JPS5818638A - Electrophotographic receptor - Google Patents

Abstract

PURPOSE:To obtain an image enhanced in contrast and sensitivity and capable of preventing rise of residual potential and its remarkable cycle rise through the ordinary Carlson process, by providing an interlaye containing an organic zirconium compound between a photodonductive layer and a protective layer. CONSTITUTION:A photoconductive layer 3 is formed on a conductive substrate 4. This layer may be composed of either of inorganic and organic photoconductors, and either of a single layer and laminated layers. A 10mum thick interlayer 2 containing at least one organic zirconium compound selected from a zirconium complex and a zirconium ester is formed on the layer 3 by coating a solution of said zirconium compound and drying it to make up a photoreceptor, thus permitting the obtained photoreceptor to be high in contrast, low in residual potential, and resistant to deterioration of chargeability and photosensitivity even after repeated cycles of charging and exposure.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrophotographic photoreceptor, more specifically, an electrophotographic photoreceptor O11 having a photoconductive layer 01111Klil1 layer.
%O adjusted to llL.

There are many photoconductors used in electrophotographic processes including charging, exposure, etc. (OIO has been put into practical use (for example, see US Patent No. 2,297,819), 11 For example, an organic photoconductive material is directly provided on a suitable conductive substrate by coating or vapor deposition.
A certain v% has ZmO, C in the binder! i, Tl
One in which an inorganic photoconductive material such as O3 is dispersed, one in which an inorganic photoconductive material such as O3 is dispersed, one in which an amorphous selenium or a 70 alloy is deposited, and one in which an inorganic photoconductive material such as O3 is deposited, or %O laminated on two or more layers of the above-mentioned outgo conductive layer
etc. are used (for example, 41 [148-53
No. 94, 41 Kosho 1B No. 46-3005, II# Kosho 4
(Refer to No. 8-14271), these photoreceptors have a certain amount of % to achieve both electrobalance, optical properties, and mechanical properties. In some cases, it has been proposed to provide a photoreceptor 1111Kll11 layer in order to improve the characteristics suitable for the developing section O process.

ζo*wtymox is called a protective layer, and if kept, a thin resin film t-1! liK setup, charging and wam
m light < Carlson process) K to perform m image formation %O
It is. However, when a photoreceptor provided with an O-resistant insulation layer is used, a high residual potential and a significant increase in its cycle are observed in many cases.

This high residual potential and cycle increase can be considerably improved by making the heat insulating layer t' 1μ or less, but the film becomes easy to peel off and the resistance to long-term use is V%40. Another surface layer is provided with a resin layer of high electrical resistance, called an insulating layer, and is subjected to a static elimination process (using a special method (e.g., U.S. Pat. It is something that forms. However, photoreceptors with an insulating layer of at least 2 gH must use a special latent image formation process, with a charging step of at least 2 gH! Therefore, there is a problem of complications and invitations.

The invention @ relates to the former photoreceptor provided with a protective layer, and it is possible to achieve %A without using a special latent image forming process.
The present invention relates to a photoreceptor in which stirrup IIO can be formed using the so-called Carlson process.

The present applicant previously proposed a low-resistance protective layer as a solution to the above-mentioned drawbacks (41 Application No. 4-41111).
No. 1, ljj No. 14-65671, No. 54-6rh
(Refer to No. 72 and No. 54-65673) However, in these methods, by providing a low resistance protective layer,
~20sO can be used as a protective layer! , 4I, which can prevent high residual potential and a large cycle increase, has the disadvantage that the chargeability of the entire photoreceptor decreases, and as a result, images with sufficient contrast cannot be obtained. It has been found that this tendency is most pronounced when the photoconductive layer has high sensitivity.

An object of the present invention is to provide an electrophotographic photoreceptor that can eliminate such drawbacks t-1ii*.

Invention@O The purpose is to provide a photoconductive layer on a conductive support.

This can be achieved by an electrophotographic photoreceptor in which an intermediate layer and a protective layer are sequentially laminated, in which the intermediate layer contains at least one type of organic zirconium compound.

The structure of the electrophotographic photoreceptor of the present invention is shown in attached WJ1N. In Wi, 1 is a low-resistance transparent protective layer made of an organic polymer compound to which a suitable organic compound is added.

2 is an organic zirconium compound-containing intermediate layer, 3 is a photoconductive layer, and 4 is a conductive support.

20 The intermediate layer must not be immersed in the solvent used for applying at least the upper protective layer 51-).

In addition to serving as a barrier layer, this intermediate layer can also function as a photoconductor, a protective layer, and an OII adhesion layer. Examples of organic zirconia^ compounds suitable for this intermediate layer 2 include the following %O.

1. Zirconium complex a, zirconitum intermediate compound zirconium tetrakis acetyl acetoacetate, zirconium diptoxybisarytyl acetonate, zirconium tripto diacetylacetonate, zirconium tetrakis ethyl acetoacetate, zirconium butyl citris ethyl acetoacetate , zirconium diptoxybisethyl acetoacetate, zirconium tryptocymonoethyl acetoacetate, zirconium tetrasethyl lactate, zirconium diptoxybisethyl lactate.

Bisacetylacetonate bisethylacetoacetate zirconium, monoacetylacetonate trisethylacetoacetate zirconium, bisacetylacetonate pisethyl lactate zirconium.

b, other complexes Zirconium trif 04 acetylacetone.

1 Zirpnium ester zircoequum 1-butyrate, zircoela penta-globilate.

These compounds can also be used singly as a warm mixture of %211 or more. Furthermore, from the viewpoint of improving the adhesion of 11, controlling the resistance value, and other layer weights, it can also be used as an O-temperature mixture with the above-mentioned organometallic compound and an organic*M compound having the same value.

The thickness of the intermediate layer 20 is set arbitrarily, but it is 1041 or less,
It is preferable that * is one voice or less ugly.

This intermediate layer can be formed by coating by an appropriate method such as gray coating, dip*a cloth, knife coating, and alu coating.

The photoconductive layer of the photoreceptor of the present invention is polyvinylcarbazole/2,4 in a vacuum evaporated film of IS, S・-T@gold%S@-M alloy, or a multilayer vacuum-deposited film of a suitable combination thereof.
．． 7-) Liet0-9-fluorenone (rvt/TM
F') O organic photoconductor such as ZmO'P Inorganic photoconductor such as CdS dispersed in a binder No. 5 i is a stacked charge generation layer and charge transport layer vIl! can be used.

In addition, as a protective layer, a suitable organic compound or an inorganic compound added to an organic polymer compound can generally be used. When adding a compound or using an electronically conductive material, or when adding a particle size of 0 to an organic polymer,
．． 3, preferably 0.15 Jla or less metals and metal oxides are dispersed. When an electron conductive material is used, it is opaque at first, but when it becomes less than α3, it becomes substantially transparent and light transmission is not hindered.

In addition, the materials used for such a protective layer are as follows: metallocetate/and a compound having at least one metalcene skeleton in its molecular structure; tetrazole; and a compound having at least one metalcene skeleton in its molecular structure; Compounds having: gold, silver, and an average particle size of 8.3μ or less;
Metals such as aluminum, iron, steel, nickel, etc. 11 Ash saponified zinc, titanium oxide, *tin oxide, #! bismuth.

Powders of metal oxides such as indium oxide and antimony oxide; powders containing tin oxide and antimony oxide in single particles, etc.

Next, the electrophotographic photoreceptor 1-* of the present invention will be explained with reference to comparative examples and examples.

Comparative Example 1 Parts by weight of polycarbonate and 20 weight parts of dimethyl 7-dichloromethane were dissolved and placed on a Kos*taa substrate. ! as III arrival II C! 5
A photoreceptor having a protective layer of 10 tones was obtained by coating and drying the photoreceptor. 0As2Se to apply the above protective layer
3. The deposited film is positively charged to an initial potential v soo v,
This operation of exposing with light having a wavelength of t'4110*alto was repeated at a speed change of 401i1/min. At this time, the residual potential was stable at OV. On the other hand, mu sls@s with a protective layer
When the vapor-deposited metal was charged and exposed under the above conditions, the initial potential was 2.
00 Y, and the residual potential was stable at 100V.

Therefore, the Mu3S-axis photoreceptor with the protective layer had significantly lower electrostatic contrast than the photoreceptor without the protective layer.

Example 1 A Mu18@B vapor deposited film was formed on the M substrate in the same manner as in Comparative Example 1, and then a resin consisting of 1 part by weight of zirconium tetrabutyrate and 10 parts by weight of isogumivir alcohol was applied thereon. A liquid dip coating was applied and dried at 40° C. for 2 hours to form an intermediate layer having a thickness of 5° to 5°C.Then, the same protective layer as in the comparative example was applied thereon. When this photoreceptor was repeatedly charged and exposed in the same manner as in Comparative Example 1, the initial potential was 5oov, and the g-resistance potential was 103 V (1e1-). Therefore, the electrostatic contrast was 797 V''C, and only the protective layer was O. Compared to a photoreceptor, its properties were significantly improved, and the values were similar to those of a photoreceptor without a protective layer.

Example 2 In the same manner as in Comparative Example 1, a GV shadow was formed on an M substrate by vapor deposition. Next, on top of that, 1 part by weight of zircoeu^tetra-sulfur tylacetonate, 72 parts of methyl (trimethoxy7)
1 part by weight of Inglobil alcohol aot amount s
A resin solution consisting of 5 parts by weight of phosphorus-butyl alcohol was applied by spraying.

After drying at 40° C. for 2 hours, a 0.3 s thick intermediate layer was formed.

Next, a protective layer having the same thickness as Comparative Example 1 and having a thickness of 15 μm was provided thereon. When this photoreceptor was charged and exposed repeatedly in the same manner as in Comparative Example 1, the initial potential was 935 V and the residual potential was 14 V.
It was 5V. Therefore, the electrostatic contrast of this photoreceptor was 790 V, which was the same value as that of a photoreceptor without high stability.

Example 3 A KA-S vapor-deposited film was formed on an M substrate in the same manner as in Comparative Example 1. Next, 2 parts by weight of zirconium tetraacetylacetonate and γ-acryloxyglobyl trimethoxylane ( Product name, [1M503b Shin-Etsu Chemical Co., Ltd. 11) A solution consisting of 1 part by weight and 20 parts by weight of butanol was spray applied, 100' OK was applied, and dried for 2 hours.
o, 6s thick intermediate layer was provided, then Comparative Example 1
The protective layer was provided with the same thickness of t-ioμ.

When this photoreceptor was charged and exposed using the same method as in Comparative Example 1, the initial potential was 91SV and the residual potential was 115V.The electrostatic contrast of this photoreceptor was 800V.
The electrostatic contrast was the same as that of a photoreceptor with a protective layer.

Comparative Example 2 S・(50# thick) vapor deposited film provided on M cylinder with length 300cm and! On the photoconductor of the two-layer lid made of @-Tc alloy vapor deposited film (ljI thickness), polyurethane resin (manufactured by Kansai Bay/To Co., Ltd., Rethane 4000) with a particle size of 0.1 s for solid content of 70 parts by weight was applied. A resin solution containing 30 parts by weight of tin oxide as shown below was applied and dried to form a protective layer of 10 μm. When this photoreceptor was repeatedly charged and exposed in the same manner as in Comparative Example 1, the initial potential was 150 V and the residual potential was 85 V, resulting in a significantly low electrostatic contrast.

Example 4 Zirconium tetra-butyrate 2 weight S on top of the same S/S*-T double layer photosensitive layer as in Comparative Example 2.

A solution consisting of 1 part by weight of dimethyl(dimethoxy)silane and a weighted part of Inglovir alcohol was spray applied,
It was dried at 0° C. for 3 hours to provide a Q, 5μ thick intermediate layer.

Next, the same protective layer as in Comparative Example 2 was provided thereon to a thickness of 20jI. When this photoreceptor was repeatedly charged and exposed in the same manner as in Comparative Example 2, the initial potential was 9 sV, and the residual potential was 19 sV.
It was 5 Y. Therefore, the electrostatic contrast of this O photoreceptor was soov, which was the same as that of the protective layer coated photoreceptor. - When a copy test was conducted using this photoreceptor using a magnetic brush development method, an extremely clear image identical to the exposed pattern was obtained.

[Brief explanation of drawings]

The drawings show the structure of the electrophotographic photoreceptor of the present invention. Symbols in the figure: 1...Low resistance film holding layer; 2...Intermediate layer; 3...Photoconductive layer; 4, . . . Conductive support.

Claims (1)

[Scope of Claims] l An electrophotographic photoreceptor comprising a photoconductive layer, an intermediate layer, and a protective layer sequentially laminated on a conductive support, wherein the intermediate layer contains at least 4i types of organic zircoequum compounds. What to do vII # Electrophotographic photoreceptor with mold. 1. The electrophotographic photoreceptor according to claim 1, wherein the organic zirconicum compound is a compound selected from the group consisting of zircoequum anchors and hiszircoeum esters.