JPH06208231A - Electrophotographic receptor - Google Patents

Abstract

PURPOSE:To obtain the electrophotographic receptor which has no picture flaw and which is high sensitivity and excellent in repetivive performance by using an aluminum substrate which is subjected to warhing by water or to a positive oxidation to the electrically conductive substrate and incorporating the electric charge generating material expressed by a specified formula in a electric charge generating layer. CONSTITUTION:The constituting layer is formed by providing an electric charge generating layer on an electrically conductive substrate and providing an electric charge transfer layer on that. And the aluminum substrate which is subjected to washing by water or to a positive oxidation to the electrically conductive substrate is used and the electric charge generating layer is incorporated with the electric charge generating material expressed by formula I or II. In formula I or II, Z is the atom group forming a bivalent arom. ring which may have a substd. group. and as the constituting layer, the photosensitive photoreceptor may have the intermediate layer consisting of polyamide resin between the electrically conductive substrate and the electric charge generating layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoconductor used for electrophotography, and more particularly to a high-sensitivity photoconductor having no image defects and good potential characteristics.

[0002]

2. Description of the Related Art As a conventional electrophotographic photoreceptor, a photosensitive layer made of an inorganic photoconductive material or a photosensitive layer made of an organic photoconductive material is provided on a plate-shaped, belt-shaped or drum-shaped aluminum substrate. Photoconductors are known.

The electrophotographic performance of the photoconductor is largely influenced by the surface condition and material of the aluminum substrate. That is, if the mechanical smoothness of the surface of the substrate is poor and there are irregularities or scratches, electrical defects occur and black spots, black streaks, etc. occur during image formation. Therefore, mirror finishing is usually performed with a diamond bite or the like. Further, the aluminum substrate usually contains magnesium, iron, silicon, copper, manganese and the like as alloy components in order to secure desired mechanical strength.

When a photosensitive member made of an organic material is manufactured using a conductive base member made of any of these aluminum alloys, a charge generation layer (CGL) is thinly applied and formed on the base member on the order of submicron, and is formed thereon. Charge transport layer (CTL)
It is formed with a film thickness of 10 to 30 μm. In order to obtain a high-quality electrophotographic image-bearing photoreceptor, it must be a very uniform film free from foreign substances. Therefore, high cleanliness is required on the surface of the substrate.

The rotary drum-shaped substrate made of the aluminum alloy is generally finished by cutting the surface of a tubular material, and a cutting fluid is usually used during the cutting. This cutting fluid is used for the purpose of cooling action, lubricating action, cleaning action, etc. Specifically, petroleum-based, polybutene-based, kerosene, white kerosene, etc. are used.

Further, in order to prevent the occurrence of image defects, the surface of the substrate is cleaned by a contact type cleaning means using a brush, an abrasive or the like after cutting the substrate.

If foreign matter is present on the surface of the substrate and an uneven portion is formed in the charge generation layer, white spots are generated on the obtained image. However, even if a substrate that has been cleaned to a level where the presence of foreign matter can be almost ignored is used, minute white spots may occur on the image in a high temperature environment. This is because free carriers are injected from the conductive base material into the charge generation layer. In order to suppress this free carrier injection, charge injection blocking that has a required resistance value at the interface between the base material and the charge generation layer is performed. In many cases, a layer (barrier layer) is provided. As the barrier layer, a resin film having a relatively low resistance typified by polyamide or the like applied on a substrate, an anodized film formed by subjecting the surface of an aluminum alloy substrate to anodizing treatment, and the like are known. . The film quality, resistance, etc. of the aluminum alloy anodized film can be controlled by the film forming conditions (anodizing condition, sealing treatment condition). In order to form an anodized film that is suitable as a barrier layer, the film formation conditions are limited to a relatively narrow range, but the film obtained is not only suitable as a barrier layer, but also hard and stable in film quality and easy to handle. Since it is easy, it has been widely used.

Further, in the case of a substrate made of an aluminum alloy surface-treated with cutting oil as described above, in order to sufficiently remove the cutting oil, Freon such as Freon 11, 112, 113 and trichloroethylene are used. , 1,1,1-trichloroethane, perchlorethylene, methylene chloride, etc. must be washed with a chlorine-based solvent. Therefore, using a large amount of such a solvent may cause ozone depletion or carcinogenesis. There is a problem in environmental pollution and work safety from the viewpoint of sex.

Therefore, instead of an organic solvent as the cleaning liquid, an aqueous cleaning method using a detergent aqueous solution is under study. However, when water-based cleaning that uses a detergent solution as the cleaning liquid for cleaning the surface of the substrate after cutting the substrate is used, the cleaning efficiency is inevitably lower than that of organic solvent cleaning, and the surface of the substrate that causes image defects is inevitable. Cutting powder, environmental foreign matter, cutting oil, etc. generated during processing remain on the substrate surface. When a pigment conventionally used for such a water-cleaned aluminum substrate is used as a charge-generating material, white spots occur in the obtained image and a local decrease in density occurs. Furthermore, the charging potential,
The sensitivity decreases, and the residual potential further increases with repetition. Therefore, there has been a demand for a material having less image defects, good sensitivity, and good repeatability even if a water-based base material that has been subjected to a cutting process after being used as an aluminum base material is used.

Furthermore, in the above-mentioned results of various studies in the anodizing treatment of aluminum, it was found that the anodizing treatment of a substrate as a barrier layer on an aluminum substrate as a conductive substrate as described above would result in a minute white image on the image. Although it is possible to reduce the loss to some extent, it has been found that it is impossible to eliminate it even if various improvements are made by changing the film quality of the alumite layer (anodized film layer).

On the other hand, there is known a technique of covering various defects on the surface of an aluminum substrate and providing an undercoat layer of, for example, polyamide resin or polyvinyl butyral resin for the purpose of adjusting image quality when used as a photoreceptor.

However, in the photoconductor provided with the undercoat layer, fatigue deterioration is apt to occur in the process of repeated image formation, the charging property and the charge retention property are lowered, and the residual potential is increased, so that the image quality is deteriorated. is there.

The number of such image defects increases as the sensitivity of the photosensitive member increases, and is affected by the environment such as temperature and humidity conditions during image formation.

[0014]

In view of the above situation, the present invention further takes advantage of the low cost, light weight, and easily processable aluminum-based alloy as a substrate material, and has no environmental or occupational health problems. It is an object of the present invention to provide a substrate that has been subjected to water-based cleaning or anodization to complement its performance, to provide a photoreceptor having no image defects, high sensitivity, and good repeatability.

[0015]

The above-mentioned problems can be solved by the following constitutions. A charge generation layer on a conductive substrate,
In an electrophotographic photoreceptor on which a charge transport layer is provided to form a constituent layer, the conductive support is an aluminum substrate which is either water-based washed or positively oxidized, and The problem can be solved by any of the electrophotographic photoreceptors characterized in that the charge generating layer contains the charge generating substance represented by the general formula [I] or [II].

However, in the general formulas [I] and [II], Z is an atomic group forming a divalent aromatic ring which may have a substituent.

In the bisimidazopyridonoperylene (denoted as BIPP) compound represented by the general formula [I] or [II], preferred examples of the aromatic group represented by Z include, for example, a benzene ring. , Naphthalene ring, anthracene ring, phenanthrene ring, pyridine ring, pyrimidine ring, pyrazole ring, anthraquinone ring, etc., and particularly preferably benzene ring or naphthalene ring.
The aromatic ring represented by Z may be substituted, and as the substituent, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an asyl group, an acyloxy group, an amino group, a carbamoyl group, a halogen atom, Examples thereof include a nitro group and a cyano group.

BIPP preferably used in the present invention
However, the present invention is not limited thereto.

[0019]

[Chemical 3]

In the electroconductive support used in the electrophotographic photosensitive member of the present invention, a specific aluminum alloy is used as the base material. This aluminum alloy is magnesium (Mg) 0.1-3 wt%, silicon (Si) 0.01-0.8 wt%,
An aluminum-based alloy containing 0.01 to 0.4 wt% of iron (Fe) as an additive component. More preferably Mg 0.2-2.0
%, Si 0.02 to 0.6%, Fe 0.02 to 0.2%. Further, as other additive components, copper (Cu) may be contained in an amount of 0.01% by weight or less and the other metal may be included in an amount of 0.1% by weight or less.

Magnesium (Mg) as an additive component contributes to improvement of machinability and mechanical strength. Also Al-M
g Metallic compounds do not cause pitting corrosion but general corrosion, so they do not cause image defects. However, if the proportion of Mg is less than 0.1% by weight, such effects are not sufficiently exhibited. On the contrary, when the ratio of Mg exceeds 3% by weight, M
g, Si phase crystallization, intergranular corrosion, and stress corrosion are accelerated.

Silicon (Si) as an additive component contributes to improvement of mechanical strength and corrosion resistance. However, if the proportion of Si is
If it is less than 0.01% by weight, such an effect is not sufficiently exhibited. On the other hand, when the Si content exceeds 0.8% by weight, a coarse Si phase precipitates and becomes a surface defect.

Iron (Fe), which is an additive component, forms an intermetallic compound of Fe—Al—Si based on Fe—Al with coexisting aluminum or silicon, and appears as a hard spot in the aluminum matrix. In particular, this hard spot has an iron content of 0.4%
When the amount of iron increases at the boundary, the amount of iron increases sharply, which adversely affects, for example, mirror cutting. Therefore, the preferable iron content in the aluminum alloy of the present invention is 0.4% or less, more preferably 0.2% or less.

The content ratio of the additive component in the aluminum-based alloy constituting the substrate is measured by using a wavelength dispersive X-ray fluorescence analyzer "System 3080" manufactured by Rigaku Denki Co., Ltd.

The aqueous cleaning of the present invention is applied to an aluminum substrate surface-treated by a conventional method.

The water-based cleaning is usually performed by washing-rinsing-drying.
The process consists of cleaning to remove cutting oil and aluminum chips on the surface of the raw pipe, rinsing to remove the cleaning liquid, and drying to remove water.

In the drying step, it is very difficult to uniformly dry water, and various methods have been studied (hot air drying, air ring blow drying, hot pure water pulling drying, etc.).

Of these drying methods, when hot-pure water pulling-up and drying are selected, it is most preferable because the water can be uniformly and completely removed.

An embodiment of water-based cleaning will be described below.

[Washing] The cutting oil, the aluminum cutting powder, and the like adhering to the surface of the conductive substrate are removed with an aqueous detergent solution.

As a removing method, a method of immersing in a detergent aqueous solution (including simple immersion, rotation of a raw pipe, and shaking) -Ultrasonic cleaning (US cleaning) Arrangement of ultrasonic waves → bottom of tank, side, diagonal , And combinations of these types of ultrasonic waves → 28KHz, 40KHz, simultaneous multiple wave, multi-frequency alternating oscillation, etc. ・ Scrubbing with a brush or sponge Preferred sponge shape → Sponge described in JP-A-3-257456
(Kanebo Belclean is commercially available), and usually the first tank = detergent US cleaning, the second tank = detergent sponge + detergent shower are combined.

There are various commercially available detergents, examples of which are shown in Table 1.

[0033]

[Table 1]

Comparing the neutral detergent and the alkaline detergent,
An alkaline detergent is preferable because it has better detergency.

Rinsing Remove detergent from the aluminum substrate with detergent.

The removal method is the same as the cleaning step. From the viewpoint of preventing redeposition of stains, non-contact methods such as immersion and ultrasonic waves are preferable (brushes and sponges are not preferable).

As the rinsing water to be dipped, water in which ions and fine particles are generally called pure water or ultrapure water is used.

[Drying] Water adhering to the surface of the aluminum substrate is removed.

Examples of the removing method include hot air drying, air blow drying, and warm pure water pull-up and drying. However, warm pure water pull-up and drying are preferred in order to make the surface of the tube uniform.

The hot pure water is pulled up and dried by immersing the aluminum substrate in the hot pure water until the temperature becomes the same as that of the hot pure water (from several seconds to several seconds).
After several tens of seconds), the aluminum substrate is slowly pulled up vertically at a constant speed, and the water film on the surface is dried by the heat capacity of the aluminum substrate. Lifting speed is 0.1 cm / sec ~
It is 2.0 cm / sec (preferably 0.5 to 1.0 cm / sec), but it is preferably slower if tact allows. As for the temperature of the hot pure water, the higher the temperature, the faster the drying. However, if the temperature is too high, the steam may cause uneven drying. In the present invention,
The temperature of the hot pure water in the drying step is preferably 60 to 90 ° C, more preferably 70 to 80 ° C.

The pure water used for washing the base material tube according to the present invention preferably has the following characteristics.

Specific resistance: 10 MΩcm or more, preferably 17 MΩcm
cm or more Fine particles: 100 particles / ml or less (fine particles of 0.2 μm or more), preferably 30 particles / ml or less Bacteria: 0.1 colonies / ml or less Anodizing treatment in the present invention is performed by cutting the surface of an aluminum substrate to smooth the surface. It is performed after the pretreatment. The degreasing treatment may be acid-based, alkali-based or neutral, and etching acid-based or alkali-based may be used.

The anodic oxidation treatment can be carried out according to a usual method, but there is no particular limitation, but the so-called sulfuric acid method is preferable because the chemicals are inexpensive, the cost is excellent, and the film formation rate is high and the productivity is excellent. Basically, it is not limited to the sulfuric acid method, but may be a single solution or a mixed solution of oxalic acid, phosphoric acid, chromic acid, etc., and the electrolysis method is not particularly limited, such as constant current, constant voltage, pulse method, two-step electric field method. .

Of the anodic acid coatings thus formed, those that are porous are often chemically active,
Since the film resistance, corrosion resistance, stain resistance, etc. are not always sufficient, it is desirable to carry out a sealing treatment to inactivate. As the sealing treatment, boiling water, hydration sealing using water vapor, inorganic sealing using a heavy metal aqueous solution and the like are preferable.

The thickness of the anodized film is 0.5 to 50 μm, preferably 2 to 20 μm.

In the present invention, the intermediate layer having a barrier effect has a layer thickness of 0.01 to 5 μm, preferably 0.05 to 3 μm. Below 0.01 μm injection of charges from the substrate into the photosensitive layer cannot be prevented. Due to the basic unevenness, pinholes are likely to occur in the photosensitive layer. 5 μm
Above the residual potential of the photosensitive layer cannot be effectively removed.

Further, the binder used in the intermediate layer is selected in consideration of electrical resistance, environment resistance, adhesiveness with other layers, insolubility in the solvent of other layers, etc., but in the present invention, it is selected. Polyamide resin is most preferred.

As the polyamide, alcohol-soluble polyamide is most preferable, and copolymerized nylon, N-alkoxymethyl-modified nylon and the like can be used.

Various forms of the layer structure of the photoconductor are known, and the photoconductor of the present invention may take any of these forms, but it is a laminated type or dispersion type function-separated type photoconductor. desirable. In this case, the structure is usually as shown in FIGS. In the layer structure shown in (a), a charge generation layer (CGL) 2 containing a charge generation substance (CGM) is formed on a conductive support 1, and a charge transport substance (CTM) is formed thereon.
Is a photosensitive layer (PCL) 4 formed by laminating a charge-transporting layer (CTL) 3 containing a resin, and (b) is an adhesive layer between the PCL 4 having the layer structure of (a) and the conductive support 1. An intermediate layer (ASL) 5 such as a barrier layer is provided.
The layer structure of (C) is obtained by forming PCL4 in which CGM is dispersed in a layer containing CTM and a binder on a conductive support, and (D) is the PCL4 of the layer structure of (C) and a conductive support. ASL5 is provided between the two. Figure 1 (a)
In the configurations (1) to (4), a protective layer may be further provided on the outermost layer, and CGL2 may contain CTM. In the present invention, a photoreceptor having at least two layers of CGL and CTL is particularly preferable.

For CGL2, for example, a coating solution prepared by the following method is used as the conductive support 1 or CTL3.
It can be formed directly on top of it, or by applying it on the ASL5 such as an adhesive layer or a barrier layer if necessary.

A solution prepared by dissolving the above CGM together or separately in a suitable solvent, or a solution prepared by further mixing and dissolving a binder resin and / or CTM as required.

Fine particles (preferably having a particle size of 5 μm or less, more preferably 1 μm or less) are dispersed in the CGM together or separately using a ball mill, a sand grinder or the like, and if necessary, a binder resin and / or CT.
A dispersion liquid in which M is added and mixed and dispersed.

Solvents or dispersion media used to form CGL include butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-dimethylformamide, acetone, methylethylketone, methylisobutylketone, cyclohexanone, Benzene, toluene, xylene, chloroform, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethane, dichloromethane, tetrahydrofuran , Dioxane, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve and the like, but the present invention is not limited thereto.

CTL containing at least CTM
Can be formed in the same manner as the above CGL.

Any binder resin can be used for forming CGL or CTL, but it is preferable to use a film-forming high molecular polymer which is hydrophobic, has a high dielectric constant and is electrically insulating. . Examples of such high molecular weight polymers include, but are not limited to, the followings.

P-1) Polycarbonate P-2) Polyester P-3) Methacrylic acid P-4) Polyacrylic resin P-5) Polyvinyl chloride P-6) Polyvinylidene chloride P-7) Polystyrene P-8) Polyvinyl Acetate P-9) Styrene-Ptadiene Copolymer P-10) Vinylidene Chloride-Acrylonitrile Copolymer P-11) Vinyl Chloride-Vinyl Acetate Copolymer P-12) Vinyl Chloride-Vinyl Acetate-Maleic Anhydride Copolymer P-13) Silicone resin P-14) Silicone-alkyd resin P-15) Phenol formaldehyde resin P-16) Styrene-alkyd resin P-17) Poly-N-vinylcarbazole P-18) Polyvinyl butyral P-19) Polyvinyl Formal These binder resins may be used alone or as a mixture of two or more kinds. Can.

In the CGL formed as described above, the weight ratio of the CGM made of BIPP represented by the general formula [I] and / or the general formula [II] and the binder is preferably from 100: 0 to 1000. is there. If the CGM content is lower than this range, the photosensitivity is low and the residual potential increases, and if it is high, the dark decay and the receptive potential decrease.

When CTM is contained in CGL, the weight ratio of CGM to CTM is from 10: 0 to 10:10.
It is preferably 00, particularly preferably 10: 0 to 10:
Is 100.

The film thickness of the formed CGL is preferably 0.
01 to 10 μm.

The CTL formed as described above
In the above, CTM is preferably 20 to 200 parts by weight, and particularly preferably 30 to 150 parts by weight, per 100 parts by weight of the binder resin in CTL.
Parts by weight.

The thickness of the formed CTL is preferably 5 to 60 μm, particularly preferably 10 to 40 μm.

The CTM used in the present invention is not particularly limited, and examples thereof include oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives, bisimidazolidine derivatives. , Styryl compounds, hydrazone compounds, pyrazoline derivatives, amine derivatives, oxazolone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly
-N-vinylcarbazole, poly-1-vinylpyrene, poly-9
-Vinyl anthracene and the like.

In the present invention, however, the CTM is preferably selected in consideration of the transporting ability of holes generated at the time of light irradiation to the surface of the photoreceptor or the side of the support, as well as the combination with the CGM such as BIPP. Examples of such CTM include compounds represented by the following general formula (A) or (B).

[0064]

[Chemical 4]

However, Ar ₁ , Ar ₂ and Ar ₄ each represent a substituted or unsubstituted aryl group, Ar ₃ represents a substituted or unsubstituted arylene group, and R ₁ is a hydrogen atom, a substituted or unsubstituted alkyl group. Represents a group or a substituted or unsubstituted aryl group.

Specific examples of such compounds are described in JP-A-58-654.
No. 40, pages 3-4 and 58-198043, pages 3-6.

[0067]

[Chemical 5]

In the formula, Ar ₁ , Ar ₄ and Ar ₅ each represent a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, and R ₁ and R ₂ are hydrogen. An atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted Represents a naphthyl group. Ar ₂ and Ar ₃ represent a substituted or unsubstituted arylene group, preferably a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthylene group.

Specific examples of the above-mentioned compounds are described in, for example, JP-A 64-322.
No. 65, p. 4-10.

Organic amines can be added to the PCL of the present invention for the purpose of improving the charge generation function of CGM.
It is particularly preferable to add a secondary amine.

Examples of the secondary amine include dimethylamine, diethylamine, dipropylamine, di-isopropylamine, dibutylamine, di-isobutylamine, diamylamine, di-isoamylamine, dihexylamine, di-isohexylamine, dipentyl. Amine, di-isopentylamine, di-octylamine, di-
Examples thereof include isooctylamine, di-nonylamine, di-isononylamine, didecylamine, di-isodecylamine, dimonodecylamine, di-isomonodecylamine, didodecylamine and di-isododecylamine.

The addition amount of such organic amines is C
The number of moles is equal to or less than the equivalent of GM, preferably in the range of 0.2 times to 0.005 times.

In the present invention, CGL may contain one or more electron-accepting substances for the purpose of improving sensitivity, reducing residual potential and reducing fatigue during repeated use.

Examples of the electron accepting substance which can be used here include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride and 3-nitrophthalic anhydride. , 4-nitrophthalic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, paranitrobenzonitrile , Picryl chloride, quinone chlorimide, chloranil, bulmannyl, dichlorodicyanoparabenzoquinone, anthraquinone, dinitroanthraquinone, 2,7-dinitrofluorenone, 2,4,7-trinitrofluorenone,
2,4,5,7-Tetranitrofluorenone, 9-fluorenylidene [dicyanomethylene malonodinitrile], polynitro-9
-Fluorenylidene- [dicyanomethylene malonodinitrile], picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-benzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthal Examples thereof include acids, meritic acid, and other compounds having a high electron affinity.

The amount of the electron-accepting substance added is, by weight ratio, charge generating substance: electron-accepting substance = 100: 0.01 = 200, preferably 100: 0.1 to 100.

The electron accepting substance may be added to the CTL. The amount of the electron-accepting substance added to the layer is C by weight.
TM: electron acceptor = 100: 0.01-100, preferably 10
0: 0.1 to 50.

A leveling agent may be added to CGL. As the leveling agent, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil are used, and the amount thereof is preferably about 0 to 1% by weight based on the binder resin.

In addition, the photoreceptor of the present invention may further contain an antioxidant, an ultraviolet absorber or the like for the purpose of protecting PCL, if necessary, and may also contain a dye for correcting color sensitivity. .

[0079]

EXAMPLES The present invention will be described in detail with reference to examples.

An example A group relating to still water cleaning and an example B group relating to anodic oxidation will be described separately.

Example A group: Example A1 (aluminum blank) An aluminum alloy drawn tube according to the present invention was prepared, and after both ends inlay processing, mirror surface processing was performed with a diamond cutting tool.

Size of blank tube: φ80 mm × 355.5 mm Surface roughness of blank tube: 0.3 s or less (cleaning of aluminum blank tube) (1) (ultrasonic cleaning) Nonionic activator (SE-115 manufactured by Sonic Fellow) Ultrasonic cleaning for 60 seconds at 40 ° C using a 10% aqueous solution. The ultrasonic oscillator is 28
Place kHz at both the bottom and side of the tank. Combined use of rotation and vibration.

(2) (Sponge scrubbing) In the above-mentioned aqueous surfactant solution (40 ° C.), a Bellclean (manufactured by Kanebo Ltd.) sponge was rubbed on the base tube for rubbing and washing.

(3) (Rinse) Ultrasonic cleaning (frequency 28 KHz) was performed in ultrapure water (specific resistance 5 Ωcm or more; 40 ° C.).

(4) (Drying) It is immersed in ultrapure water at 40 ° C. for 1 minute and the raw tube is pulled up at a pulling rate of 0.5 cm / sec to dry the raw tube.

As a coating binder for ASL, 1.5 g of polyamide CM8000 (manufactured by Toray) was dissolved in 100 ml of a mixed solution of methanol / butanol (4/1 wt ratio).

BIGL (Exemplary Compound A-1) 7.5 g as CGL coating material CGL, butyral resin Elex BX-L (manufactured by Sekisui) 1.5 g as a binder, and methyl ethyl ketone 300 ml as a solvent.
Was dispersed in a sand grinder for 10 hours.

11.25 g of the compound (T-1) described in [Chemical Formula 6] as a coating material CTM for CTL
And BPZ type polycarbonate as a binder; 15 g of Iupilon Z-300 (manufactured by Mitsubishi Gas Chemical Co., Inc.) in dichloroethane
It was dissolved in 100 ml.

Preparation of Photoreceptor ASL paint was dip-coated on the aluminum drum that had been subjected to the water-based cleaning to form an ASL having a dry film thickness of 0.2 μm.

Next, the obtained CGL paint was dip-coated to form a CGL having a dry film thickness of 0.5 μm. Then the CT
L coating material was applied by dip to form a CTL having a dry film thickness of 20 μm, and a photoreceptor sample A1 was obtained.

Example A2 Photoreceptor sample 2 was prepared in the same manner as in Example A1 except that ASL was not applied.

Comparative Example (A1) In Example A1, the CGM of the coating composition for CGL was replaced with the exemplified compound A-1, and the perylene compound (C-
A comparative photoconductor (A1) was prepared in the same manner except that 1) was used.

Comparative Example (A2) A comparative photoreceptor (A2) was prepared in the same manner as in Comparative Example (A1) except that ASL was not applied.

[0094]

[Chemical 6]

The following characteristic evaluations were carried out on the photoreceptor samples obtained as described above, and the results are shown in Table 2.

[Image Evaluation] Electrophotographic copying machine “U-Bix 4
045 ”(manufactured by Konica Corporation), and the built-in blank paper chart was actually taken.

(1) White voids The particle size and number of white voids were measured using an image analysis device "Omnicon 3000 type" (manufactured by Shimadzu Corporation), and the number of white voids of φ (diameter) of 0.05 mm or more / cm ² It was judged by the following evaluation code.

Evaluation code 0.05 mm or more White spots / cm ² Practicality ◎ 0 Suitable ○ 1 to 3 〃 △ 4 to 10 Practical limit × 11 to 20 Not suitable × × 21 or more 〃 (2) Image density Density by reflection densitometer Measurement (3) Image quality The two factors of image density and white spots are comprehensively evaluated.

◎: Image density 1.3 or more and 0.3 mm or more 0 blanks (A4 print) ○: Image density 1.2 or more, 0.3 mm or more but less than 0.5 mm 5 blanks or less and 0.5 mm or more 0 blanks ( A4 print) △: Image density 1.2 or more and 0.3 mm or more White voids 6 or more (A
4 prints) or image density of less than 1.2 and 0.3 or more and less than 0.5 mm of blank areas 5 or less (A4 print) ×; Image density of less than 1.2 and 0.3 mm or more of blank areas 6 or more (A
4 prints) [Durability evaluation] The "U-Bix 4045" was modified and a surface electrometer was installed, and the process of charging → exposure → static elimination was repeated 10,000 times, and the black and white paper potentials of the first and 10,000th The residual potential change amount ΔVr (V) was measured.

White paper potential; drum surface potential when copying a document surface having a density of 0.0, Vw (V) Black paper potential; drum surface potential when copying a document surface having a density of 1.30, Vb (V)

[0101]

[Table 2]

Example Group B: Example B1 (Anodic oxidation treatment of aluminum substrate) An aluminum substrate having an outer diameter of 80 mm and a length of 355.5 mm was mirror-finished by surface cutting, and then washed with a commercially available neutral degreasing agent. Then, after washing with water, etching treatment was performed by dipping in a 5 wt% NaOH solution at 40 ° C. for 30 seconds, washing with water, and anodization.

For the anodizing treatment, the bath temperature was adjusted with a 15 wt% sulfuric acid solution.
A 6 μm film was formed at 20 ° C. and a current density of 1 A / dm ² . After anodic oxidation, washing with water was performed, and subsequently, a pore-sealing treatment was performed by immersing in a nickel acetate solution at 50 ° C. for 10 minutes.

(Formation of photosensitive layer) (Application of ASL) Polyamide CM8000 (manufactured by Toray) 1.5
An ASL having a film thickness of 0.2 μm was formed by dip coating with a solution consisting of 100 g of methanol butanol mixed solution (weight ratio of methanol: butanol = 4: 1).

(Coating of CGL) Exemplified Compound (A-1) 7.
CGL having a film thickness of 0.5 μm was formed by dip coating with CGL paint obtained by dispersing with 5 g, butyral resin Elex BX-L (manufactured by Sekisui Co., Ltd.), and 300 ml of MEK.

(Coating of CTL) Bisphenol Z-type polycarbonate resin, Iupilon Z-300 (manufactured by Mitsubishi Gas Chemical Co., Inc.) A CTL coating consisting of 11.75 g of the above CTM compound (T-1) and 100 ml of dichloroethane was used for dip coating. A CTL of about 20 μm was formed (drying: 90 ° C., 1 hour) Example B2 A photoreceptor sample was prepared in the same manner as in Example 1 except that ASL was not applied.

Comparative Example (B1) A photoconductor sample was prepared in the same manner as in Example B1 except that the exemplified compound (A-1) was used in place of CGM in place of the above (C-1).

Comparative Example (B2) A photosensitive sample was prepared in the same manner as Comparative Example (B1) except that ASL was not applied.

The photoreceptor samples obtained as described above were evaluated for characteristics similar to those in Example A group, and the results are shown in Table 3.

[0110]

[Table 3]

[0111]

EFFECT OF THE INVENTION It is possible to achieve an electrophotographic image having good electrical characteristics, good durability and high image quality.

[Brief description of drawings]

FIG. 1 is a sectional view of an example of a photoconductor of the present invention.

[Explanation of symbols]

 1 Aluminum Alloy Conductive Substrate 2 Carrier Generation Layer 3 Carrier Transport Layer 4 Photosensitive Layer 5 Intermediate Layer

Claims (3)

[Claims] 1. An electrophotographic photosensitive member comprising a conductive substrate on which a charge generation layer and a charge transport layer are provided to form a constituent layer, wherein the conductive support is an aluminum substrate subjected to aqueous cleaning. An electrophotographic photosensitive member characterized in that the charge generating layer contains a charge generating substance represented by the following general formula [I] or [II]. [Chemical 1] [In the general formulas [I] and [II], Z is an atom group forming a divalent aromatic ring which may have a substituent. ] 2. An electrophotographic photosensitive member comprising a conductive substrate on which a charge generation layer and a charge transport layer are provided to form a constituent layer, wherein the conductive support is an anodized aluminum substrate. An electrophotographic photosensitive member characterized in that the charge generating layer contains a charge generating substance represented by the following general formula [I] or [II]. [Chemical 2] [In the general formulas [I] and [II], Z is an atom group forming a divalent aromatic ring which may have a substituent. ] 3. The electrophotographic photosensitive member according to claim 1, wherein an intermediate layer made of a polyamide resin is provided between a conductive substrate and a charge generation layer as a constituent layer of the photosensitive member.