JPH0683091A - Electrophotographic sensitive body and manufacture thereof - Google Patents

Abstract

PURPOSE:To improve abrasion resistance and oxidation resistance, etc., of an electrophotographic sensitive body without adversely affecting the photographic sensitivity characteristics and to provide the sensitive body having excellent durability. CONSTITUTION:A photosensitive layer of the electrophotographic sensitive body is formed on a support. Thereafter the photosensitive layer is subjected to the plasma vapor deposition under an oxygen contg. atmosphere concurrently by using a vapor deposition source consisting of at least aluminum or an aluminum compound together with a vapor deposition source consisting of zinc or a zinc compound to form an aluminum oxide layer contg. at least zinc on the surface of the photosensitive layer. Thus the electrophotographic sensitive body provided on the support with the photosensitive layer, the surface of which is covered with the aluminum oxide layer contg. at least zinc, can be manufactured.

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 an electrophotographic copying machine and the like and a method for manufacturing the same.

[0002]

2. Description of the Related Art A photoreceptor for electrophotography is often formed by providing a photosensitive material layer of, for example, selenium type, amorphous silicon type, organic photo semiconductor type or the like on a support. However, selenium-based photosensitive materials are considered not to be used in the future because they are not only costly but also have a high risk of environmental pollution, and amorphous silicon-based photosensitive materials are widely used due to their high cost. Has not yet reached. On the other hand, a photoreceptor using an organic photo-semiconductor-based photosensitive material is less expensive than selenium-based or amorphous silicon-based, but inferior in abrasion resistance and oxidative deterioration, and has insufficient durability. It has the drawback of being

On the other hand, in order to improve the durability of the photoconductor
In addition, there is no proposal to form a protective layer on the photosensitive layer.
, For example, Al on the amorphous silicon photosensitive layer.₂O₃,
Si₃N _Four, BN, SiC, etc., the contact angle with water is 45
A technique of providing a protective layer of not less than ° (Japanese Patent Laid-Open No. 22132/1985)
No.) or Al on the photosensitive layer₂O₃, SiO₂, Si₃N_Four, BN, SiC
 , TiO₂In addition to providing a protective film such as Ta₂O_FiveOver
The technique of providing a coat (Japanese Patent Laid-Open No. 61-188544)
Yes, and silicone-based or fluorine-based resin on the photoreceptor layer
Of forming a plasma-polymerized protective film of Japanese Patent Application Laid-Open No. 1-19
1857 and JP-A-1-191858).

[0004]

However, among these various protective films, the organic protective film is generally soft and inferior in durability to the inorganic protective film, and the hard inorganic protective film is durable. However, there was a problem that the photosensitive characteristics of the photosensitive layer were impaired. Therefore, the present invention has an object to provide an electrophotographic photoreceptor having excellent durability by improving abrasion resistance, oxidation resistance and the like without impairing the photosensitivity.

[0005]

In the electrophotographic photosensitive member of the present invention which can achieve the above object, a photosensitive layer having a surface coated with an aluminum oxide layer containing at least zinc is provided on a support. Further, such an electrophotographic photosensitive member is prepared by forming a photosensitive layer on a support, and then using an evaporation source composed of at least aluminum or an aluminum compound and an evaporation source composed of zinc or a zinc compound in combination with an oxygen-containing material. It can be manufactured by simultaneously performing plasma deposition in an atmosphere to form an aluminum oxide layer containing at least zinc on the surface of the photosensitive layer.

The support used in the electrophotographic photosensitive member of the present invention may be one that has been conventionally used in electrophotographic photosensitive members, and may be, for example, a cylindrical member made of aluminum. It is not particularly limited. The photosensitive layer provided on such a support may be a single layer type or a function separation type in which a charge generation layer and a charge transfer layer are laminated, but it is formed of an organic photosensitive material. In the electrophotographic photosensitive member provided with the formed photosensitive layer, the protective effect of the protective film formed by the method of the present invention is particularly remarkable.

In manufacturing the electrophotographic photosensitive member of the present invention, a plasma deposition apparatus as shown in FIG. 1 can be used. The apparatus in the figure is provided with a main evaporation source 2 formed of a tungsten wire and a sub evaporation source 3 made of a molybdenum boat in a vacuum chamber 1, and a filament 4 for generating thermoelectrons and a mesh grid 5 are provided. A counter electrode 6 for mounting the body to be vapor-deposited is provided between them. The counter electrode 6 can be cooled if necessary so that the temperature does not rise excessively. It is also possible to sequentially deposit a photosensitive layer and a protective film on the surface of a support using this device, but by attaching a support provided with a photosensitive layer in advance to this device and plasma-depositing only the protective film. Good.

In order to form a protective film on the surface of the photosensitive layer using this apparatus, for example, an aluminum wire is cut into short pieces and suspended on the main evaporation source 2, and zinc powder is placed on the auxiliary evaporation source 3 to form a pair. The photoreceptor on which the protective film is to be formed is attached to the electrode 6. Then, the vacuum chamber 1 is evacuated to the level of 10 ⁻⁴ Torr and then a gas containing oxygen is supplied to heat the filament 4 and apply a positive voltage to each of the filament 4 and the grid 5 to form the counter electrode 6. Plasma is generated between them. After that, the main evaporation source 2 and the sub evaporation source 3 are respectively heated,
The temperature of the photosensitive member attached to the counter electrode 6 is kept within the range of 50 to 100 ° C., and the metal oxide is deposited on the surface of the photosensitive member while reacting the metal vapor and oxygen. At this time, the zinc content in the protective film can be appropriately adjusted by controlling the heating of the main evaporation source 2 and the sub evaporation source 3.

[0009]

The protective film formed on the surface of the electrophotographic photosensitive member according to the present invention is hard and has excellent wear resistance because it contains aluminum oxide as a main component, but it also contains a zinc component, so that it is a photosensitive layer. It does not impair the original photosensitive characteristics of.

[0010]

【Example】

(Example 1) A support having a vapor-deposited film of aluminum having a thickness of 10 μm provided on a polyester film having a thickness of 0.5 mm, a charge generation layer having a thickness of 0.6 μm, which is made of a vapor-deposited film of titanyl phthalocyanine, and Polyvinylcarbazole and trinitrofluorenone as charge transfer agents
20 μm of Panlite L-1250 resin containing mg / g each
And a charge transfer layer wet-coated to a thickness of 1 to form a photoreceptor A.

This photoconductor A is attached to the counter electrode 6 of the apparatus shown in FIG. 1, 12 parts by weight of an aluminum wire having a purity of 99.99% is used for the main evaporation source 2, and a purity of 9 is used for the auxiliary evaporation source 3.
The inside of the vacuum chamber 1 was evacuated to 1 × 10 ⁻⁴ Torr by using 9.9% zinc powder at a ratio of 6 parts by weight, respectively.
While supplying oxygen so as to maintain the 10 ^-4 Torr level, plasma deposition is performed for 40 minutes while suppressing the film formation rate to 6 Å / sec or less, during which the temperature of the photoconductor does not exceed the range of 50 to 100 ° C. Then, a photoreceptor B of the present invention having a co-deposited film of aluminum oxide and zinc oxide having a thickness of about 1300 nm was obtained.

(Second Embodiment) For the same photoreceptor A as that used in the first embodiment, an aluminum wire is used as the main evaporation source 2.
4 parts by weight, zinc powder was used for the sub-evaporation source 3 at a ratio of 3 parts by weight, and a mixed gas of argon and oxygen was supplied instead of oxygen, and the same method as in the first embodiment was performed. Plasma deposition was carried out to obtain a photoreceptor C of the present invention having a co-deposition film of aluminum oxide and zinc oxide with a thickness of about 800 nm.

With respect to the photoconductors B and C of the present invention provided with a protective film of an aluminum oxide containing zinc as described above, and the photoconductor A having no protective film for comparison, their charging characteristics and photosensitivity are shown. The properties were evaluated using a paper analyzer (Kawaguchi Denki, SP-428). In the test, the surface potential (Vs) when the photoreceptor was negatively charged at -5 kV for 5 seconds was measured, and then the surface of the photoreceptor was irradiated with a tungsten lamp so that the illuminance was 35 lux, and the surface potential was Vs. Exposure amount (lux ・
sec) is calculated as the half-exposure amount (E _1/2 ), and further 30 lux
The surface potential (Vr) after irradiation with an exposure amount of sec was measured. Then, such measurement was continuously performed 100 times, the first result and the 100th result were compared, and the results are shown in Table 1.

The hardness of the surface of these photoconductors is
The results were shown in Table 1 in accordance with the method of ISK-5401 for the pencil scratch test for coating film.

[0015]

[Table 1] Table 1 ────────────────────────────────── Photoconductor A ^* B C ──── ─────────────────────────────── 1st 100th 1st 100th 1st 100th ──────── ────────────────────────── Vs (V) -755 -830 -890 -910 -930 -900 E _1/2 (lux ・ sec ) 6.0 9.1 6.4 6.6 6.5 6.8 Vr (V) -3 -40 -3 -7 -5 -10 ───────────────────────────── ─────── Pencil scratch test 2H 9H or more 9H or more ────────────────────────────────── * : Comparative example

[0016]

EFFECT OF THE INVENTION The electrophotographic photosensitive member of the present invention not only has excellent wear resistance and little oxidative deterioration and exhibits excellent durability, but also has excellent chargeability and sensitivity. In view of the chemical composition of the protective film, the same effect can be expected not only in the photosensitive layer using the organic material but also in the electrophotographic photosensitive member having the photosensitive layer using the inorganic material.

[Brief description of drawings]

FIG. 1 is a configuration diagram of an example of a plasma deposition apparatus suitable for carrying out a method for manufacturing an electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 1 Vacuum tank 2 Main evaporation source 3 Secondary evaporation source 4 Filament 5 Grid 6 Counter electrode

Claims (2)

[Claims] 1. An electrophotographic photoreceptor comprising a support and a photosensitive layer having a surface coated with an aluminum oxide layer containing at least zinc. 2. After forming a photosensitive layer on a support, plasma deposition is simultaneously performed in an oxygen-containing atmosphere by using at least an evaporation source made of aluminum or an aluminum compound and an evaporation source made of zinc or a zinc compound in combination. A method for producing an electrophotographic photosensitive member, comprising forming an aluminum oxide layer containing at least zinc on the surface of the photosensitive layer.