JPS63146046A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain an org. photoconductive electrophotographic sensitive body having high sensitivity, excellent scratching resistance and ozone resistance and good durability by incorporating a specific compd. into a photosensitive layer. CONSTITUTION:The compd. expressed by formula I is incorporated into the photosensitive layer of the electrophotographic sensitive body formed by providing the photosensitive layer contg. an electric charge generating layer and charge transfer layer as main constituting components on a conductive base. In formula, R1 and R2 respectively denote an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, R3-R6 respectively denote a hydrogen atom, halogen atom, alkyl group, alkenyl group, cycloalkyl group, etc. More specifically, the hydroquinone diether series compd. not only prevents ozone oxidation to a greater extent but also contributes to the improvement in the other electrophotographic characteristics and physical properties.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to an electrophotographic photoreceptor, and particularly to improvements to the Ariiso photoconductive electrophotographic photoreceptor.

[Prior art 1] In electrophotographic copying using the Carlson method, after the surface of a photoreceptor is charged, an electrostatic latent image is formed by exposure, and the electrostatic latent image is developed with toner, and then the visible image is formed. Transfer and fix onto paper, etc. At the same time, 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 electrophotographic properties such as good charging characteristics and sensitivity, and low dark decay, but also has excellent properties such as printability, abrasion resistance, moisture resistance, etc. It is also required to have good physical properties and resistance to ozone generated during corona discharge, ultraviolet rays during exposure, etc. (IT environmental resistance). Photoreceptors with a photosensitive layer mainly composed of an inorganic photoconductive substance such as cadmium sulfide are widely used.On the other hand, various organic photoconductive substances are used as materials for the photosensitive layer of electrophotographic photoreceptors. In recent years, it has been actively developed and researched to use it as a
-vinylcarbazole and 2.4,7. -) An organic photoreceptor having a photosensitive layer containing 17 nitro-9-fluorenone is described. 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 the charge generation function and charge transport function to different substances in the photosensitive layer. ing. In such so-called function-separated □-type electrophotographic photoreceptors, it is possible to select substances that promote each function from a wide range of materials, so it is relatively easy to create electrophotographic photoreceptors with arbitrary characteristics. It is possible to create one. 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 Publication No. 8, there is amorphous selenium. Does this exist? ! ! Combined with a charge transport material. In addition, many electrophotographic photoreceptors using organic dyes or organic pigments as carrier-generating substances have been proposed.
No. 47-37543, No. 55-22834 - No. 5
It is already known from various publications such as No. 4-79632 and No. 56-116040. 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, it has been found that using such negative charging causes the following problems. That is, the first problem is that ozone is likely to be generated in the H atmosphere when negatively charged by a charger (which worsens the ring Ti conditions.Also, the problem of starvation is that the development of the negatively charged photoreceptor Toner of positive polarity is required, but gJ1'ii is difficult to achieve with positive polarity toner due to the triboelectrification series that is applied to ferromagnetic charged particles.Therefore, an organic photoconductive material is used. It has been proposed to use a positively charged photoreceptor.For example, in the case of a positively charged photoreceptor in which a charge transport layer is formed with a Mi layer on a charge generation layer and the charge transport layer is formed of a substance with a high electron transport ability. , the charge transport layer contains trinitrofluorenone, etc., but the second substance is unsuitable because it is carcinogenic.On the other hand, for positive charging, a charge generation layer is laminated on a charge transport layer with a large hole transport ability. A photoreceptor may be considered, but this has a very thin charge-generating layer on the surface side, resulting in poor printing durability and is not a practical layer structure. No. 361541
- No. 1 Mei 1'j shows a product containing thiapyrylium salt (charge generating substance) so as to form a eutectic complex with polycarbonate (Baingu resin). However, this known photoreceptor has the disadvantage of -γ, in that it has a large memory phenomenon and tends to generate ghosts. U.S. Patent No. 3,357,989 #I also discloses a photoreceptor containing phthalocyanine, but the characteristics of phthalocyanine change depending on the crystal type, and the crystal type needs to be strictly controlled. Furthermore, 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. Due to the above-mentioned circumstances, conventionally, it has been difficult to use a photoreceptor using an organic photoconductive substance for positive charging, and for this reason, it has been used mostly for negative charging. OBJECT OF THE INVENTION The object of the present invention is to provide a highly conductive electrophotographic photosensitive material that can be used for positive charging, has good sensitivity, has excellent scratch resistance and ozone resistance, and is durable. It's about offering your body.

[Configuration and effects of the invention]

The above-mentioned object of the present invention is to provide an electrophotographic photoreceptor in which a photosensitive layer containing a charge generating substance and a charge transporting substance as main components is provided on a conductive support, and the photosensitive layer contains a compound represented by the following general formula. Achieved by forcing. In the general formula, R1 and R2 each represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and R,, R,, R, and R6 are each a hydrogen atom or a rodene atom. , alkyl group, alkenyl group, cycloalkyl group, aryl group, alkoxy group, alkylthio group,
Represents an aryloxy group, an arylthio group, an acyl group, an acylamino group, an alkylamino group, an alkoxycarbonyl group, or a sulfonamide group. Ozone deterioration of the photoreceptor is caused by repeatedly applied corona discharge, but it is also thought to be enhanced by singlet oxygen generated by exposure. The degree of ozone oxidation varies depending on the structure of the photosensitive layer of the photoreceptor, the types of charge-generating substances and charge-transporting substances, etc., but charge-transporting substances are more susceptible to oxidation, especially organic photoconductive materials. When using substances, the impact is extremely large. As a result of intensive studies on improving ozone deterioration (particularly potential drop) of photoreceptors, the present inventors found that the hydroquinone ether compound represented by the above general formula not only strongly prevents ozone oxidation, but also It was discovered that this also contributes to improvement of photographic properties and physical properties, leading to the present invention. The present invention will be explained in more detail below. In the above general formula of the compound used in the present invention, the halogen atom may be, for example, fluorine, chlorine, bromine, or iodine, and the alkyl group may be linear or branched, preferably having 1 to 1 carbon atoms. Examples include methyl, ethyl, butyl, thi-butyl, 2-ethyl-hexyl, 3,5.5-trimethylhexyl, 2,2-trimethylpentyl, octyl, t-octyl, dodecyl, 5ee-dodecyl, hexadecyl,
The alkenyl group such as octadecyl or eicosyl may be linear or branched, and preferably has carbon atoms rlL2 to 32, such as allyl,
Cycloalkyl groups such as butenyl, octenyl or oleyl are preferably 5 to 7, for example cyclopentyl, cyclohexyl or cycloheptyl, aryl groups such as phenyl or 7,000, and heterocyclic groups are preferably 5 to 7. Heterocyclic groups containing ~6 nitrogen atoms, oxygen atoms and/or sulfur atoms are preferred, such as furyl, pyranyl, tetrahydropyranyl, imidazolyl, pyrrolyl, pyrimidyl, bilanonyl, tri7nonyl, chenyl, quinolyl, oxacylyl,
Examples include thiazolyl and pyrinol. Examples of alkoxy groups include methoxy, ethyne, propoxy, t-butoxy, hexyloxy, dodecyloxy, octatecyloquine, and dodecyloxy; examples of alkylthio groups include aryloxy groups such as methylthio, butylthio, octylthio, tocosylthio, and tocosylthio; Examples of arylthio groups include phenylthio and the like; examples of acyl groups include acetyl,
Buta/yl, oct/yl, dodecanoyl, benzoyl, cinnamoyl or su7toyl, etc.; examples of the acylami7 group include acetylamino7, octanoylamino or benzoylamino; alkylamino examples include, for example, methylamino, ditylami7, Mono- or difulkylamino groups such as noethylamino, isopropylamino, 11 nooctylamino or nobucylamino, alkoxycarbonyl groups include, for example, methoxycarbonyl, ethoxycarbonyl, nonyloxycarbonyl, hexadecyloxycarbonyl or tocosyloxycarbonyl, and sulfonamide groups. Examples include methylsulfonamide, octylsulfonamide, and phenylsulfonamide. Furthermore, each of these groups may have a substituent, such as a halogen atom, a hydroquine group, a carboxy group, a sulfo group, a sia/group, an alkyl group (especially one having 1 to 32 carbon atoms), an alkenyl group (especially one having 1 to 32 carbon atoms). having 2 to 32 carbon atoms),
alkoxy group, alkylthio group, alkenyloxy group,
alkenylthio group, aryl group, aryloxy group, arylthio group, 7 arylami groups, 7 fulkylami groups,
Flukylami 7 groups, acyl groups, acyluoquine groups, 7-ruami 7 groups, carbamoyl groups, sulfonamide groups, sulfamoyl groups, flukyl carbonyl groups, aryloxycarbonyl groups or heterocyclic groups (especially 5 to 6 nitrogen atoms, oxygen atoms) and/or sulfur) containing a V atom). These substituents may be further substituted with the above-mentioned substituents. In the general formula, R1 and R2 are each preferably a linear or branched alkyl group or alkenyl group having 1 to 32 carbon atoms, and substituents for these alkyl groups and 1 alkenyl group include a hydroxy group, Preferred are a cyano group, a carboxy group, a halogen atom, an aryl group, an alkoxy group having 1 to 32 carbon atoms, an aryloxy group, or a flukoxycarbonyl group having 1 to 32 carbon atoms. Further, Ri, It+, Rs and VB2 are hydrogen atoms, each preferably a straight y (4-shaped or branched alkyl group or alkenyl group having 1 to 32 carbon atoms),
As the substituents for these alkyl groups and alkenyl groups, the same substituents as R1 and R2 are preferable.
This is the case where one is an alkyl group or an alkenyl group and the remaining two are hydrogen atoms. 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. In addition, compounds are shown by showing substituents instead of structural formulas. , / Kii゛, Shimokanpaku-to)' Below margin These compounds are described in Journal of the Chemical Society (J, Chcm, Soc,), 2904-2
914 pages (1965) and The Journal of
Organic Chemistry (J, Org, Chew)
, Vol. 23, pp. 75-76. Addition of the compound represented by the general formula of the present invention (hereinafter referred to as the compound of the present invention); 11 is not constant depending on the layer structure of the photoreceptor, the type of charge transport material, etc.; 01 to 100% by weight,
Preferably 1 to 50 weights! i%, particularly preferably from 5 to 25
It is used in a range of 117% by weight. Next, the structure of the photoreceptor of the present invention will be explained using a circular surface. The photoreceptor of the present invention has a support l (
A conductive support or sheet (a conductive layer provided on a conductive support or sheet) containing a charge generating substance 5 (hereinafter sometimes referred to as CGM) and a binder resin as necessary. The layer 2 (hereinafter sometimes referred to as CGL) is the layer 2, and the charge transport layer 3 (hereinafter sometimes referred to as CGL) contains a charge transport material 6 (hereinafter sometimes referred to as CTM) and a binder resin as necessary. After providing the photosensitive layer 4 having a laminated structure with CTI, 3 as the lower layer and CGI, 2 as the h layer on the support l as shown in FIG. 2, as shown in FIG. As shown in FIG. It will be done. In addition, the same kI as in Figure 2! In the composition, the upper layer CG [, C
Both G11 and CTM may be contained, and the photosensitive layer]
A second protective layer (OCL) may be provided, and an intermediate layer may be provided between the support and the photosensitive layer. FIG. 4 shows an example of this. That is, the intermediate layer 7 is provided on the support 1''2,
It contains CTM6a and binder resin.
This photoreceptor has a photosensitive layer 4 laminated with L3, CGIII5.01M6b, and CGL2 containing a binder resin, and is further provided with a protective layer 8 containing a binder as a main component. The compound of the present invention comprises CG1. , CTl
7. Single layer structure It may be contained in any one of the photosensitive layers or OCL, or it may be contained in multiple layers. In the photoreceptor having a laminated structure as the lower layer.Next, as a charge generating material suitable for the present invention, any organic pigment soaked in an inorganic pigment can be used as long as it absorbs visible light and generates a free charge. Can be used for 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, etc. In addition, i-machine pigments such as those shown in the following representative examples may be used. (1) Azo pigments such as monoazo pigments, polyazo pigments, metal complex azo pigments, pyrazolone azo pigments, stilbene azo and deazole azo pigments. (2) Perylene pigments such as perylenic anhydride and perylenic acid imide. (3) Anthraquinone derivatives, anthraquinone derivatives, dibenzpyrenequinone derivatives, pyrant derivatives, violanthrone derivatives and isoviolant derivatives. Anthraquinone or polyquinone pigments such as (4) Innovoid pigments such as indigo derivatives and thioinnovo derivatives (5) Phthalocyanine pigments such as metal phthalonanine and metal-free phthalonanine (6) Nophenylmethane pigments, triphenylmethane pigments , carbonium pigments such as xanthine pigments and acridine pigments (7) xanthine pigments such as azine pigments, oxanone pigments and thiazine pigments (8) methine pigments such as anine pigments and azomethine pigments (9) quinoline pigments (10) 21・[L-based pigments (11) Nitroso-based pigments (12) Benzoquinone and naphthoquinone-based pigments (13)
Naphthalimide Pigments (14) Perinone Pigments such as Bisbenzimidazole Derivatives Various azo pigments that have charge-absorbing properties are used because of their good electrophotographic properties such as sensitivity, memory phenomenon, and residual potential. Quinone pigments are most preferred in terms of ozone resistance. The details are for leather use, but it is probably because Azohanawa is easily susceptible to ozone oxidation and its electrophotographic properties deteriorate, whereas polycyclic quinos are inert to ozone. Examples of the azo pigments used in the present invention include the following exemplified compound groups CI'1 to []. (I J 1 and below margin example 1 Hi sound object group CII+): Below margin.Illustration & thing [■]: ・ Below 4': White exemplified compound [■]: Also, exemplified compound consisting of the following polycyclic quinone pigment Group [■
] to [■] are most preferably used as CG14. Exemplified compound group [■): Example 1 Hi-sound group [■]: Hereinafter, blank exemplified compound group [■]: Next, f-acceptable I11' function in the present invention There are no particular restrictions on the charge transporting substance, but examples include oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thief'cyazole 8, thiazole, trifu'zole derivatives, imidazole derivatives, midazolone derivatives, and imidazole derivatives. Lysine derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline derivatives, oxacilone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N -vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthrahine, etc. 17 However, in addition to the oil force of 1# and No. C for transporting the poles generated during light irradiation to the support side, a material suitable for the combination Q with the carrier-generating substance described in 111i is preferably used, and such CTH For example, the following example 1 hardware group [1x
] or [X] is one still compound. Exemplary compound group [IM'): M, C, group C as 1.
I IIN t, XI, ] -1X V i ti +
J I history Ill'j1':. jDisclosure 11,,! IIJI! Y r XI ]: Show 1 time, 1 sound! I Mutaku group "χllJ Example 1 compound fl' [: thing r
Vl) ゛, 7゛゛＼---- Exemplary compound group (XVIJ: Mata, C1'H to L -(l'
The amine jA stele shown in bl l1l-[' The following margin 1 The layer structure of the photosensitive layer of the photoreceptor of the present invention is as described above.
There are M configuration and single WJ configuration, but CTL which becomes the surface layer,
Either CGL, single-layer photosensitive layer or OCL, or multiple layers contain one or more electron-accepting substances 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, nobromaleic anhydride, black water 7-talic acid, tetrachlor 7-talic anhydride,
Tetrabromo 7-talic anhydride, 3-nitro 7-talic anhydride,
4-Nitro-7tallic anhydride, bilomelli7tolic anhydride, mellitic anhydride, tetra-7-ethylene, tetra-7-a/x-7-methane, 0-nonitrobenzene, I6-nonitrobenzene, 1°3.5. -117 Nitrobenzene, para-nitrobenzonitrile, vicryl chloride, chlorimito, chloranil, brumanil, 2-methylna-7, noparabenzoquinone, anthraquinone, nonitroanthraquinone, trinitrofluorenone, 9 -Fluorenonedene [nocya/methylenemalonononitrile], polynitro-9-fluorenonedene [nocyanomethylenemalonononitrile], picric acid,
0-nitrobenzoic acid, 1-nitrobenzoic acid, 3,5-nonitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-nonitrosalicylic acid, 7-talic acid, etc. can be mentioned. In the present invention, examples of Bingoo 011 materials that can be used in the photosensitive layer include polyethylene, polypropylene, and acrylic! 4 fat, methacrylic cloth, vinyl chloride, vinyl chloride υ (fat, epoxy?j (so-called, polyurethane: 1 (II)
I? ,7x]-ru+H fat, Holies f ru+jI fr
eI, alkyd Ij (fat, polycarbonate resin, silicone resin, melamine (fat, etc.) addition polymerization mold (fat,
Polyaddition-type products, polycondensation-type resins, and copolymer resins containing two or more of these 84 repeating units,
Examples include insulating phases such as vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymers, and polymeric organic semiconductors such as poly-N-vinylcarbazole. . In addition, the intermediate layer functions as an adhesive layer or a barrier layer, and in addition to the above-mentioned paint resin, it may contain, for example, evapolyvinyl alcohol, ethyl cellulose, carboquine methyl cellulose, vinyl chloride-vinyl acetate copolymer, chloride Vinyl-vinyl acetate-maleic anhydride copolymer, casein, N-alkoxymethylated nylon, starch, etc. are used. Next, as a conductive support for supporting the photosensitive layer, 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. A film or drum of paper, plastic, etc. can be used. CGL can be prepared by vacuum-depositing CG14 on the support as described above, or using CCM alone or with a suitable solvent in a suitable solvent. 41 (can be provided by a method of applying and drying a mixture dissolved or dispersed with fat. When forming CGL by dispersing the above C(rM),
The CGM is preferably a granular material having an average particle size of 2μ+6 or less, preferably 1μ or less. In other words, if the particle size is too large, dispersion in the layer becomes poor (and some of the particles protrude from the surface, making the surface less slippery, and in some cases, discharge may occur at the protruding parts of the particles or Toner particles tend to adhere to the toner particles and cause toner filming phenomenon. However, if the particle size is too small, they tend to aggregate,
It is desirable to set the lower limit of the average grain size to 0.01μ because the resistance of the layer increases, the sensitivity and V repeatability decrease due to the increase of crystal defects, or there is a limit to miniaturization. CGL can be provided by the following method: That is, the CGM described above is made into fine particles in a dispersion medium using a ball mill, a homomixer, etc., and a binder resin is added and mixed and dispersed, and the resulting dispersion is applied. This is a method. In this method, when particles are dispersed under the action of an ultrasonic wave,
Uniform dispersion is possible. Solvents used to form CGL include, for example, if N
, N-trimethylformamide, benzene, toluene, quinolene, mo/chlorobenzene, 1,2-nochloroethane, nochloromethane, 1,1,2-trichloroethane, tetrahydro7rane, methyl ethyl ketone, ethyl acetate, butyl acetate, etc. I can do it. For banhgu in CCL @ 100 parts by weight, C (i M) is 20 to 200 parts by weight, preferably 25 to 100 parts by weight. If CGM is less than this, the photosensitivity will be low, leading to an increase in residual potential, and If the amount is more than this, the flicker increases and the acceptance potential decreases.The film thickness of the CGL formed as described above is preferably 1 to 10 μl, particularly preferably 3 μl in the case of positive charging vI formation. ~7 μl shoulder, and in the case of a configuration for negative charging, it is preferably 0.01 to 10 μm, particularly preferably 0.1 to 3 μl. That is, in the configuration for positive charging, since C(:L is the surface layer) It lacks scratch resistance, and in order to improve durability it is necessary to increase the thickness of the CGL film, which causes a decrease in sensitivity.As a means of suppressing this, C7M is added to CCL, but this CTH is not as strong as CGH. Since it has a structure that is susceptible to oxidation by ozone, it is easily deteriorated by ozone, which impairs the durability of the photoreceptor.The present invention solves this vicious cycle by adding the compound of the present invention. Further, CTL can be formed by using the above-mentioned CTM in the same manner as the above-mentioned CCL (that is, by coating the CTM alone or dissolving and dispersing it together with the above-mentioned binder resin and drying it). CTM per 100 parts by weight of Pine Goo resin is 2
The amount is 0 to 200 parts by weight, preferably 30 to 150 parts by weight. If the content of CT- is lower than this, the photosensitivity is poor and the residual potential tends to be high, and if the content is higher than this, the solvent) 8M,
Sexuality becomes worse. The thickness of the CTN formed is preferably 5 to 50 μs,
1. It is preferably 5 to 30 μl for potatoes. It is preferable that the film thickness ratio of L and CTL to C and C is 1:(1 to 30). In the case of a single-layer structure, CGM is a binder↑j (the proportion contained in fat is 20 to 200 parts by weight, preferably 1 to 2 parts by weight).
The amount is 5 to 100 ffl parts. If the content of CGH is less than this, the photosensitivity will be low and the residual potential will increase, and if the content is more than this, the attenuation and acceptance potential will decrease. Next, the force 1 force that CTM contains against the binder resin is pine goo tree ry! 20-2 to 100 parts by weight
00 parts by weight, preferably 30 to 1501 parts by weight. If the content ratio of CTH is less than this, the photosensitivity will be poor and the residual potential will be high.If the content ratio of CTH is more than this, the solvent solubility will be poor. The amount ratio of CTM to I is preferably 1:3 to 1:2 by weight.The protective layer provided as necessary in the present invention has a volume resistivity of 10"Ω·010 or more, preferably 1010Ω・CIf1 or more, more preferably io”
A transparent TLL (lff1) with a diameter of Ω cm or more is used.The binder is a resin that is cured by light or heat and contains at least 50% by weight of fat.As the resin that is cured by light or heat, For example, thermosetting acrylic resin, polyurethane resin, polyester resin, urethane resin, urea resin, 71/- Luso 3 (shield, polyester resin, alrekind resin, melamine resin, photocurable/cinnamic acid resin, etc.) or these. Copolymerization or cocondensation (
In addition, all of the thermosetting fats used in electrophotographic materials are used.Also, in the protective layer of 11-7, there are additives for improving processability and physical properties (/r+, public prevention). Thermoplasticity 1.!1 Kamawo 5
It is allowed to contain less than 0% by weight. Thermoplastic full? Examples of t include polypropylene, acrylic resin, methacrylic (fat, salt f1 vinyl resin, cloth for vinyl acetate, epoxy resin, butyral resin, polycarbonate of fat, methacrylic resin, or copolymerized υ of these (fat, e.g. chloride). Vinyl-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride copolymer O
(All of the above-mentioned protective layer contains an electron-accepting substance. You may
The pond may contain an ultraviolet absorber or the like for the purpose of protecting the CGM if necessary, and is dissolved in a solvent together with the above-mentioned baingoo, applied and dried by, for example, dip coating, spray coating, blade coating, roll coating, etc. The layer thickness is 2 μm or less, preferably 1 μm or less. [Example] The present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.Example 1 On a conductive support made of a polyester film laminated with aluminum foil, Vinyl chloride - vinyl acetate -
An intermediate layer having a thickness of 0.1 .mu.m was formed from a maleic anhydride copolymer (Suresoku MF-10, manufactured by Ukisui Kagaku Kogyo Co., Ltd.). Next, CTM (IX-75) / Bolicar Ponetoku f visit (Panlite L-1250, Teijin Chemicals 5!!) =
1 containing 16.5% by weight of 75/+00 (weight ratio),
2-nochloroethane was coated on the intermediate layer by dip coating and dried to obtain a CTL with a thickness of 15 μl. 4,10-Nobromoanthrone ('+T-3)/Panrai) L-1250 was then sublimated as CCM.
CTH
(IX-75) was added to Panlite (-1250) by 75 weight F6, and the compound of the present invention (21) was added to CTH by 10 weight. Monochlorobenzene was processed into this dispersion. /1゜2-nochloroethane = 3/7 (volume ratio) was prepared and sprayed onto CTL soil to a thickness of 5 μl.
A photoreceptor of the present invention having a photoreceptor layer having a laminated structure was obtained. Comparative Example 1 A comparative photoreceptor was obtained in the same manner as in Example 1 except that compound (21) in CGL was removed. Example 2 Compound (5) was replaced with compound (21) in Example 1.
A photoreceptor of the present invention was obtained in the same manner as Example M except that 3) was added. Example 3 Photoreceptor (
(same as the photoreceptor of Comparative Example I) on which thermosetting acrylic-melamine-epoxy (1:l:1) resin 1,55iI! 0.155 parts by weight of the compound (21) of the present invention was added to monochlorobenzene/1, 1.21 dichloroethane (1/
1 volume ratio) mixed solvent 100ff! A coating solution obtained by dissolving the photoreceptor of the present invention was spray-coated and dried to form a protective layer of 1 μR/7: to obtain a photoreceptor of the present invention. Example 4 Primer 1''+191(
Toshiba Silicon Co., Ltd.) was spray applied to 0.1μxFi, and then silicone hard coat Toss Guard 51o was applied on top of that.
(manufactured by Toshiba Henricon) 100 parts by weight of compound (21) 1
Spray coat a solution consisting of 0 parts by weight and dry to 1 μR.
Maintenance: 11 layers were formed to obtain a photoreceptor of the present invention. Temperature Example 5 An intermediate layer exactly the same as in Example 1 was formed on a conductive support made of a polyester film laminated with aluminum foil. Next, as a coating liquid for CTL, Petit Larlij resin (Elex 0X-1, manufactured by Sekisui Chemical Co., Ltd.) was used at a concentration of 8% and CTM (
A solution obtained by dissolving [-75) in methyl ethyl ketone to a concentration of 6% by weight was applied onto the intermediate layer and dried to form a CTL having a shoulder thickness of 10 μm. Next, paint condition 5 on CGH (N-7) Ooh.
PainL CondiLioncr, RCd
Devi1 Co., Ltd.) for 30 minutes, and carbonate υ1 fat (Panlite L-1250, mentioned above) was mixed with 1.2-nochloroethane/1.1.2-)lichloroethane mixed solvent for 0.5 minutes. After adding 8.33% of the solution and dispersing for 3 minutes, polycarbonate resin, CTM (lX-75) and compound (21) were added at 3.3% and 2%, respectively. .6% by weight and 0.26 weight!
A solution obtained by dissolving in a mixed solvent of 1,2-nochloroethane/1.1.2-trichloroethane so as to obtain 19.
12 was added and the mixture was further dispersed for 300 minutes. The thus obtained dispersion was spray-coated onto the CTC and dried to form a CGL of 5 μw FJ, thereby obtaining a photoreceptor according to the present invention having a photosensitive layer having a laminated structure. Comparative Example 2 A comparative photoreceptor was obtained in the same manner as in Example 5 except that compound (21) in CGL was removed. Example 6 Compound (5) was replaced with compound (21) in Example 5.
Except for adding 3): llI: +1! A photoreceptor of the present invention was obtained in the same manner as in Example 5. Example 7 A photoreceptor obtained by removing the compound (21) from the CGL of Example 5 (
A protective layer containing the compound (21) used in Example 3 was provided on the photoreceptor (same as the photoreceptor of Comparative Example 3) to obtain a photoreceptor of the present invention. Example 8 Photosensitive 1V obtained by removing compound (21) from CGL of Example 5
A protective layer containing the compound (21) used in Example 4 was provided thereon to obtain a photoreceptor of the present invention. Example 9 An intermediate layer exactly the same as in Example 1 was formed on a polyester film on which aluminum was vapor-deposited. Then the sublimated 4,10-nobromoanthrone (
Vl-3)40. 40 r H+ in a porcelain ball mill
The mixture was ground for 24 hours, 20 g of Panlite L-1250 (described above) and 1,2-nochloroethane 1300++e were added, and 241L7 was further dispersed to obtain a CGL coating liquid. This was applied onto the intermediate layer to provide a CGL with a V thickness of 1 μm. Then CTM (rX-61) 7.5g, Panlite L
-125010y and compound (21) 0.757 at 1
．． A solution dissolved in 80 zl of 2-nochloroethane was added to the C
A photoreceptor of the present invention was prepared by coating on GL to form a CTL with a V thickness of 15 μl. Comparative Example 3 A comparative photoreceptor was obtained in the same manner as in Example 9 except that compound (21) in the CTL was removed. Example 10 An intermediate layer exactly as in Example 1 was formed on a conductive support made of polyethylene terephthalate having a thickness of 100 μl and deposited with aluminum. Next, a bisfuji compound (■-7>1.5
y is 1,2-nochloroethane/monoethane/-ruamine (
A dispersion solution which was dispersed in a mixed solvent (volume ratio 1000/1) for 8 hours using a ball mill was applied to the above intermediate layer 2 and sufficiently dried to provide a CGL of 0.3IJ1□rl. Then styryl compound (IX-13) 11 as CTM
, 25, Panlite L-1250 (supra) 152 and compound (21) 1.1259 were dissolved in 1,2-nochloroethane 10011.
A CTC of 15 μzF7 was formed by coating the photoreceptor on top and drying sufficiently to form a photoreceptor of the present invention. Comparative Example 4 A comparative photoreceptor was prepared in the same manner as in Example 10 except that compound (21) in the CTL was removed. Examples 11 to 18 Compound (5) was substituted for compound (21) in Example 1.
5), (57), (54), (56), (62), (6
A photoreceptor of the present invention was obtained in the same manner as in Example 1 except that 7), (72), and (77) were added, respectively. The ozone resistance of the 22 types of photoreceptors thus obtained was evaluated in the following manner. That is, 7) An ozone generator (manufactured by Kuchimoto Ozone Co., Ltd., 0-1-2μ) and an ozone monitor (manufactured by Ebara Tengyo Co., Ltd., EC- 2001 type) f,: Using the installed ozone fatigue tester, a photoreceptor was deposited at an ozone concentration of 90111) 1n, and Vl, lower 1, ? Gender: J, tested 7 times. That is, +6KV for a positive charging photoreceptor, -6K for a negative charging photoreceptor.
After applying a voltage of V and causing the photosensitive layer to rise by corona discharge for 5 seconds, it is opened for 5 seconds (the potential at this time is taken as the initial potential Vo), and then the illuminance on the surface of the photosensitive layer is reduced to 1.
The sample was irradiated with a tungsten lamp under a condition of 4 lux, and this operation was repeated 100 times. The residual potential V after 100 cycles is further determined and V 7 V o X I OO
(!6) was used to evaluate the ozone properties of alcohol. In addition, the exposure ffi, E (lux seconds) required to reduce the initial potential to ±600 V to ±100 V was also measured. V/VOX
The larger the 100(%) value, the less ozone deterioration, and the smaller the E (lux seconds) value, the higher the sensitivity of the photoreceptor. Show your results to someone else. As is clear from the table below with separate margins, by adding the compound of the present invention, does the potential decrease due to corona charging in the presence of ozone improve? g is done. Furthermore, addition of the compound of the present invention causes almost no decrease in sensitivity.

[Brief explanation of the drawing]

FIGS. 1 to t12I are cross-sectional views of the photoreceptor of the present invention.

Claims (1)

[Scope of Claims] An electrophotographic photoreceptor in which a photosensitive layer containing a charge generating substance and a charge transporting substance as main components is provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula. An electrophotographic photoreceptor characterized by: General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. , hydrogen atom, halogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, acyl group, acylamino group, alkylamino group, alkoxycarbonyl group or sulfonamide group represents. ]