JPH0776839B2 - Substrate processing method for electrophotographic laminated photoreceptor - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating the surface of an electrophotographic photosensitive member used for a photosensitive drum of an electrostatic copying machine or a laser beam printer, and more particularly to a photosensitive layer having a charge generating layer and a charge transporting layer. The present invention relates to a method for treating a base of a laminated type photoreceptor including

In this specification, the term aluminum is used to include an aluminum alloy.

[0003]

2. Description of the Related Art Generally, an electrophotographic photosensitive member is composed of a conductive support made of aluminum and a photosensitive layer coated thereon. As the photosensitive layer, an inorganic photoconductive material such as selenium is used. Organic photoconductors using organic materials (so-called OPC photoconductors) have come to be used because of their excellent film-forming properties, light weight, low cost, and the like.

Recently, in order to further improve the function and characteristics of the organic photoreceptor, the photosensitive layer is recently replaced with a charge generation layer (CG).
L) and a charge transporting layer (CTL) are provided, and an organic photoreceptor called a laminated type is provided.

With the expansion of the use of electrophotographic photoconductors for laser beam printers and the like, high image reliability at the time of reversal development is also required for the above-mentioned laminated photoconductors. In particular, small black spot noise and image fog have become a problem when used in a high temperature and high humidity environment.

Then, as a laminated type photoreceptor in which such small black spot noise and fog are eliminated, an aluminum support is subjected to anodization treatment, and then the concentration is 1 to 15 wt% and the temperature is 50 to 80.
It has been proposed to perform a pore-sealing treatment using a nickel acetate aqueous solution at a temperature of 60 ° C (Japanese Patent Laid-Open No. 63-116163).

[0007]

However, even in the case of performing the sealing treatment as described above, under the high temperature and high humidity harsh environment, the small black spot noise of the image still occurs, and the demand for the image quality is increased. It has been found by the research of the inventors that the above conditions cannot be fully satisfied.

Therefore, the present invention has an object to manufacture and provide a laminated type photoreceptor for electrophotography which can further suppress small black spot noise and realize high image quality.

[0009]

In order to achieve the above object, the present invention provides a laminated photoreceptor for electrophotography having a charge generation layer and a charge transport layer on the surface of an aluminum support made of an Al--Mg--Si alloy . A method of undercoating, wherein the aluminum support is anodized, and thereafter, a temperature of 30 to 5 containing nickel acetate of 1 g / l or more and less than 10 g / l.
10 ℃ nickel acetate solution or nickel acetate at 0 ℃
The gist of the present invention is to provide a ground treatment method for a laminated type photoreceptor for electrophotography, which comprises contacting with a nickel acetate solution containing 100 g / l at a temperature of 30 ° C. or higher and lower than 50 ° C. for 1 minute or longer.

The aluminum that constitutes the support is A
For Al-Mg-Si alloys such as 6063 and AA6463
Limited. This is because, when viewed the behavior of the intermetallic compound in the anodized, is like A3003 to impairing homogeneity remaining in the film during in undissolved than, A6063, AA64
Since the Al-Mg-Si based alloy such as 63 is eluted, a homogeneous and sound film can be obtained. Further, in the case of pure aluminum, although the film is sound, there is a problem that the mechanical strength as a part is poor. In addition, Al such as A5052
-Although Mg-based alloys also give relatively good results, Al-
It does not reach the Mg-Si alloy.

The aluminum support is anodized in order to improve the charge injection preventing property and the rectifying property as well as providing the adhesion between the photosensitive layer and the support by the anodized film. The type of such anodizing treatment is not particularly limited, and a sulfuric acid method using sulfuric acid as an electrolytic solution or an oxalic acid method using oxalic acid may be used. Further, other processing conditions are not limited, but the thickness of the anodized film is preferably regulated to 1 μm or more. If it is less than 1 μm, the adhesion to the photosensitive layer, the rectifying property, etc. may be deteriorated. It is preferable to secure a thickness of about 5 to 10 μm. If necessary, the aluminum support may be subjected to pretreatments such as degreasing, washing with water, and etching before the anodizing treatment.

The aluminum support that has been subjected to the anodizing treatment is then subjected to treatment such as washing with water if necessary, and then contacted with an aqueous solution of nickel acetate. This is the N
This is because the i ions are adsorbed to the fine pores in the porous layer of the anodic oxide film to smooth the inflow of electrons, obtain good rectifying characteristics, and to obtain high image quality without black spot noise. For this reason, the concentration of nickel acetate in the nickel acetate aqueous solution must be 1 to 100 g / l, in other words, 0.1 to 10 w / v%. 1 g / l
If it is less than 100 g / l, the adsorption of nickel acetate ions is insufficient. The preferable range of the nickel acetate concentration is 1 g / l or more and less than 10 g / l, and most preferably 2 to 7 g / l. The temperature of the nickel acetate aqueous solution is such that the nickel acetate concentration is 1 g / l or more 10
If it is less than g / l, it should be set to 30 to 50 ° C, and if the concentration of nickel acetate is 10 to 100 g / l, it should be set to 30 ° C or more and less than 50 ° C. If the liquid temperature is less than 30 ° C, it will be insufficient to promote the adsorption of Ni ions,
After all, it causes black spot noise. On the other hand, the temperature exceeds 50 ° C (when the nickel acetate concentration is 1 g / l or more and less than 10 g / l) or 50 ° C or more (the nickel acetate concentration is 10% or more).
˜100 g / l), it is presumed that a hydrated oxide of aluminum is formed, which impairs electrical characteristics such as rectification characteristics and causes black spot noise. A particularly preferable temperature of the nickel acetate solution is 37 to 47 ° C. Furthermore, it is necessary to secure a treatment time of 1 minute or more in order to perform the necessary and sufficient adsorption of Ni ions. However, even if the processing for more than 20 minutes is performed, N
The i-ion adsorption effect is saturated, which is a waste of time. Particularly preferably, it is set to 5 to 15 minutes. A method of contacting the conductive support with the nickel acetate aqueous solution may be a shower method or the like, but an immersion method can be adopted as a method that is surely treated and suitable for mass production.

The conductive support which has been subjected to the above-mentioned base treatment is subsequently coated with a laminated photosensitive layer having a charge generation layer and a charge transport layer. As a material for the photosensitive layer, a conventionally known material may be appropriately used. For example, the charge generation layer, the binder resin is dissolved using a suitable solvent, various azo pigments, perylene pigments, phthalocyanine pigments, polycyclic quinone pigments, indico pigments,
A solution in which a pigment such as a quinacridone pigment is added to 10 to 200 parts by weight with respect to 100 parts by weight of a binder resin and dispersed by a method such as a ball mill, a vibration mill, a sand mill or a roll mill has a thickness of about 0.1 to 1 μm. It may be formed by applying to. In addition, the charge transport layer is an electron-donating substance composed of a derivative of pyrazoline, triphenylmethane, oxadiazole, carbazole, hydrazone, styryl, imidazole, trinitrofluorenone, tetranitroxanthone, tetracyanoethylene, tetracyanoquinodiene. It may be formed by dissolving a substance having a charge transporting property such as electron accepting property such as methane in a resin having a film forming property and applying it to 5 to 30 μm. Examples of the binder resin used in the charge generation layer and the charge transport layer include polyester, polycarbonate, polymethacrylic acid ester, polyvinyl butyral, silicone resin, epoxy resin, melamine resin, urethane resin and polystyrene.

[0014]

Operation: From anodized Al-Mg-Si alloy
On aluminum support, nickel acetate concentration: 1 to 1
Nickel acetate of 00g / l, liquid temperature: 30 to 50 ° C (when the nickel acetate concentration is 1 g / l or more and less than 10 g / l) or 30 ° C or more and less than 50 ° C (when the nickel acetate concentration is 10 to 100 g / l) It is presumed that Ni ions are adsorbed to the fine pores of the anodic oxide film while suppressing the formation of hydrated oxides by contacting the aqueous solution for 1 minute or more, which effectively acts to prevent the generation of black spot noise in the image. It is supposed to do.

[0015]

As described above, according to the present invention, an aluminum support made of an anodized Al-Mg-Si alloy is treated with a nickel acetate aqueous solution under specific conditions different from conventional ones. As is clear from the embodiment, the image quality can be improved by suppressing black noise and fogging, not only in a normal temperature environment but also in a severe environment of high temperature and high humidity. As a result, it can be suitable as a photoconductor for an electrostatic copying machine, a laser beam printer, or the like.

[0016]

Embodiments of the present invention will be described below.

A3003, A5052, A6063, A
Prepare each aluminum alloy tube made of A6463,
It was used as a support.

Then, each of the above supports was pretreated.
Pretreatment is degreasing (surfactant, 65 ° C x 10 minutes), washing with water (running water, 1 minute), etching (NaOH, 10 g / l,
30 ° C x 30 seconds), water washing (running water, 1 minute), neutralization (HNO
₃ , 13w / v%, room temperature x 5 minutes), washed with water (running water, 5 minutes)
Was carried out sequentially.

Next, using H ₂ SO ₄ : 14 w / v% sulfuric acid aqueous solution (solution temperature 20 ° C.), the current density was 1 A / dm ^2.
× Approximately 7μ thick after anodizing for 25 minutes
m anodized film was formed.

After washing with water (running water, 5 minutes) twice, each support was immersed in pure water and an aqueous solution of nickel acetate. The immersion treatment was performed under the condition that the concentration of nickel acetate, the liquid temperature, and the immersion time were changed as shown in Table 1.

Then, the support is washed with water (pure water, 1
Min) and after drying, a photosensitive layer having a charge generation layer and a charge transport layer was formed on the surface of the support by coating as follows. That is, the CGL layer was prepared by diluting metal-free phthalocyanine to 4% with tetrahydrofuran to give a film thickness of about 0.
It was formed by coating and drying so as to have a thickness of 5 μm. Then C
The T agent (hydrazone compound) and the CT resin (polycarbonate) were dissolved in methylene chloride at a ratio of 1: 2, coated so that the film thickness was about 20 μm, and dried to form a CTL layer.

With respect to the various photoconductors obtained as described above, a temperature of 3
Under a high temperature and high humidity environment of 5 ° C. and a humidity of 85%, an initial surface potential (V ₀ ) is −750 V and a developing bias (V _b ) is −.
The generation state of black spots on the white paper portion on the image when the reversal development was performed at 500 V was examined. The results are shown in Table 1.

[0023]

[Table 1] As can be seen from Table 1 above, according to the present invention, it was confirmed that black spot noise in the case of reversal development can be suppressed.
Also, from the comparison between No13 and No25, A3003
With a support made of gold, the effect of suppressing black spot noise is poor,
Furthermore, from comparison of No13 and No26, as a support
Al-Mg-Si based alloy is better than Al-Mg-based alloy
It can also be seen that there is less black spot noise than that using.

Claims (2)

[Claims] 1. A method for preparing an underlayer for an electrophotographic laminate type photoreceptor having a charge generation layer and a charge transport layer on the surface of an aluminum support made of an Al—Mg—Si alloy . After the anodizing treatment of the aluminum support, a temperature of 1 g / l or more and less than 10 g / l of nickel acetate was added.
A method for treating the underlayer of a laminated photoreceptor for electrophotography, which comprises contacting with a nickel acetate solution at 0 to 50 ° C. for 1 minute or more. 2. A surface treatment method for an electrophotographic laminate type photoreceptor having a charge generation layer and a charge transport layer on the surface of an aluminum support comprising an Al—Mg—Si alloy . After anodizing the aluminum support, it is brought into contact with a nickel acetate solution containing nickel acetate in an amount of 10 to 100 g / l at a temperature of 30 ° C. or higher and lower than 50 ° C. for 1 minute or longer. Body surface treatment method.