of the present invention, a good image was obtained even after repeated use. On the other hand, in Comparative Examples 3 and 4 using an intermediate layer in which the methoxymethylated polyamide was not crosslinked, an abnormal image occurred due to repeated use, and in Comparative Examples 3 and 5 in which the intermediate layer was a thin film, discharge breakdown occurred. I was Further, in Comparative Examples 5 and 6 in which no titanium oxide was added,
An abnormal image occurred due to repeated use of the photoconductor. Therefore, it was found that a highly durable photoconductor was realized by the present invention.

Example 8 First, a first intermediate layer was formed as follows. 150 parts by weight of alkyd resin Veccosol 1307-60EL (solid content 60% by weight) (manufactured by Dainippon Ink and Chemicals), 100 weight parts of melamine resin Super Beckamine L-110-60 (solid content 60% by weight) (manufactured by Dainippon Ink and Chemicals) Was dissolved in 500 parts by weight of methyl ethyl ketone, and 600 parts by weight of titanium oxide powder CR-EL (manufactured by Ishihara Sangyo) was dispersed by a ball mill for 72 hours. Thus, a first intermediate layer coating liquid formed of the inorganic pigment-dispersed thermosetting resin was prepared. This was applied to an aluminum drum having a diameter of 30 mm and a length of 340 mm, dried at 130 ° C. for 20 minutes, and had a thickness of 3.8 μm.
m of the first intermediate layer was formed.

Next, a second intermediate layer was formed as follows. Eighty parts by weight of methoxymethylated polyamide (30% by mole of methoxymethylation) were dissolved in a mixture of 700 parts by weight of methanol and 300 parts by weight of n-butanol. Thereafter, 40.0 parts by weight of tartaric acid (solid content: 10% by weight) dissolved in methanol was added to prepare a second intermediate layer coating liquid. This is applied on the first intermediate layer formed of the above-described inorganic pigment-dispersed thermosetting resin, and dried at 130 ° C. for 20 minutes to form a second intermediate layer having a crosslinked body having a thickness of 0.25 μm. did.

Next, a charge generation layer was formed as follows. Butyral resin SREC BMS (manufactured by Sekisui Chemical) 5
Parts by weight were dissolved in 150 parts by weight of cyclohexanone, 15 parts by weight of the trisazo pigment of the structural formula (22) used in Example 1 was added, and the mixture was dispersed in a ball mill for 72 hours. Further, 210 parts by weight of cyclohexanone was added and dispersed for 5 hours. This was diluted with cyclohexanone while stirring so that the solid content became 1.0% by weight. The thus-obtained coating solution for a charge generation layer is dip-coated on the second intermediate layer, dried at 120 ° C. for 10 minutes, and has a thickness of about 0.2 μm.
Was formed.

Next, a charge transport layer was formed as follows. 9.0 parts by weight of the charge transport material of the structural formula (23) used in Example 1 and polycarbonate resin Panlite C-1
400 (manufactured by Teijin Chemicals) 10 parts by weight, 0.03 parts by weight of 2,5-di-tert-butylhydroquinone, 0.06 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite, silicone oil KF 0.002 parts by weight of -50 (manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 85 parts by weight of methylene chloride. The coating solution for a charge transport layer obtained in this manner is dip-coated on the above-mentioned charge generation layer.
After drying for 0 minutes, a charge transporting layer having a thickness of 18 μm was formed, thereby producing an electrophotographic photoreceptor.

The photoreceptor obtained as described above was mounted on a laser printer SP-90 (manufactured by Ricoh) and charged at 22 ° C. /
In an environment of 50% RH and 10 ° C./15% RH, initial and 5%
Measure VD and VL after printing 10,000 sheets (A4 landscape)
The images were evaluated visually. SP-90 is 22 ° C /
When the photoconductor is mounted in an environment of 50% RH, the initial VD,
The initial VL was adjusted to be -900V and -200V, respectively. Table 4 shows the measured values and the results of the image evaluation.
(Evaluation environment: 22 ° C./50% RH) and Table 5 (Evaluation environment: 10 ° C./15% RH).

Example 9 A photoconductor was prepared in the same manner as that of Example 8 except that the drying temperature of the second intermediate layer was changed to 90 ° C. After producing the photoreceptor, the same test as in Example 8 was performed, and the results are shown in Tables 4 and 5 described below.

Example 10 A photoconductor was prepared in the same manner as in Example 8, except that the thickness of the second intermediate layer was changed to 0.005 μm. After producing the photoreceptor, the same test as in Example 8 was performed, and the results are shown in Tables 4 and 5 described below.

Example 11 Example 8 was repeated except that the thickness of the second intermediate layer was changed to 1.5 μm.
A photoreceptor was produced in exactly the same manner as described above. After producing the photoconductor,
The same test as in Example 8 was performed, and the results are shown in Table 4 below.
And Table 5.

Example 12 The methoxymethylation rate of a methoxymethylated polyamide was 1
A photoconductor was prepared in the same manner as in Example 8, except that 3 mol% of the photoconductor was used. Example 8
The same test was performed, and the results are shown in Tables 4 and 5 below.
It was shown to.

Comparative Example 7 A photoconductor was prepared in the same manner as in Example 8, except that tartaric acid was not added, the drying temperature was 80 ° C., and the methoxymethylated polyamide was not crosslinked. After producing the photoreceptor, the same test as in Example 8 was performed, and the results are shown in Tables 4 and 5 described below.

Comparative Example 8 The procedure of Example 8 was repeated, except that the methoxymethylated polyamide was replaced with polyamide Amilan CM-4000 (copolyamide, manufactured by Toray Industries Inc.), and no tartaric acid was added.
A photoconductor was produced in exactly the same manner as in Example 8. After producing the photoreceptor, the same test as in Example 8 was performed, and the results are shown in Tables 4 and 5 described below.

Comparative Example 9 A photoconductor was prepared in the same manner as in Example 8, except that the second intermediate layer of crosslinked methoxymethylated polyamide was not provided. After producing the photoreceptor, the same test as in Example 8 was performed, and the results are shown in Tables 4 and 5 described below.

[0185]

[Table 4]

[0186]

[Table 5]

Comparing the results of Examples 8 to 12 with the results of Comparative Examples 7 to 9, it was found that in the examples using the photoreceptor of the present invention, the images obtained after repeated use in any environment were good or had no problem in practical use. On the other hand, in the comparative example, an abnormal image was generated after repeated use especially in a low-temperature and low-humidity environment. In Comparative Example 9 in which the second intermediate layer was not provided, soiling occurred in both environments. In addition, comparing the increase of the absolute value of VL after repeated use under each environment of Table 4 and Table 5, the Example shows 10 to 50 V, whereas the intermediate without methoxymethylated polyamide was crosslinked. In Comparative Examples 7 and 8 having layers, 150 V and 10
It was higher than 0V. Therefore, it was found that the photoreceptor of the present invention was highly durable, and was able to suppress an increase in the light portion potential after repeated use.

Example 13 A photoconductor was prepared in the same manner as in Example 8, except that the conductive support was changed to a nickel belt having an inner diameter of 60 mm produced by electroforming. The photoconductor sample thus obtained was evaluated based on the JIS K 5400 grid tape method. In the crosscut tape method, a cut that penetrates the coating film on the test piece and reaches the bare ground is cut in a grid pattern, an adhesive tape is stuck on the crosscut, and the adhesion state of the coating film after peeling is visually observed. It is a method of observing. As a result, the evaluation score is 1
0, each cut was thin and both sides were smooth, indicating that there was no peeling at every intersection of the cut and each square.

Example 14 A photoconductor was prepared in the same manner as in Example 12, except that the conductive support was changed to a nickel belt having an inner diameter of 60 mm produced by electroforming. When the photoreceptor sample thus obtained was evaluated based on the crosscut tape method similar to that in Example 13, the evaluation score was 8, the intersection of the cuts was slightly peeled off, and the square at a glance There was no peeling, and the area of the defective portion was within 5% of the entire square area.

When the results of Examples 13 and 14 are compared,
It can be seen that Example 13 using a methoxymethylated polyamide having a methoxymethylation rate of 30 mol% was less likely to peel off than Example 14 using a methoxymethylated polyamide having a methoxymethylation rate of 13 mol%. It was found that by using a polyamide having a higher methoxymethylation rate, the adhesiveness of each layer forming the photoreceptor was improved, and a photoreceptor having high mechanical strength could be produced.

Example 15 First, a first intermediate layer was formed as follows. Alkyd resin Beccolite M6401-50 (solid content 50% by weight)
Dissolve 150 parts by weight (manufactured by Dainippon Ink and Chemicals) and 85 parts by weight of melamine resin Super Beckamine L-105-60 (solid content 60% by weight) (manufactured by Dainippon Ink and Chemicals) in 500 parts by weight of methyl ethyl ketone and oxidize it. Titanium powder C
R-EL (produced by Ishihara Sangyo) 650 parts by weight with a ball mill
Dispersed for 2 hours. Thus, a first intermediate layer coating liquid composed of a thermosetting resin in which an inorganic pigment was dispersed was prepared. This was applied to an aluminum drum having a diameter of 30 mm and a length of 301 mm, dried at 130 ° C. for 20 minutes, and obtained with a thickness of 3.5 μm.
m of the first intermediate layer was formed.

Next, a second intermediate layer was formed as follows. 50 parts by weight of a methoxymethylated polyamide (a methoxymethylation rate of 32 mol%) and 50 parts by weight of a melamine resin (Sumitex Resin M-3 (solid content: 80% by weight) (manufactured by Sumitomo Chemical Co., Ltd.)) are mixed with 800 parts by weight of methanol and 25 parts by weight.
It was dissolved in 0 parts by weight of the n-butanol mixture. afterwards,
60.0 parts by weight of tartaric acid (solid content: 10% by weight) dissolved in methanol was added to prepare a second intermediate layer coating liquid composed of a crosslinked product. This was applied on the above-mentioned first intermediate layer, dried at 130 ° C. for 20 minutes, and dried in a second layer having a thickness of 0.3 μm.
An intermediate layer was formed.

Next, a charge generation layer was formed as follows. Butyral resin SREC BMS (manufactured by Sekisui Chemical) 5
Parts by weight were dissolved in 150 parts by weight of cyclohexanone, and the trisazo pigment 1 of the structural formula (22) used in Example 1 was added thereto.
5 parts by weight were added, and the mixture was dispersed in a ball mill for 72 hours. Further, 210 parts by weight of cyclohexanone was added and dispersed for 5 hours. This was diluted with cyclohexanone while stirring so that the solid content became 1.0% by weight. The coating solution for a charge generation layer thus obtained was applied onto the second intermediate layer by dip coating and dried at 120 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.3 μm.

Further, a charge transport layer was formed as follows. 9.5 parts by weight of the charge transporting material of the structural formula (24) used in Example 4, polycarbonate resin Panlite C-1
400 (manufactured by Teijin Chemicals) 10 parts by weight, 0.02 parts by weight of 2,5-di-tert-butylhydroquinone, 0.08 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite, silicon 0.002 parts by weight of Oil KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 85 parts by weight of methylene chloride. The thus-obtained coating solution for a charge transport layer was applied onto the charge generation layer by dip coating.
After drying for 20 minutes, a charge transport layer having a thickness of 20 μm was formed, and an electrophotographic photosensitive member was produced.

The photoreceptor obtained as described above was mounted on a facsimile BL-100 (manufactured by Ricoh) at a temperature of 22 ° C./50%.
Initial and 5000 in RH and 10 ° C / 15% RH environment
VD and VL after printing 0 sheets (A4 landscape) were measured, and the image was visually evaluated. BL-100 is 2
Initial V when photoreceptor is mounted in 2 ° C / 50% RH environment
D and the initial VL were adjusted to be -800 V and -200 V, respectively. The measured values and the results of the image evaluation are shown in Table 6 (evaluation environment: 22 ° C./50% RH) and Table 7 (evaluation environment: 10 ° C./15% RH) described later.

Example 16 A photoconductor was prepared in the same manner as that of Example 15 except that the drying temperature of the second intermediate layer was changed to 85 ° C. After producing the photoreceptor, evaluation was performed in the same manner as in Example 15, and the results are shown in Tables 6 and 7 described below.

Example 17 A photoconductor was prepared in the same manner as that of Example 15 except that the thickness of the second intermediate layer was changed to 0.004 μm. After producing the photoreceptor, evaluation was performed in the same manner as in Example 15, and the results are shown in Tables 6 and 7 described below.

Example 18 Example 18 was repeated except that the thickness of the second intermediate layer was changed to 1.7 μm.
In the same manner as in Example 5, a photoconductor was prepared. After producing the photoreceptor, evaluation was performed in the same manner as in Example 15, and the results are shown in Tables 6 and 7 described below.

Example 19 The methoxymethylation rate of a methoxymethylated polyamide was 1
A photoconductor was prepared in the same manner as in Example 15 except that 2.5 mol% of the photoconductor was used. After producing the photoreceptor, evaluation was performed in the same manner as in Example 15, and the results were shown in Table 6 below.
And 7.

Comparative Example 10 A photoconductor was prepared in the same manner as that of Example 15 except that tartaric acid was not added, the drying temperature was 70 ° C., and the methoxymethylated polyamide and the melamine resin were not crosslinked.
After producing the photoreceptor, evaluation was performed in the same manner as in Example 15, and the results are shown in Tables 6 and 7 described below.

Comparative Example 11 A photoconductor was prepared in the same manner as in Example 15 except that polyamide amilan CM-4000 (manufactured by Toray) was used instead of methoxymethylated polyamide, and no tartaric acid was added. After producing the photoreceptor, evaluation was performed in the same manner as in Example 15, and the results are shown in Tables 6 and 7 described below.

Comparative Example 12 A photoconductor was prepared in the same manner as that of Example 15 except that the second intermediate layer composed of a crosslinked product of methoxymethylated polyamide and melamine resin was not provided. After producing the photoreceptor, evaluation was performed in the same manner as in Example 15, and the results are shown in Tables 6 and 7 described below.

[0203]

[Table 6]

[0204]

[Table 7]

The results of Examples 15 to 19 and Comparative Examples 10 to 12 are compared.
While good or problem-free practical images were obtained after repeated use in any of the environments, abnormal images occurred in the comparative examples especially after repeated use in a low-temperature and low-humidity environment. In Comparative Example 12 in which the second intermediate layer was not provided,
Ground fouling occurred in both environments. In addition, in a low-temperature and low-humidity environment shown in Table 7, when the increase in the absolute value of VL after repeated use is compared, the methoxymethylated polyamide and the melamine resin are crosslinked, whereas the Example shows 10 to 80 V. In Comparative Examples 10 and 11 having no intermediate layer,
They were higher than 180V and 150V, respectively. Therefore, it was found that the photoreceptor of the present invention was highly durable, and was able to suppress an increase in the light portion potential after repeated use.

Example 20 A photoconductor was prepared in the same manner as that of Example 15 except that the conductive support was changed to a nickel belt having an inner diameter of 80 mm and manufactured by electroforming. The photoreceptor thus obtained was evaluated on the basis of the same JIS K 5400 grid tape method as in Example 13, and the evaluation score was 10.

Example 21 A photoreceptor was produced in exactly the same manner as in Example 19, except that the conductive support was changed to a nickel belt having an inner diameter of 80 mm produced by electroforming. The photoconductor thus obtained was evaluated on the basis of the same JIS K 5400 grid tape method as in Example 13, and the evaluation score was 8.

When the results of Examples 20 and 21 are compared,
It can be seen that Example 20 using a methoxymethylated polyamide having a methoxymethylation rate of 32 mol% was less likely to peel off than Example 21 using a methoxymethylated polyamide having a methoxymethylation rate of 12.5 mol%. It was found that by using a polyamide having a higher methoxymethylation rate, the adhesiveness of each layer forming the photoreceptor was improved, and a photoreceptor having high mechanical strength could be produced.

Example 22 First, an intermediate layer was formed as follows. Methoxymethylated polyamide (methoxymethylation rate 28 mol%) 30
Parts by weight and methylated melamine resin Super Beckamine L-
Dissolve 50 parts by weight of 105-60 (nonvolatile content 60%) (manufactured by Dainippon Ink and Chemicals) in 500 parts by weight of methanol,
250 parts by weight of surface-untreated titanium oxide CREL (purity: 99.7% by weight) (manufactured by Ishihara Sangyo) was added thereto, and dispersed by a ball mill for 72 hours. Thereafter, 36.0 parts by weight of tartaric acid (solid content: 10%) dissolved in methanol was added to prepare an intermediate layer coating solution. This is 30 mm diameter x 3 length
The composition was applied to a 40 mm aluminum drum and dried at 130 ° C. for 25 minutes to form an intermediate layer having a thickness of 7.0 μm. Next, a charge generation layer was formed as follows. 5 parts by weight of butyral resin SREC BMS (manufactured by Sekisui Chemical) is dissolved in 150 parts by weight of cyclohexanone, and 15 parts by weight of the trisazo pigment of the structural formula (22) used in Example 1 is added thereto. Done. Further, 210 parts by weight of cyclohexanone was added and dispersed for 5 hours. This was diluted with cyclohexanone while stirring so that the solid content became 1.0% by weight. The thus-obtained coating solution for a charge generation layer was dip-coated on the above-mentioned intermediate layer,
Drying was performed at 10 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.3 μm.

Next, a charge transport layer was formed as follows. 9.0 parts by weight of the charge transport material of the structural formula (23) used in Example 1 and polycarbonate resin Panlite C-1
10.0 parts by weight of 400 (manufactured by Teijin Chemicals) and 0.002 parts by weight of silicone oil KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 85 parts by weight of methylene chloride. The thus-obtained coating solution for a charge transport layer is dip-coated on the charge generation layer and dried at 130 ° C. for 20 minutes to form a charge transport layer having a thickness of 26 μm, thereby producing an electrophotographic photoreceptor. did.

The photoreceptor obtained as described above was mounted on a copier Imagio MF-200 (manufactured by Ricoh Co., Ltd.), and after repeated use in different environments, the obtained image was evaluated. Evaluation environment: 22 ° C / 50% RH, 10 ° C / 15%
RH and 30 ° C./90% RH. VD and VL were measured initially and after copying 12,000 sheets (A4 landscape) in each environment, and the obtained images were visually evaluated. The measured values and the results of the image evaluation are shown in Tables 8 to 10 described below.
It was shown to. The MF-200 sets the initial VD and the initial VL to -850 V and -2 when the photoconductor is mounted.
It was adjusted to be 00V. The IMAGEO MF-200 employs a contact charging means using a roller and a reversal developing method.

Example 23 The surface-untreated titanium oxide was converted to KA-20 (purity: 96.0%).
A photoconductor was prepared in the same manner as in Example 22 except that the photoconductor was changed to (Titanium Industry). The same test as in Example 22 was performed on the obtained photoconductor, and the results are shown in Tables 8 to 1 described below.
0.

Comparative Example 13 A photoconductor was prepared in the same manner as that of Example 22 except that tartaric acid was not added, the drying temperature was 95 ° C., and the methoxymethylated polyamide and the melamine resin were not crosslinked. The same test as in Example 22 was performed on the obtained photoconductor, and the results are shown in Tables 8 to 10 described below.

[0214]

[Table 8]

[0215]

[Table 9]

[0216]

[Table 10]

Examples 22 and 2 using the photosensitive member of the present invention
In No. 3, in any environment, the image after repeated use was good or had no problem in practical use. On the other hand, in the photoreceptor of Comparative Example 13 in which the methoxymethylated polyamide was not crosslinked, the image density decreased in all environments after repeated use. Further, comparing the VLs after 12,000 copies, in Examples 22 and 23, it was -220 to -285 V, which was within a certain range in all environments, whereas in Comparative Example 13, it was -38.
It turned out that it fluctuated by 0--550V and environment. Therefore, it can be seen that the photoreceptor of the present invention has reduced environmental dependence, and can suppress an increase in the light portion potential, that is, deterioration of the photoreceptor due to repeated use. Further, comparing the results of Example 22 and Example 23, it was found that Example 22 having higher purity of titanium oxide gave better results.

Example 24 First, an intermediate layer was formed as follows. Methoxymethylated polyamide (methoxymethylation rate 33 mol%) 49
Parts by weight and butylated melamine resin Super Beckamine G-
821-60 (solid content 60%) (Dainippon Ink & Chemicals) 3
5 parts by weight are dissolved in 360 parts by weight of methanol and 100 parts by weight of n-butanol, and 420 parts by weight of untreated surface titanium oxide TA-300 (purity: 98.0% by weight) (manufactured by Fuji Titanium Industry) are dissolved therein. In addition, ball mill dispersion was performed for 100 hours using a ball mill. Thereafter, 22 parts by weight of hypophosphorous acid (solid content: 10%) dissolved in methanol was added to prepare a coating solution for an intermediate layer. This was applied to an aluminum drum having a diameter of 80 mm and a length of 360 mm,
After drying for a minute, an intermediate layer having a thickness of 3.5 μm was formed.

Next, a charge generation layer was formed as follows. Butyral resin Esrec BMS (manufactured by Sekisui Chemical) 4
Parts by weight were dissolved in 150 parts by weight of cyclohexanone, and the trisazo pigment 1 of the structural formula (22) used in Example 1 was added thereto.
6 parts by weight were added, and the mixture was dispersed in a ball mill for 72 hours. Further, 210 parts by weight of cyclohexanone was added and dispersed for 5 hours. This was diluted with cyclohexanone while stirring so that the solid content became 1.0% by weight. The coating solution for a charge generation layer thus obtained was applied onto the above-mentioned intermediate layer by dip coating, and dried at 120 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.3 μm.

Further, a charge transport layer was formed as follows. 9.5 parts by weight of the charge transporting material of the structural formula (24) used in Example 4, a polycarbonate resin Panlite K-1
300 (manufactured by Teijin Chemicals) 10 parts by weight, silicone oil KF
0.002 parts by weight of -50 (manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 85 parts by weight of methylene chloride. The charge transport layer coating solution obtained in this way is dip-coated on the charge generation layer,
After drying at 130 ° C. for 20 minutes, a charge transport layer having a thickness of 20 μm was formed, and an electrophotographic photosensitive member was produced.

A photocopier Imagio 420V (manufactured by Ricoh Co., Ltd.) was obtained by modifying the photoreceptor obtained as described above as follows.
Mounted on. And under the environment of 20 ° C / 52% RH,
The initial image and the image after 3000 sheets (A4 landscape) were visually evaluated. The results are shown in Table 11 below. Details of modification Charging method: Contact charging method using a roller Initial VD: -600V Initial VL: -150V Developing bias: -400V Developing method: Reversal developing method

Example 25 A photoconductor was prepared in the same manner as that of Example 24 except that the methoxymethylated polyamide was changed to a methoxymethylated polyamide having a methoxymethylation ratio of 14 mol%. After producing the photoreceptor, the image was evaluated in the same manner as in Example 24, and the results were shown in Table 11 below.
It was shown to.

Example 26 Example 24 was repeated except that the drying temperature of the intermediate layer was changed to 90 ° C.
A photoreceptor was produced in exactly the same manner as described above. After producing the photoconductor,
The image was evaluated in the same manner as in Example 24, and the results are shown in Table 11 below.

Comparative Example 14 A photoconductor was prepared in the same manner as that of Example 25 except that hypophosphorous acid was not added, the drying temperature was 90 ° C., and the methoxymethylated polyamide and the melamine resin were not crosslinked. After producing the photoreceptor, the image was evaluated in the same manner as in Example 24, and the results are shown in Table 11 below.

[0225]

[Table 11]

Examples 24 to 26 using the photosensitive member of the present invention
In the test, images obtained after repeated use were good or had no problem in practical use. On the other hand, in the photoconductor of Comparative Example 14 in which the methoxymethylated polyamide is not cross-linked,
After repeated use, the image density decreased. Therefore, it can be seen that the photoreceptor of the present invention has suppressed photoreceptor deterioration due to repeated use. Further, Example 24 having a methoxymethylation ratio of 33 mol% and Example 2 having a methoxy methylation ratio of 14 mol%
Comparing Example 5, it was found that Example 24 having a methoxymethylation ratio of 15 mol% or more had higher durability.

Example 27 A photoconductor was prepared in the same manner as in Example 24 except that the support was changed to an aluminum drum having a diameter of 30 mm and a length of 340 mm, and the thickness of the charge transport layer was changed to 15 μm.

The photosensitive member obtained as described above was mounted on a copier Imagio MF-2200M (manufactured by Ricoh), and
In an environment of 0 ° C./52% RH, the initial and 1000
The image after copying (A4 landscape) was visually evaluated.
The results of the image evaluation are shown in Table 12 below. Note that M
The F-2200M sets the initial VD and the initial VL to -600 V and -100 V, respectively, when the photoconductor is mounted,
Further, the developing bias was adjusted to be -450V.
The MF-2200 uses a contact charging unit using a roller, and employs a reversal developing method.

Comparative Example 15 In Example 27, the drying temperature was 95 ° C. without adding hypophosphorous acid, and the methoxymethylated polyamide and the melamine resin were not crosslinked. Further, the thickness of the intermediate layer is set to 0.3 μm.
m. Except for this, the photoconductor was manufactured in the same manner as that of Example 27. After producing the photoreceptor, the image after repeated use was evaluated in the same manner as in Example 27. The results are shown in Table 12 below.

Comparative Example 16 In Example 27, the drying temperature was 95 ° C. without adding hypophosphorous acid, and the methoxymethylated polyamide and the melamine resin were not crosslinked. Further, the thickness of the intermediate layer is set to 7.0 μm.
m. Except for this, the photoconductor was manufactured in the same manner as that of Example 27. After producing the photoreceptor, the image after repeated use was evaluated in the same manner as in Example 27. The results are shown in Table 12 below.

Comparative Example 17 In Example 27, the intermediate layer did not contain titanium oxide and was made only of resin. The thickness of the intermediate layer was 0.3 μm. Except for this, the photoconductor was manufactured in the same manner as that of Example 27. After producing the photoreceptor, in the same manner as in Example 27,
The image after repeated use was evaluated. The results are shown in Table 12 below.

Comparative Example 18 In Example 27, the intermediate layer did not contain titanium oxide and was made only of resin, and the thickness of the intermediate layer was 2.0 μm.
Except for this, the photoconductor was manufactured in the same manner as that of Example 27. After producing the photoreceptor, the image after repeated use was evaluated in the same manner as in Example 27. The results are shown in Table 12 below.

[0233]

[Table 12]

In Example 27 using the photoreceptor of the present invention,
Good images were obtained after repeated use. On the other hand, in Comparative Examples 15 and 16 in which the methoxymethylated polyamide was not crosslinked, abnormal images occurred after repeated use. Comparative Examples 17 and 1 to which no titanium oxide was added
8, an abnormal image occurred after repeated use. Furthermore, in Comparative Examples 15 and 17 in which the thickness of the intermediate layer was small, discharge breakdown occurred. Therefore, the photoreceptor of the present invention
It can be seen that the deterioration of the photoconductor due to repeated use was suppressed.

Example 28 In this example, a coating solution for an intermediate layer was prepared as follows. Methoxymethylated polyamide fine resin FR-
102 (Methoxymethylation rate 30 mol%) (manufactured by Lead City)
30 parts by weight and 50 parts by weight of a butylated melamine resin Super-Beckamine G-821-60 (nonvolatile content: 60%) (manufactured by Dainippon Ink and Chemicals) are added to 200 parts by weight of methanol, 50 parts by weight.
It was dissolved in a mixed solvent of parts by weight of n-butanol and 250 parts by weight of methyl ethyl ketone, and 250 parts by weight of untreated surface titanium oxide CR-EL (manufactured by Ishihara Sangyo) was added thereto, followed by dispersion in a ball mill for 70 hours. Thereafter, 30.0 parts by weight of hypophosphorous acid (solid content: 10%) dissolved in methanol was added to prepare an intermediate layer coating solution.

The dispersion stability of the intermediate layer coating solution was evaluated by the following method. The particle size distribution of the coating solution immediately after preparation and the particle size distribution of the solution stored only by stirring with a stirrer for 40 days were measured with CAPA-700 (manufactured by Shimadzu Corporation), respectively.
The content of coarse particles having a particle size of 1.0 μm or more was determined. The measurement results are shown in Table 13 described below.

Example 29 Example 2 was repeated, except that 15.0 parts by weight of boric acid (solid content of methanol solution: 10%) was added instead of hypophosphorous acid.
In the same manner as in No. 9, a coating solution for an intermediate layer was prepared. This intermediate layer coating liquid was measured in the same manner as in Example 28 to evaluate the dispersion stability. The results are shown in Table 1 below.
3 is shown.

[0238]

[Table 13]

From the results shown in Table 13, it can be seen from Example 2 that an acid catalyst was added using a mixed solvent of alcohols and ketones of the present invention.
Samples Nos. 8 and 29 had good dispersibility even after storage for 40 days, indicating that the effects of the present invention could be confirmed.

Example 30 A photoreceptor was prepared as follows using the coating solution for the intermediate layer prepared in Example 28, and the coating solution immediately after preparation and the coating solution stored only by stirring with a stirrer for 40 days. . First, each of the two types of intermediate layer coating solutions was applied to an aluminum drum having a diameter of 30 mm and a length of 340 mm,
After drying at 120 ° C. for 20 minutes, an intermediate layer having a thickness of 6.0 μm was formed.

Next, a charge generation layer was formed as follows. 18 parts by weight of the A-type titanyl phthalocyanine pigment were put into a glass pot together with zirconia beads having a diameter of 2 mm, and 350 parts by weight of methyl ethyl ketone were further added.
Ball milling was performed for 5 hours. Thereafter, a resin solution in which 10 parts by weight of polyvinyl butyral resin SREC BX-1 (manufactured by Sekisui Chemical) was dissolved in 600 parts by weight of methyl ethyl ketone was added, and ball milling was further performed for 2 hours to prepare a coating liquid for a charge generation layer. . The coating solution for a charge generation layer obtained in this manner is dip-coated on the above-mentioned intermediate layer, dried at 80 ° C. for 20 minutes, and has a thickness of about 0.3 μm.
Was formed.

Next, a charge transport layer was formed as follows. 9.0 parts by weight of the charge transport material of the structural formula (23) used in Example 1 and polycarbonate resin Panlite C-1
10.0 parts by weight of 400 (manufactured by Teijin Chemicals) and 0.002 parts by weight of silicone oil KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 80 parts by weight of tetrahydrofuran. The coating solution for a charge transport layer thus obtained was applied onto the charge generation layer by dip coating, and dried at 130 ° C. for 20 minutes to form a charge transport layer having a thickness of 28 μm, thereby producing an electrophotographic photoreceptor. .

The photoreceptor thus obtained was mounted on a copier Imagio MF-200 (manufactured by Ricoh), and the initial image and the image after copying 2000 sheets were visually evaluated. The results of the image evaluation are shown in Table 14 below. In addition, Imagio MF-200 has an initial VD and an initial VL
Was adjusted to -950 V and -200 V, respectively, and the developing bias was adjusted to -600 V. The IMAGEO MF-200 employs a contact charging means using a roller and a reversal developing method.

Example 31 A photoreceptor was prepared in the same manner as in Example 30, using the coating solution for the intermediate layer prepared in Example 29 and the coating solution stored only by stirring with a stirrer for 40 days. did. Example 30 With respect to the two types of photoconductors,
Table 14 shows the results of image evaluation performed in the same manner as described above.

[0245]

[Table 14]

From the results shown in Table 14, with the photosensitive members of Examples 30 and 31, good images were obtained after repeated use of the photosensitive members, regardless of which coating solution was used. It was found that the photoreceptor prepared using the intermediate layer coating liquid using the mixed solvent of alcohols and ketones and the acid catalyst of the present invention has high durability and can suppress abnormal images even after repeated use.

Example 32 In this example, a coating solution for an intermediate layer was prepared as follows.
60 parts by weight of copolyamide PLATAMIDM12
76F (manufactured by Elf Atochem Japan) was dissolved in 100 parts by weight of formic acid, and the mixture was stirred at 60 ° C. Next, after dissolving 60 parts by weight of paraformaldehyde in 100 parts by weight of methanol to which alkali was added, the solution was maintained at 60 ° C.
The above polyamide solution was gradually added and stirred for 10 minutes.
Next, 60 parts by weight of methanol was added, and stirring was continued at 60 ° C. for 20 minutes. The obtained reaction solution was poured into 1500 ml of an acetone / water mixture (1: 1), and 30%
Ammonia water was added dropwise to neutralize. The resulting precipitate was washed with water to obtain a polyamide having a methoxymethylation rate of 33 mol%. The obtained methoxymethylated polyamide 4
5 parts by weight and butylated melamine resin Super Beckamine L
25 parts by weight of −110-60 (solid content: 60%) (manufactured by Dainippon Ink and Chemicals) are dissolved in 300 parts by weight of methanol and 150 parts by weight of methyl ethyl ketone, and titanium oxide TA-300 (manufactured by Fuji Titanium Industries) 330 is added thereto. The weight part was added, and the mixture was dispersed by a ball mill for 100 hours. Thereafter, boric acid dissolved in methanol (solid content 1
(0%) was added to obtain a coating solution for an intermediate layer. The methoxymethylation rate was 1 for the sample resin.
A thin film is formed on a rock salt plate using an 8% methanol solution,
The IR absorption spectrum was measured, and the peak ratio of the spectrum was 1
Calculated from 080 cm ^-1 / 1370 cm ^-1 .

The dispersion stability of the intermediate layer coating solution was evaluated by the following method. The particle size distribution of the coating solution immediately after preparation and the particle size distribution of the solution stored only by stirring with a stirrer for 2 months were measured with CAPA-700 (manufactured by Shimadzu Corporation), respectively.
The content of coarse particles having a particle size of 1.0 μm or more was determined. The measurement results are shown in Table 15 described below.

Example 33 In Example 32, the conditions for modifying the polyamide to methoxymethylation were changed to obtain a methoxymethylated polyamide having a methoxymethylation rate of 12 mol%. A coating solution for an intermediate layer was obtained in the same manner as in Example 32 except that the methoxymethylation ratio was changed. The coating solution for the intermediate layer was prepared in Example 3
Measurement for evaluating dispersion stability was performed in the same manner as in Example 2.
The results are shown in Table 15 described below.

Example 34 In Example 32, the conditions for modifying the polyamide to methoxymethylation were changed to obtain a methoxymethylated polyamide having a methoxymethylation rate of 15 mol%. A coating solution for an intermediate layer was obtained in the same manner as in Example 32 except that the methoxymethylation ratio was changed. The coating solution for the intermediate layer was prepared in Example 3
Measurement for evaluating dispersion stability was performed in the same manner as in Example 2.
The results are shown in Table 15 described below.

Example 35 Example 32 was repeated except that the butylated melamine resin was changed to the methylated melamine resin Super Beckamine L-105-60 (solid content: 60%) (manufactured by Dainippon Ink and Chemicals, Inc.). An intermediate layer coating solution was obtained in exactly the same manner. This intermediate layer coating liquid was measured in the same manner as in Example 32 to evaluate the dispersion stability. The results are shown in Table 15 described below.

[0252]

[Table 15]

From the results shown in Table 15, the coating solutions of Examples 32 to 35 did not show a large decrease in dispersibility after storage for 2 months. Therefore, it was found that the coating liquid used in the method for producing a photoreceptor of the present invention had excellent dispersion stability.

Example 36 A photosensitive member was prepared as follows using the coating solution for the intermediate layer prepared in Example 32 and the coating solution immediately after preparation and the coating solution stored only by stirring with a stirrer for 2 months. did. First, each of the two kinds of coating liquids is applied to a diameter of 80 m.
mx 360mm length aluminum drum, 110 ℃
For 30 minutes to form an intermediate layer having a thickness of 4.0 μm.

Next, a charge generation layer was formed as follows. Butyral resin Esrec BMS (manufactured by Sekisui Chemical) 4
Parts by weight were dissolved in 150 parts by weight of cyclohexanone, and 16 parts by weight of the trisazo pigment represented by the structural formula (22) was added thereto and dispersed in a ball mill for 72 hours. Further, 210 parts by weight of cyclohexanone was added and dispersed for 5 hours. This was diluted with cyclohexanone while stirring so that the solid content became 1.0% by weight. The thus-obtained coating solution for a charge generation layer was dip-coated on the above-mentioned intermediate layer,
For 10 minutes to form a charge generation layer having a thickness of about 0.3 μm.

Further, a charge transport layer was formed as follows. 9.5 parts by weight of the charge transport material of the structural formula (23) used in Example 1 and polycarbonate resin Panlite TS-
2050 (manufactured by Teijin Chemicals) 10 parts by weight, silicone oil K
0.002 parts by weight of F-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 85 parts by weight of tetrahydrofuran. The thus-obtained coating solution for a charge transport layer is dip-coated on the charge generation layer and dried at 130 ° C. for 20 minutes to form a charge transport layer having a thickness of 28 μm, thereby producing an electrophotographic photoreceptor. did.

The two types of photoconductors obtained as described above were mounted on a copier Imagio 420V (manufactured by Ricoh) modified as described below, and repeatedly used to evaluate images. The image evaluation was performed by visually observing the initial image and the image after 3000 copies in an environment of 20 ° C./52% RH. The results of the evaluation are shown in Table 16 below. Details of modification Charging method: Contact charging method using rollers Initial VD: -600 V Initial VL: -180 V Developing bias: -400 V Developing method: Reversal developing method

Example 37 The same photosensitive material as in Example 36 was used for the intermediate layer coating liquid prepared in Example 33, except that the coating liquid immediately after preparation and the coating liquid stored only by stirring with a stirrer for 2 months were used. Prepared. Table 16 shows the results of image evaluation of the two types of photoconductors produced in the same manner as in Example 36.

Example 38 The same photosensitive material as in Example 36 was used for the intermediate layer coating solution prepared in Example 34, using the coating solution immediately after preparation and the coating solution stored for 2 months only by stirring with a stirrer. Prepared. Table 16 shows the results of image evaluation of the two types of photoconductors produced in the same manner as in Example 36.

Example 39 The same photosensitive material as in Example 36 was used for the intermediate layer coating liquid prepared in Example 35, except that the coating liquid immediately after preparation and the coating liquid stored for 2 months only by stirring with a stirrer were used. Prepared. Table 16 shows the results of image evaluation of the two types of photoconductors produced in the same manner as in Example 36.

[0261]

[Table 16]

In the measurement of the particle size distribution in the coating solutions of Examples 32 to 35 described above, there was no decrease in dispersibility after storage for 2 months, and Example 3 was actually prepared using those coating solutions.
With the photoconductors of Nos. 6 to 39, even after repeated use, an image having no problem in actual use could be obtained. Therefore, by using the photoreceptor manufacturing method of the present invention, a photoreceptor capable of obtaining a good image can be manufactured even when a coating solution stored for a long time is used.

Example 40 First, an intermediate layer was formed as follows. Methoxymethylated polyamide resin Resin F30K (Methoxymethylation rate 3
0 mol%) (15 parts by weight from Teikoku Chemical Sangyo) and 75 parts by weight of butylated melamine resin Super-Beckamine G-821-60 (60% non-volatile content) (Dainippon Ink and Chemicals)
It was dissolved in a mixed solvent of 50 parts by weight of methanol, 150 parts by weight of n-butanol, and 150 parts by weight of methyl isobutyl ketone, and 200 parts by weight of untreated surface titanium oxide KA-20 (manufactured by Titanium Industries) was added thereto. For 96 hours. Thereafter, 30 parts by weight of boric acid (solid content: 10%) dissolved in methanol was added to prepare an intermediate layer coating solution. This coating solution for the intermediate layer was stored for 3 months only by stirring with a stirrer. This is 30mm diameter
Apply to a 340 mm long aluminum drum,
After drying for 0 minutes, an intermediate layer having a thickness of 3.0 μm was formed.

Next, a charge generation layer was formed as follows. Butyral resin SREC BMS (manufactured by Sekisui Chemical) 5
Parts by weight were dissolved in 150 parts by weight of cyclohexanone, and 15 parts by weight of the trisazo pigment of the structural formula (22) was added thereto, followed by dispersion in a ball mill for 72 hours. Further, 210 parts by weight of cyclohexanone was added and dispersed for 5 hours. This was diluted with cyclohexanone while stirring so that the solid content became 1.0% by weight. The thus-obtained coating solution for a charge generation layer was dip-coated on the above-mentioned intermediate layer,
For 10 minutes to form a charge generation layer having a thickness of about 0.3 μm.

Further, a charge transport layer was formed as follows. 9.0 parts by weight of the charge transporting material of the structural formula (24) used in Example 4, polycarbonate resin Panlite C-1
10.0 parts by weight of 400 (manufactured by Teijin Chemicals) and 0.002 parts by weight of silicone oil KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 85 parts by weight of methylene chloride. The coating solution for a charge transport layer obtained in this manner is dip-coated on the charge generation layer and dried at 130 ° C. for 20 minutes to form a charge transport layer having a thickness of 29 μm, thereby producing an electrophotographic photoreceptor. did.

The photoreceptor obtained as described above was mounted on a copier Imagio MF-2200 (manufactured by Ricoh Co., Ltd.).
In an environment of ° C./52% RH, the images at the initial stage and after 8000 copies (A4 landscape) were visually evaluated. The results of the image evaluation are shown in Table 17 described below. It should be noted that when the photoconductor is mounted, Imagio MF-2200 has an initial V
D and the initial VL are -750V and -200V, respectively.
The developing bias was further adjusted to -500V. The MF-2200 uses a contact charging unit using a roller, and employs a reversal developing method.

Example 41 A photoconductor was prepared in the same manner as that of Example 40 except that the drying condition of the intermediate layer was changed to 95 ° C. for 30 minutes. After producing the photoreceptor, the image after repeated use was evaluated in the same manner as in Example 40. The results are shown in Table 17 below.

Example 42 A photoconductor was prepared in the same manner as that of Example 40 except that the drying condition of the intermediate layer was changed to 185 ° C. for 30 minutes. After producing the photoreceptor, the image after repeated use was evaluated in the same manner as in Example 40. The results are shown in Table 17 below.

[0269]

[Table 17]

From the results in Table 17, it can be seen that the photoreceptor is repeatedly used even when the photoreceptor is manufactured using the coating solution for the intermediate layer after storage for three months by using the method for producing the photoreceptor of the present invention. It was found that the image obtained in this way had no problem in practical use. Furthermore, the drying temperature of the intermediate layer is
Even when the temperature was changed to 95 ° C., 115 ° C., and 185 ° C., it was found that an image having no practical problem could be obtained with the photoreceptor using the coating solution after storage for 3 months.

Example 43 In this example, a coating solution for an intermediate layer was prepared as follows. Methoxymethylated polyamide fine resin FR-
301 (methoxymethylation ratio 20 mol%) (manufactured by Lead City)
30 parts by weight and 50 parts by weight of butylated melamine resin Super-Beckamine G-821-60 (nonvolatile content: 60%) (manufactured by Dainippon Ink and Chemicals) are 200 parts by weight of methanol, 50 parts by weight of n-butanol, 250 parts by weight Was dissolved in a mixed solvent of methyl ethyl ketone, and 250 parts by weight of untreated surface titanium oxide CREL (manufactured by Ishihara Sangyo) was added thereto, followed by dispersion in a ball mill for 72 hours. Thereafter, 60.0 parts by weight of maleic acid (solid content: 10%) dissolved in methanol was added to prepare an intermediate layer coating solution.

The dispersion stability of the coating solution for the intermediate layer was evaluated by the following method. The particle size distribution of the coating solution immediately after preparation and the particle size distribution of the solution stored only by stirring with a stirrer for one month were measured with CAPA-700 (manufactured by Shimadzu Corporation), respectively.
The content of coarse particles having a particle size of 1.0 μm or more was determined. The measurement results are shown in Table 19 described later.

Examples 44 to 48 In place of maleic acid in Example 43, the following Table 1 was used.
A coating solution for an intermediate layer was prepared in the same manner as in Example 43, except that the organic acid shown in 8 was added in the following amount. Measurements for evaluating the dispersion stability of these intermediate layer coating liquids were performed in the same manner as in Example 43. The results are shown in Table 19 below.

[0274]

[Table 18]

[0275]

[Table 19]

From the results shown in Table 19, in Examples 43 to 48 using a mixed solvent of alcohols and ketones, even if an acid catalyst was added, after storage for one month, the dispersibility was the same as that immediately after the preparation. I knew I was doing it.

Example 49 The photoreceptor was prepared as follows by using the coating solution for the intermediate layer prepared in Example 43 and the coating solution immediately after preparation and the coating solution stored for one month only by stirring with a stirrer. did. First, the two kinds of coating liquids were applied to an aluminum drum having a diameter of 30 mm and a length of 340 mm, and dried at 120 ° C. for 20 minutes to form an intermediate layer having a thickness of 5.0 μm.

Next, a charge generation layer was formed as follows. 18 parts by weight of the A-type titanyl phthalocyanine pigment were put into a glass pot together with zirconia beads having a diameter of 2 mm, and 350 parts by weight of methyl ethyl ketone were further added.
Ball milling was performed for 5 hours. Thereafter, a resin solution in which 10 parts by weight of polyvinyl butyral resin SREC BX-1 (manufactured by Sekisui Chemical) was dissolved in 600 parts by weight of methyl ethyl ketone was added, and ball milling was further performed for 2 hours to prepare a coating liquid for a charge generation layer. . The coating solution for a charge generation layer obtained in this manner is dip-coated on the above-mentioned intermediate layer, dried at 80 ° C. for 20 minutes, and has a thickness of about 0.3 μm.
Was formed.

Further, a charge transport layer was formed as follows. 9.0 parts by weight of the charge transport material of the structural formula (23) used in Example 1 and polycarbonate resin Panlite C-1
10.0 parts by weight of 400 (manufactured by Teijin Chemicals) and 0.002 parts by weight of silicone oil KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 80 parts by weight of tetrahydrofuran. The thus-obtained coating solution for a charge transport layer is dip-coated on the charge generation layer and dried at 130 ° C. for 20 minutes to form a charge transport layer having a thickness of 28 μm, thereby producing an electrophotographic photoreceptor. did.

The two types of photoreceptors obtained as described above were mounted on a copier Imagio MF-200 (manufactured by Ricoh) and repeatedly used to evaluate images. The image evaluation was performed under the environment of 20 ° C./52% RH and the initial image
The image after copying 0 sheets was visually observed. The results of the evaluation are shown in Table 20 below. Note that the initial VD is -95.
0 V, the initial VL to -200 V, and the developing bias to -6.
Each was adjusted to 00V. The IMAGEO MF-200 employs a contact charging means using a roller and a reversal developing method.

Examples 50 to 54 For each of the coating solutions for the intermediate layers prepared in Examples 44 to 48, the photoreceptors using the coating solution immediately after preparation and the coating solution stored only by stirring with a stirrer for one month were used. It was produced in the same manner as in Example 49. In the fifty-fifth embodiment, the thirty-fourth embodiment
The photoreceptor was manufactured using the coating liquids prepared in the above and in the order of the numbers of the examples below. Table 20 shows the results of image evaluation of each of the two types of photoreceptors produced in the same manner as in Example 49.

[0282]

[Table 20]

With the photoreceptors manufactured using the coating solutions of Examples 43 to 48 described above, good images could be obtained even after repeated use. Therefore, it was found that the photoreceptor producing a good image can be produced using the coating solution stored for one month by using the photoreceptor manufacturing method of the present invention.

Example 55 In this example, a coating solution for an intermediate layer was prepared as follows. 60 parts by weight of copolyamide Amilan CM400
0 (manufactured by Toray Industries, Inc.) was dissolved in 100 parts by weight of formic acid, and the mixture was stirred at 60 ° C. Next, after dissolving 60 parts by weight of paraformaldehyde in 100 parts by weight of methanol to which alkali was added, the temperature was maintained at 60 ° C., and the polyamide solution was gradually added, followed by stirring for 10 minutes. Next, 60 parts by weight of methanol was added, and stirring was continued at 60 ° C. for 20 minutes. The obtained reaction solution was mixed with 1500 ml of an acetone / water mixture (1: 1).
1) and neutralized by dropwise addition of 30% aqueous ammonia. The precipitate was washed with water to obtain a polyamide having a methoxymethylation rate of 35 mol%. 45 parts by weight of the obtained methoxymethylated polyamide and butylated melamine resin Super Beckamine L-110-60 (solid content 6
(0%) 25 parts by weight (manufactured by Dainippon Ink and Chemicals) are dissolved in 300 parts by weight of methanol and 150 parts by weight of methyl ethyl ketone, and 330 parts by weight of untreated surface titanium oxide TA-300 (manufactured by Fuji Titanium Industry) are added thereto. , 1 with a ball mill
Ball mill dispersion was performed for 00 hours. Thereafter, 22 parts by weight of tartaric acid (solid content: 10%) dissolved in methanol was added to prepare a coating solution for an intermediate layer. The methoxymethylation ratio was measured in the same manner as in Example 32.

The dispersion stability of the intermediate layer coating solution was evaluated by the following method. The particle size distribution of the coating solution immediately after preparation and the particle size distribution of the solution stored only by stirring with a stirrer for 1.5 months were measured with CAPA-700 (manufactured by Shimadzu Corporation), and coarse particles having a particle size of 1.0 μm or more were measured. Was determined. The measurement results are shown in Table 21 described below.

Example 56 A methoxymethylated polyamide having a methoxymethylation rate of 10 mol% was obtained in the same manner as in Example 55, except that the conditions for modifying the polyamide to methoxymethylation were changed. A coating solution for an intermediate layer was obtained in the same manner as in Example 55 except that the methoxymethylation ratio was changed. Example 5 of this coating solution for intermediate layer
As in the case of No. 5, measurement for evaluating the dispersion stability was performed.
The results are shown in Table 21 below.

Example 57 A methoxymethylated polyamide having a methoxymethylation rate of 15 mol% was obtained in the same manner as in Example 55 except that the conditions for modifying the polyamide to methoxymethylation were changed. A coating solution for an intermediate layer was obtained in the same manner as in Example 55 except that the methoxymethylation ratio was changed. Example 5 of this coating solution for intermediate layer
As in the case of No. 5, measurement for evaluating the dispersion stability was performed.
The results are shown in Table 21 below.

Example 58 In Example 55, the butylated melamine resin was replaced with a methylated melamine resin Super Beckamine L-105-60 (solid content: 60%).
%) (Dai Nippon Ink Chemicals)
In the same manner as in Example 5, a coating solution for an intermediate layer was obtained. This intermediate layer coating liquid was measured in the same manner as in Example 55 to evaluate the dispersion stability. The results are shown in Table 21 below.

[0289]

[Table 21]

From the results shown in Table 21, the coating solutions of Examples 55 to 58 did not show a large decrease in dispersibility after storage for 1.5 months. Therefore, it was found that the coating liquid used in the method for producing a photoreceptor of the present invention had excellent dispersion stability.

Example 59 Using the coating solution for the intermediate layer prepared in Example 55 and the coating solution stored only by stirring with a stirrer for 1.5 months, a photoconductor was prepared as follows. did. 2
Each type of coating liquid is 80mm in diameter x 360m in length
m, and dried at 110 ° C for 30 minutes.
An intermediate layer having a thickness of 3.5 μm was formed.

Next, a charge generation layer was formed as follows. Butyral resin Esrec BMS (manufactured by Sekisui Chemical) 4
Parts by weight were dissolved in 150 parts by weight of cyclohexanone, and the trisazo pigment 1 of the structural formula (22) used in Example 1 was added thereto.
6 parts by weight were added and dispersed for 72 hours in a ball mill.
Further, 210 parts by weight of cyclohexanone was added and dispersed for 5 hours. This was diluted with cyclohexanone while stirring so that the solid content became 1.0 wt%. The coating solution for a charge generation layer thus obtained was applied onto the intermediate layer by dip coating, and dried at 120 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.3 μm.

Further, a charge transport layer was formed as follows. 9.5 parts by weight of the charge transport material of the structural formula (23) used in Example 1 and polycarbonate resin Panlite TS-
2050 (manufactured by Teijin Chemicals) 10 parts by weight, silicone oil K
0.002 parts by weight of F-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 85 parts by weight of tetrahydrofuran. The coating solution for a charge transport layer obtained in this manner is dip-coated on the charge generation layer and dried at 130 ° C. for 20 minutes to form a charge transport layer having a thickness of 30 μm, thereby producing an electrophotographic photoreceptor. did.

The two types of photoreceptors obtained as described above were mounted on a copier Imagio 420V (manufactured by Ricoh Co., Ltd.) modified as described below and repeatedly used to evaluate images. The image evaluation was performed by visually observing the initial image and the image after 3000 copies in an environment of 20 ° C./52% RH. The results of the evaluation are shown in Table 22 below. Contents of modification Charging method: Contact charging method using a roller Initial VD: -600 V Initial VL: -150 V Developing bias: -400 V Developing method: Reversal developing method

Examples 60 to 62 For the coating liquids for the intermediate layers prepared in Examples 56 to 58, photoreceptors using the coating liquid immediately after preparation and the coating liquid stored only by stirring with a stirrer for 1.5 months. Was produced in the same manner as in Example 59. In Example 60, the coating liquid prepared in Example 56 was used, and the photoconductors were prepared using the coating liquids corresponding to the numbers in the following Examples. The results of image evaluation of each of the two types of photoconductors produced in the same manner as in Example 59 are shown in Table 22 described later.

[0296]

[Table 22]

In the photosensitive members of Examples 59 to 62, which were prepared by actually using the coating solutions of Examples 55 to 58, images having practically no problem were obtained even after repeated use. . Therefore, it has been found that the photoreceptor of the present invention can produce a photoreceptor capable of obtaining an image having no problem in practical use even when a coating solution stored for 1.5 months is used.

Example 63 Boric acid was maleic acid and the thickness of the charge transport layer was 26 μm.
An electrophotographic photoreceptor was produced in exactly the same manner as in Example 40 except that The drying condition of the intermediate layer is 115
C. for 30 minutes.

The photoreceptor obtained as described above was mounted on a copier Imagio MF-2200 (manufactured by Ricoh Co., Ltd.).
Initial temperature and 10000 in an environment of C / 52% RH
The image after copying (A4 landscape) was visually evaluated.
The results of the image evaluation are shown in Table 23 below. The Imagio MF-2200 sets the initial VD and the initial VL when the photoconductor is mounted at -850 V and -200 V, respectively.
And the developing bias was further adjusted to -500V. The IMAGEO MF-2200 uses a contact charging unit using a roller, and employs a reversal developing method.

Example 64 A photoconductor was prepared in the same manner as that of Example 63 except that the drying condition of the intermediate layer was 95 ° C. for 30 minutes. After producing the photoreceptor, the image after repeated use was evaluated in the same manner as in Example 63. The results are shown in Table 23 below.

Example 65 A photoconductor was prepared in the same manner as that of Example 63 except that the drying condition of the intermediate layer was changed to 185 ° C. for 30 minutes. After producing the photoreceptor, the image after repeated use was evaluated in the same manner as in Example 63. The results are shown in Table 23 below.

[0302]

[Table 23]

From the results shown in Table 23, when the method of manufacturing a photoreceptor of the present invention is used, the photoreceptor is repeatedly used even when the photoreceptor is manufactured using the coating solution for the intermediate layer after storage for 3 months. It was found that the image obtained in this way had no problem in practical use. Furthermore, the drying temperature of the intermediate layer is
Even when the temperature was changed to 95 ° C., 115 ° C., and 185 ° C., it was found that an image having no practical problem could be obtained with the photoreceptor using the coating solution after storage for 3 months.

[0304]

The electrophotographic photoreceptor of the present invention has a small environmental dependency of the photosensitivity, and when used in an electrophotographic apparatus, the photoreceptor can be used repeatedly under high-temperature, high-humidity and low-temperature, low-humidity environments. Good images can be obtained. Furthermore, even if the thickness of the intermediate layer is increased, an increase in the residual potential can be suppressed, and a photosensitive member that is hardly deteriorated even when used for a long time can be manufactured. Since the thickness of the intermediate layer can be increased, discharge breakdown that is likely to occur in a thin film when a contact-type charging unit is used is suppressed. Therefore, an abnormal image due to discharge breakdown is less likely to occur. At the same time, by increasing the thickness of the intermediate layer, scratches and irregularities on the surface of the conductive support can be reliably concealed, so that a step of controlling the surface of the support is not required, and the photoconductor can be provided at low cost. Further, the electrophotographic photoreceptor of the present invention has excellent mechanical strength.

According to the method for producing an electrophotographic photoreceptor of the present invention, the N-alkoxymethylated polyamide constituting the intermediate layer can be reliably cross-linked, so that the photoreceptor has low environmental dependency and can be used at a high temperature. An electrophotographic photoreceptor capable of obtaining a good image even when repeatedly used in an environment of high humidity, low temperature and low humidity can be manufactured. Furthermore, since a coating liquid for an intermediate layer having high dispersion stability can be prepared, it is not necessary to frequently change the coating liquid during production. Therefore, the time required for manufacturing can be reduced, and the cost can be reduced at the same time.

Since the electrophotographic apparatus, process cartridge and electrophotographic process of the present invention use the electrophotographic photoreceptor of the present invention, they provide good images even when repeatedly used under high-temperature, high-humidity and low-temperature, low-humidity environments. can do.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of the electrophotographic photosensitive member of the present invention.

FIG. 2 is a cross-sectional view of another example of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a sectional view of still another example of the electrophotographic photosensitive member of the present invention.

FIG. 4 is a cross-sectional view of still another example of the electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 Reference Signs List 1 conductive support 2 intermediate layer 2a first intermediate layer 2b second intermediate layer 3 photoconductive layer 3a charge generation layer 3b charge transport layer

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 2000-223843 (P2000-223843) (32) Priority date July 25, 2000 (July 25, 2000) (33) Priority claim country Japan (JP) F term (reference) 2H068 AA43 AA44 AA50 BA03 BB28 BB37 BB58 CA29 CA33 DA63 DA69 DA69 EA14 FA27

Claims (19)

[Claims] 1. An electrophotographic photoreceptor, comprising: a conductive support; an intermediate layer provided on the conductive support; and a photoconductive layer provided on the intermediate layer. Contains an inorganic pigment and a binder resin, and the binder resin is a cross-linked N-alkoxymethylated polyamide or N
-An electrophotographic photoreceptor, which is a crosslinked product of an alkoxymethylated polyamide and a melamine resin. 2. The intermediate layer comprises a first intermediate layer and a second intermediate layer, wherein the first intermediate layer comprises a thermosetting resin in which an inorganic pigment is dispersed, and wherein the second intermediate layer comprises a crosslinked N-alkoxy. The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor is composed of a crosslinked product of a methylated polyamide or an N-alkoxymethylated polyamide and a melamine resin. 3. The electrophotographic photoconductor according to claim 1, wherein the inorganic pigment is titanium oxide and / or aluminum oxide. 4. The electrophotographic photoreceptor according to claim 3, wherein said titanium oxide is surface-untreated titanium oxide. 5. The purity of the titanium oxide is 99.5% by weight.
The electrophotographic photosensitive member according to claim 3, wherein: 6. The electrophotographic photoreceptor according to claim 1, wherein the N-alkoxymethylated polyamide has an N-alkoxymethylated ratio of 15 mol% or more. 7. The electrophotographic photoreceptor according to claim 1, wherein the N-alkoxymethylated polyamide is a methoxymethylated polyamide. 8. The electrophotographic photosensitive member according to claim 1, wherein the melamine resin is a butylated melamine resin. 9. The electrophotographic photosensitive member according to claim 2, wherein the second intermediate layer has a thickness of 0.01 to 1 μm. 10. A method for producing an electrophotographic photoreceptor, comprising: providing a conductive support; and coating a coating liquid for forming an intermediate layer containing an inorganic pigment and a binder resin on the conductive support. Forming a coating film, and the binder resin is a crosslinked N-alkoxymethylated polyamide or a crosslinked product of an N-alkoxymethylated polyamide and a melamine resin; and heating the coating film to form an intermediate layer. A method for producing an electrophotographic photoreceptor having a photoconductive layer on the intermediate layer. 11. A method for producing an electrophotographic photoreceptor, comprising: providing a conductive support; and forming a first intermediate layer comprising a thermosetting resin having an inorganic pigment dispersed on the conductive support. Forming; a second layer containing a binder resin on the first intermediate layer.
A coating film is formed by applying a coating liquid for forming an intermediate layer, and the binder resin is a crosslinked N-alkoxymethylated polyamide or a crosslinked product of an N-alkoxymethylated polyamide and a melamine resin; Is heated to form a second intermediate layer; a method for producing an electrophotographic photosensitive member, wherein a photoconductive layer is provided on the second intermediate layer. 12. The method for producing an electrophotographic photosensitive member according to claim 10, wherein a heating temperature at the time of forming said intermediate layer or said second intermediate layer is 100 to 180 ° C. 13. The method according to claim 10, wherein the coating liquid for forming an intermediate layer or the coating liquid for forming a second intermediate layer contains an acidic catalyst. 14. The electrophotographic photoreceptor according to claim 13, wherein a mixed solvent with an alcohol and a ketone to which an inorganic acid is added is used as a solvent used in the coating solution for forming an intermediate layer. Manufacturing method. 15. The electrophotographic photoreceptor according to claim 13, wherein a mixed solvent with an alcohol and a ketone to which an organic acid is added is used as a solvent used in the coating solution for forming the intermediate layer. Manufacturing method. 16. An electrophotographic apparatus comprising: the electrophotographic photosensitive member according to claim 1; a charging unit; and a developing unit. 17. The electrophotographic apparatus according to claim 16, wherein said charging means is a means for contact charging. 18. A process cartridge, comprising: the electrophotographic photosensitive member according to claim 1; and at least one unit selected from a charging unit, an image exposing unit, a developing unit, and a transferring unit. And a process cartridge detachably attached to the main body of the electrophotographic apparatus. 19. An electrophotographic process, comprising: forming an electrostatic latent image on the surface of the electrophotographic photosensitive member according to claim 1; and reversely developing the electrostatic latent image. .