JPS63153554A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain the good sensitivity and the excellent anti-pollution property of the titled body by incorporating a specific compd. to the titled body, thereby enabling to apply to positive and negative electrification. CONSTITUTION:The titled body is formed by providing the layers composed of an electric charge generating substance (CGM) 5 and an electric charge transfer substance (CTM) 6 on an electric conductive supporting body 1. The titled body contains the compd. shown by the formula I wherein R and R1 are each alkyl, aryl, aralkyl group or a hetero ring. The photosensitive body layer provided on the electric conductive supporting body 1 may be composed of a monolayer structure which mixes the CTM 6 and the CGM 5, or a plural- layer structure which is constituted by the layer contg. the CTM 6 as an under layer and the layer contg. the CGM 5 as an upper layer or vice versa. And as necessary, a protective layer (OCL) 8 may be provided on the photosensitive layer. Thus, the reduction of voltage caused by corona electrification by irradiating UV ray is improved, and the lowering of the sensitivity can be practically eliminated.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to electrophotographic photoreceptors, and more particularly to improvements in organic photoconductive electrophotographic photoreceptors.

[Conventional technology]

In an electrophotographic copying machine using the Carlson method, the surface of a photoreceptor is charged, an electrostatic latent image is formed by exposure, the electrostatic latent image is developed with toner, and the visible image is then transferred to paper, etc. , make it established.

On the other hand, the photoreceptor is subjected to removal of adhered toner, neutralization of static electricity, and surface cleaning, and is used repeatedly over a long period of time.

Therefore, as an electrophotographic photoreceptor, it not only has good charging characteristics and sensitivity, but also has electrophotographic characteristics such as low dark decay.
In addition, it has good physical properties such as printing durability, abrasion resistance, and moisture resistance after repeated use, as well as resistance to ozone generated during corona discharge, ultraviolet rays during exposure, etc. (It environmental resistance). required.

Conventionally, inorganic photoreceptors having a photoreceptor layer containing an inorganic photoconductive substance such as selenium, zinc oxide, or cadmium sulfide as a main component have been widely used as electrophotographic photoreceptors.

On the other hand, the use of various organic photoconductive substances as materials for photoreceptor layers of electrophotographic photoreceptors has been actively researched and developed in recent years.

For example, Japanese Patent Publication No. 10496/1983 describes an organic photoreceptor having a photoreceptor layer containing poly-N-vinylcarbazole and 2,4,7-)linitro-9-fluorenone. However, this photoreceptor is not necessarily satisfactory in sensitivity and durability. In order to improve these drawbacks, attempts have been made to develop organic photoreceptors with high sensitivity and durability by assigning charge generation and charge transport functions to different materials in the photoreceptor layer. being done. In such so-called function-separated type electrophotographic photoreceptors, substances that exhibit each function can be selected from a wide range of materials, so it is relatively easy to produce electrophotographic photoreceptors with arbitrary characteristics. Is possible.

Many substances have been proposed as charge-generating substances that are effective for such functionally separated electrophotographic photoreceptors. Examples of using inorganic substances include, for example, Japanese Patent Publication No. 43-1619
As described in No. 8, there is amorphous selenium. This is combined with an organic charge transport material.

In addition, many electrophotographic photoreceptors using organic dyes or organic pigments as charge-generating substances have been proposed. For example, one having a photoreceptor layer containing a bisazo compound was published in
No. 7-37543, No. 55-22834, No. 54-7
It is already known from No. 9632, No. 56-116040, etc.

By the way, known photoreceptors using organic photoconductive substances are generally used for negative charging. The reason for this is that when negative charging is used, the mobility of holes among the charges is large, which is advantageous in terms of photosensitivity and the like.

However, the problem with using such a negative charge is that
Ozone is likely to be generated in the atmosphere when negatively charged by the charger, worsening the environmental conditions.

Further, a positive polarity toner is required for development of a negatively charged photoreceptor, but it is difficult to manufacture a positive polarity toner in view of the triboelectric charging sequence with respect to ferromagnetic charged particles.

Therefore, a photoreceptor using an organic photoconductive substance is used with positive charging, for example, a charge transport layer is laminated on a charge generation layer.
Positively charged photoreceptors and the like have been proposed in which the charge transport layer is formed of a material with a high electron transport ability.

However, if the charge transport layer contains, for example, trinitrofluorenone, problems may arise, such as that the substance is carcinogenic. On the other hand, a positively charged photoreceptor in which a charge generation layer is laminated on a light charge transport layer with high hole transport ability is considered, but with this mechanism, the charge generation layer on the surface side needs to be extremely thin, and printing durability is limited. The layer structure is not practical because of poor properties.

In addition, as a positively charged photoreceptor, U.S. Patent No. 3,615,41
No. 4 shows a product containing a thiapyrylium salt (charge generating substance) so as to form a complex with polycarbonate (baing resin). However, with this photoreceptor,
The drawbacks are that the memory phenomenon is large and ghosts are likely to occur. Also, in U.S. Patent No. 3,357,989, 7
Although a photoreceptor containing talocyanine is shown,
7 Talocyanine has properties that change depending on the crystal type, and
It is necessary to strictly control the crystal type, and furthermore, the short wavelength sensitivity is insufficient and the memory phenomenon is large, making it unsuitable for copying machines that use light sources in the visible wavelength range.

Various attempts have been made to obtain positively charged photoreceptors, but all of them require improvements in terms of photosensitivity, memory phenomenon, occupational hygiene, etc., and durability such as ultraviolet resistance and ozone oxidation resistance. There are many problems.

Therefore, from a functional standpoint, a laminated structure in which the upper layer (surface layer) is a charge generation layer containing a charge generation substance that generates holes and electrons when irradiated with light, and the lower layer is a charge transport layer containing a charge transport substance having a hole transport function. It is conceivable to make the photoreceptor the basic form of a photoreceptor for both positive and negative charging, and to supplement what is lacking.

In addition, in such a photoreceptor, if a charge generating substance having, for example, an electron-withdrawing group is used in the structure, the movement of electrons to cancel the positive charge on the surface of the photoreceptor becomes faster.
It is thought that high sensitivity characteristics can be obtained.

However, since the positively charged photoreceptor is formed with a layer containing a charge generating substance as a surface layer, it is vulnerable to external effects such as light irradiation, especially short wave light irradiation such as ultraviolet light, corona discharge, humidity, ozone oxidation, and mechanical friction. As a result, the electrophotographic performance deteriorates during the storage of the photoreceptor and during the image formation process, resulting in a decrease in image quality.

In a negatively charged photoreceptor having a conventional charge transport layer as a surface layer, the effects of the various external effects described above are extremely small, and rather the charge transport layer has the effect of protecting the underlying charge generation layer.

Therefore, it is conceivable to provide a thin protective layer made of an insulating and transparent resin to protect the layer containing the charge-generating substance from external effects, but the protective layer may block the charges generated during light irradiation. The effect of light irradiation will be lost, and if the protective layer that forms the surface layer is thick, it will lead to a decrease in sensitivity and the effect of blocking excess ultraviolet rays will be small. It cannot be left to the protection layer alone.

[Purpose of the invention]

The object of the present invention is to provide an organic photoconductive electrophotographic material that can be applied to positive and negative charging, has good sensitivity, excellent environmental resistance, particularly has good ultraviolet resistance and oxidation resistance, and has good durability. The purpose is to provide a photoreceptor.

[Structure and effects of the invention]

The object of the present invention is to provide a charge generating substance (
CG M) and charge transport material (CT M)
This is achieved by an electrophotographic photoreceptor having a layer containing the following, which is characterized by containing a compound represented by the following general formula.

General formula % Formula % In the formula, R and R3 represent alkyl, aryl, aralkyl or heterocyclic groups.

The photoreceptor layer provided on the conductive support according to the present invention is CT
It may be a single-layer structure in which M and CGM are mixed, or a multi-layer structure in which a layer containing CTM is a lower layer and a layer containing CGM is an upper layer, or vice versa. Further, a protective layer (marked as OCL) may be provided as necessary.

The compound according to the present invention is added to at least one of the above layers, but is preferably added to the surface layer of the photoreceptor layer. In addition, it may be in a form where it is most concentrated on the surface layer and gradually decreases toward the inside.

The present invention will be explained in detail below.

In the electrophotographic process based on the Carlson process, a light source that generates ultraviolet rays is generally used for image exposure, erasing exposure, pre-transfer exposure, cleaning exposure, etc. Repeated irradiation with energetic ultraviolet light is sufficient to cleave the organic compound molecules used in the photoreceptor. That is, C forming the photoreceptor
GM, CTM, binders, etc. cause radical dissociation, lose their original molecular structure, and deteriorate, resulting in deterioration of the photoreceptor. Specifically, they cause a decrease in sensitivity, an increase in residual potential, etc. occurs, resulting in a decline in image quality.

The combined deterioration induced and derived from ultraviolet rays or ultraviolet rays and ozone in the photoreceptor is caused by various exposure treatments and corona discharge that are repeatedly applied, but it is also thought to be enhanced by singlet oxygen generated by exposure. In addition, the degree of combined deterioration caused by ultraviolet rays etc. varies depending on the layer structure of the photoreceptor, the type of CGM or CTM, etc., but CTM is more susceptible to deterioration, especially when organic photoconductive materials are used. The impact is extremely large.

As a result of intensive studies regarding the improvement of composite deterioration (particularly potential drop) of photoreceptors, the present inventors found that a specific α, β unsaturated ketone compound represented by the above general formula in the photoreceptor layer causes composite deterioration. It has been found that this method not only prevents the damage from occurring, but also contributes to improving other electrophotographic properties and physical properties.

Stabilization of the compound according to the present invention, that is, a compound generally regarded as an ultraviolet absorber, against organic substances 8!1 The decomposition energy possessed by ultraviolet #X (sometimes referred to as UV) is U■ This is thought to be due to the energy being transformed into vibration energy within the absorbent.

The energy of this vibration is released as thermal energy from the UV absorber, but the thermal energy is already insufficient to degrade the organic material, and the photoreceptor is protected from harm caused by repeated UV irradiation. Seem.

Typical specific examples of the compounds of the present invention are shown below, but the compounds used in the present invention are not limited thereto.

R-C-CH=CH-R.

The amount of the compound represented by the above general formula used in the present invention (hereinafter referred to as the compound of the present invention) is not constant depending on the layer structure of the photoreceptor, the type of CTM, etc.
0.1 to 100% by weight, preferably 1% by weight based on CTM
It is used in an amount of 50 to 50% by weight, particularly preferably 5 to 25% by weight.

Next, the structure of the photoreceptor of the present invention will be explained with reference to the drawings.

The photoreceptor of the present invention has a support 1 as shown in FIG.
(A conductive layer provided on a conductive support or sheet)
A charge generating layer (hereinafter referred to as CGL) 2 containing C0M5 and a binder resin as required is the lower layer, and C
As shown in FIG. 2, a photoreceptor layer 4 having a laminated structure having a charge transport layer (hereinafter referred to as CTL) 3 containing TM6 and a binder resin as an upper layer is provided, as shown in FIG. A photoreceptor layer 4 having a laminated structure with CTL3 as a lower layer and CGL2 as an upper layer is provided on the support 1, and as shown in FIG. Examples include those provided with a photoreceptor layer 4 having a layered structure.

In addition, both CGM and CTM may be contained in the upper CGL layer with the same layer configuration as shown in FIG. 2, and a protective layer (
OCL) may be provided, and an intermediate layer may be provided between the support and the photoreceptor layer. An example is shown in FIG.

That is, the intermediate layer 7 is provided on the support 1, and the CT
CTL3 and C0M containing M6a and binder resin
5. CGL2 containing CTM6b and binder resin
This photoreceptor has a photoreceptor layer 4 which is a laminated layer, and is further provided with OCL8 whose main component is pine.

The compound of the present invention is CGL that constitutes a photoreceptor.

It may be contained in any of the CTL, single-layer structure photoreceptor layer, or OCL, or may be contained in multiple layers.

The effect of the present invention is more clearly exhibited in a photoreceptor having a laminated structure in which CGL is an upper layer and CTL is a lower layer.

Next, as CGM suitable for the present invention, both inorganic pigments and organic pigments can be used as long as they absorb visible light and generate free charges. In addition to inorganic pigments such as amorphous selenium, trigonal selenium, selenium-arsenic alloy, selenium-tellurium alloy, cadmium sulfide, cadmium selenide, cadmium selenide sulfide, mercury sulfide, lead oxide, lead sulfide, the following representative examples Organic pigments such as those shown are used.

(1) Azo pigments such as monoazo pigments, polyazo pigments, metal complex azo pigments, pyrazolone azo pigments, stilbene azo and thiazole azo pigments.

(2) Perylene pigments such as perylene anhydride and perylene imide.

(3) Anthraquinone-based or polycyclic quinone-based pigments such as anthraquinone derivatives, anthanthrone derivatives, dibenzpyrenequinone derivatives, pyrantrone derivatives, violanthrone derivatives, and isoviolanthrone derivatives.

(4) Indigoid pigments such as indigo derivatives and thi□oindigo derivatives.

(5) 7-thalocyanine pigments such as metallic 7-thalocyanine and non-metallic 7-thalocyanine.

(6) Carbonium pigments such as phenylmethane pigments, triphenylmethane pigments, xanthine pigments, and acridine pigments.

(7) Xanthine pigments such as azine pigments, oxazine pigments and thiazine pigments.

(8) Methine pigments such as cyanine pigments and azomethine pigments.

(9) Quinoline pigment.

(10) Nitro pigment.

(11) Nitroso pigment 9 (12) Benzoquinone and 7-toquinone pigment (13)
7 Talimide pigment.

(14) Perinone pigments such as bisbenzimiguzole derivatives.

Examples of the azo pigments used in the present invention include those shown in the following exemplary structural compound groups (1) to (V), and some examples of preferable specific compounds among the exemplary structural compound groups: are also listed.

For details of the preferred specific compounds, please refer to the patent application filed in 1983.
Reference is made to No.-195881.

, enemy.

Exemplary structural compound group [I]: Exemplary structural compound group CII): Exemplary structural compound 1! f, CIll).

In addition, the following exemplary structural compound groups [VI] to [■] consisting of polycyclic quinone pigments are most preferable as CGM\---,'' Exemplary structural compound group [■]: Exemplary structural compounds JIT, (Vll)・Examples Structural compound 11T (■) Next, CTM that can be used in the present invention is 9A- Although there is no particular restriction, examples include oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazole derivatives, Imidazolidine derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline derivatives, oxazolone derivatives, benzodeazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N- It may be vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene, etc.

However, compounds that have an excellent ability to transport holes generated during light irradiation to the support side and are suitable for combination with the above-mentioned CGM are preferably used, and examples of such C 'It'' M include, for example, the following exemplified structural compounds [ IX] or (X)
The sudhir compound shown is used. Several examples of individual specific compounds in the group of exemplified structural compounds are listed below, and for the complete details, refer to Japanese Patent Application No. 1988-1.95881.

tq- Exemplary structural compound flT, (IX)・Also, Ci'
As M, hydrazone compounds represented by the following exemplary structural compound groups [Kari] to (XV) can also be used. Regarding the complete details of specific compounds on the opposite side, Patent Application No. 1988-19588
No. 1 is referred to.

Exemplary Structural Compound 1 (XV): Exemplary Structural Compound Group (XVI:l) In addition, amine derivatives shown in the following Exemplary Structural Compound Group [X■] can also be used as CTMs.

For details, refer to Japanese Patent Application No. 195881/1981.

The layer structure of the photoreceptor of the present invention has a laminated structure and a single layer structure as described above, and CTL is used as the surface layer.

One or more electron-accepting substances are added to CGL, OCL, a single photoreceptor layer, or one or more layers of OCL for the purpose of improving sensitivity, reducing residual potential or fatigue during repeated use, etc. can be made to contain.

Electron-accepting substances that can be used in the photoreceptor of the present invention include:
For example, succinic anhydride, maleic anhydride, dibromaleic anhydride, 7-talic anhydride, tetrachloro-7-talic anhydride, tetrabromo-7-talic anhydride, 3-nitro-7-talic anhydride, 4
-Nitro-7-talic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyano-7-thalic anhydride, 0-dinitrobenzene, 1-dini(lobenzene,
1, 3, 5. - trinitrobenzene, paranitrobenzonitrile, picryl chloride, quinone chlorimide,
Chloranil, brumanil, 2-methylnaphthoquinone, dichlorodicyanobarabenzoquinone, anthraquinone, dinitroanthraquinone,) linitrofluorenone, 9-
Examples include fluorenylidene [dicyanomethylenemalonodinitrile], polynitro-9-fluorenylidene [dicyanomethylenemalonodinitrile], picric acid, heptatalic acid, and the like.

Examples of binder resins that can be used in the photoreceptor layer in the present invention include polyethylene, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, and polycarbonate. Addition polymer resins such as resins, silicone resins, and melamine resins, polyaddition resins, polycondensation resins, and copolymer resins containing two or more of the repeating units of these resins, such as vinyl chloride-vinyl acetate copolymer resins. Polymer resin, vinyl chloride
In addition to insulating resins such as vinyl acetate-maleic anhydride copolymer resins, polymeric organic semiconductors such as poly-N-vinylcarbazole may be used.

Further, the intermediate layer functions as an adhesive layer or a barrier layer, and in addition to the binder resin, for example, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-anhydrous Maleic acid copolymer, casein, N
- Flucoxymethylated nylon, starch, etc. are used.

Next, the conductive support supporting the photoreceptor layer may be a metal plate made of aluminum or nickel, a metal drum or metal foil, a plastic film coated with aluminum, tin oxide, indium oxide, etc., or a conductive material coated thereon. One ends up using a film or drum of paper, plastic, etc.

The CGL can be provided by vacuum-depositing the above-mentioned CGM on the support, or by applying a solution or dispersion of CGM alone or together with a suitable binder resin in a suitable solvent and drying it.

When the above CGM is dispersed to form a CGL, it is preferable that the CGM is powder with an average particle size of 2μ or less, preferably 1μ or less. As well as the dispersion becomes poor, some particles protrude from the surface, resulting in poor surface smoothness, and in some cases, discharge may occur at the protruding parts of the particles, or toner particles may adhere there, resulting in toner filming. phenomenon is likely to occur.

However, if the particle size of 111 is too small, it tends to agglomerate, increasing the resistance of the layer, increasing crystal defects and reducing sensitivity and repeatability, or because 111 has a limit in terms of miniaturization. It is desirable to set the lower limit of the average particle size to 0.01 μm, and -1° CGL can be provided by the following method.

That is, this is a method in which the CGL described above is made into fine particles in a dispersion medium by ball milling, homogenization, etc., and a dispersion obtained by adding Neuinda resin and mixing and dispersing is applied. In this method (1) when particles are dispersed under the action of ultrasound,
Uniform dispersion is possible.

Examples of solvents used to form CTL include N, N
-dimethylformamide, benzene, toluene, xylene, monochlorobenzene, 1. Z-dichloroethane, dichloromethane, 1,1.2-)lichloroethane, tetrahydro7rane, methyl ethyl ketone, ethyl acetate, butyl acetate and the like can be mentioned.

In the functional separation layer configuration as shown in FIGS. 1, 2, and 4,
20 to 20 per 100 weight of CGM binder resin in CGL
0 parts by weight, preferably 25 to 100 parts by weight. CG
If M is less than this, the photosensitivity will be low and the residual potential will increase, and if it is more than this, dark decay will increase and the acceptance potential will decrease.

The thickness of the CGL formed as described above is preferably 1 to 10 μm, particularly preferably 3 to 7 μm in the case of a positive charging configuration, and preferably 0.01 μm in the case of a negative charging configuration. ~10 μm, particularly preferably 0.1 to 3 μm.

In the configuration for positive charging, since the CGL is a surface layer, it lacks scratch resistance, and in order to improve durability, it is necessary to increase the thickness of the CGL film, but this causes a decrease in sensitivity. CTM is added to CGL as a means to suppress this. The ratio of CGM to CTM in this case is 30 to 400 parts by weight of CTM to 100 parts by weight of CGM.

However, since this CTM has a structure that is more susceptible to complex deterioration than CGM, it is easily deteriorated by ultraviolet rays and the like, which impairs the durability of the photoreceptor.

The present invention eliminates this vicious cycle by adding the compound of the present invention.

Next, CTL can be formed by forming the above-mentioned CTM in the same manner as the above-mentioned CGL (that is, by applying and drying the CTM alone or dissolved and dispersed together with the above-mentioned binder resin).

The amount of CTM in CTL is 2 per 100 parts by weight of binder resin.
The amount is 0 to 200 parts by weight, preferably 30 to 150 parts by weight.

If the CTM content is less than this, the photosensitivity will be poor and the residual potential will tend to be high, and if it is more than this, the solvent solubility will be poor.

The thickness of the CTL to be formed is preferably 5 to 50μ gloss,
Particularly preferably, it is 5 to 30μ.
The film thickness ratio of TL is preferably 1:(1 to 30).

In the case of the single-layer structure shown in FIG. 3, the proportion of CGM contained in the binder resin is 20 to 200 parts by weight, preferably 25 to 100 parts by weight, based on 100 parts by weight of the binder resin.

If the content of CGM is less than this, the photosensitivity will be low and the residual potential will increase, and if it is more than this, dark decay and acceptance potential will decrease.

In addition, the ratio of CTM to the binder resin is
The amount is 20 to 200 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight of the binder resin.

If the content of CTM is less than this, the photosensitivity will be poor and the residual potential will tend to be high (and if it is more than this, the solvent solubility will be poor).

In the case of a single layer structure, the weight ratio of CTM to CGM in the photoreceptor layer is preferably 1:3 to 1:2. Further, the thickness of the photoreceptor layer in this case is 7 to 50 μm, preferably 10 to 30 μm.

In the present invention, the OCL binder provided as necessary has a volume resistance of 108 Ωelfi or more, preferably 10
A transparent resin having a resistance of 10 ΩC or more, more preferably 10 13 Ωam or more is used. Further, the binder is exposed to light or heat = 4
It contains at least 50% by weight of a resin that hardens by 0-.

Examples of such resins that harden with light or heat include thermosetting acrylic resins, silicone resins, epoxy resins, urethane resins, urea resins, phenol resins, polyester resins, alkyd resins, melamine resins, and photocurable cinnamic acid resins. In addition to these copolymerized or cocondensed resins, all of the photo- or thermosetting resins used in electrophotographic materials can be used. If necessary, the CGL may contain less than 50% by weight of a thermoplastic resin for the purpose of improving processability and physical properties (preventing cracks, imparting flexibility, etc.). Examples of such thermoplastic resins include polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, butyral resin,
Polycarbonate) 111 resin, silicone resin, or copolymer resins thereof, such as vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, and vinyl carbazole. Polymer organic semiconductors and other thermoplastic resins used in electrophotographic materials can all be used.

Further, the OCL may contain an electron-accepting substance,
In addition, if necessary, an antioxidant or the like may be included for the purpose of protecting the CGL, which is dissolved in a solvent together with the binder, applied and dried by, for example, dip coating, spray coating, blade coating, roll coating, etc. Hereinafter, the layer thickness is preferably 1 μm or less.

〔Example〕

EXAMPLES The present invention will be described below with reference to Examples, but the implementation of the present invention is not limited thereby.

Example 1 On a conductive support consisting of a polyester film laminated with aluminum foil and an aluminum drum,
An open layer with a thickness of 0,111 m was formed from a vinyl chloride-vinyl acetate-maleic anhydride copolymer (S-LEC MF-10, manufactured by Tanemizu Chemical Industry Co., Ltd.).

Then CT M (1'!-75)/polycarbonate resin (Panlite L-1250. manufactured by Teijin Chemicals) = 7
1 containing 1665% of 5/100 (weight ratio),
A 2-dichloroethane solution was dip coated onto the intermediate layer and dried to obtain a CTL having a noodle thickness of 15 μm.

Then, 4,10-nobromoanthrone (Vl-3)/Panrai) L-1250 was sublimed as CGM.
= 50/100 (weight ratio) was ground in a ball mill for 24 hours, 1,2-dichloroethane was added to make it 9% by weight, and the mixture was further dispersed in a ball mill for 24 hours.
([-75) is 75% by weight based on L-1250 and 10% by weight of the compound (1) of the present invention based on CTM.
wt% added. Add monochlorobenzene to this dispersion to obtain monochlorobenzene/1,2-dichloroethane=3
/7 (volume ratio) was prepared and a CGL having a thickness of 5 μm was formed on the CTL by a spray coating method to obtain a photoreceptor sample 1 of the present invention having a photoreceptor layer having a laminated structure.

Comparative Example (1) A comparative photoreceptor sample (1) was obtained in the same manner as in Example 1 except that compound (1) in CGL was removed.

Example 2 Compound (2) was substituted for compound (1) in Example H1.
Photoreceptor 2 was obtained in the same manner as in Example 1 except that .

Example 3 On a photoreceptor (same as the photoreceptor of Comparative Example 1) obtained by removing compound (1) from the CGL of Example 1, 1.55% of thermosetting acrylic-melamine-epoxy (1:1:1) resin was applied. 0.155 parts by weight of the compound (1) of the present invention was added to monochlorobenzene/1,1,2-trichloroethane (j
/ 1 volume ratio) A coating solution obtained by dissolving in 100 parts by weight of a mixed solvent was spray applied and dried to form a 1μ-thick OCL.
was formed to obtain photoreceptor 3 of the present invention.

Example 4 Primer PH91 for silicone hard coat (manufactured by Toshiba Silicon Corporation) was spray-coated to a thickness of 0.1μI on the photoreceptor obtained by removing compound (1) from the CGL of Example 1, and then a silicone hard coat was further applied on top of the photoreceptor. A solution containing Tosgard 510 (manufactured by Toshiba Silicon Co., Ltd.) and compound (1) added in an amount of 10 parts by weight per 44 parts by weight of 100 resin was spray-coated and dried to form a 1 μm0 cL photoreceptor of the present invention. I got 4.

Example 5 An intermediate layer exactly as in Example 1 was formed on a conductive support consisting of a polyester film laminated with aluminum foil and an aluminum drum.

Next, 8% by weight of butyral resin (S-LEC BX-1, manufactured by Block Chemical Co., Ltd.) and CTM (ff-
75) A solution obtained by dissolving 6% by weight in methyl ethyl ketone is applied onto the intermediate layer and dried to form a 10μ
A thick CTL was formed.

Next, 0.2 g of CG M (R1-7) was applied to a paint conditioner (Paint Conditioners R).
(manufactured by ED Devi1) for 30 minutes, and to this was added 1 portion of polycarbonate resin (Panlite L-1250, mentioned above).
, 2-dichloroethane/1,1,2-)lichloroethane mixed solvent to a concentration of 0.5% by weight.
．． After adding 3g and dispersing for 3 minutes, polycarbonate resin, CTM (ff-75) and compound (1) were added at 3.3% by weight, 2.6% by weight and 0.26% by weight, respectively.
1.2-dichloroethane/1,1.2 to give weight%
-) Solution 1 obtained by dissolving in dichloroethane mixed solvent
9.1ir was added and dispersed for an additional 30 minutes.

The thus obtained dispersion was spray-coated onto the CTL and dried to form a CGL with a thickness of 5 μm, thereby obtaining a photoreceptor 5 according to an embodiment of the present invention having photoreceptor layers having a laminated structure.

Comparative Example (2) A comparative photoreceptor (2) was obtained in the same manner as in Example 5 except that compound (1) in CGL was removed.

Example 6 Compound (2) was substituted for compound (1) in Example 5.
Photoreceptor 6 of the present invention was obtained in the same manner as in Example 5 except that .

Example 7 OCL containing the compound (1) used in Example 3 was provided on a photoreceptor (same as the photoreceptor of Comparative Example 2) obtained by removing compound (1) from the CGL of Example 5, and the present invention A photoreceptor 7 was obtained.

Example 8 OCL containing the compound (1) used in Example 4 was provided on a photoreceptor obtained by removing compound (1) from the CGL of Example 5 to obtain photoreceptor 8 of the present invention.

Example 9 An intermediate layer exactly the same as in Example 1 was formed on a polyester film laminated with aluminum foil and an aluminum drum.

Then sublimed 4,10-dibromoanthrone (
■-3) 40g in a porcelain ball mill at 40rpm for 24 hours
Pulverized for a while, Panlite L-1250, (mentioned above) 20g
and 1.300 ml of 1,2-dichloroethane were added thereto, and the mixture was further dispersed for 24 hours to obtain a CGL coating solution. This was applied onto the intermediate layer to form a CGL having a thickness of 1 μm.

Then 7.5 g of CT M (rX-61), 10 g of Panlite L-1250 and 0.75 g of compound (1)
was dissolved in 80 ml of 1,2-dichloroethane and applied to the CGL to form a CTL with a film thickness of 15 μm,
Photoreceptor 9 of the present invention was created.

Comparative Example (3) A comparative photoreceptor (3) was obtained in the same manner as in Example 9 except that compound (1) in CTI- was omitted.

Example 10 On a conductive support consisting of a polyester film laminated with aluminum foil and an aluminum drum,
An intermediate layer exactly the same as in Example 1 was formed.

Then bisazo compound (■-7) 1.51 as CGL
9 to 1,2-dichloroethane/monoethanolamine (
1000/1 volume ratio) A dispersion solution that was dispersed in 100 mN of a mixed solvent for 8 hours using a ball mill was applied on the intermediate layer,
After sufficiently drying, a 0.3 g thick CGL was provided.

Then styryl compound (IX-43) 11 as CTM
．． 25g, Panlite L-1250 (above) 15g and compound (1) 1.1251? A solution prepared by dissolving 1,2-dichloroethane 10oIIIN was applied onto the CGL and sufficiently dried to form a 15 μm thick CTL, thereby producing the photoreceptor 10 of the present invention.

Comparative Example (4) A comparative photoreceptor (4) was prepared in the same manner as in Example 10 except that compound (1) in the CTL was removed.

The above Example Samples 1 to 10 and Comparative Example Samples (1) to (4)
Regarding UV resistance, we conducted a 20,000-shot photo test on chargeability and quantitatively measured changes in sensitivity due to UV exposure.

In the chargeability live-action test, a sample photoreceptor drum was attached to a modified experimental machine U-Bix 2812 MR (manufactured by Konishiroku Photo Industry Co., Ltd.), and the sample photoreceptor drum was charged positively or negatively, and the photoreceptor was subjected to image exposure. The unit cycle consisting of each process and fixing is repeated 20,000 times, and the positive and negative charging potentials at the beginning of the live-action test are ±Vo, and the charging potentials after the end of the 20,000-time test are 20,000 times.

Changes in sensitivity due to UV exposure can be determined by irradiating ultraviolet rays of known intensity onto a photoreceptor sheet obtained by cutting a sample film, and before and after the irradiation, the potential of the photoreceptor, which has been charged to 10 or 1600 cm, is adjusted to ± It was determined using an exposure amount E600 that extends to 100V.

Sensitivity S of photoreceptor 1. It is defined as the relationship tE''0cc 1 /S, and the smaller E600, the greater the sensitivity S, and the higher the contrast of the image.

If the sensitivity before and after UV exposure is 5o=S+, then its reciprocal ratio Rs; (1/S+)/(1/So)=
S o/S represents UV1it property, and the larger Rs is, the more UV resistant it is.

UV irradiation is done using a physical and chemical mercury lamp S HL-100U
Using V-2 (manufactured by Toshiba Corporation), the sample photoreceptor sheet was
Placed in the 0cII separation block other electromagnetic waves and UV intensity 15
Irradiation was performed at 00 cd/m2 for 100 minutes, and sensitivity was measured using an electrostatic test 1fl (Kawaguchi Electric Seisakusho: Model 5P-428).

Note to Table 1: Sample numbers in parentheses are comparative samples.As is clear from Table 1, by adding the compound of the present invention,
Potential drop due to corona charging under ultraviolet irradiation is significantly improved. Furthermore, it can be seen that there is almost no decrease in sensitivity due to the addition of the compound of the present invention.

[Brief explanation of the drawing]

FIGS. 1 to 4 are cross-sectional views of the photoreceptor of the present invention. 1...Support 2... Charge generation layer (CGL) 3... Charge transport layer (CT L) 4...Photosensitive layer 5... Charge generating material (CGM) 6...Charge transport material (CTM) 7...middle class 8...Protective layer (OCL)

Claims (1)

[Scope of Claims] An electrophotographic photoreceptor having a layer containing a charge-generating substance and a charge-transporting substance on a conductive support, characterized by containing a compound represented by the following general formula. Electrophotographic photoreceptor. General formula ▲ Numerical formula, chemical formula, table, etc. are available ▼ [In the formula, R and R_1 represent alkyl, aryl, aralkyl, or heterocyclic groups. ]