JPH11184135A - Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the electrophotographic photoreceptor having superior solvent cracking resistance and high mechanical strength and good direct charging resistance and small memory by incorporating a polymer specified in structural units in the surface layer of the photoreceptor and a specified azo compound in a photosensitive layer. SOLUTION: This electrophotographic photoreceptor is provided with the surface layer containing the polymer having structural units represented by formula I and the photosensitive layer containing the azo compound represented by formula II: (CPI-N=N)n -A, and in formulae I and II, X is a -CR9R10 - group or a simple bond; each of R9 and R10 is an H atom or a trifluoromethyl group or the like; each of R1 -R8 is an H or halogen atom or an alkyl group or the like; A is an aryl group or a simple bond or a -(CH2 =CH2 )m -group or the like; (m) is 1 or 2; CPI is a group represented by formula III or the like; (n) is 1, 2, or 3; R11 is an alkyl or aryl group; and R12 is an H atom or a cyano group or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member. The present invention relates to an electrophotographic photosensitive member containing a generated substance, and a process cartridge and an electrophotographic apparatus having the electrophotographic medium.

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
As shown in JP-A No. 1 (1993), a photoconductive material comprising a support coated with an insulating substance is used in which the electric resistance changes in accordance with the amount of irradiation received during image exposure, and in a dark place. The basic characteristics required of an electrophotographic photoreceptor using this photoconductive material are (1) that it can be charged to an appropriate potential in a dark place, (2) that the potential is less dissipated in a dark place, and (3) And (3) quickly dissipating the charge by light irradiation.

[0003] Conventionally, selenium,
Inorganic photoreceptors having a photosensitive layer mainly containing an inorganic photoconductive compound such as zinc oxide and cadmium sulfide have been widely used. However, these satisfies the conditions (1) to (3), but are not necessarily satisfactory in thermal stability, moisture resistance, durability and productivity.

In order to overcome the disadvantages of inorganic photoconductors, electrophotographic photoconductors containing various organic photoconductive compounds as main components have been actively developed in recent years. For example, US Pat.
No. 851 discloses a photoreceptor having a charge transport layer containing triallylpyrazolin, and US Pat. No. 3,871,880 discloses a charge generating layer comprising a derivative of perylene pigment and
Photoreceptors comprising a charge transport layer comprising a condensate of propylene and formaldehyde are known.

Electrophotographic photoreceptors using these organic photoconductive compounds are used as function-separated type photoreceptors in which a charge transport layer and a charge generation layer are laminated in order to satisfy both electrical and mechanical properties. In many cases. On the other hand, it is needless to say that the electrophotographic photoreceptor is required to have sensitivity, electrical characteristics, and even optical characteristics according to the electrophotographic process applied.

In particular, in the case of an electrophotographic photosensitive member that is repeatedly used, an external electrical or mechanical force such as corona or direct charging, image exposure, toner development, a transfer process, and surface cleaning is directly applied to the surface of the electrophotographic photosensitive member. For,
Durability against them is also required.

More specifically, electrical deterioration due to ozone and nitrogen oxides during charging, mechanical deterioration in which the surface is worn or scratched due to discharge during charging, and rubbing of a cleaning member, and electrical deterioration Durability is required.

[0008] The electrical degradation is particularly problematic in that carriers stay in a portion irradiated with light and a potential difference is generated from a portion not irradiated with light. This phenomenon occurs as a photo memory.

The photocurrent is repeatedly turned on and off in the photoconductor by charging and exposure. As a result, electric charges moving in the photoconductor remain at trap sites in the photoconductor, resulting in a residual potential. When this is repeatedly used, the potential of the photosensitive member fluctuates. Unlike an inorganic photoreceptor, an organic photoreceptor having many soft materials is inferior in durability against mechanical deterioration.

Various attempts have been made to satisfy the durability characteristics required for the photoreceptor as described above.

As a resin often used in the surface layer and having good abrasion and electrical properties, a polycarbonate resin having bisphenol A as a skeleton has been attracting attention. However, not all of the above-mentioned problems can be solved. It has such problems.

(1) It has poor solubility and exhibits good solubility only in a part of halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane. In addition, since these solvents have a low boiling point, When a photoreceptor is manufactured using a coating solution prepared with the above solvent, the coated surface is likely to be whitened. It also takes time to control the solid content of the coating liquid.

(2) Solvents other than halogenated aliphatic hydrocarbons are partially soluble in tetrahydrafuran, dioxane, cyclohexanone or a mixed solvent thereof, but the solution gels in a few days. Inferior aging,
It is not suitable for photoconductor production.

(3) Further, even if the above formulas (1) and (2) are improved, solvent cracks are liable to occur in the polycarbonate resin having bisphenol A as a skeleton.

(4) In addition, in the case of a conventional polycarbonate resin, the coating formed of the resin does not have lubricity, so that the photosensitive member is easily damaged, and the cleaning setting for reducing the abrasion amount of the electrophotographic photosensitive member is reduced. In some cases, image defects such as toner fusion occur, or cleaning failure or toner fusion occurs due to early deterioration of the cleaning blade.

For the solution stability mentioned in the above (1) and (2), use of a polycarbonate Z resin having a bulky cyclohexylene group as a structural unit of the polymer, or copolymerization with bisphenol Z or bisphenol C, etc. Has been solved by

[0017] Solvent cracks can also be solved by using a silicone-modified polycarbonate or an ether-modified polycarbonate as disclosed in JP-A-6-51544 and JP-A-6-75415. . However, compared to conventional polycarbonate resins, these modified polycarbonates have a structure that has flexibility against internal stress in the polymer in order to prevent solvent cracks, and as a result, the mechanical There was a disadvantage that the strength was reduced.

Further, in recent years, a direct charging system in which a voltage is applied directly to a charging member and a charge is applied to an electrophotographic photosensitive member as disclosed in JP-A-57-17826 and JP-A-58-40566. Is becoming mainstream.

This is a method in which a roller-shaped charging member made of a conductive rubber or the like is brought into direct contact with an electrophotographic photosensitive member to apply an electric charge. The scorotron generates a significantly smaller amount of ozone than a scorotron or the like. While about 80% of the current flowing through the charger flows through the shield, it is wasted, whereas direct charging has the advantage that it is very economical without this waste.

However, direct charging has a disadvantage that charging stability is very poor because of charging by discharge according to Paschen's rule. As a countermeasure, a so-called AC / DC charging method in which an AC voltage is superimposed on a DC voltage has been devised (Japanese Patent Application Laid-Open No. 63-149668).

Although the charging system has improved the stability during charging, the amount of discharge on the surface of the electrophotographic photosensitive member is greatly increased due to the superposition of AC, so that the shaving amount of the electrophotographic photosensitive member is increased. A new drawback has arisen, requiring not only mechanical strength but also electrical strength. Further, there has been a drawback that charge retention is likely to occur at the interface between the charge transport layer and the charge generation layer due to the application of an AC voltage, and the potential of the light portion is likely to fluctuate.

Also, the phenomenon that the light portion potential fluctuates due to the application of transfer charge is becoming more remarkable with the speeding up of the electrophotographic apparatus.

[0023]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems in the case where a conventional polycarbonate resin is used as a surface layer, to provide excellent solvent crack resistance, high mechanical strength, and direct charging. Good electrical resistance due to high sensitivity and excellent repetition characteristics due to durability, small memory, little change in bright part potential due to transfer charging, little change in bright part potential even in charging method with AC voltage superimposed, An object of the present invention is to provide an electrophotographic photosensitive member that can be easily manufactured, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

[0024]

According to a first aspect of the present invention, there is provided an electrophotographic photosensitive member having a photosensitive layer on a support, wherein the surface layer of the electrophotographic photosensitive member is represented by the following formula (1). An electrophotographic photosensitive member comprising a polymer having a structural unit represented by the formula (2), wherein the photosensitive layer contains an azo compound represented by the formula (2), and a process cartridge and an electronic device having the electrophotographic photosensitive member. It is a photographic device.

[0025]

Embedded image [In the formula (1), X is -CR ₉ R _10- (R ₉ and R ₁₀ are the same or different and each represents a hydrogen atom, a trifluoromethyl group,
An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms), an optionally substituted α, ω-alkylene group having 2 to 10 carbon atoms, 1,1-cycloalkyl having 5 to 11 carbon atoms alkylene group, a single bond, -O -, - S -, - SO- or -SO ₂ - is. R _{1 to} R ₈ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group or an aryl group which may be substituted. (CPI-N = N) _n -A (2) [In the formula (2), A represents an optionally substituted aryl group, or a single bond thereof,-(CH = CH) _m- , -CH = N
-, -CO-, -O-, -S-, -CONH-, -NY
— Or —CH ₂ — (m is 1 or 2, and Y is a hydrogen atom, an alkyl group which may be substituted or a phenyl group), and CPI is represented by the following formula (3): Indicated by (4) or (5), n is 1, 2 or 3. ]

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image [In the formulas (3), (4) and (5), R ₁₁ is an alkyl group or an aryl group which may be substituted, and R ₁₂ is a hydrogen atom, a cyano group, a carboxyl group, an ester group or an acyl group. . ]

In a second aspect of the present invention, there is provided an electrophotographic photosensitive member having a photosensitive layer on a support, wherein the surface layer of the electrophotographic photosensitive member comprises a structural unit represented by the above formula (1). An electrophotographic photoreceptor comprising an union and the photosensitive layer containing an azo compound represented by the following formula (12) or (13), a process cartridge having the electrophotographic photoreceptor, and an electrophotograph. Device.

[0030]

Embedded image

[0031]

Embedded image [In the formulas (12) and (13), B and B 'are the same or different,

[0032]

Embedded image (R _{21 to} R ₂₄ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a nitro group). ]

Further, according to a third aspect of the present invention, there is provided an electrophotographic photosensitive member having a photosensitive layer on a support, wherein the surface layer of the electrophotographic photosensitive member has a structural unit represented by the above formula (1). An electrophotographic photoreceptor containing an union, wherein the photosensitive layer contains an azo compound represented by the following formula (16), and a process cartridge and an electrophotographic apparatus having the electrophotographic photoreceptor.

[0034]

Embedded image [In the formula (16), R ₃₁ and R ₃₂ are the same or different,
It is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ₃₃ is a hydrogen atom or a halogen atom. ]

The electrophotographic photoreceptor and the process cartridge and the electrophotographic apparatus having the electrophotographic photoreceptor according to the present invention are particularly excellent in solvent crack resistance and mechanical strength due to the polymer contained in the photoreceptor surface layer. In addition, the photosensitive layer can have both electric resistance characteristics and AC characteristics, and the charge generating material contained in the photosensitive layer has high sensitivity, excellent repetition characteristics due to durability, small memory, and good electrophotographic characteristics. You can do it. Further, by the combination of the polymer and the charge generating substance, it is possible to suppress the fluctuation of the light portion potential upon repeated use and the fluctuation of the light portion potential upon application of transfer charging.

Although the exact reason is unclear, it is assumed that the polymer used in the present invention has high crystallinity and orients the charge transport material to some extent. It is presumed that the barrier at the injection interface becomes lower.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION The halogen atom in the present invention includes a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a butyl group, and a tertiary butyl group.
Examples of the alkylene group include a dimethylene group, a trimethylene group, and a tetramethylene group.Examples of the cycloalkylene group include a cyclopentylene group and a cyclohexylene group.Examples of the alkenyl group include an ethenyl group, an isophenyl group, and a butenyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group, examples of the aryl group include a phenyl group and a naphthyl group, and examples of the acyl group include an acetyl group and a benzoyl group. Examples of the substituent that may be mentioned include a halogen atom, an alkyl group and an aryl group as described above.

Specific examples of the structural unit represented by the formula (1) are shown in Table 1 below, but are not limited thereto.

[0039]

[Table 1]

[0040]

[Table 2]

The polymer having a structural unit represented by the formula (1) used in the present invention is prepared by converting a bisphenol represented by the following formula (10) into a mixture of a terephthalic acid chloride and an isophthalic acid chloride in the presence of an alkali. It can be synthesized by mixing and interfacial polymerization in a solvent / water system.

The ratio between terephthalic acid chloride and isophthalic acid chloride is determined in consideration of the solubility of the polymer and is not defined. However, if the ratio of any chloride is 3
Care must be taken when the content is 0 mol% or less, since the solubility of the synthesized polymer is extremely reduced. Usually, it is preferable to synthesize at a ratio of 1/1.

[0043]

Embedded image [In the formula (10), X and R _{1 to} R ₈ have the same meanings as in the formula (1).]

In the electrophotographic photoreceptor of the present invention, a polymer composed of the same structural unit represented by the formula (1) is also composed of two or more different types of structural units represented by the formula (1). It may be a copolymer.

Preferred examples include Structural Unit Examples 1, 2 and 7. In the case of a polymer composed of the same structural units, the polymer comprising Structural Unit Example 1 is particularly preferred, and two or more kinds are preferred. In the case of a copolymer composed of different types of structural units represented by the formula (1), a copolymer composed of structural unit examples 1 and 2 is particularly preferable.

Among the azo compounds represented by the formula (2),
Particularly preferred examples include a bis-azo compound represented by the following formula (7), (8) or (9).

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

Among the azo compounds represented by the formula (12) or (13), a particularly preferred example is the following formula (1)
The bis-azo compound represented by 4) or (15) is exemplified.

[0051]

Embedded image

[0052]

Embedded image

Among the azo compounds represented by the formula (16), a particularly preferred example is a tris-azo compound represented by the following formula (17) or (18).

[0054]

Embedded image

[0055]

Embedded image Hereinafter, the configuration of the electrophotographic photosensitive member used in the present invention will be described.

In the electrophotographic photoreceptor of the present invention, even if the photosensitive layer is a single-layer type containing a charge transport material and a charge generation material in the same layer, the charge transport layer containing the charge transport material and the charge generation material May be separated into a charge-generating layer containing, but from the standpoint of electrophotographic characteristics, a stacked type is preferable. In the case of the stacked type, a charge generation layer may be stacked on the charge generation layer, or a charge generation layer of the charge transport layer may be stacked.

The support to be used may be any one having conductivity, such as a metal such as aluminum and stainless steel, or a metal provided with a conductive layer, paper and plastic. The shape may be a sheet or a cylinder. No.

A conductive layer may be provided for covering a scratch on the support. This can be formed by dispersing conductive powder such as carbon black and metal particles in a binder resin. The thickness of the conductive layer is preferably from 5 to 40 μm, and particularly preferably from 10 to 30 μm.

An intermediate layer having an adhesive function is provided thereon. Examples of the material for the intermediate layer include polyamide, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, casein, polyurethane, and polyether urethane. These are applied by dissolving in an appropriate solvent.
The thickness of the intermediate layer is preferably from 0.05 to 5 μm, and particularly preferably from 0.3 to 1 μm.

A charge generation layer is preferably formed on the intermediate layer. The charge generation layer used in the present invention is formed by coating and drying a binder resin and a coating material in which the charge generation substance mainly used in the present invention is dispersed in a solvent. In the case of the function separation type, the charge generating layer disperses the charge generating material together with the binder resin and the solvent by a method such as a homogenizer, an ultrasonic dispersion, a ball mill, a vibration ball mill, a sand mill, an attritor, a roll mill, and a liquid collision type high-speed disperser. I do. As the binder resin used here, for example, polyester resin, polyacryl resin, polyvinyl carbazole resin, phenoxy resin, polycarbonate resin, polystyrene resin, polyvinyl acetate resin, polysulfone resin, polyarylate resin, vinylidene chloride resin, polyvinyl benzal resin and poly Butyral resin and the like are mainly used. The ratio of the charge generating substance to the binder resin is preferably from 1/10 to 10/1, and more preferably from 1.5 / 1 to 3/1. The dispersion is applied and dried to form a charge generation layer. The thickness of the charge generation layer is preferably 5 μm or less, particularly preferably 0.05 μm.
It is preferably from 1 to 2 μm.

When the charge transporting layer is to be a surface layer, it is formed by applying and drying a paint in which a charge transporting substance and a binder resin mainly composed of the polymer used in the present invention are dissolved in a solvent. Examples of the charge transport material used include a triarylamine compound, a hydrazone compound, a stilbene compound, a pyrazoline compound, an oxazole compound, a triallylmethane compound, and a thiazole compound. The charge transport material is preferably combined with 0.5 to 2 times the amount of the binder resin, applied and dried to form a charge transport layer. The thickness of the charge transport layer is preferably from 5 to 40 μm, and particularly preferably from 15 to 30 μm.

FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.

In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around a shaft 2 in a direction of an arrow at a predetermined peripheral speed. The photoreceptor 1 rotates during the rotation process.
The peripheral surface is uniformly charged with a predetermined positive or negative potential by the primary charging means 3, and then receives image exposure light 4 from an image exposure means (not shown) such as slit exposure or laser beam scanning exposure. Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 1.

The formed electrostatic latent image is then transferred to developing means 5
The toner image developed is transferred from the paper supply unit (not shown) to the transfer material 7 fed out between the photoconductor 1 and the transfer unit 6 in synchronization with the rotation of the photoconductor 1 and fed. The image is sequentially transferred by the means 6.

The transfer material 7 which has undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing, thereby being printed out of the apparatus as a copy.

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

In the present invention, a plurality of components such as the above-described electrophotographic photosensitive member 1, primary charging means 3, developing means 5 and cleaning means 9 are integrally connected as a process cartridge. The process cartridge may be configured to be detachable from a main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. For example, a process in which at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photoreceptor 1 to form a cartridge, and is detachable from the apparatus main body using a guide unit such as the rail 12 of the apparatus main body. The cartridge 11 can be used.

When the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 is read and transmitted from the original, or the original is read by a sensor and converted into a signal, and the exposure is performed according to this signal. Laser beam scanning,
Light emitted by driving the LED array, driving the liquid crystal shutter array, and the like.

The electrophotographic photosensitive member of the present invention can be used not only for an electrophotographic copying machine but also for a laser beam printer,
It can be widely used in electrophotographic applications such as RT printers, LED printers, liquid crystal printers, and laser plate making.

Hereinafter, description will be made in accordance with embodiments. In the examples, "parts" represents parts by weight. Example 1-1 An 80φ, 360 mm aluminum cylinder was used as a support, and a coating composed of the following materials was applied to the support by a dip coating method.
The film was thermally cured at 40 ° C. for 30 minutes to form a conductive layer having a thickness of 15 μm.

Conductive pigment: SnO ₂ coated barium sulfate 10 parts Resistance adjusting pigment: titanium oxide 2 parts Binder resin: phenol resin 6 parts Leveling material: silicone oil 0.001 parts Solvent: methanol, methoxypropanol 0.2 / 0.8 20 parts

Next, a solution prepared by dissolving 3 parts of N-methoxymethylated nylon and 3 parts of copolymer nylon in a mixed solvent of 65 parts of methanol and 30 parts of n-butanol was applied thereon by dip coating. An intermediate layer having a thickness of 0.5 μm was formed.

Next, the following structural formula

[0074]

Embedded image Was dispersed for 4 hours in a sand mill using φ1 mm glass beads for 4 hours, and 100 parts of methyl ethyl ketone was added to disperse the compound for the charge generation layer. A dispersion was prepared. This was applied by a dip coating method to form a charge generation layer having a thickness of 0.3 μm.

Next, 10 parts of a charge transport material having the following structural formula

[0076]

Embedded image And 10 parts of the polymer described in Condition 1-1 in Table 2 were dissolved in a mixed solvent of 30 parts of monochlorobenzene and 70 parts of dichloromethane.

This polymer is prepared from a predetermined biphenol (0.0
Sodium hydroxide (0.8 g) and tetramethylammonium chloride (1 g) were dissolved in 100 ml of water and charged into a 1-liter mixer.
Dichloroethane (30 ml) was added to terephthalic acid chloride (0.005 mol) and isophthalic acid chloride (0.05 mol).
05mol) was added thereto with stirring.
After stirring for 2 minutes at high speed and leaving for 2 hours, a 1,2-dichloroethane solution was recovered, and a large amount of hexane was added thereto to recover a polymer. In addition, the thing which performed the purification process by water washing | cleaning, chloroform dissolution, and methanol dripping after collection | recovery was used.

This paint is applied by a dip coating method,
After drying at 120 ° C. for 2 hours, a charge transport layer having a thickness of 18 μm was formed.

Next, the evaluation will be described.

The apparatus used was NP3825 manufactured by Canon.
The prepared electrophotographic photoreceptor is subjected to 28 ° C., 90% R
A paper passing durability test (HH durability) was performed under H. The sequence was an intermittent mode in which the print was stopped once for each print.

The surface potential (bright portion potential) of the electrophotographic photosensitive member was measured at the initial stage of durability and at 10,000 sheets.

Further, at the time of measurement, -150 was applied by the transfer charger.
The light area potential when a current of μA was applied and transfer was measured, and the value of light area potential (without transfer) -light area potential (with transfer) was shown as a transfer memory.

When the toner ran out, the toner was replenished and an endurance test was performed until a problem occurred in the image.

Further, the plate was abraded for 15 minutes using a Taber abrasion tester using a polishing tape, and the weight loss at that time was measured.

Further, 3000 L of a part of the electrophotographic photosensitive member is used.
After illuminating with a white fluorescent lamp for 13 minutes at ux for 10 minutes, the bright portion potential was measured, and the value of the bright portion potential (before irradiation) -the bright portion potential (after irradiation) was taken as the photo memory value.

Further, regarding the solvent cracking property, sebum was adhered to the surface and allowed to stand for 48 hours, and the presence or absence of solvent cracking was observed by microscopic observation.

Table 3 shows the results.

Next, the measurement in direct charging was performed.

The apparatus was modified with a direct charging method using a roller using conductive rubber by modifying the charged part of NP3825 manufactured by Canon Inc. The roller was supplied with a peak-to-peak voltage of 2 KV as an AC voltage at a frequency of 1000 Hz. The produced electrophotographic photosensitive member was subjected to a paper passing durability test (HH durability) at 28 ° C. and 90% RH using this apparatus. The sequence was an intermittent mode in which the print was stopped once for each print.

The light portion potential of the electrophotographic photosensitive member was measured at the initial stage of durability and at 10,000 sheets. The transfer memory was also measured in the same manner.

Table 4 shows the results.

[0092]

[Table 3] The mixing ratio between terephthalic acid chloride and isophthalic acid chloride was 1: 1 in molar ratio.

Example 1-2 The following structural formula was used for the charge generating material of the charge generating layer.

[0094]

Embedded image An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1, except that the compound was used. The results are shown in Tables 3 and 4.

[Example 1-3] The charge generating material of the charge generating layer was represented by the following structural formula

[0096]

Embedded image An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1, except that the compound was used. The results are shown in Tables 3 and 4.

Examples 1-4 to 1-14 Electrophotography was performed in the same manner as in Example 1-1, except that the binder resin for the charge transport layer used was one of the conditions 1-2 to 1-12 shown in Table 2. The body was created and evaluated. The results are shown in Tables 3 and 4.

[0098]

[Table 4]

[0099]

[Table 5]

[Comparative Examples 1-1 to 1-5] The same as Example 1-1 except that the charge generating material of the charge generating layer and the binder resin of the charge transporting layer used were those of the conditions 1 to 5 in Table 5. An electrophotographic photoreceptor was prepared and evaluated. The results are shown in Tables 6 and 7.

[0101]

[Table 6]

[0102]

[Table 7]

[0103]

[Table 8]

[0104]

[Table 9]

[Example 2-1] The charge generating material of the charge generating layer was represented by the following structural formula

[0106]

Embedded image An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1, except that the compound of the formula (1) was used and the binder resin for the charge transporting layer used was that of the condition 2-1 in Table 8. The results are shown in Tables 9 and 10.

[0107]

[Table 10] The mixing ratio between terephthalic acid chloride and isophthalic acid chloride was 1: 1 in molar ratio.

Example 2-2 The following structural formula was used for the charge generating material of the charge generating layer.

[0109]

Embedded image An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 2-1 except that the compound was used. The results are shown in Tables 9 and 10.

[Examples 2-3 to 2-13] Electrophotography was performed in the same manner as in Example 2-1 except that the binder resin for the charge transporting layer used was one of the conditions 2-2 to 2-12 shown in Table 8. The body was created and evaluated. The results are shown in Tables 9 and 10.

[0111]

[Table 11]

[0112]

[Table 12]

[Comparative Examples 2-1 to 2-4] Example 2 except that the charge generating material of the charge generating layer and the binder resin of the charge transporting layer used were those of the conditions 2-1 to 2-4 in Table 11. -1
An electrophotographic photoreceptor was prepared and evaluated in the same manner as described above. The results are shown in Tables 12 and 13.

[0114]

[Table 13]

[0115]

[Table 14]

[0116]

[Table 15]

[0117]

[Table 16]

[Example 3-1] The following structural formula was used for the charge generating material of the charge generating layer.

[0119]

Embedded image Table 14 was used as the binder resin for the charge transport layer
An electrophotographic photoreceptor was prepared in the same manner as in Example 1-1 except that the condition 3-1 was used.

Next, the evaluation will be described.

The device is a Hewlett-Packard LBP
"Laser Jet 4plus" was modified and used. In the modification, the primary charger was changed to corona charging (DC applied voltage to the wire was -6 KV, grid bias was -700 V), and the amount of laser light was made variable. The prepared electrophotographic photoreceptor was subjected to a paper-passing durability test at 28 ° C. and 90% RH using this apparatus. The sequence was an intermittent mode in which the print was stopped once for each print.

The surface potential (bright portion potential) of the electrophotographic photosensitive member was measured at the initial stage of durability and at 10,000 sheets.

Further, at the time of measurement, +10 μm
The light area potential when the current A was applied and transfer was performed was measured, and the value of the light area potential (without transfer) -the light area potential (with transfer) was shown as a transfer memory.

When the toner ran out, the toner was replenished and an endurance test was performed until a problem occurred in the image.

A Taber abrasion tester using a polishing tape was used for abrasion for 15 minutes, and the weight loss at that time was measured.

Further, 3000 L is applied to a part of the electrophotographic photosensitive member.
After illuminating with a white fluorescent lamp for 13 minutes at ux for 10 minutes, the bright portion potential was measured, and the value of the bright portion potential (before irradiation) -the bright portion potential (after irradiation) was taken as the photo memory value.

Further, regarding the solvent cracking property, sebum was adhered to the surface and allowed to stand for 48 hours, and the presence or absence of solvent cracking was observed by microscopic observation.

Table 15 shows the results.

Next, the measurement in direct charging was performed.

The apparatus is a Hewlett-Packard LBP
The charging member of "Laser Jet 4plus" was replaced with a roller which has been conventionally used, and a direct charging system was used.

The prepared electrophotographic photosensitive member was converted to 28
A paper passing durability test (HH durability) was performed at 90 ° C. and 90% RH. The sequence was an intermittent mode in which the print was stopped once for each print.

The light potential of the electrophotographic photosensitive member was measured at the initial stage of durability and at 10,000 sheets. The transfer memory was also measured in the same manner.

Table 16 shows the results.

[0134]

[Table 17] The mixing ratio between terephthalic acid chloride and isophthalic acid chloride was 1: 1 in molar ratio.

Example 3-2 The following structural formula was used for the charge generating material of the charge generating layer.

[0136]

Embedded image An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 3-1 except that the compound was used. The results are shown in Tables 15 and 16.

[Examples 3-3 to 3-13] Electrophotography was performed in the same manner as in Example 3-1 except that the binder resin for the charge transport layer used was one of the conditions 3-2 to 3-12 shown in Table 14. The body was created and evaluated. The results are shown in Tables 15 and 16.

[0138]

[Table 18]

[0139]

[Table 19]

[Comparative Examples 3-1 to 3-4] Example 3 except that the charge generating material of the charge generating layer and the binder resin of the charge transporting layer used were those of the conditions 3-1 to 3-4 in Table 17. -1
An electrophotographic photoreceptor was prepared and evaluated in the same manner as described above. The results are shown in Tables 18 and 19.

[0141]

[Table 20]

[0142]

[Table 21]

[0143]

[Table 22]

[0144]

[Table 23]

[0145]

The electrophotographic photoreceptor of the present invention has excellent solvent cracking resistance without impairing mechanical strength, is highly sensitive, and has excellent repetition characteristics due to durability.
Provided are an electrophotographic photoreceptor having a small photo memory and a transfer memory, and excellent in repetition characteristics even when directly charged by applying an AC voltage, and easily manufactured, and a process cartridge and an electrophotographic apparatus having the electrophotographic photoreceptor. It has become possible.

[Brief description of the drawings]

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

Claims (11)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a support, wherein the surface layer of the electrophotographic photosensitive member contains a polymer having a structural unit represented by the following formula (1): Contains an azo compound represented by the following formula (2): Embedded image [In the formula (1), X is -CR ₉ R _10- (R ₉ and R ₁₀ are the same or different and each represents a hydrogen atom, a trifluoromethyl group,
An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms), an optionally substituted α, ω-alkylene group having 2 to 10 carbon atoms, 1,1-cycloalkyl having 5 to 11 carbon atoms alkylene group, a single bond, -O -, - S -, - SO- or -SO ₂ - is. R _{1 to} R ₈ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group or an aryl group which may be substituted. (CPI-N = N) _n -A (2) [In the formula (2), A represents an optionally substituted aryl group, or a single bond thereof,-(CH = CH) _m- , -CH = N
-, -CO-, -O-, -S-, -CONH-, -NY
— Or —CH ₂ — (m is 1 or 2, and Y is a hydrogen atom, an alkyl group which may be substituted or a phenyl group), and CPI is represented by the following formula (3): Indicated by (4) or (5), n is 1, 2 or 3. ] Embedded image Embedded image [In the formulas (3), (4) and (5), R ₁₁ is an optionally substituted alkyl group or aryl group. R ₁₂ is a hydrogen atom, a cyano group, a carboxyl group, an ester group or an acyl group. ] 2. The electrophotographic photosensitive member according to claim 1, wherein the structural unit represented by the formula (1) is a structural unit represented by the following formula (6). Embedded image 3. The electrophotographic photosensitive material according to claim 1, wherein the azo compound represented by the formula (2) is a bis-azo compound represented by the following formula (7), (8) or (9). body. Embedded image Embedded image Embedded image 4. An electrophotographic photosensitive member having a photosensitive layer on a support, wherein the surface layer of the electrophotographic photosensitive member contains a polymer having a structural unit represented by the following formula (1): Contains an azo compound represented by the following formula (12) or (13). Embedded image [(In the formula (1), X is -CR ₉ R _10- (R ₉ and R ₁₀ are the same or different and each represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms, or 6 to 12 carbon atoms. Which is an aryl group having 2 to 10 carbon atoms which may be substituted
Α, ω-alkylene group, 1,1-cycloalkylene group having 5 to 11 carbon atoms, single bond, -O-, -S-, -SO-
Or —SO ₂ —. R _{1 to} R ₈ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group or an aryl group which may be substituted. ] Embedded image [In the formulas (12) and (13), B and B 'are the same or different. (R _{21 to} R ₂₄ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a nitro group). ] 5. The electrophotographic photoreceptor according to claim 4, wherein the structural unit represented by the formula (1) is a structural unit represented by the following formula (6). Embedded image 6. The electrophotographic photosensitive material according to claim 4, wherein the azo compound represented by the formula (12) or (13) is a bis-azo compound represented by the following formula (14) or (15). body. Embedded image Embedded image 7. An electrophotographic photosensitive member having a photosensitive layer on a support, wherein the surface layer of the electrophotographic photosensitive member contains a polymer having a structural unit represented by the following formula (1): Contains an azo compound represented by the following formula (16): Embedded image [In the formula (1), X is -CR ₉ R _10- (R ₉ and R ₁₀ are the same or different and each represents a hydrogen atom, a trifluoromethyl group,
An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms), an optionally substituted α, ω-alkylene group having 2 to 10 carbon atoms, 1,1-cycloalkyl having 5 to 11 carbon atoms alkylene group, a single bond, -O -, - S -, - SO- or -SO ₂ - is. R _{1 to} R ₈ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group or an aryl group which may be substituted. Embedded image [In the formula (16), R ₃₁ and R ₃₂ are the same or different,
It is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ₃₃ is a hydrogen atom or a halogen atom. ] 8. The electrophotographic photosensitive member according to claim 7, wherein the structural unit represented by the formula (1) is a structural unit represented by the following formula (6). Embedded image 9. An azo compound represented by the formula (16):
9. The electrophotographic photoreceptor according to claim 7, which is a tris-azo compound represented by the following formula (17) or (18). Embedded image Embedded image 10. An electrophotographic apparatus, wherein the electrophotographic photosensitive member according to claim 1 and at least one unit selected from the group consisting of a charging unit, a developing unit and a cleaning unit are integrally supported. A process cartridge which is detachable from a main body. 11. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposing unit, a developing unit, and a transferring unit.