JPS5836897B2 - Denshisha Shin Kankou Zairiyou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrophotographic photosensitive material, and more specifically, in an electrophotographic photosensitive material in which an inorganic layer and an organic photoconductor layer are provided on a conductive support, the present invention relates to an electrophotographic photosensitive material in which an inorganic layer and an organic photoconductor layer are provided on a conductive support. The present invention relates to an electrophotographic material whose layers are treated with a silane coupling agent.

Some electrophotographic photosensitive materials have an inorganic layer and an inorganic semiconductor or organic semiconductor photoconductor layer on a conductive support, and in order to form an electrostatic latent image on this photosensitive material, the surface of the photoconductive layer must be The Carlson process, which involves charging and imagewise exposure, is used.

However, this type of photosensitive material has the drawback that the photoconductive layer lacks mechanical strength and can be damaged by repeated use.

In recent years, the durability of photosensitive materials has been improved by providing a transparent resin protective film on the photoconductive layer, adding various binders to the photoconductive layer, or providing an adhesive layer between the support and the photoconductive layer. Attempts are being made to improve this.

For example, regarding protective films, Japanese Patent Publications No. 42-23910, No. 42-19748, No. 43-24748, No. 48-
No. 2965, No. 38-15446, No. 46-3713
No. 48-22036, U.S. Patent No. 3,14
0,174, etc., and various binders are shown in Japanese Patent Publication No. 13947/1983, Japanese Patent Publication No. 41-17188, Japanese Patent Publication No. 43-24753, etc., and adhesive layers are described in Japanese Patent Publication No. 261/41/1989. No. 48-2614
It is shown in No. 2, etc.

However, even if the above-mentioned methods of providing a protective film and adhesive layer or adding various binders are applied to electrophotographic materials in which an inorganic layer and a photoconductor layer are provided on a conductive support, the photoconductor The original optical attenuation characteristics (sensitivity) were reduced, or the adhesion between each layer was still insufficient, resulting in insufficient mechanical strength.

The present invention provides an electrophotographic photosensitive material in which the adhesiveness between a support and an organic photoconductor layer is improved without degrading the light attenuation characteristics inherent to the organic photoconductor. (x=1~2), Al203, WO3, La
An organic photoconductor layer is provided through an inorganic layer made of 203, CeO2, ZrO, ZnS, LaF3, or CeF3, and a silane coupling agent is applied to the inorganic layer, or a silane coupling agent is applied to the inorganic layer, or a silane coupling agent is applied to the inorganic layer. It is characterized in that it contains a silane coupling agent.

The silane coupling agents mentioned here include, for example, vinylchlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyllutris (β-methoxyethoxy).
Silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltris(β-methoxyethoxy)silane, β-(3.4-epoxysilane/\xyl)ethyltrimethoxysilane, r-glycidoxy Probyltrimethoxysilane, vinyltriacetoxysilane, γ-mercabutopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β
-(Aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β-1(aminoethyl)-γ-aminopropyltrimethoxysilane, N,N-bis(β-hydroxyethyl)-γ-aminopropyltriethoxysilane , γ-chloropropyltrimethoxysilane, etc.

Silane coupling agents have two or more reactive groups with different reactivity introduced into their molecules, one of which is inorganic (glass, glass fiber, quartz, pigment, metal, etc.).
One is the reactive group (methoxy group, silanol group, etc.) that chemically bonds with metal oxides, silica sand, etc.), and the other is the reactive group (vinyl group) that chemically bonds with organic materials (various synthetic resins). , epoxy group, methacrylic group, etc.), and as a result, the silane coupling agent not only increases the binding properties of organic materials, but also plays a strong role as an intermediary between organic materials and inorganic materials.

A silane coupling agent having such a function is diluted with water or an organic solvent, and then applied to a conductive support provided with an inorganic layer by means such as dipping or spraying, or a silane coupling agent is diluted with water or an organic solvent, or the silane coupling agent is diluted with water or an organic solvent. A silane coupling agent is added to the body layer conditioning solution to contain the silane coupling agent in the organic photoconductor layer.

The amount of silane coupling agent applied to the inorganic layer is 0.
The amount of silane coupling agent added to the organic photoconductor layer is preferably 0.01 to 10% by weight. When added, a layer with relatively weak cohesive force is formed, so 0.1 to 0.25 weight of the rice cake is more preferably effective.

In the present invention, the conductive support is aluminum,
Examples include plates or cylinders made of metal such as copper or stainless steel, plastic films coated with metal thin films, and conductive glass plates.

As the inorganic layer, SiOx (x-=1 to 2), AA2
03 sWO3 * La2 o3, Ce02,
Z r O , Zn S , L a F 3 , C
Metal oxides, metal sulfides, or metal halides such as eF3 are effective.

In addition, as the organic photoconductor used for the organic photoconductor layer,
Examples of film-type organic semiconductors include poly-N-vinyl-rubazole, poly-N-vinyl-3,6-dibromo-rubazole, pyrene-formaldehyde resin, polyvinyldibenzothiophene, and polyvinylanthracene.

In addition, dyes generally used for electrophotography as sensitizers, such as methylene blue and benzopiIJIJum, or electron acceptors such as 2,4,7-trinitro-9-fluorenone are added to the organic photoconductor layer. You can also.

In addition, in order to further improve the durability of the electrophotographic photoreceptor of the present invention, it is also possible to further provide a protective film on the organic photoconductor layer.

To form an electrostatic latent image on the photosensitive material thus obtained,
This is carried out by a curling process or a modification thereof, and then an image can be obtained through development, transfer, and fixing by conventional methods.

As described above, the present invention skillfully utilizes the properties of a silane coupling agent to provide an electrophotographic material with an inorganic layer interposed between a conductive support and a photoconductor layer, which has sufficient durability to withstand repeated use. Furthermore, the electrophotographic properties of the photoconductive layer are not impaired.

Example 1 S l0 on polyester film deposited with aluminum
2 was vapor deposited to a thickness of 0.3 μm, and then a solution with the following composition was applied using a doctor blade, and dried at 60° C. for 10 minutes and 100° C. for 2 minutes to form an organic photoconductive film with a thickness of 16 μm. A body coating layer was obtained.

Poly N-vinyl Rubazol 2.12,4,
7 = l-linitro 9-fluorenone 3.3g
Polyester Adhesive 49.000 0.
12g (DuPont) Silicone oil AK-1000 0.014
g-Worker Chemical GMBH β-(3,4-epoxycyclo\xyl) 0. 1
g Ethyltrimethoxysilane tetrahydrofuran 4 2.0.
9 Using the photosensitive material thus obtained, 6. The OKV is negatively charged by corona discharge, irradiated with 20lux white tungsten light, and the exposure amount El/2 (AI'ux Sec) at which the surface potential attenuates to 1/2 after the light irradiation, 1/
Exposure amount E 1/5 (lux, se
c) Exposure amount E 1/10 (
lux, sec) was measured.

A 16 μm photoreceptor was obtained in the same manner as described above, except that a conditioning liquid obtained by removing the silane coupling agent from the organic photoconductive coating liquid was applied as a conventional photoreceptor using a doctor blade, and the light attenuation characteristics of the surface potential were determined. The results were measured and compared with the present invention.

As shown in Table 1, the sensitivity of the photoreceptor according to the present invention was almost the same as that of the conventional method.

Next, the dry-developed or wet-developed image was electrostatically transferred to high-quality paper and fixed using a known method, resulting in a positive image faithful to the original image without background stains.

Even after repeating the above steps and copying 10,000 copies, the photosensitive material of the present invention showed no decrease in sensitivity or disturbance of images.

On the other hand, when an image test was conducted using the same method using a conventional photosensitive material, the sensitivity decreased after 3,000 sheets, and the background was stained and the image was distorted.

A comparative photosensitive material was also obtained in the same manner as the photosensitive material of the present invention, except that a solution having the same composition as above was applied directly onto a polyester film deposited with aluminum without depositing SiO2.

When an image test was conducted in the same manner using this comparative light-sensitive material, the sensitivity decreased after 2000 copies.

Example 2 Approximately 0.3 of La203 was applied to a 0.2 mm thick aluminum plate.
It was deposited to a thickness of 5μ, and then a solution consisting of the following composition was applied with a doctor blade and heated at 180°C for 3 minutes at 60°C.
It was dried at .degree. C. for 12 minutes to obtain an organic photoconductor coating layer with a thickness of 12 .mu.m.

Poly N-vinyl Rubazol 2.0g2,
4,7,1-trinitro-9-fluorenone 3.3g Polyester Adhesive 49.000 0.47
2g (DuPont) Silicone oil AK-1000 0.014
g Worker Chemical GMBH γ-glycidoxypyltrimethoxy 0.15g
420 g of Sifuntetrahydrofuran Using the thus obtained photosensitive material, the light attenuation characteristics of the surface potential were measured in the same manner as in Example 1.

As a comparative product, the sensitivity of a photoreceptor was measured in the same manner as described above, except that a photosensitive solution was prepared from the above formulation without the silane coupling agent.

As shown in Table 2, the sensitivity of the photoreceptor according to the present invention was almost the same as that of the conventional method.

However, as in Example 1, in the repeated image production test, the conventional method showed a decrease in sensitivity after 5,000 sheets, and the background became dirty.
While the image is distorted, the photosensitive material of the present invention has a distortion of 1 0.0
Even after repeated testing of 00 sheets, no decrease in sensitivity or disturbance of images was observed.

A comparative photosensitive material was also obtained in the same manner as the photosensitive material of the present invention, except that a solution having the same composition as above was directly applied onto an aluminum plate without vapor-depositing La203.

When an image test was conducted in the same manner using this comparative light-sensitive material, the sensitivity decreased after 3000 copies.

Example 3 ZnS was evaporated to a thickness of 0.35 μm on a 2-layer aluminum plate, and a solution consisting of the following composition was applied with a doctor blade and dried at 60°C for 3 minutes and at 180°C for 15 minutes. An organic photoconductor coating layer having a thickness of 14 μm was obtained.

Poly N-vinyl Rubazol 2.0 g2
, 4.7-trinitro-9-fluorenone 3.3g Silicone oil AK-1000 0.014.
! ? Worker Chemical GMBH vinyltris(β-methoxyethoxy)silane 0.2
g Using the thus obtained photosensitive material, the light attenuation characteristics were measured in the same manner as in Example 1. As a result, there was no disadvantage in sensitivity, and even in the same image test as in Example 1, no background stains were observed. A positive image faithful to the original image was obtained, and this image showed no change even after repeated testing of 5,000 sheets.

It should be noted that a repeated test of 1,000 sheets of a photosensitive material prepared in the same manner as described above except that the silane coupling agent was omitted from the above recipe resulted in a decrease in sensitivity and a disturbance in the images.

A comparative photosensitive material was also obtained in the same manner as the photosensitive material of the present invention, except that a solution having the same composition as above was directly applied onto an aluminum plate without vapor-depositing ZnS.

The sensitivity of this comparative light-sensitive material decreased after repeated testing of 750 sheets.

Claims (1)

[Claims] 1 SiOx (x-=1 to 2
), M203, WO3, La203, CeO2, Zr
An organic photoconductor layer is provided through an inorganic layer made of O, ZnS, LaF3 or CeF3, and a silane cobblestone is coated on the inorganic layer, or a silane is added to the organic photoconductor layer. An electrophotographic light-sensitive material characterized by containing a coupling agent.