JPS63159859A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve environmental resistance, more particularly UV resistance, oxidation resistance and durable properties as well as sensitivities by incorporating a specific compd. into an electrophotographic sensitive body. CONSTITUTION:The compd. expressed by the formula is incorporated into the electrophotographic sensitive body having layers contg. an electric charge generating material (CGM) and charge transfer material (CTM) on a conductive base. In the formula, R1-R3 are a hydrogen atom, halogen atom and amino, substd. amino, hydroxy, heterocyclic, alkyl, alkenyl, cycloalkyl, aralkyl, aryl, and substd. aryl groups. The photosensitive layer may be of the single-layer structure formed by intimate mixing of CTM and CGM or the double-layer constitution consisting of the layer contg. CTM as a lower layer and the layer contg. CGM as an upper layer or the constitution reverse therefrom. A protective layer may be provided thereto at need. The amt. of the compd. to be added is 0.1-100wt.%, more preferably 1-50wt.%, more particularly preferably 5-25wt.% by the weight of CTM.

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. , take root.

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 and ultraviolet rays during exposure (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. 50-10496 describes an organic photoreceptor having a photoreceptor layer containing poly-N-vinylcarbazole and 2,4,7-)dinitro-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. 7-3754a, No. 55-22H4, No. 54-79
It is already known from No. 632, 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 the poles 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 a 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 charge transport layer with a high hole transport ability is considered, but with this mechanism, the first 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 discloses a material containing a thiapyrylium salt (charge generating substance) so as to form a complex with polycarbonate (binder resin). However, with this photoreceptor,
The drawbacks are that the memory phenomenon is large and ghosts are likely to occur. Further, U.S. Patent No. 3,357.989 discloses a photoreceptor containing phthalocyanine, but the characteristics of phthalocyanine change depending on the crystal form, and the crystal form must be strictly controlled. It lacks short wavelength sensitivity and has a large memory phenomenon, 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, a deuteron-attracting group is used in the structure, the movement of electrons to cancel the positive charge on the surface of the photoreceptor becomes faster, resulting in high sensitivity characteristics. I can see what you can get.

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 oxidation11 mechanical friction, etc. 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 cause a decrease in sensitivity and will have little residual UV blocking effect. It cannot be left to the layers 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 (
This is achieved by an electrophotographic photoreceptor having a layer comprising a charge transport material (referred to as CGM) and a charge transport material (referred to as CTM), which is characterized by containing a compound represented by the following general formula. be done.

In the formula, R+, R and R3 do not represent a hydrogen atom, a halogen atom, or an amino, substituted amino, hydroxy, heterocycle, alkyl, alkenyl, cycloalkyl, aralkyl, aryl, or substituted aryl group.

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. undergo radical dissociation, lose their original molecular structure, and deteriorate, resulting in deterioration of the photoreceptor. Specifically, it causes a decrease in sensitivity, an increase in residual potential, etc., and the occurrence of fogging. , the image quality deteriorates.

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. Furthermore, 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
are more susceptible to deterioration, and the effect is particularly significant when organic photoconductive materials are used.

As a result of intensive studies on improving the composite deterioration (particularly potential drop) of the photoreceptor, the present inventors found that a specific triazine compound represented by the above general formula in the photoreceptor layer not only significantly prevents the composite deterioration. It has been found that this also contributes to improvements in other electrophotographic properties and physical properties.

The stabilization mechanism of the compound according to the present invention, that is, a compound generally regarded as an ultraviolet absorber, against organic substances is as follows:
This is thought to be due to the fact that the decomposition energy possessed by ultraviolet light (sometimes referred to as UV) is transformed into vibrational energy within the UV absorber.

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.

(9)-NH(Σoo■-cc -○(10)-
The amount of addition of NH (>-5OJ -Crt -N(CHs)), a compound represented by the above general formula used in the present invention (hereinafter referred to as the compound of the present invention), depends on the layer structure of the photoreceptor and the type of CTM. Although it is not constant due to
0.1 to 100% by weight, preferably 1% 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 l as shown in FIG.
(Part 2 where a conductive layer is provided on a conductive support or sheet)
A charge generation layer (hereinafter referred to as CGL) 2 containing 00M5 and a binder resin as required is formed as a lower layer;
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, and a single layer structure containing CGMSCTM and a binder resin as necessary on a support l as shown in FIG. Examples include those provided with a photoreceptor layer 4.

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
CTL 3 and 00M5 containing M6a and binder resin, CTM6b and C containing binder resin
This photoreceptor has a photoreceptor layer 4 in which GL2 is laminated, and is further provided with OCL8 whose main component is a binder.

The compound of the present invention includes CGL, CTL, which constitutes the photoreceptor,
It may be contained in either the single-layered photoreceptor layer or the OCL, or it may be contained in multiple layers.

The effects of the present invention are 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 the 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 perylenic anhydride and perylenic acid imide (3) Anthraquinone derivatives , anthantrone derivatives, dibenzpyrenequinone derivatives, pyracitrone derivatives,
Anthraquinone or polycyclic quinone pigments such as violanthrone derivatives and isoviolanthrone derivatives (4) Indigoid pigments such as indigo derivatives and thioindigo derivatives (5) Phthalocyanine pigments such as metal phthalocyanines and metal-free phthalocyanines (6) Diphenylmethane pigments pigments, carbonium pigments such as triphenylmethane pigments, xanthine pigments and acridine pigments (7) quinone imine pigments such as azine pigments, oxazine pigments and thiazine pigments (8) methine pigments such as cyanine pigments and azomethine pigments (9) quinoline Pigments (10) Nitro pigments (11) Nitroso pigments (12) Benzoquinone and naphthoquinone pigments (13)
Naphthalimide pigments (14) Perinone pigments such as bisbenzimidazole derivatives Examples of azo pigments used in the present invention include those shown by the following exemplary structural compound groups (-I) to (V). , several examples of individual preferable specific compounds in the group of exemplified structural compounds 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.

The following ″-6 1 □, l ゛・,=・′ Exemplary structural compound group [I]: Exemplary structural compound group [■]: Exemplary structural compound group [■]: Exemplary structural compound group [■]: Exemplary structural compound group [■]: In addition, the following exemplary structural compound groups (Vl) to [■] consisting of polycyclic quinone pigments are the most preferred exemplary structural compound groups as CGM [■]: Exemplary structural compound groups [■]: Acceptable, Below Margin exemplified structural compound group [■]: Next, CTMs that can be used in the present invention are not particularly limited, but include, for example, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, and imidacilone derivatives. , imidazolidine derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline derivatives, oxacilone derivatives, benzothiazole derivatives,
Benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives,
It may be an aminostilbene derivative, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene, or the like.

However, in addition to its excellent ability to transport holes generated during light irradiation to the support side, those suitable for combination with the above-mentioned CGM are preferably used, and such CTMs include, for example, the following exemplary structural compound group [IX] or ( A still compound represented by X) 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. 1988-1958.

Exemplary structural compound group [■]: Exemplary structural compound group (X) In addition, the following exemplary structural compound group (X[) to [
Hydrazone compounds represented by XV) can also be used.

For the complete details of the specific compounds on the opposite side, please refer to the patent application 1986-1.
Reference is made to No. 95881.

Exemplary Structural Compound Group [■] Exemplary Structural Compound Group (XI[I): Exemplary Structural Compound Group (XV): Exemplary Structural Compound Group (XVI): Also, as a CTM, amines shown in the following exemplary structural compound group [X■] Derivatives can also be used.

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 may be added to CGL, OCL, single photoreceptor layer, OCL, or multiple layers for the purpose of improving sensitivity, reducing residual potential or fatigue during repeated use, etc. It 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, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4
-Nitrophthalic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, 0-dinitrobenzene, m-dinitrobenzene,
1, 3, 5. - trinitrobenzene, varanitrobenzonitrile, picryl chloride, quinone chlorimide,
Chloranil, brumanil, 2-methylnaphthoquinone, dichlorodicyanobarabenzoquinone, anthraquinone, dinitroanthraquinone, trinitrofluorenone, 9-
Examples include fluorenonedine [dicyanomethylenemalonodinitrile], polynitro-9-fluorenonedine [dicyanomethylenemalonodinitrile], picric acid, phthalic 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
-Alkoxymethylated 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. Films or drums of paper, plastic, etc. can be used.

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.

When CGL is formed by dispersing the above CGM, it is preferable that the CGM is a powder having an average particle size of 2 μm or less, preferably 1 μm or less. In other words, if the particle size is too large, dispersion in the layer will be poor, and some of the particles will protrude from the surface, resulting in poor surface smoothness. Toner particles tend to adhere and a toner filming phenomenon occurs easily.

However, if the above particle size is too small, it tends to aggregate,
It is desirable to set the lower limit of the average grain size to 0.01 μm because the resistance of the layer increases, the sensitivity and repeatability decrease due to an increase in crystal defects, or there is a limit to miniaturization.

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 using a ball mill, a homomixer, etc., a binder resin is added, and a dispersion obtained by mixing and dispersing is applied. When the particles are dispersed under the action of ultrasound in this method, homogeneous dispersion is possible.

Examples of solvents used to form CTL include N, N
Examples include -dimethylformamide, benzene, toluene, xylene, monochlorobenzene, 2-dichloroethane, dichloromethane, 1,1.2-)lichloroethane, tetrahydrolalan, methyl ethyl ketone, ethyl acetate, butyl acetate, and the like.

In the functional separation layer configuration as shown in FIG. 1.2 and FIG. 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 film 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. ~IOμm1 Particularly preferably 0.1 to 3μ
It is m.

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

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 formed CTL is preferably 5 to 50μ1
1, particularly preferably from 5 to 30 μm. Further, the film thickness ratio of CGL and CTL is preferably 1:(1 to aO).

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, per 100 parts by weight of the binder resin.

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.

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 Ωcm or more, preferably 10I0
A transparent resin having a resistance of ΩCm or more, more preferably 10 13 Ωcm or more is used. Further, the binder contains at least 50% by weight of a resin that is cured by light or heat.

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 resins, silicone resins, or copolymer resins thereof, such as vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-maleic anhydride copolymer resins, poly-N-vinylcarbazole, and other polymeric organic semiconductors , and all other thermoplastic resins used in electrophotographic materials can 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 CGL, which is dissolved in a solvent together with the binder, and applied and dried to a thickness of 2 μm or less by, for example, dip coating, spray coating, blade coating, roll coating, etc. , preferably with a layer thickness of 1 μm or less.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereby.

Example 1 A vinyl chloride-vinyl acetate-maleic anhydride copolymer (
An intermediate layer having a thickness of 0.1 μm was formed using S-LEC MF-10 (manufactured by Tsukimizu Kagaku Kogyo Co., Ltd.).

Next, CT M (IX-75)/polycarbonate resin (Penlight L-1250, manufactured by Ondai Kasei Co., Ltd.') =
1 containing 16.5% by weight of 75/100 (weight ratio)
, 2 to dichloroethane solution was dip coated onto the intermediate layer and dried to obtain a CTL with a thickness of 15 μm.

Then, 4,1o-dibromoanthrone (Vl-3)/Panlite L-125 was sublimed as CGM.
CTM (
IX-75) at 75% by weight based on Panlite L-1250 and compound (2) of the present invention at 1% by weight based on CTM.
Added 0% by weight. Monochlorobenzene was added to this dispersion and monochlorobenzene/1,2-dichloroethane=3
A CGL with a thickness of 5 μm was formed on the CTL by a spray coating method to obtain a photoconductor sample 1 of the present invention having a laminated photoconductor layer.

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

Example 2 Compound (3) was substituted for compound (2) in Example 1.
Photoreceptor sample 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 (2) from the CGL of Example 1, 1.55% of thermosetting acrylic-melamine-epoxy (1:1:1) resin was applied. Parts by weight and 0.155 parts by weight of the compound (2) of the present invention were added to monochlorobenzene/1,1.2-)lichloroethane (17
A coating solution obtained by dissolving in 100 parts by weight of a mixed solvent (1 volume ratio) was spray coated and dried to form an OCL having a thickness of 1 μm, thereby obtaining photoreceptor sample 3 of the present invention.

Example 4 A silicone hard coat primer PH91 (manufactured by Toshiba Silicon Co., Ltd.) was spray-coated to a thickness of 0.1 μm on the photoreceptor obtained by removing compound (2) from the CGL of Example 1, and a silicone hard coat was further applied on top of it. A solution containing Tosgard 510 (manufactured by Toshiba Silicon Corporation) and compound (2) added in an amount of 10 parts by weight to 100 parts by weight of the resin was spray applied and dried to form a 1 μmo CL, and a photoreceptor sample of the present invention was prepared. I got 4.

Example 5 An intermediate layer exactly the same 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 Sekisui Chemical Co., Ltd.) and CTM (I
X-75) A solution obtained by dissolving 6% by weight in methyl ethyl ketone was applied onto the intermediate layer and dried to form a CTL with a thickness of 10 μm.

Next, apply CG M (IV-7) 0.29 to a paint conditioner.
Red Devil (manufactured by Tsuji) for 30 minutes, and polycarbonate resin (Panlite L-1250, mentioned above) was added to this.
A solution of 0.5% by weight of 1,2-dichloroethane/1,1.2-)dichloroethane was added and dispersed for 3 minutes, and then polycarbonate resin, CTM ( IX-75) and compound (2) in 1,2-dichloroethane/1 to give a concentration of 3.3% by weight, 2.6% by weight, and 0.26% by weight, respectively.
A solution 19.19 obtained by dissolving in a mixed solvent of , 1,2-trichloroethane was added, and the mixture was further dispersed for 300 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 photoreceptor sample 5 of the embodiment of the present invention having photoreceptor layers having a laminated structure.

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

Example 6 Compound (3) was substituted for compound (2) 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 (2) used in Example 3 was provided on the photoreceptor (same as the photoreceptor and body of Comparative Example 2) obtained by removing compound (2) from the CGL of Example 5, and the present invention was applied. Photoreceptor 7 of the invention was obtained.

Example 8 OCL containing the compound (2) used in Example 7 was provided on a photoreceptor obtained by removing compound (2) 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 (
Vl-3) 40g in a porcelain ball mill at 4Orpm 2
Grind for 4 hours, Panlite L-1250, (mentioned above) 20
1,300 m of 9 and 1,2-dichloroethane (7) were added and further dispersed for 24 hours to obtain a CGL coating solution. This was coated on the intermediate layer to form a CGL film with a thickness of 1 μm.

Then c T M (IX-61)? , 59, Panlite L-1250tog and compound (2) 0.759
was dissolved in 80 mff of 1,2-dichloroethane and applied to the CGL to form a CTL having a thickness of 15 μm, thereby producing the photoreceptor 9 of the present invention.

Comparative Example (3) A comparative photoreceptor (3) was obtained in the same manner as in Example 9 except that compound (2) in the CTL was removed.

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) 1.59 as CGL
to 1,2-dichloroethane/monoethanolamine (1
A dispersion solution prepared by dispersing in 100 m of a mixed solvent (volume ratio: 000/1) for 8 hours in a ball mill was applied onto the above intermediate layer and sufficiently dried to provide a CGL having a thickness of 0.39.

Then styryl compound (IX-43) 11 as CTM
．． 259, Panlite L-1250 (supra) 159 and compound (2) 1.1251? A solution of 1,2-dichloroethane loOmff was applied onto the CGL and sufficiently dried to form a CTL with a thickness of 15 μm, 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 (2) in the CTL was removed.

The above Example Samples 1-10 and Comparative Example Samples (1) to (4)
Regarding UV resistance, we conducted a 20,000-times actual photographic test on chargeability and constant measurement of sensitivity change 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 actual photo-taking test are ±V, and the charging potentials after the end of the 20,000-times test are ±V.

Sensitivity changes 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 + or -600, is adjusted to ± Exposure to blue to 1oov i1 E 80
It was calculated using Q.

The sensitivity S of the photoreceptor is defined as the relationship EaO0ocl/S, and the smaller E77 is, the greater the sensitivity S is and the higher the contrast of the image.

If the sensitivities before and after UV exposure are respectively So and S, then the reciprocal ratio Rs; (1/S 1)/'(1/S o)-
9o/S represents UV resistance, and the larger Rs is, the more U
This means that it is resistant to V.

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 at a distance of 0cm to block other electromagnetic waves and UV intensity 150
Irradiation was performed for 100 minutes at 0 cd/ll1fi, and sensitivity was measured using an electrostatic tester (Kawaguchi Electric Seisakusho: Model 5P-428).

These results are shown in Table 1.

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]

1 to 4 are cross-sectional views of the photoreceptor of the present invention. l...Support 2... Charge generation layer (CGL) 3...Charge transport layer (CTL) 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.▼ [In the formula, R_1, R_2, and R_3 are hydrogen atoms, halogen atoms, or amino, substituted amino, hydroxy, heterocycle, alkyl, alkenyl, cycloalkyl, aralkyl, and aryl, Represents each substituted aryl group. ]