JPS59154454A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To render a photosensitive body to be formed on a conductive substrate high in photosensitivity, photosensitive in the longer wavelength region, and panchromatic by incorporating a perylene compd. in it. CONSTITUTION:A photosensitive layer 2a formed on a conductive substrate 1 contains a perylene compd. 3 for generating and transferring an electrostatic charge carrier necessary for photodecay, represented by a formula not shown here. The layer 2a is formed by coating the substrate 1 with a dispersion contg. this compd. dispersed into a binder soln. and drying it. A preferable thickness of the layer 2a is 3-50mum and a preferable content of the compd. 3 in the layer 2a is 10-70wt% of it. A metal, such as aluminum is vapor deposited to a plastic film, etc. are used for said substrate 1 of a photosensitive body, and all the insulating resin adhesive to the substrate can be used for the binder. Such a photosensitive body is high in photosensitivity in a longer wavelength region and panchromatic.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrophotographic photoreceptor. Specifically, the present invention relates to an electrophotographic photoreceptor having a photosensitive layer containing a perylene compound on a conductive support.

Conventionally, inorganic photoconductive substances such as selenium, cadmium sulfide, and zinc oxide have been widely used in the photosensitive layer of electrophotographic photoreceptors. In recent years, research on organic photoconductive materials has progressed, and some have been put into practical use as electrophotographic photoreceptors. Organic photoconductive materials have advantages over inorganic materials in that they are lighter in weight, easier to form into films, and easier to manufacture photoreceptors.

Many studies have been conducted on photoconductive polymers such as polyvinylcarbazole as organic photoconductive materials, but these polymers alone have poor film properties, flexibility,
Adhesion is poor, and plasticizers, binders, etc. are added to improve these defects, but this tends to cause other problems such as decreased sensitivity and increased residual potential, making it difficult to put it into practical use. It was extremely difficult.

On the other hand, with organic low-molecular photoconductive compounds, if a polymer with excellent film properties, flexibility, and adhesive properties is selected as a binder, it is possible to easily obtain a photoreceptor with excellent mechanical properties. It has been difficult to find compounds suitable for making sensitive photoreceptors.

In recent years, photoreceptors using conductive substances and specific perylene compounds have been reported (e.g., JP-A-47-303).
30, German Published Patent No. 2237539, JP-A-57-
2694 and JP-A-57-176O46), either the sensitivity is not sufficient, or the light absorption in the long wavelength region is poor (because there is no good absorption in the long wavelength region, the photosensitivity in the long wavelength region is poor, for example, there is a problem with the wavelength of light. Ta.

As a result of intensive research, the present inventors found that the following specific perylene compounds have high sensitivity and photosensitivity even in the long wavelength region.
, they found that it is panchromatic and arrived at the present invention.

That is, the present invention relates to an electrophotographic photoreceptor characterized in that a photosensitive layer containing a perylene compound represented by the following formula [[] is provided on a conductive support.

----------------CI] The perylene compound of formula [I] used in the present invention is already known as a coloring pigment in JP-A-57-139144, and is described in the above patent specification. As described, it can be easily synthesized from perylenetetracarboxylic dianhydride and p-methoxybenzylamine,
The particularly excellent photoconductivity of this compound has not been previously known, and was discovered for the first time by the present inventors.
The present invention was completed based on this new knowledge.

The electrophotographic photoreceptor of the present invention can have various structures. Examples are shown in Figures 1-4. The photoreceptor shown in FIG. 1 has a photosensitive layer (2a) formed by dispersing a perylene compound (3) in a binder (4) on a conductive support (1). The photoreceptor shown in FIG. 2 has a photosensitive layer (2+
)). The photoreceptors shown in FIGS. 3 and 4 have a charge phase generation layer (6) mainly composed of a perylene compound (3).
) and a charge transport layer (
A photosensitive layer (2c) or (2d) consisting of 7) is provided, respectively.

In the case of the photoreceptor shown in FIG. 1, perylene compound (3) c,
The light attenuation button serves both the generation and transport of the necessary charge carriers. In the case of the photoreceptor of FIG. 2, the charge transport material together with the binder forms the charge transport medium (5) 1-, while the perylene compound (3i) acts as a charge carrier generating material. Although it does not have the ability to generate charge carriers like perylene compounds, it has the ability to accept and transport charge carriers generated from perylene compounds.In other words, in the photoreceptor shown in Figure 2, the 1fX charge required for light attenuation is The production of the carrier is carried out by a perylene compound (3),
On the other hand, the charge carrier axis [transfer plate top [2] and the charge transport W body (
5). 6 and 41, the perylene compound (3) contained in the charge generation layer (6) generates charge carriers, while the charge transport Hiroshi 7) receives charge phase material injection and transports it.The effect is that the generation of charge carriers necessary for light attenuation is performed by the perylene compound, and the transport of charge carriers is performed by the charge transport medium. The mechanism is the same as in the case of 11 & light body in FIG.

The photoreceptor shown in Figure 8g1 can be prepared by dispersing a perylene compound in a binder solution, applying this dispersion to a conductive support, and drying it. The photoreceptor shown in FIG. 2 can be prepared by dispersing a perylene compound in a solution containing a charge transporting substance and a binder, coating this dispersion on a conductive support, and drying it. The photoreceptor shown in Fig. 6 can be prepared by vacuum-depositing a perylene compound on a conductive substrate, or by applying a dispersion obtained by dispersing fine particles of a perylene compound in a binder solution and drying. ,
It can be produced by applying a solution containing a charge transporting substance and a binder thereon and drying it. The photoreceptor shown in Fig. 4 can be produced by applying a solution containing a charge transport substance and a binder on a conductive support and drying it, and then vacuum-depositing a tilted perylene compound thereon, or by depositing fine particles of a perylene compound in a solvent or binder solution. It can be prepared by coating and drying a dispersion obtained by dispersing the liquid into a liquid. Coating is usually done using a roll coater, wire bar, doctor blade, etc.

The thickness of the photosensitive layer is as follows in the case of the photoreceptor shown in FIGS. 1 and 2.
6-50μ, good +, ku! ′is~2oμ. In the case of the photoreceptor shown in FIGS. 3 and 4, the thickness of the charge carrier generation layer is 5μ or less, preferably Gjo, 01 to 2μ, and the thickness of the charge transport medium layer is 3 to 50μ, preferably 5
~20μ. In addition, in the photoreceptor shown in FIG. 1, the ratio of the perylene compound in the photosensitive layer is 10 to 7
0% by weight, preferably 30 to 50% by weight. In the photoreceptor shown in FIG. 2, the proportion of the perylene compound in the photosensitive layer is 1 to 50% by weight, preferably 10 to 50% by weight,
The proportion of the charge transport material is 10 to 90% by weight, preferably 10 to 60% by weight.

The proportion of the charge transport material in the charge transport medium layer in the photoreceptor of FIGS. 6 and 4 is 10 to 95% by weight, preferably 1.
o~60%. In addition, in producing any of the photoreceptors shown in FIGS. 1 to 4, a plasticizer can be used together with a binder.

As the conductive support for the photoreceptor of the present invention, for example, a metal plate or foil made of aluminum or the like, a plastic film deposited with a metal such as aluminum, or paper treated with electrical conductivity is used. As binders, vinyl polymers such as polystyrene, polyacrylamide, and poly-N-vinylcarbazole, and condensation resins such as polyamide resins, polyester resins, epoxy resins, phenoxy resins, and polycarbonate resins are used. Any resin that is adhesive to the body can be used.

In addition, well-known charge transport substances can be used, such as derivatives of heterocyclic compounds such as pyrazole, pyrazoline, oxadiazole, thiazole, and imidazole, hydrazone derivatives, triphenylmethane derivatives, poly-N-vinylcarbazole and its derivatives. etc. are simple.

Among them, IJ, -N--vinylcarbazole and its derivatives! Valid for one temple. Further, these charge transport materials can be used alone or in combination of two or more kinds.

In the photoreceptor obtained as described above, an adhesive layer or a barrier layer can be provided between the conductive support and the photosensitive layer, if necessary. Materials for these layers include polyamide,
It is made of nitrocellulose, casein, polyvinyl alcohol, etc., and its film thickness is preferably 1 μm or less.

The photoreceptor of the present invention has very high sensitivity and is panchromatic in the visible range, and has little accumulation of residual potential and small fluctuations in surface potential and sensitivity due to repeated use, and has excellent durability.
i] - It has excellent advantages such as high flexibility.

Below, the present invention will be specifically explained with reference to examples.
All "parts" represent "parts by 1-P'".

Super Example 1 10 parts of polyester resin (Sieve Product Name 1-Vylon 200 manufactured by Toyobo Co., Ltd.), 10 parts of perylene compound, and 56 parts of tetrahydrofuran were pulverized and mixed in a vibration chamber, and the resulting dispersion was aluminum-deposited polyester. The photoreceptor was coated on a film with a wire bar and dried to produce a photoreceptor having the shape and condition shown in FIG. 1, having a photosensitive layer of about 12 microns. Next, the photosensitive layer surface of this photoreceptor was coated with an electrostatic multilayer paper tester (Mode 1).
SP 428 (manufactured by Kawaguchi Electric Seisakusho Co., Ltd.) was installed in well 1,
First, the photoreceptor is charged in a dark place by corona discharge of all voltages of applied Yi, discharged in the dark for 10 seconds2, and then the photoreceptor layer is irradiated with light from a tungsten lamp so that the surface has an illuminance of 5 lux. The surface potential is 1 in the dark.
The time taken for the surface potential to decrease to % of the surface potential after standing for 0 seconds was measured, and the photosensitivity E% (lux/second) was determined.
3A = 44 lux fist seconds.

Example 2 9 parts of poly-N-vinylcarbazole (trade name [-Tubicol 210J +++i manufactured by Nanko T1 Sangyo Co., Ltd.), 6 parts of a perylene compound, and 140 parts of tetrahydroflough were pulverized and mixed in a ball mill, and the resulting dispersion was mixed. A photoreceptor of the form shown in Fig. 2 with a photosensitive layer of about 9μ in thickness was prepared by coating and drying it on a polyester film on which aluminum had been vapor-deposited using a wire bar. When corona discharge was performed at an applied voltage of -6 KV and measured according to Example 1, the E% was 215.2 lux·sec.

Example: Polyarylate resin (trade name U-polymer U-,,,-
100 Uniti Chikisha) 6 parts, N-ethylcarbazole-
6-methylidene-N-amino-tetrahydroquinoline 6
1 part of the perylene compound and 60 parts of tetrahydrofuran were pulverized and mixed in a ball mill, and the resulting dispersion was coated on a polyester film coated with aluminum using a wire bar and dried to form a photosensitive layer with a thickness of 1 to about 9 μm. A photoreceptor of the form shown in Fig. 2 was made. Next, the sensitivity of this photoreceptor was measured according to Example 1 by carrying out corona discharge at an applied voltage of -6 KV, and found to be 1.%: 6 lux·sec.

Example 4 3 parts of perylene compound was added to phenoxy resin (trade name) PKH
1 part of Meiji Union Carbide Co., Ltd.) was dissolved in 2 parts of dioxa and 5 parts of dioxa. Grind and mix using a vibrating mill. The resulting dispersion was coated onto an aluminum-deposited polyester film using a wire bar and dried. A charge generation layer having a thickness of 1 μm was formed. On this charge generation layer, N-ethylcarbazole-6-methylidene-N-aminoindoline 5
Part, polycarbonate resin (product name [Panrai] L-1
A solution prepared by dissolving 5 parts of 250WJ (manufactured by Teijin Kasei) in 65 parts of methylene chloride was applied using a wire bar and dried to a thickness of 1.
A charge transport layer of 01z was formed to obtain a photoreceptor having the form shown in FIG. Thus, the preparation 1. The sensitivity of the photoreceptor is determined by the applied voltage -
A corona discharge of 6KV was carried out and the measurement was carried out according to Example 1.
P■, where E 3A = 6.5 lux salary seconds.

Example 5 In Example 4, 2,5-bis(
A photoreceptor was prepared in the same manner as in Example 4 except that p-diethylaminophenyl)-1,ro,4-oxadiazole was used. The sensitivity of the thus obtained photoreceptor was measured according to Example 1 and was found to be E 3'' = 11.4 lux·sec.

Example 6 In Example 4, the charge transport layer forming solution and t2
1 part of N-vinylcarnosol (same product as in Example 2), 2.5 parts of m-terphenyl, and 0 parts of picric acid.
．． A photoreceptor was prepared in exactly the same manner except that a solution of 01 parts dissolved in 165 parts of dioxane was used. The sensitivity of this photoreceptor was measured according to Example 1 and was found to be E3A-9 lux·sec.

When the spectral sensitivity of this photoreceptor was measured by irradiating it with light adjusted so that the light intensity after passing through an interference filter was 5/1w/cyi', the spectral sensitivity shown in Figure 5 was obtained. Ta.

For comparison, a photoreceptor was prepared in the same manner as in Example 6, except that a perylene compound of a formula well known in the art as a photoconductive material for a photoreceptor was used in place of the perylene compound of formula [I].

When the sensitivity was measured in accordance with Example 1, E3A=i
It was o lux seconds. Further, the spectral sensitivity of this photoreceptor was measured in the same manner as above (C), and the spectral sensitivity as shown in FIG. 5 was obtained.

From a comparison of these results, it will be understood that the photoreceptor of the present invention has higher sensitivity in the long wavelength region and is panchromatic than a photoreceptor using a conventionally well-known perylene compound.

Example 7 Polycarbonate resin (same product as Example 4) 6 parts, 4,
4'-Benzylidene bis-(N, N-diethyl-
m-) Luidine) dissolved in 60 parts of tetrahydrofuran to form an aluminum-deposited polyester film.
Second, a charge transport layer having a thickness of about 10 μm was formed by coating and drying using a wire bar. Next, in Example 4,
The paint used to form the charge generation layer is -F of the charge transport layer.
A charge generating layer having a thickness of about 0.8 μm was formed by coating and drying using a wire bar to obtain a photoreceptor having the form shown in FIG. 4 at t7. The sensitivity of the thus prepared photoreceptor was measured according to Example 1 by performing corona discharge at an applied voltage of -+-6KV.
! A=15 lux·sec.

[Brief explanation of drawings]

1 to 4 are enlarged partial sectional views of the electrophotographic photoreceptor according to the present invention. FIG. 5 is a chart showing the spectral sensitivities of the photoreceptor of Example 5 and the photoreceptor of Comparative Example. (1+-------One conductive support (2a), (
2b), (2c), (2a:)------One photosensitive layer (
3)------ Perylene compound (41---
-1--Binder #5)--1 Charge transport medium (6)--1 Charge conjugate generating layer (7
)-----Charge Transport Layer Agent Patent Attorney Katsutoshi Takahashi Procedural Amendment (Voluntary) 1981 3 JJ j/ ``1 Mr. Kazuo Wakasugi, Commissioner of the Patent Office■, Minor Case Indication: 1982 Patent Application No. 27896 2 Name of the invention: Photoreceptor for electrophotography 3 Relationship with the person making the amendment Patent applicant: 3-35-58 Sakashita, Itabashi-ku, Tokyo 174 (28
8> Dainippon Ink & Chemicals Co., Ltd. Representative Yo Mura
Kuni Shigeru 4, Agent: Dainippon Ink Chemical Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo, 103 Japan] Drawing fi, supplemented with Figure 5 of the appendix of the contents of the amendment. (That’s all)゛

Claims (1)

[Claims] A photoreceptor for electrophotography, characterized in that the photoreceptor layer contains a perylene compound represented by the following formula.