JP2000338699A - Electrophotographic photoreceptor, its production, process cartridge and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an electrophotographic photoreceptor causing no image defects in any environment, less liable to a change in potential and having good electrophotographic characteristics in an easy and stable manner at a low cost. SOLUTION: The electrophotographic photoreceptor has a photosensitive layer on an aluminum substrate. The surface of the substrate on the photosensitive layer side has been polished by rotating the substrate to a polishing means with plural grinding stones, moving it in the direction of the rotational axis under rotation and vibrating at least one of the grindings tones in the direction of the rotational axis and the surface of the substrate contains aluminum, oxygen and titanium or aluminum, oxygen and zirconium. Each of the process cartridge and the electrophotographic device has the electrophotographic photoreceptor.

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, a method for manufacturing the photosensitive member, and a process cartridge and an electrophotographic apparatus having the photosensitive member.

[0002]

2. Description of the Related Art An electrophotographic photosensitive member basically comprises a photosensitive layer for forming a latent image by charging and exposure using light, and a substrate on which the photosensitive layer is provided.

On the other hand, an electrophotographic photoreceptor is required to have sensitivity, electrical characteristics, and optical characteristics according to an applied electrophotographic process.

[0004] Further, in any environment from low temperature and low humidity to high temperature and high humidity, it is required to have environmental stability such that the characteristics are sufficiently exhibited.

Typical image defects include image streaks, black spots on a white background, white spots on a black background, background fog on a white background, and a single wavelength of a digital copier or a laser beam printer. In the case of an apparatus that performs exposure using a light source, there are interference fringes and the like generated due to factors such as the surface shape of the substrate and the thickness unevenness of the photoconductor.

Therefore, when producing a photoreceptor, it is necessary to take some measures in advance so that these image defects do not occur.

Factors that have a great influence on the occurrence of image defects as described above include the state of the surface of the substrate.

A substrate that has not been subjected to any treatment after molding usually does not necessarily have an optimum surface condition as a photoreceptor. Therefore, a problem due to the surface state often occurs.

In order to solve this problem, Japanese Patent Laid-Open Publication Nos. 1-123246, 64-86153 and 4-242742-9 disclose conventional techniques.
It is described that a photosensitive layer is formed after the surface of an aluminum substrate is cut by a lathe. In particular, it has been practiced to cut the surface of the substrate of the digital photoreceptor into irregularities by cutting, thereby preventing interference fringes.

However, when the aluminum base is cut in this way, since continuous processing traces remain in the circumferential direction, streak-like image defects appear in a halftone image, and in particular, digital images and laser scanning Moire was likely to occur due to the relationship with the line.

When so-called centerless processing is used to grind the cylindrical surface using a rotating grindstone, irregular irregular surfaces can be obtained. However, a hard grindstone is rotated at high speed to grind the cylindrical surface. In some cases, deep scratches were made on some parts, and the scratches sometimes caused image defects when the photoreceptor was manufactured.

On the other hand, a method of performing a chromate treatment on the surface of an aluminum substrate to form a chromate conversion coating as disclosed in, for example, JP-A-54-12733 and JP-A-57-62056. JP 58
A method of forming a boehmite film on the surface of an aluminum substrate as disclosed in JP-A-14841 and JP-A-64-29852, and JP-A-57-2
There has been proposed a method such as a method of forcibly oxidizing the surface of an aluminum substrate at a high temperature to form an oxide film as disclosed in Japanese Patent No. 9051.

[0013]

However, for example, a substrate having a certain level of performance can be obtained with respect to the chromate treatment method. However, since the treatment solution contains chromium, it is very difficult to treat the waste solution, and it is preferable from the viewpoint of environmental safety. Absent.

Regarding the boehmite treatment, the crystal state of the surface is not always suitable for the substrate of the electrophotographic photosensitive member, and a certain effect can be obtained with respect to the electrophotographic characteristics. At present, there is no product that satisfies all characteristics, such as insufficient image quality due to inappropriateness.

The purpose of these surface treatments is to prevent the film formed on the substrate surface from causing unevenness in electrophotographic characteristics and images due to charges partially injected from the substrate into the photosensitive layer.

As a method of preventing this partial injection and eliminating image defects, there is a method of providing an aluminum oxide layer by anodizing the surface of an aluminum substrate (JP-A-2-7070 and JP-A-5-7070). -34964 and the like).

This method is a good method for solving the above-mentioned object. However, in order to form the film uniformly on the surface of the substrate so as not to cause unevenness in the film thickness, the film thickness must be kept at a certain value or more under ordinary forming conditions. Must be about 5 to 6 μm or more. Therefore, it must be formed much thicker than the film thickness actually required as the charge injection preventing layer, leading to an increase in cost.

Accordingly, an object of the present invention is to prevent image defects from occurring in any environment from low temperature and low humidity to high temperature and high humidity,
Also, an electrophotographic photoreceptor having good electrophotographic characteristics with little potential fluctuation, a method for easily and inexpensively manufacturing the photoreceptor stably, and a process cartridge and an electrophotographic apparatus having the photoreceptor are provided. To provide.

[0019]

As a result of investigations to solve the above problems, a specific surface roughening treatment was performed on the surface of an aluminum substrate used for an electrophotographic photosensitive member.
Performing a specific chemical conversion treatment, that is, forming an insoluble film having a specific composition on the substrate by a chemical reaction between the substrate and an acidic aqueous solution containing a specific metal element without using an external electric force, An electrophotographic photoreceptor having excellent characteristics can be obtained without interference fringes. The cost and the adverse effect on the environment can be extremely reduced. The production apparatus can be simplified as compared with anodizing treatment. In this regard, we have found it to be a very effective tool.

That is, according to the present invention, in an electrophotographic photosensitive member having a photosensitive layer on an aluminum substrate, the surface of the substrate on the photosensitive layer side is rotated while rotating the substrate with respect to a polishing means having a plurality of grindstones. An electrophotographic photoreceptor, which is polished by moving in an axial direction and vibrating at least one grindstone in the direction of the rotation axis, and containing aluminum, oxygen and titanium, or aluminum, oxygen and zirconium. It is.

[0021] The present invention also provides a step of polishing by moving an aluminum substrate in a rotation axis direction while rotating the aluminum substrate with respect to a polishing means having a plurality of whetstones, and vibrating at least one whetstone in the rotation axis direction. A method for producing an electrophotographic photosensitive member, comprising: a step of subjecting the polished substrate to a chemical conversion treatment with an acidic aqueous solution containing a titanium salt or a zirconium salt; and a step of forming a photosensitive layer.

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

[0023]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, the surface roughness of the substrate on the photosensitive layer side is 0.5 to 3 in maximum height (Rmax).
0 μm, 0.5 to 1.8 μm in ten point average roughness (Rz),
The polishing means used in the present invention, which preferably has an average peak interval (Sm) of 10 to 100 μm, has a plurality of grindstones, and preferably arranges these grindstones on a substantially straight line.

The rotation speed of the aluminum substrate is 300 to 8
A range of 00 rpm is preferred. If it is less than 300 rpm, the polishing amount by the grindstone is large, the polishing resistance is increased, and deep scratches are easily generated. On the other hand, if it exceeds 800 rpm, the amount of polishing is reduced, and polishing is difficult.

The feed speed of the aluminum substrate is preferably in the range of 0.5 to 1.5 m / min in relative speed.
If it is less than 0.5 m / min, the polishing amount may increase and the roughness may become too coarse. 1.5m / min
If it exceeds 300, the polishing amount will be small, and it will be difficult to obtain a predetermined roughness.

The amplitude of the vibration of the grindstone is preferably in the range of 0.5 to 1.5 mm. The frequency is 2000 to 2500c.
pm is preferred. Although the purpose can be realized by vibrating at least one of the grinding wheels, it is preferable to vibrate all the grinding wheels in order to continuously and stably perform polishing.

The pressing force of the grindstone is 1.0 to 2.0 kgf / c
A range of m ² is preferred.

Green silicon carbide is preferably used as the abrasive. Green silicon carbide is because fine abrasive grains cause micro-destruction during polishing and new blades are formed one after another, so that good polishing action can be obtained.

It is preferable to use a grindstone having a particle size of about # 220 as a grinding stone to be polished first. This is due to the fact that the abrasive grains are easily polished due to the coarse abrasive grains, and there is little adhesion of chips to the grindstone, and there is little damage to the cylindrical tube.

Next, the grinding wheels to be polished are # 220 to # 320.
It is preferable to use one having a particle size of the order. This is because only the surface portion polished by the grindstone is polished, and the generation of chips is small, so that the chips are little attached to the grindstone.

Further, the grinding wheels to be polished next are # 320 to #
It is preferable to use one having a particle size of about 400. Since only the surface polished by the previous grindstone is polished, there is little generation of chips and there is little reduction in the polishing effect due to the adhesion of the chips to the grindstone and clogging, and it has a continuous polishing effect. by.

The grindstone used for the polishing has a width of 13 m.
It is preferably a rectangular parallelepiped having a length of 50 mm, a depth of 50 mm, and a height of 20 mm, and the surface to be contacted by the grindstone is chamfered to approximately 15 mmR so as to conform to the shape of the aluminum base.

For lubrication and cooling during polishing,
It is preferable to use a polishing liquid, and particularly, an oily polishing liquid is suitably used.

Further, the deflection during rotation of the aluminum substrate,
In order to suppress vibration, it is preferable to use a nylon grindstone before and after a grindstone having green silicon carbide abrasive grains.

In the polishing by such vibration, it is necessary to reduce the amount of polishing in order to obtain a desired roughness without generating deep scratches.
Preferably, the polishing allowance is 2 to 10 μm, and 2 to 6 μm.
m is more preferable.

As the aluminum substrate, it is preferable to use an aluminum pipe that has been drawn or ironed or an aluminum pipe that has been cut.

When cleaning the substrate after polishing in the present invention, the surface shape of the polished surface is more complicated than the cutting surface of the cutting tool, and the cleaning is relatively difficult. Considering the effect on water, a washing method using a jet water flow is appropriate. It is more effective to use a suitable surfactant or ultrasonic wave in the water washing method.

The surface roughness was measured using a surface roughness measuring machine (Surfcoder SE-3300 manufactured by Kosaka Laboratories) under the following measurement conditions.

Cut-off value 0.8 mm, reference length 0.8
mm, evaluation length 8.0 mm, Gaussian filter.

The chemical conversion treatment in the present invention is a treatment for forming a film of a specific composition on a substrate by bringing the substrate into contact with a specific solution without applying an external electric force as in anodic oxidation.

The metal of the metal salt used in the present invention is titanium and zirconium. The aluminum substrate having the chemical conversion film of the present invention in which aluminum and oxygen coexist is extremely excellent as a substrate for an electrophotographic photosensitive member. Has characteristics.

The titanium salt and zirconium salt to be added are preferably fluorine compounds. Examples of the titanium salt include titanium hydrofluoric acid and its sodium salt, potassium salt, ammonium salt, and titanium sulfate, and examples of the zirconium salt include potassium zircon fluoride and zirconium sulfate.

The concentration of the metal salt in the acidic aqueous solution is preferably in the range of 0.01 g to 2 g / liter in terms of the amount of the metal.

The concentration of fluorine ions in the acidic aqueous solution is preferably in the range of 0 to 10 g / liter. In this range, the etching reaction on the substrate surface occurs appropriately, and a uniform film is easily formed.

The pH of the acidic aqueous solution of the present invention is preferably adjusted to a range of 1.0 to 5.5 with ammonia, sodium hydroxide or the like.

When the pH is less than 1.0, the etching reaction occurs violently, and it is difficult to obtain a good film. When the pH exceeds 5.5, the film formation rate is low and only a thin film is hardly obtained. It is difficult to obtain.

In the present invention, the acidic aqueous solution is preferably heated to 30 to 90 ° C. in that the reaction is stably performed.

The method of bringing the substrate into contact with the acidic aqueous solution may be any of a dipping method and a spraying method using a spray, but the dipping method is preferred from the viewpoint of production efficiency.

The substrate after the chemical conversion treatment is used after being washed and dried.

The composition of the substrate surface in the present invention is measured by Auger electron beam spectroscopy, and is assumed to be within a range of 50 ° (5 × 10 ⁻³ μm) from the outermost surface of the substrate.

In the present invention, the content of titanium or zirconium is 4 to the content of aluminum.
It is preferably in the range of １００100 atm%.

The total thickness of the titanium or zirconium-containing chemical conversion film formed on the substrate surface is preferably 1 μm or less, more preferably 50 ° (5 × 10 ⁻³ μm) or more. When the film thickness exceeds 1 μm, it is difficult for the electric charge to escape, so that the residual potential increases and ghosts are easily generated. On the other hand, 50 ° (5 × 10 ^-3 μm)
If less than the above, it is difficult to obtain a remarkable effect of the present invention.

In the present invention, the acidic aqueous solution preferably further contains phosphoric acid, phosphate, tannin or tannic acid from the viewpoint of corrosion resistance and adhesion of the coating film.

Examples of the phosphoric acid and phosphate include condensed phosphates of phosphoric acid or its sodium, potassium and ammonium salts, pyrophosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid and alkali metal salts thereof such as sodium and potassium salts. No. Further, organic phosphoric acid compounds such as phytic acid, nitrodiethanol ethylene phosphonic acid, 2-hydroxyethyl methacryl-1-acid phosphonic acid, 2-ethylhexyl acid phosphonic acid and ethane-1-hydroxy-1,1-diphosphonic acid are used. You can also.

The concentration of phosphoric acid or phosphate in the acidic aqueous solution is preferably in the range of 0.05 to 50 g / liter in terms of phosphate ions. Within this range, a particularly good and uniform chemical conversion film can be obtained, and the stability of the treatment liquid is also particularly good.

Examples of the tannin or tannic acid include kepracho, depudito, tannic acid from China, tannic acid from Turkey, hamamelitannic acid, kepric acid, smack tannin, quintuple tannin, tannin from ergic acid, and the like.

The concentration of tannin or tannic acid in the acidic aqueous solution is preferably in the range of 0.1 to 10 g / liter.

In the present invention, the acidic aqueous solution is
It preferably contains hydrofluoric acid, boric acid, silicic acid and salts thereof. Since these have a function of etching the surface of the aluminum substrate when the chemical conversion treatment is performed on the aluminum substrate, a very uniform chemical conversion film can be obtained.

From the above, it is preferable that the chemical conversion film of the present invention contains phosphorus and fluorine.

The aluminum substrate is not particularly limited as long as it is aluminum. Pure aluminum and A
1-Mn, Al-Mg, Al-Cu, Al-Si
And aluminum alloys such as Al-Mg-Si-based and Al-Cu-Si-based. More specifically, JIS
6000 series aluminum alloy such as A6063 and JI
A 3000 series aluminum alloy such as SA3003 can be used. The shape is not particularly limited, but is preferably a drum shape.

Next, the photosensitive layer of the electrophotographic photosensitive member used in the present invention will be described.

The structure of the photosensitive layer of the present invention may be a single-layer type containing both a charge generating substance and a charge transporting substance in the same layer, and a charge generating layer containing a charge generating substance and a charge containing a charge transporting substance. It is roughly classified into a laminated type having a transport layer.

Hereinafter, an electrophotographic photosensitive member having a laminated photosensitive layer will be described.

The structure of the photoreceptor includes a structure in which a charge generation layer and a charge transport layer are laminated on a substrate in this order, and a structure in which a charge transport layer and a charge generation layer are laminated in this order.

The charge transport layer comprises a polycyclic aromatic compound having a structure such as biphenylene, anthracene, pyrene and phenanthrene in the main chain or side chain; a nitrogen-containing ring compound such as indole, carbazole, oxadiazole and pyrazoline; a hydrazone compound And a solution in which a charge transport material such as a styryl compound or the like is dissolved in a resin having a film-forming property is applied and dried.

Examples of the resin having a film forming property include polyester, polycarbonate, polystyrene, polymethacrylate and polyarylate.

The thickness of the charge transport layer is preferably 5 to 40.
μm, more preferably 10 to 30 μm.

The charge generation layer is made of an azo pigment such as Sudan Red and Diane Blue; a quinone pigment such as pyrene, quinone and anthantrone; a quinocyanine pigment; a perylene pigment; an indigo pigment such as indigo and thioindigo; It is formed by applying a dispersion of a substance dispersed in a resin such as polyvinyl butyral, polystyrene and polyvinyl acetate, and an acrylic resin, followed by drying or vacuum deposition of the pigment.

The thickness of the charge generation layer is preferably 5 μm or less, more preferably 0.01 to 3 μm.

The single-layer type photosensitive layer is formed by applying a solution obtained by dispersing and dissolving the above-mentioned charge generating substance and charge transporting substance in the above-mentioned resin, and drying the applied solution.

The thickness of the photosensitive layer is preferably 5 to 40 μm.
m, more preferably 10 to 30 μm.

In the present invention, between the substrate and the photosensitive layer,
An undercoat layer having a barrier function and an adhesive function can be provided. The undercoat layer is formed by applying and drying a solution in which casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, alcohol-soluble polyamide, polyurethane, gelatin and the like are dissolved.

The thickness of the undercoat layer is preferably 0.1 to 3 μm.

In the present invention, a protective layer may be provided on the photosensitive layer.

The materials constituting the protective layer include polyester, polyacrylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide,
Polypropylene, polyimide, polyamide imide, polysulfone, polyacryl ether, polyacetal, phenol, acrylic, silicone, epoxy, urea,
Examples include allyl, alkyd, butyral, phenoxy, phosphazene, acrylic-modified epoxy, acrylic-modified urethane, and acrylic-modified polyester resin.

The thickness of the protective layer is preferably from 0.2 to 10 μm.

Each of the above-mentioned layers is made of polytetrafluoroethylene, polyvinylidene fluoride, a fluorine-based graft polymer, a silicone-based graft polymer, a fluorine-based block polymer, a silicone-based block, in order to improve the cleaning property and the wear resistance. A lubricant such as a polymer and a silicone oil may be contained.

Further, additives such as an antioxidant may be added for the purpose of improving weather resistance.

Further, a conductive powder such as conductive tin oxide and conductive titanium oxide may be dispersed in the protective layer for the purpose of controlling the resistance.

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

In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around an axis 2 at a predetermined peripheral speed in a direction indicated by an arrow. The photoreceptor 1 rotates during the rotation process.
The peripheral surface is uniformly charged with a predetermined positive or negative potential by the primary charging means 3 and then receives exposure light 4 from exposure means (not shown) such as 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-developed image developed by the toner image is transferred from a paper supply unit (not shown) between the photoconductor 1 and the transfer unit 6 in synchronization with the rotation of the photoconductor 1 and fed to a transfer material 7 fed therefrom. The image is sequentially transferred by the transfer unit 6.

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

After the transfer of the image, the surface of the photoreceptor 1 is cleaned by removing the untransferred toner by the cleaning means 9, and the pre-exposure light 10 from the pre-exposure means (not shown).
Is used for image formation repeatedly after the charge removal processing. 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, among the above-mentioned components such as the electrophotographic photosensitive member 1, the primary charging means 3, the developing means 5 and the cleaning means 9, a plurality of components 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, 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 the cartridge is detachably attached to the apparatus main body using guide means such as the rail 12 of the apparatus main body. Process cartridge 1
It can be 1.

When the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is reflected light or transmitted light from the original, or the original is read by a sensor, converted into a signal, and a laser beam is emitted in accordance with the signal. Beam scanning, LED
Light emitted by driving the 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.

[0088]

Example 1 An aluminum alloy JIS standard A 6063 material was extruded by a porthole extruding method with an outer diameter of 30.0 mm and an inner diameter of 20.0 mm.
It was continuously extruded into a 8.0 mm pipe shape and cut into a length of 254 mm to form a cylindrical tube. Maximum height (Rma
x) is 2.0 μm and ten-point average roughness (Rz) is 0.6 μm
Met.

Next, polishing was performed under the following conditions using a super finishing machine (TS-21, manufactured by Toyo Advanced Technologies Co., Ltd.).

Rotational speed of cylindrical tube: 690 rpm Feeding speed of cylindrical tube: 1.1 m / min Grinding wheel amplitude: 1.0 mm Grinding wheel frequency: 2200 cpm Grinding stone pressure: 1.5 kgf / cm ² Kind of grinding stone: nylon, GC220, GC320, GC
400, size of nylon whetstone: width 13mm, depth 50mm, height 20m
m

The substrate polished under the above conditions was washed with a water washing device using a jet water stream. Then, it was washed again with pure water using an ultrasonic oscillator.

From the change in the outer diameter, the polishing allowance was 5 μm. When the surface roughness of the substrate thus produced was measured, the maximum height (Rmax) was 1.5 μm, the ten-point average roughness (Rz) was 1.2 μm, and the average peak interval (Sm) was 32.
μm.

This substrate was placed in a 20% sulfuric acid aqueous solution at 40 ° C. for 3 hours.
After immersion for a minute, the substrate was washed with pure water and air-dried.

An acidic aqueous solution containing phytic acid as an organic phosphoric acid and titanium hydrofluoric acid and a titanium ammonium fluoride as a metal salt (trade name: Palcoat 37)
53, manufactured by Nippon Parkerizing Co., Ltd., pH 3.8) at a temperature of 40 ° C., the above-mentioned aluminum cylinder was immersed in this aqueous solution, subjected to a chemical conversion treatment for 1 minute, washed with pure water, and naturally dried I let it. Chemical conversion film thickness is 200
Was Å.

Next, 4 parts by weight of an oxytitanium phthalocyanine pigment and a polyvinyl butyral resin (trade name: BX)
1, 2 parts by weight of Sekisui Chemical Co., Ltd.) and 34 parts by weight of cyclohexanone were dispersed in a sand mill for 8 hours, and 60 parts by weight of tetrahydrofuran was added to prepare a dispersion for a charge generation layer.

This dispersion was dip-coated on an aluminum cylinder previously subjected to a chemical conversion treatment, and dried by heating at 95 ° C. for 10 minutes to form a 0.2 μm-thick charge generation layer.

Next, a solution prepared by dissolving 50 parts by weight of a triarylamine compound represented by the following formula and 50 parts by weight of a bisphenol Z-type polycarbonate resin in 400 parts by weight of monochlorobenzene was applied onto the charge generating layer by dip coating.
The resultant was dried by heating at 10 ° C. for 1 hour to form a charge transport layer having a thickness of 20 μm.

[0098]

Embedded image

(Evaluation) Elemental analysis was performed using a scanning Auger electron spectrometer while performing argon ion etching on the surface of the substrate after the chemical conversion treatment, washing, and drying from the outermost surface in the depth direction of the substrate. As a result, aluminum, titanium and oxygen were detected as main constituent elements.
The obtained graph is shown in FIG. In this embodiment, the relationship between the depth and the sputtering time is 110 ° in terms of SiO _2.
/ Min, but this value can be changed as appropriate.

Table 1 shows that the composition ratio of the element at the outermost surface of the substrate and at a depth of 50 ° from the surface is 10
It is shown as an element ratio when it is set to 0.

From these results, it is understood that the chemical conversion film on the surface of the substrate is a film in which titanium is incorporated in an oxide film of aluminum. As a result of the analysis, nitrogen, fluorine, phosphorus and the like were detected as other contained elements. It is presumed that these elements were taken into the chemical conversion film from substances contained in the phosphoric acid and the fluorine compound in the acidic aqueous solution used in the chemical conversion treatment.

Next, the obtained electrophotographic photosensitive member was subjected to normal temperature and normal humidity (23 ° C., 60% Rh), high temperature and high humidity (32.5 ° C., 85%).
% Rh) and a low-temperature and low-humidity environment (15 ° C., 10% Rh) for 48 hours, and then installed in a commercially available reversal developing laser beam printer to output a solid white image under each environment.

The state of background fog in this solid white image was visually evaluated. Table 2 shows the results.

At the same time, the values of the dark potential and the light potential in each environment were measured. Table 2 shows the results.

The presence or absence of interference fringes was also evaluated visually.

Example 2 An aluminum alloy of JIS A 6063 was extruded by a porthole extrusion method to have an outer diameter of φ30.15 mm and an inner diameter of 2
It was continuously extruded into a 8.0 mm pipe shape and cut into a length of 254 mm. Thereafter, cutting was performed with a lathe to produce a cylindrical tube having a maximum height (Rmax) of 1.5 μm and a ten-point average roughness (Rz) of 0.6 μm.

Next, polishing was performed under the following conditions using an apparatus of a superfinishing machine (TS-21, manufactured by Toyo Advanced Technologies Co., Ltd.).

Rotation speed of cylindrical tube: 680 rpm Feeding speed of cylindrical tube: 1.1 m / min Grinding wheel amplitude: 1.0 mm Grinding wheel frequency: 2200 cpm Grinding stone pressure: 1.3 kgf / cm ² Kind of grinding stone: nylon, GC220, GC320, GC
400, size of nylon whetstone: width 13mm, depth 50mm, height 20m
m

The substrate polished under the above conditions was washed with a water washing device using a jet water flow. Then, it was washed again with pure water using an ultrasonic oscillator.

From the change in the outer diameter, the polishing allowance was 4 μm. When the surface roughness of the substrate thus manufactured was measured, the maximum height (Rmax) was 1.5 μm, the ten-point average roughness (Rz) was 0.8 μm, and the average peak interval (Sm) was 30.
μm.

The substrate was placed in a 20% aqueous sulfuric acid solution at 40 ° C. for 3 hours.
After immersion for a minute, the substrate was washed with pure water and air-dried.

Using the aluminum cylinder thus obtained, tannic acid,
Liquid containing zirconium fluoride and zirconium sulfate as ammonium salt and metal salt (trade name: Palcoat 3756, manufactured by Nippon Parkerizing Co., Ltd., pH
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that 3.2) was used. The results are shown in Tables 1 and 2. The chemical conversion film had a thickness of 150 °.

Example 3 An aluminum alloy JIS standard A 3003 material was subjected to a port hole extrusion method by an outer diameter of φ30.15 mm and an inner diameter of 2
It was continuously extruded into a 8.0 mm pipe shape and cut into a length of 254 mm. Thereafter, cutting was performed with a lathe to produce a cylindrical tube having a maximum height (Rmax) of 1.5 μm and a ten-point average roughness (Rz) of 0.6 μm.

Next, polishing was carried out under the following conditions using a super-finishing machine (TS-21, manufactured by Toyo Advanced Technologies Co., Ltd.).

Rotation speed of cylindrical tube: 680 rpm Feeding speed of cylindrical tube: 1.1 m / min Grinding wheel amplitude: 1.0 mm Grinding wheel frequency: 2200 cpm Grinding stone pressure: 1.6 kgf / cm ² Kind of grinding stone: nylon, GC220, GC320, GC
400, size of nylon whetstone: width 13mm, depth 50mm, height 20m
m

The substrate polished under the above conditions was washed with a water washing device using a jet water stream. Then, it was washed again with pure water using an ultrasonic oscillator.

From the change in the outer diameter, the polishing allowance was 4 μm. When the surface roughness of the substrate thus produced was measured, the maximum height (Rmax) was 1.8 μm, the ten-point average roughness (Rz) was 1.2 μm, and the average peak interval (Sm) was 32.
μm.

This substrate was placed in a 20% sulfuric acid aqueous solution at 40 ° C. for 3 hours.
After immersion for a minute, the substrate was washed with pure water and air-dried.

Using the aluminum cylinder thus obtained, a solution containing phytic acid as an acidic aqueous solution for chemical conversion treatment and a solution containing zircon hydrofluoric acid and ammonium zircon fluoride as metal salts (trade name: Palcoat 3753T, Nippon Parkerizing Co., Ltd., pH
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that 3.5) was used. The results are shown in Tables 1 and 2. The chemical conversion film had a thickness of 180 °.

Example 4 As an acidic aqueous solution for chemical conversion treatment, a solution containing zirconium fluoride and sodium zircon hydrofluoride as salts of phosphoric acid and metal (trade name: Alsurf 301N-1,
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that Nippon Paint Co., Ltd., pH 4.0) was used. The results are shown in Tables 1 and 2. The chemical conversion film had a thickness of 300 °.

Comparative Example 1 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the chemical conversion treatment was not performed. Table 2 shows the results.

Comparative Example 2 An aqueous ammonia having a concentration of 0.3% was prepared and heated to 95 ° C.

The aluminum cylinder before the chemical conversion treatment used in Example 1 was immersed in the heated aqueous ammonia for 5 minutes to perform a surface treatment, and then dried to form a boehmite film on the cylinder surface.

An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that this aluminum cylinder was used instead of the chemical conversion-treated aluminum cylinder of the present invention. Table 2 shows the results.

Comparative Example 3 Instead of the acidic aqueous solution of the present invention, a chromium phosphate-based chemical conversion treatment solution containing no titanium and zirconium (trade name: Alchrome 3701, Nippon Parkerizing Co., Ltd.)
The solution was immersed in a solution maintained at 30 ° C. for 1 minute for chemical conversion treatment to form a chromate-based chemical film on the cylinder surface.

An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that this aluminum cylinder was used instead of the chemical conversion-treated aluminum cylinder of the present invention. Table 2 shows the results.

[0127]

[Table 1]

[0128]

[Table 2]

[0129]

As described above, according to the present invention,
An electrophotographic photoreceptor having good electrophotographic properties with no image defects occurring in any environment and with little potential fluctuation, a method for easily and inexpensively and stably producing the electrophotographic photoreceptor, A process cartridge having an electrophotographic photosensitive member and an electrophotographic apparatus can be provided.

[Brief description of the drawings]

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

FIG. 2 is a view showing the composition ratio of elements constituting the surface of an aluminum substrate of the electrophotographic photoreceptor of the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor: Adult Tanaka 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor: Tomohiro Kimura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Yoichi Kawamorita 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term (reference) 2H068 AA52 AA54 AA58 AA59 CA32 EA05 EA07 FA27

Claims (18)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on an aluminum substrate, wherein the surface of the substrate on the photosensitive layer side moves in the direction of the rotation axis while rotating the substrate with respect to a polishing means having a plurality of whetstones. Has been polished by vibrating at least one grindstone in the direction of the rotation axis,
And an electrophotographic photosensitive member containing aluminum, oxygen and titanium, or aluminum, oxygen and zirconium. 2. The electrophotographic photoreceptor according to claim 1, wherein the content of titanium or zirconium on the surface of the substrate on the photosensitive layer side is 4 to 100 atm% with respect to the aluminum content. 3. The electrophotographic photosensitive member according to claim 1, wherein the surface of the substrate on the photosensitive layer side further contains phosphorus. 4. The electrophotographic photosensitive member according to claim 1, wherein the surface of the substrate on the photosensitive layer side further contains fluorine. 5. The electrophotographic photosensitive member according to claim 1, wherein the surface of the substrate on the photosensitive layer side is a film formed by a chemical conversion treatment. 6. The film according to claim 5, wherein the thickness of the film is 1 μm or less.
The electrophotographic photosensitive member according to the above. 7. The substrate has a surface roughness on the photosensitive layer side of 0.5 to 3.0 μm in maximum height (Rmax) and a ten-point average roughness (Rmax).
z): 0.5 to 1.8 μm, average interval between peaks (Sm): 10
The electrophotographic photoreceptor according to any one of claims 1 to 6, which has a thickness of from 100 to 100 µm. 8. A step in which the aluminum substrate is moved in the direction of the rotation axis while rotating with respect to the polishing means having a plurality of grinding stones, and polishing is performed by vibrating at least one grinding stone in the direction of the rotation axis. A method for producing an electrophotographic photoreceptor, comprising a step of subjecting a substrate to a chemical conversion treatment with an acidic aqueous solution containing a titanium salt or a zirconium salt, and a step of forming a photosensitive layer. 9. The method according to claim 8, wherein the titanium salt and the zirconium salt are fluorine compounds. 10. The method for producing an electrophotographic photosensitive member according to claim 8, wherein the pH of the acidic aqueous solution is 1.0 to 5.5. 11. The method for producing an electrophotographic photosensitive member according to claim 8, wherein the temperature of the acidic aqueous solution is 30 to 90 ° C. 12. The acidic aqueous solution further comprises phosphoric acid, phosphate,
The method for producing an electrophotographic photoreceptor according to any one of claims 8 to 11, comprising at least one compound selected from the group consisting of tannin and tannic acid. 13. The acidic aqueous solution further contains at least one compound selected from the group consisting of hydrofluoric acid, borofluoric acid, silicic acid and salts thereof.
3. The method for producing an electrophotographic photosensitive member according to any one of 2. 14. The rotation speed of the substrate is 300 to 800 rpm.
The method for producing an electrophotographic photosensitive member according to claim 8, wherein m is m. 15. The moving speed of the substrate is 0.5 to 1.5 m /
The method for producing an electrophotographic photosensitive member according to any one of claims 8 to 14, wherein the min. 16. The vibration amplitude of the grinding wheel is 0.5 to 1.5 m.
16. The method for producing an electrophotographic photoreceptor according to claim 8, wherein m and the frequency are from 2000 to 2500 cpm. 17. 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. 18. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an exposing unit, a developing unit, and a transferring unit.