JPH063845A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve electric characteristics and durability and to remove black spots in reversal development by specifying the diameter and proportion of crystallizing material in an aluminum alloy on the surface of a conductive base body. CONSTITUTION:A hydrated aluminum alloy layer is formed on the surface of an aluminum alloy conductive base body, on which a photosensitive layer is formed. The aluminum alloy on the conductive base body surface contains crystallizing material of <=5mum diameter and <=2% area ratio. Thereby, the obtd. photosensitive body has improved electrostatic changeability, charge holding property and optical attenuation property, high durability with little fatigue deterioration against repeated formation of images, and no picture image defect such as black spot, fog, or uneven density even when the picture image is formed by reversal development. The aluminum alloy is preferably an aluminum- magnesium alloy containing each <=0.2wt.% of iron content and silicon content.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoconductor used in electrophotography, and more particularly to a photoconductor suitable for reversal development.

[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. However, alloy components such as iron and silicon are
In the process of substrate processing such as extrusion molding or drawing molding, an aluminum alloy is often formed and crystallized to form a large number of fine crystallized substances, and an aluminum melt is often formed around it. These crystallized substances and the aluminum melt in the vicinity thereof often cause image defects when a photosensitive layer is formed thereon and an image is formed.

Therefore, for example, Japanese Patent Application Laid-Open No. 64-79339 proposes that the iron content be 0.2% by weight or less and the silicon content be 0.1% by weight or less.
It has been proposed to make the crystallized material area ratio 0.5 μm or less and the crystallized substance area ratio 0.5% or less.

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

However, the photoreceptor provided with the undercoat layer is liable to suffer fatigue deterioration in the course of repeated image formation, resulting in a decrease in chargeability and charge retention and an increase in residual potential and deterioration in image quality. is there.

Then, for example, in JP-A-64-29852, a hydrated aluminum oxide layer is provided on an aluminum substrate,
Charge generation material (CGM) and charge transport material (CT
A photoreceptor provided with a photosensitive layer containing M) has been proposed.

The hydrated aluminum oxide layer is formed, for example, by treating with pure water at a temperature of about 100 ° C., and the hydration process is easy and easy, and since it has a rectifying property, it is high on the photoreceptor. It is described that sensitivity can be improved and excellent chargeability, charge retention, repeatability and the like can be imparted.

[0009]

However, as a result of the study by the present inventors, the photoreceptor using the aluminum substrate provided with the hydrated aluminum oxide layer has excellent electrophotographic performance as described above. It has been found that when an image is formed by the reversal development method, image defects such as black spots are generated under severe environmental conditions or repeated use. For example, in a copying machine or printer using a laser beam, spot image exposure is performed on a photosensitive member to form a dot-shaped electrostatic latent image, and this is developed by a reversal development method to form an image. At this time, fogging or uneven density consisting of black spots is observed.

Such image defects increase as the sensitivity of the photosensitive member increases, and are affected by the environment such as temperature and humidity conditions during image formation.

As a result of intensive studies by the present inventors, the crystallized substance in the aluminum alloy on the surface of the aluminum base tube is not always covered with a sufficiently hydrated aluminum oxide layer during the hydration process, and the electrical property is still high. I knew I had a flaw. That is, when the crystallized substances in the alloy on the surface of the aluminum base tube are fine, they are covered with a hydrated aluminum oxide layer and do not appear as image defects, but when they exceed a certain limit, image defects are generated, and crystallized substances It has been found that the size and the degree of occurrence of are related to the surface component of the aluminum substrate.

That is, when the relationship between the aluminum substrate and the image defect was photographically examined, a portion having a large crystallized substance became a black spot. Moreover, the pattern of the halftone unevenness is similar to the unevenness of the hydrated aluminum oxide film which can be visually observed (FIG. 1 (1)).

Further, when the formation state of the hydrated aluminum oxide film on the crystallized substance portion was examined, there was an elution portion of aluminum around the crystallized substance. It was found that the hydrated aluminum oxide film was not formed on the aluminum elution part of (in the case of long-term hydration and oxidation treatment, it is eventually covered with the hydrated aluminum oxide film). (FIGS. 1 (2) and (3)).

As a result of further study on the elution of aluminum around the crystallized substance, Al is likely to be eluted in the presence of a metal having a greater ionization tendency than Al. It was also found that Al does not elute in the presence of a metal having a smaller ionization tendency than Al, but rather promotes the hydration oxidation reaction.

On the other hand, with regard to crystallized substances, it is known that Fe and Si easily form crystallized substances, and Mg forms a solid solution with Al and does not form crystallized substances.

Therefore, the size and amount of the crystallized substances are limited. The aluminum alloy composition in which the crystallized substances are difficult to form. The aluminum alloy composition in which aluminum is difficult to elute. I knew I needed to.

[0017]

OBJECTS OF THE INVENTION The object of the present invention is to provide excellent charging property, charge retention property and light attenuation property, and in repeating image formation,
It is an object of the present invention to provide an electrophotographic photosensitive member which has little fatigue deterioration and high durability and which does not cause image defects such as black spots even when an image is formed by a reversal development method.

[0018]

The above object is to provide an electrophotographic photoreceptor in which a hydrated aluminum oxide alloy layer is provided on the surface of a conductive substrate made of an aluminum alloy, and a photosensitive layer is provided on the layer. The diameter of crystallized substances contained in the aluminum alloy on the surface of the conductive substrate is 5 μm or less, and the ratio of the crystallized substances in the aluminum alloy on the surface of the conductive substrate is 2% or less in area ratio, preferably It is achieved by the electrophotographic photoreceptor of 1% or less.

In a preferred embodiment of the present invention, the aluminum alloy is an aluminum-magnesium alloy, the iron content and the silicon content in the alloy are each 0.2 wt% or less, and the aluminum alloy is A photoreceptor having an ionization tendency smaller than that of aluminum and having an alloy component other than the iron component and the silicon component of 0.2% by weight or less.

The constitution of the present invention will be described in detail below.

Method of forming hydrated aluminum oxide film:
In the present invention, the hydrated aluminum oxide layer can be formed on the aluminum substrate after washing the aluminum tube by the method described in JP-A-58-11944 and JP-A-58-14841. .

Method for cleaning aluminum substrate: Cleaning by jetting liquid (jet cleaning) Cleaning by rubbing member (rubbing cleaning) Irradiation with ultraviolet rays of 300 nm or less (UV cleaning) Ultrasonic and vapor cleaning with organic solvent Sponge Cleaning with a roller-shaped roller The method for cleaning the aluminum substrate before forming the hydrated oxide film may be any of the methods described above, but cleaning with an aqueous cleaning agent is preferable.

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 process, 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 pull-up drying is selected, the formation of a hydrated oxide film and the removal of water can be carried out at the same time, which is the most preferable combination.

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

[Cleaning] The cutting oil, aluminum cutting powder, etc. 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 immersing, rotating and oscillating a pipe), ultrasonic cleaning (US cleaning) ultrasonic arrangement → 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 Bellclean 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.

[0030]

[Table 1]

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

Rinsing Remove detergent from the aluminum substrate with detergent.

As a removing method, the same method as the cleaning step is used. 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 immersed, 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.

The removal methods include: hot air drying, air blow drying, warm pure water pulling and drying, etc., but warm pure water pulling and drying is 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,
Since the drying step and the hydrated oxide film forming step are performed at the same time, the temperature of the hot pure water is preferably 60 to 90 ° C, more preferably 70 to 80 ° C.

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

Specific resistance: 10 MΩcm or more, preferably 17 MΩcm or more Fine particles: 100 cells / ml or less (0.2 μm or more fine particles), preferably 30 cells / ml or less Bacteria: 0.1 colonies / ml or less The aluminum oxide layer is not always sufficiently formed on the crystallized substance in the surface alloy and the melt around it. That is, very small crystallized substances are coated, but crystallized substances with a grain size exceeding the limit are not coated or are incompletely coated. That is, when a photosensitive body is formed by applying a photosensitive liquid on a substrate having crystallized substances exceeding the limit and is used for image formation, black spots still occur.

In the present invention, the above limit is set to 5 μm or less, and the area ratio of crystallized substances on the surface of the shell alloy is set to 2.0% or less, preferably 1% or less.

It also serves as a main source of the crystallized substances. The iron component, the silicon component, and the other impurity components are preferably 0.2 wt% or less.

Sensitivity characteristics and charging can be achieved by using a photoconductor using an aluminum substrate which is obtained by forming a hydrated aluminum oxide layer based on the above-mentioned processing method using an aluminum alloy base pipe satisfying the above-mentioned conditions. It is possible to obtain a photoreceptor having excellent characteristics and charge retention, high durability, and free from black spots during reversal development.

Various structures are known for the structure of the electrophotographic photosensitive member, but the electrophotographic photosensitive member of the present invention can take any of these forms.

Normally, the configurations shown in FIGS. 2 (1) to 2 (4) are used. In FIG. 2 (1) and FIG. 2 (2), a hydrated aluminum oxide layer 12 is provided on an aluminum substrate 11, and a carrier generating material is provided.
A photosensitive layer 14 containing a carrier transport material is provided. The intermediate layer 13 may be provided as shown in FIG.

As shown in FIGS. 3 (4) and 3 (4), the photosensitive layer 14 may have a two-layer structure of a carrier generating layer 21 and a carrier transporting layer 22. Thus, when the photosensitive layer 14 has a two-layer structure, a photoreceptor having the best electrophotographic characteristics can be obtained. Further, in the present invention, a protective layer may be provided as the outermost layer.

As the carrier-generating substance used in the carrier-generating layer of the photosensitive layer according to the present invention, either an inorganic pigment or an organic dye can be used, so long as it absorbs light and generates a free charge. Organic pigments represented by the following representative examples are preferably used.

(1) Monoazo pigments, polyazo pigments, metal complex salt azo pigments, pyrazolone azo pigments, azo pigments such as stilbene azo and azo azo pigments (2) Perylene pigments such as perylene anhydride and perylene imide ( 3) Anthraquinone-based or polycyclic quinone-based pigments such as anthraquinone derivatives, anthanthrone derivatives, dibenzpyrenequinone derivatives, pyranthrone derivatives, violanthrone derivatives and isobiolanthrone derivatives (4) Indigoide pigments such as indigo derivatives and thioindigo derivatives (4) 5) Phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine (6) Carbonium pigments such as diphenylmethane pigment, triphenylmethane pigment, xanthene pigment and acridine pigment (7) Azine pigment, oxazine pigment and thiazine pigment Quinoneimine pigments such as gin pigments (8) Methine pigments such as cyanine pigments and azomethine pigments (9) Quinoline pigments (10) Nitro pigments (11) Nitroso pigments (12) Benzoquinone and naphthoquinone pigments (13) Na pigments Phthalimide pigments (14) Perinone pigments such as bisbenzimidazole derivatives.

Various azo pigments having an electron-withdrawing group are
Used because of good electrophotographic characteristics such as sensitivity, memory-development and residual potential.

From the viewpoint of ozone resistance, polycyclic quinone pigments are most preferable. The details are unclear, but probably because polycyclic quinones are inert to ozone.

Examples of the phthalocyanine pigment include the following, which can be preferably used in combination with the substrate according to the present invention.

(IV-1) X-type metal-free phthalocyanine (IV-2) τ-type metal-free phthalocyanine (IV-3) chloroaluminum phthalocyanine (IV-4) titanyl phthalocyanine (IV-5) vanadyl phthalocyanine (IV-6) ε-type copper phthalocyanine (IV-7) chloroindium phthalocyanine Next, the carrier transport material (CTM) usable in the present invention
There is no particular limitation, for example, oxazole derivative, oxadiazole derivative, thiazole derivative, thiazole derivative, triazole derivative, imidazole derivative, imidazolone derivative, imidazolidine derivative, bisimidazolidine derivative, styryl compound, hydrazone compound, pyrazoline derivative , Oxazolone derivative, benzthiazole derivative, benzimidazole derivative, quinazoline derivative, benzofuran derivative, acridine derivative,
Phenazine derivative, aminostilbene derivative, poly-N-
It may be one or more selected from vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene and the like. It is also possible to use different carrier transport materials for the carrier generation layer and the carrier transport layer.

As the binder resin for the carrier transport layer of the photoreceptor, for example, polyethylene, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl acetal resin, epoxy resin, polyurethane resin, phenol resin, polyester resin,
Alkyd resin, polycarbonate resin, silicone resin, addition polymerization type resin such as melamine resin, polyaddition type resin,
Polycondensation type resins, and copolymer resins containing two or more of the repeating units of these resins, such as vinyl chloride-
Insulating resin such as vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, poly-N
-Polymer organic semiconductors such as vinylcarbazole are mentioned.

When the compound of the present invention is not capable of forming a coating by itself, various binders are combined to form a photosensitive layer.

Any binder can be used as the binder used here, but it is hydrophobic and has a high dielectric constant.
It is preferable to use an electrically insulating film-forming polymer. Examples of such high molecular weight polymers include, but are not limited to, the followings.

(P-1) Polycarbonate (P-2) Polyester (P-3) Methacrylic resin (P-4) Acrylic resin (P-5) Polyvinyl chloride (P-6) Polyvinylidene chloride (P-7) Polystyrene (P-8) Polyvinyl acetate (P-9) Styrene-butadiene copolymer (P-10) Vinylidene chloride-acrylonitrile copolymer (P-11) Vinyl chloride-vinyl acetate copolymer (P-12) Chloride Vinyl-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 are used alone. There can be used as a mixture of two or more.

Further, as the solvent for forming the carrier generating layer and the transporting layer according to the present invention, N, N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, 1,2-dichloroethane is used. , 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,
It can also be used as a mixture.

When the photoreceptor of the present invention is a laminated photoreceptor, the weight ratio of the binder and the carrier transporting material to the carrier generating material in the carrier generating layer is 0 to 5 parts by weight when the carrier generating material is 1 part by weight. The carrier transport substance is preferably 0 to 1 part by weight.

When the content ratio of the carrier-generating substance is less than 15% (weight) in the carrier-generating layer, the photosensitivity is low and the residual potential is increased, and when it is more than this range, the dark decay and the receptive potential are lowered.

The thickness of the carrier generating layer formed as described above is preferably 0.01 to 10 μm, and particularly preferably
It is 0.1 to 5 μm.

The carrier transport material 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 the carrier transport layer.

The thickness of the formed carrier transport layer is
It is preferably 5 to 50 μm, particularly preferably 10 to 35 μm.

On the other hand, when the photoreceptor of the present invention has a single-layer structure,
The weight ratio of the binder and the carrier transporting material to the carrier generating material is preferably 0.2 to 5 parts by weight of the binder and 0 to 5 parts by weight of the carrier transporting material when the carrier generating material is 1 part by weight, and the film of the photosensitive layer to be formed. The thickness is preferably 5 to 50 μm, particularly preferably 10 to 30 μm.

As the binder used for the intermediate layer, the protective layer and the like, those mentioned above for the carrier generating layer and the carrier transporting layer can be used. In addition, polyamide resin, nylon resin, ethylene-vinyl acetate Polymer, ethylene-vinyl acetate-maleic anhydride copolymer,
Ethylene resins such as ethylene-vinyl acetate-methacrylic acid copolymer, polyvinyl alcohol, cellulose derivatives and the like are effective.

Organic amines can be added to the photosensitive layer of the present invention for the purpose of improving the carrier generating function of the carrier generating substance. Among the organic amines, it is particularly preferable to add a secondary amine.

Further, the above-mentioned light-sensitive layer contains storability, durability,
For the purpose of improving the environmental resistance, a deterioration inhibitor such as an antioxidant or a light stabilizer may be contained. Examples of the compound used for such a purpose include biphenyl, terphenyl, diphenyl ether, diphenyl carbonate, phenyl benzoate, diphenyl phthalate, chromanol derivatives such as tocopherol and etherified or esterified compounds thereof, polyarylalkane compounds, Hydroquinone derivatives and mono- and dietherified compounds thereof, benzophenone derivatives, benzotriazole derivatives, thioether compounds, phosphonic acid esters, phosphorous acid esters, phenylenediamine derivatives, phenol compounds, hindered phenol compounds, linear amine compounds,
Cyclic amine compounds and hindered amine compounds are effective. Specific examples of particularly effective compounds include "IRGANO
"X1010", "IRGANOX565" (made by Ciba Geigy),
Examples thereof include hindered phenol compounds such as "Sumilyzer BHT" and "Sumilyzer MDP" (manufactured by Sumitomo Chemical Co., Ltd.), and hindered amine compounds such as "Sanol LS-2626" and "Sanol LS-622LD" (manufactured by Sankyo Co.). The weight ratio of these compounds to the carrier transport substance is 0.001 to 0.1: 1.
And preferably 0.05 to 0.1: 1.

In the present invention, the carrier-generating layer may contain one or more electron-accepting substances for the purpose of improving sensitivity, reducing residual potential or 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. Acid, 4-nitrophthalic anhydride, pyromellitic dianhydride,
Mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, paranitrobenzonitrile, picrin chloride, quinone chlorimide, chloranil, bulmannyl, di Chlordicyanoparabenzoquinone, anthraquinone, dinitroanthraquinone, 2,7-dinitrofluorenone, 2,4,7-trinitrofluorenone,
2,4,5,7-Tetranitrofluorenone, 9-fluorenylidene malonodinitrile, polynitro-9-fluorenylidene-
Malonodinitrile, picric acid, o-nitrobenzoic acid, p-
Nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, meritic acid, etc.
Nos. 2-214866, 2-135362, and U.S. Pat. No. 455,659 can be mentioned as compounds having a high electron affinity.

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

The electron accepting substance may be added to the carrier transporting layer. The amount of the electron-accepting substance added to the layer is a carrier transporting substance: electron-accepting substance = 100: 0.01-1
00, preferably 100: 0.1 to 50.

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

The electrophotographic photosensitive member of the present invention has the above-mentioned constitution and, as will be apparent from the examples described later, is excellent in the charging property, the sensitivity property and the image forming property, especially when repeatedly used. Moreover, it has little fatigue deterioration and excellent durability.

Further, the electrophotographic photoconductor of the present invention can be widely used not only in electrophotographic copying machines but also in other application fields such as a photoconductor of a printer using a laser, a cathode ray tube (CRT), and a light emitting diode (LED) as a light source. .

[0073]

EXAMPLES The present invention will be specifically described below with reference to examples, but the embodiments of the present invention are not limited thereby.

Example 1 (Aluminum Base Tube) Aluminum alloy drawn tube (8 types) according to the present invention and comparative aluminum alloy drawn tube (8)
Types) were prepared, and after both end spigot processing, mirror surface processing was performed with a diamond bite.

Size of blank tube: φ40 mm × 270 mm Surface roughness of blank tube: 0.3 s or less Table 2 shows the characteristics of the blank tube.

[0076]

[Table 2]

(Cleaning of Aluminum Tube, Hydration Oxidation Process) First Tank (Ultrasonic Cleaning) 60% ultrasonic cleaning at room temperature using a 5% aqueous solution of alkaline detergent (SE-115 manufactured by Sonic Fellow). The ultrasonic oscillator is 28
Place kHz at both the bottom and side of the tank. Combined use of rotation and vibration.

Second tank (sponge scrubbing) Using a clean aqueous alkaline detergent solution (same as in the first tank), rub a Bellclean (Kanebo) sponge on the base pipe while rotating it in the same direction as the base pipe (base pipe). : 200rpm, sponge: 2
00 rpm), rub and wash for 60 seconds while showering with detergent.

Third tank (rinsing) Using pure water (25 ° C.), rinsing for 60 seconds while overflowing in a tank having the same structure as the first tank.

Fourth tank (rinsing) Same as the third tank.

Fifth tank (hydration oxidation treatment, drying) After immersing in ultrapure water at 80 ° C. for 1 minute for hydration oxidation treatment, the raw tube is pulled up at a pulling rate of 0.5 cm / sec, Dry the tube.

For comparison, two pipes were also prepared in which the fifth tank temperature was 40 ° C. and the tube was dried under the condition that a hydrated oxide film was not formed.

(Formation of Photosensitive Layer) (Coating of Carrier Generation Layer (CGL)) 3 parts by weight of τ-type metal-free phthalocyanine (TPH-278 manufactured by Toyo Ink Co., Ltd.), silicone resin solution (KR-5240 manufactured by Shin-Etsu Chemical Co., Ltd.) 10 Parts by weight, M
A CGL having a film thickness of 0.5 μm is formed by dip coating with a CGL solution consisting of 100 parts by weight of EK.

(Coating of carrier transport layer (CTL)) 20 parts by weight of bisphenol Z type polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd .; Iupilon Z-200), styryltriphenylamine of structural formula (1) shown in "Chemical Formula 1" 12 parts by weight of carrier carrier transporting material (CTM), 0.6 part by weight of antioxidant (manufactured by Ciba-Geigy Japan; Irganox-1010), 100 parts by weight of 1,2-dichloroethane, silicone oil (KF-54 by Shin-Etsu Chemical Co., Ltd.) 0.005 A CTL solution having a thickness of about 20 μm is formed by dip coating with a CTL solution consisting of parts by weight (drying:
90 ° C x 1 hour).

As a comparative photoconductor, a photoconductor in which CGL and CTL were formed in the same manner as above after UCL coating was performed using one of two raw tubes in which a hydrated oxide film was not formed Also made.

(Coating of intermediate layer (UCL)) Ethylene-based copolymer resin (ELVAX-5240 manufactured by DuPont) 2 parts by weight of UCL solution and 100 parts by weight of toluene were used to dip-coat UCL having a thickness of 0.2 μm. To form.

[0087]

[Table 3]

(Printing test 1) A total of 18 photoreceptors of 8 photoreceptors of the present invention and 10 photoreceptors for comparison prepared above were used as LP-311.
0 Printer (manufactured by Konica) Built into a modified machine and adjusted the grid voltage to -720V, then 20 ℃, 50% RH, 10 ℃, 20
Printing was performed for 100 prints in each environment of% RH, 30 ° C. and 80% RH, and the print quality was evaluated by black spots and fog at the start and after 100 prints. The results are shown in Table 4.

Print Quality Evaluation Criteria ◎: Fogging density 0.005 or less and 0.3 mm or more black spots 0 (A4 print) ○: Fogging density 0.01 or less, 0.3 mm or more and less than 0.5 mm black spots 5 or less and 0.5 mm or more black Pochi 0 (A4 print) ×; Fogging density 0.01 or less and 0.3 mm or more Black dot 6 or more (A4 printing), or fog density exceeding 0.01 and 0.3 m
5 or more black spots of m or more and less than 0.5 mm (A4 print) XX; Fogging density of more than 0.01 and 6 or more black spots of 0.3 mm or more (A4 print)

[0090]

[Table 4]

(Printing test 2) After using the drum No. 1 and adjusting the machine under the same printing conditions as in the printing test 1, at 20 ° C.,
10,000 prints in 50% RH environment, then 10 ℃, 20% R
H environment 10,000 prints, 30 ℃, 80% RH environment
A long run test was performed on 10,000 prints for a total of 30,000 prints, but good prints with almost no black spots or fog were obtained even after 30,000 prints (print quality after 30,000 prints = ○).

Example 2 A neutral detergent (FM-1 manufactured by Lion Co., Ltd.) was used as a detergent for cleaning the plain tube.
Samples were prepared in the same manner as in Example 1 except that (0) was used, and the same evaluation was performed. The results are shown in Table 5.

[0093]

[Table 5]

Example 3 (Aluminum blank) Aluminum alloy drawn pipes (8 types) according to the present invention and comparative aluminum alloy drawn pipes (4)
2 pieces each (type, 4 pieces each for No. 1 and 2) were prepared, and after both end spigot processing, mirror surface processing or rough surface processing was performed with a diamond cutting tool.

Size of raw pipe: φ180 mm × 354 mm Surface roughness of raw pipe: Mirror surface processed product = 0.3 s or less, rough surface processed product = 0.
Table 6 lists the specifications of the 7-1.0s production drum.

(Cleaning of aluminum tube, hydration oxidation treatment) First tank (ultrasonic cleaning) Ultrasonic cleaning at room temperature for 60 seconds using a 5% aqueous solution of an alkaline detergent (A-88 manufactured by Shimada Rika Kogyo Co., Ltd.). 28kHz ultrasonic oscillator
Placed on both the bottom and side of the tank. Both rotation and vibration.

Second tank (sponge scrubbing) Using an alkaline aqueous solution of detergent (same as in the first tank), rub a Bellclean (Kanebo Co., Ltd.) sponge on the base pipe and rotate it in the same direction as the base pipe (base pipe). : 100 rpm, sponge:
200 rpm), rub and wash for 60 seconds while showering with detergent.

Third tank (rinsing) Using pure water (25 ° C.), rinsing for 60 seconds while overflowing in a tank having the same structure as the first tank.

Fourth tank (rinsing) Same as the third tank.

Fifth tank (hydration oxidation treatment, drying) After immersing in ultrapure water at 75 ° C. for 3 minutes for hydration oxidation treatment, the raw tube was pulled up at a pulling rate of 0.5 cm / sec, Dry the tube.

For comparison, four pipes were also prepared in which the fifth vessel temperature was 40 ° C. and the elementary tubes were dried under the condition that a hydrated oxide film was not formed.

(Formation of Photosensitive Layer) (Coating of CGL) X-ray diffraction spectrum for Cu-Kα rays shows 9.5 ° ± 0.2 °, 24.1 ° ± 0.2 °, 2 of black angle 2θ.
2 parts by weight of crystalline Y-type titanyl phthalocyanine having a peak at 7.2 ° ± 0.2 °, silicone modified butyral resin
C consisting of 1 part by weight and 100 parts by weight of tertiary butyl acetate
A CGL having a film thickness of 0.5 μm is formed by dip coating with the GL solution.

(Application of CTL) Bisphenol Z type polycarbonate resin (Upilon Z-20 manufactured by Mitsubishi Gas Chemical Co., Inc.)
0) 20 parts by weight, 15 parts by weight of the stilbenetriphenylamine CTM of the structural formula (2) shown in "Chemical formula 1", 100 parts by weight of 1,2-dichloroethane, silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.
KF-54) 0.005 parts by weight of CTL solution is applied to form a CTL with a film thickness of about 25 μm (drying: 90 ° C.
X 1 hour).

As a comparative photoconductor, a photoconductor in which CGL and CTL were formed in the same manner as above after UCL coating was carried out using two of the four elementary tubes on which a hydrated oxide film was not formed Also made.

(Application of UCL) Polyamide resin (CM-8000 manufactured by Toray) 3 parts by weight of UCL solution and 100 parts by weight of methanol are used to form UCL having a thickness of 0.2 μm by dip coating.

[0106]

[Table 6]

(Real shooting test 1) A total of 20 photoconductors, 16 photoconductors of the present invention and 8 photoconductors for comparison, produced by Konica
VH (surface potential of unexposed area) at the first development position in a 9028 (made by Konica) remodeling machine at 20 ° C and 50% RH.
20 after adjusting the grid voltage so that the voltage becomes −850V.
Photographs were taken in each environment of ℃, 50% RH, 10 ℃, 20% RH and 30 ℃, 80% RH.

For actual shooting, VH measurement and white background copying were performed at the start, and then 100 continuous continuous copying was performed in the full color mode (chart: color image exclusive rate of 75%). After 100 more copying, VH measurement and white background copying were performed again. Then, the image quality was evaluated by VH at the 1st and 100th copies and black spots and fogging in the white background copy. The results are shown in Table 7. The potentials in the table are all negative potentials.

Image quality evaluation criteria ◎: Fog density 0.005 or less and 0.3 mm or more black spots 0 (A3 image) ○; Fog density 0.01 or less, 0.3 mm or more and less than 0.5 mm black spots 5 or less and 0.5 mm or more Black dots 0 (A3 image) ×; Fogging density 0.01 or less and 0.3 mm or more Black dots 6 or more (A3 image), or fog density exceeding 0.01 and 0.3 mm
5 or more black spots less than 0.5 mm (A3) XX; Fogging density over 0.01 and 0.3 mm or more black spots 6 or more (A3)

[0110]

[Table 7]

(Actual shooting test 2) After using the drum No. 1 and adjusting the machine under the same actual shooting conditions as in the actual shooting test 1, at 20 ° C.,
10,000 copies under 50% RH environment, 10 ℃, 20% RH continuously
Environment 10,000 copies, 30 ℃, 80% RH environment 1
We performed a long-run test of 30,000 copies with a total of 30,000 copies, but a good image with almost no black spots and fog was obtained even after 30,000 copies (image quality after 30,000 copies =
○).

[0112]

[Chemical 1]

[0113]

The electrical characteristics are good, the durability is good, and black spots can be removed in reversal development.

Furthermore, the present invention brings particularly favorable results to a photosensitive layer such as titanyl phthalocyanine, in which environmental characteristics change due to water adsorption or the like.

[Brief description of drawings]

FIG. 1 is a schematic diagram of the surface of a hydrated aluminum oxide layer of a hydrated aluminum substrate.

FIG. 2 is a sectional view of an example of a photoconductor of the present invention.

[Explanation of symbols]

 11 Aluminum Alloy Conductive Substrate 12 Hydrated Aluminum Oxide Layer 13 Intermediate Layer 14 Photosensitive Layer 21 Carrier Generation Layer 22 Carrier Transport Layer

Claims (3)

[Claims] 1. An electrophotographic photoreceptor comprising a hydrated aluminum oxide alloy layer provided on the surface of a conductive substrate made of an aluminum alloy, and a photosensitive layer provided on the layer, which is included in the aluminum alloy on the surface of the conductive substrate. Diameter of crystallized product is 5
An electrophotographic photosensitive member characterized in that it is not more than μm, and the ratio of the crystallized substances in the aluminum alloy on the surface of the conductive substrate is not more than 2% in area ratio. 2. The electrophotographic photosensitive member according to claim 1, wherein the aluminum alloy is an aluminum-magnesium alloy, and the iron component and the silicon component in the alloy are each 0.2 wt% or less. 3. The electrophotographic photosensitive member according to claim 1, wherein the aluminum alloy has a smaller ionization tendency than aluminum and an impurity component other than the iron component and the silicon component is 0.2% by weight or less.