1,2,4,5-Benzoylenebis (naphto [2,3-d] imidazole) compounds and photosensitive members containing them

Abstract: 1,2,4,5-Benzoylenebis(naphto[2,3-d]imidazole) compounds of the following formula (I) or (II): wherein R and R′ each are hydrogen atom, a halogen atom, hydroxyl group, a carboxyl group which may be esterified, a sulfonic acid group which may be esterified, a lower alkyl group, a lower alkenyl group, a lower alkoxy group, an aryl group which may be substituted, an aralkyl group which may be substituted, a carbamoyl group which may be substituted or a sulfamoyl group which may be substituted and m and n each are an integer of 1 or 2, and photosensi­ tive members for electrophotography having a photosensitive layer containing them.

Description: The present invention relates to photosensitive members containing imidazole compounds and more particularly, containing 1,2,4,5-benzoylenebis (naphtho[2,3-d]imidazole) compounds, which are organic photoconductive substances, for electrophotography. Generally, electrophotography using a photoconductive photosensitive member is one information recording means utilizing photoconductive phenomena. In electrophotography, the surface of the photosensitive member is uniformly charged by corona discharge or the like, in darkness and then, by subjecting the charged surface to image exposure, the electric charge of the exposed portion is discharged selectively to form an electrostatic latent image on the unexposed portions of the surface. The latent image is converted into a visual image by allowing charged colored fine particles (toner) to adhere to the latent image by electrostatic attraction. The basic properties required for photoconductive photosensitive members used in electrophotographic techniques of these serial processes are: (1) that the photosensitive members can be uniformly electrified in darkness at a suitable electric potential, (2) that they have a high, electric charge-retentivity in darkness and discharge of the electric charge from them is minor, (3) that they are superior in photosensitivity and quickly discharge the electric charge by photoirradiation, and the like. Moreover, it is required for the photoconductive photosensitive members to have good stability and endurance; such as, that the surface of them can be discharged easily, with a minor residual electric potential on the surface; that they have mechanical strength and are superior in flexibility; that their electric properties, especially electrification property and remaining electric potential, do not fluctuate even when they are used repeatedly; and that they are resistant to heat, light, temperature, humidity and ozone deterioration. Photosensitive members for electrophotography now used practically may be divided broadly into two groups, one utilizing inorganic materials and one utilizing organic materials. As representative photosensitive inorganic members, there can be mentioned those of selenium such as amorphous selenium (a-Se) and amorphous arsenic selenide (a-As₂Se₃), those comprising color-sensitized zinc oxide (ZnO) or cadmium sulfide (CdS) dispersed in a bonding resin and those using amorphous silicon (a-Si). As representative photosensitive organic members there are those using a charge-transfer complex of 2,4,7-trinitro-9-fluorenone (TNF) and poly-N-vinylcarbazole (PVK). These photosensitive members have many merits, but at the same time some drawbacks. For instance, photosensitive members of selenium and photosensitive members using CdS have doubtful heat-resistance and can-stability. Moreover, there is a restriction in the use of those photosensitive members that, because of their toxicity, they cannot be simply thrown away but have to be recovered. Photosensitive members comprising ZnO dispersed in resin are now practically not used, because of their low sensitivity and inferior endurance. Amorphous silicon photosensitive members having such advantages as high sensitivity and high endurance, have also the drawbacks that their manufacturing cost is high because of their complicated manufacturing process and that they give faulty images resulting from faults in the membrane which is inherent in amorphous silicon. Further, they have the disadvantages that their flexibility is not satisfactory, and that their processing into various forms such as drums and sheets is not easy. In contrast, organic photosensitive members have gained in importance because suitable organic materials without the problems on can-stability and toxicity can be selected from existing various materials, and organic materials having improved durability and low cost have become available. However, the sensitivity of organic photosensitive materials remains to be improved. The PVK-TNF charge-transfer complex series resulted from such an improvement, but did not attain sufficient sensitivity. In addition, various sensitizing methods have been proposed. At present, the main type of organic photosensitive members practically used is laminate type photosensitive members (hereinafter called "multilayer type photosensitive members") having a superior sensitizing property, which comprise a layer (hereinafter called "charge-generating layer") containing a substance which allows generation of charge-carriers by photoirradiation (hereinafter called "charge-generating substance") and a layer (hereinafter called "charge-transporting layer") consisting mainly of a substance which accepts and transports the charge carriers generated in the charge-generating layer (hereinafter called "charge-transporting substance"). As organic materials which may be used for the charge-generating layer, there are known bis-azo pigments such as chlorodianblue, polycyclic quinone series pigments such as dibromoanthanthrone, perillene, quinacridone or phthalocyanine series compounds and azulenium salts. However, some of these charge-generating materials are lacking in photoconductivity though they have a good absorption spectral property for photosensitive members, in the visual ray region, and some of them have an absorption spectral property unsuitable for photosensitive members though they have a good photoconductivity. Thus, it was very difficult to compose a photosensitive member having a good sensitivity, by striving for coexistence of the absorption spectral property and the photoconductivity. The multilayer type photosensitive members provided with such a charge-generating layer which have been hitherto proposed are, for example, 1 ○ those wherein a thin layer formed by application of an organic amine solution of chlorodianblue is used as the charge-generating layer and a hydrazone compound is used as the charge-transporting substance of the charge-transporting layer (Japanese Patent Publication No. SHO 55-42380 is referred to), 2 ○ those wherein a bis-azo compound is used as the charge-generating substance of the charge-generating layer and a hydrazone compound is used as the charge-transporting layer (Japanese Patent Application Laid-open No. SHO 59-214035 is referred to), 3 ○ those wherein an azulenium salt compound is used as the charge-generating substance of the charge-generating layer and a hydrazone compound or the like is used as the charge-transporting layer (Japanese Patent Application Laid-open No. SHO 59-53850 is referred to), 4 ○ those wherein a perillene derivative is used as the charge-generating substance of the charge-generating layer and an oxadiazole derivative is used as the charge-transporting layer (U.S.P. No. 3871882 is referred to), and the like. However, these photosensitive members 1 ○ - 4 ○ still had insufficient sensitivity, as they were used in practice. Moreover, these hitherto known multilayer type photosensitive members had a problem in their stability when they were used repeatedly. Therefore, notwithstanding the above-mentioned many merits of the organic photoconductive substances, compared with inorganic ones, they were not widely used for photosensitive members for electrophotography because photosensitive members using them were inferior in sensitivity and endurance. The present invention seeks to provide organic photosensitive members for electrophotography having a high sensitivity and a superior stability on repeated use, and is based on the discovery that a specific group of novel imidazole compounds are suitable as the organic photoconductive substances. According to the invention there is now provided a photosensitive member comprising on a conductive support a photosensitive layer containing a compound of the formula (I) or (II): in which each of R and R' is a hydrogen or halogen atom or a hydroxy, C₁-C₅ alkyl, C₂-C₅ alkenyl or C₁-C₅ alkoxy group; an aryl or aralkyl group which may carry one or more substitutents selected from halogen atoms and nitro, cyano, C₁-C₅ alkyl, C₁-C₅ alkoxy and di(C₁-C₅ alkyl)amino groups; a carboxy or sulfo group which may be esterified by an alkyl group or by an aryl group which may be substituted in the manner specified above; a carbamoyl group which may be substituted by methoxyphenyl, nitrophenyl, dimethoxychlorophenyl, carbazolyl, dibenzofuranyl or 3-methoxydibenzofuranyl, or a sulfamoyl group and each of m and n is 1 or 2 or in which each of m and n is 1 and R and R' are the same and in the 5 and 5' positions and each is a carbamoyl group substituted by phenyl, p -methylphenyl, p -chlorophenyl, o -chlorophenyl, o -methyl- p -chlorophenyl, o -methoxy- p -chlorophenyl, o -ethoxyphenyl, 2-naphthyl, 7-bromo-2-naphthyl, N,N-diphenyl, N-methyl-N-phenyl or N-methyl-N- p -methylphenyl or is SO₃Na. The photosensitive members of the present invention have a high sensitivity and exhibit only a minor change or fluctuation in sensitivity and chargeability upon repeated use, that is they are of superior endurance. They exhibit excellent performance not only in electrophotography, such as laser printers and CRT printers as well as copying machines, but also widely in solar batteries and photosensors. DE-A-2148101 describes the reaction of pyromellitic anhydride with various aromatic diamines including 2,3-diaminonaphthalene. However, the resulting compounds are described in that document in the context only of their use as pigment dyestuffs. The present invention is described below in greater detail by way of example only with reference to the accompanying drawings, in which Figures 1 to 8 are enlarged sectional views of photosensitive members of the present invention. In the general formulae (I) and (II), each of R and R' is a hydrogen or halogen atom, or a hydroxy, C₁-C₅ alkyl, C₂-C₅ alkenyl or C₁-C₅ alkoxy group; an aryl or aralkyl group which may carry one or more substitutents selected from halogen atoms and nitro, cyano, C₁-C₅ alkyl, C₁-C₅ alkoxy and di(C₁-C₅ alkyl)amino groups; a carboxy or sulfo group which may be esterified by an alkyl group or by an aryl group which may be substituted in the manner specified above or -SO₃Na; a carbamoyl group which may be substituted by methoxyphenyl, nitrophenyl, dimethoxychlorophenyl, carbazolyl, dibenzofuranyl or 3-methoxydibenzofuranyl, or a sulfamoyl group and each of m and n is 1 or 2 or in which each of m and n is 1 and R and R' are the same and in the 5 and 5' positions and each is a carbamoyl group substituted by phenyl, p -methylphenyl, p -chlorophenyl, o -chlorophenyl, o -methyl- p -chlorophenyl, o -methoxy- p -chlorophenyl, o -ethoxyphenyl, 2-naphthyl, 7-bromo-2-naphthyl, N,N-diphenyl, N-methyl-N-phenyl or N-methyl-N- p -methylphenyl The halogen atoms may be fluorine, chlorine, bromine or iodine atoms. The alkyl groups may be straight or branched chain alkyl groups having from one to five carbon atoms, such as methyl, ethyl, propyl and isopropyl groups. The alkenyl groups may be vinyl or allyl groups. The alkoxy groups have from one to five carbon atoms, such as methoxy, ethoxy, propoxy and isopropoxy groups. Examples of aryl groups are phenyl and naphthyl groups. Examples of aralkyl groups are benzyl and phenethyl groups. Examples of the substituents for the aryl groups are C₁-C₅ alkyl groups, such as methyl and ethyl groups; a halogen atoms, such as fluorine, chlorine, bromine and iodine atoms; nitro groups; cyano groups; C₁-C₅ alkoxy groups, such as methoxy and ethoxy groups; and di-C₁-C₅ alkylamino groups, such as dimethylamino and diethylamino groups. The aryl groups may carry one or more of these substituents. Chlorine atoms and nitro groups are preferred substituents. Examples of the substituents for the aralkyl groups are the same as those described above for the aryl groups. Examples of carboxyl groups which may be esterified are the carboxyl group, alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups, and aryloxycarbonyl groups such as phenoxycarbonyl and naphthoxycarbonyl groups; and examples of the sulfonic acid group which may be esterified are the sulfonyl group, alkoxysulfonyl groups and aryloxysulfonyl groups. Examples of the substituents for the carbamoyl group are methoxyphenyl, nitrophenyl, dimethoxy-chlorophenyl, carbazolyl and dibenzofuranyl groups. The imidazole compounds may be prepared by utilizing known processes. For example, they may be prepared by treating pyromellitic anhydride of the following formula (III) with an aromatic diamine of the following general formulae (IV) and (V) (in which R, R', m and n have the meanings specified above) in an inert solvent, at an elevated temperature, preferably at 100 - 350°C, particularly temperature higher than 200°C. The reaction is carried out to completion. A reaction time of 3 - 24 hours is usually preferred (Bull. Chem. Soc. Japan, 25, 411 - 413 (1952); ibid. 27, 602 - 605 (1954) are referred to). Examples of an inert solvents are nitrobenzene, aprotic polar solvents, such as N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide, basic solvents, such as quinoline, and chlorinated solvents, such as o-dichlorobenzene, and mixtures of such solvents. The photosensitive layers of the members of the present invention may contain two or more of the imidazole compounds represented by the above general formulae (I) and (II). Preferred imidazole compounds of the general formulae (I) and (II) are as follows: The imidazole compounds of the formulae (I) and (II) have photoconductivity, and so when photosensitive members for electrophotography are prepared using them, various types of photosensitive layers may be utilised. For example, the imidazole compounds may be dispersed in a polymer binder and applied on a conductive support, to make a photosensitive layer. In another process, the imidazole compounds may be utilized as a charge-generating substance, since their charge-generating ability is especially superior among their photoconductive properties. That is, the imidazole compounds may be dispersed in a binder polymer containing a charge-transporting substance (the binder polymer is not necessarily used when the charge-transporting substance has a coating membrane-forming ability), to form a photosensitive layer. Further, it may be used to prepare the so-called multilayer type photosensitive members for electrophotography having a multilayer type photosensitive layer which comprises a laminate of a charge-generating layer containing the imidazole compounds and a charge-transporting layer. Suitable conductive supports are those substrates which per se have conductivity, such as aluminum, aluminum alloy, copper, zinc, stainless steel, nickel, chromium and titanium, plastics having a conductive coating membrane layer formed by a vacuum evaporation method or the like, of aluminum, aluminum alloy, indium oxide or tin oxide, substrates comprising plastics, paper, or the like, impregnated with conductive particles or plastics having conductive polymers. Figures 1 - 8 show representative forms of the photosensitive members for electrophotography of the present invention. In the photosensitive members of Fig. 1 and Fig. 2, the imidazole compounds of the present invention act as a photoconductor, and charge-generation and charge-transportation are effected through the imidazole compounds. In the Fig. 2, 1 denotes a conductive support, 2 denotes the imidazole compound, 4 denotes a photosensitive layer, 5 denotes an undercoating layer and 8 denotes a binder. In Fig. 3 and Fig. 4 are shown those photosensitive members in which a photosensitive layer 4 comprising a dispersion of the imidazole compound 2 as the charge-generating substance in a charge-transporting substance-containing layer 3 is provided directly or through an undercoating layer 5 on a conductive support 1. As shown in Fig. 5 - Fig. 8, a multilayer type photosensitive layer 4 comprising a laminate of a charge-generating layer 6 consisting mainly of the imidazole compound of the present invention, as the charge-generating substance, and a charge-transporting layer 7 consisting mainly of a charge-transporting substance, may be provided on a conductive support 1 to prepare photosensitive members. An undercoating layer 5 may be interposed between the conductive support 1 and the photosensitive layer 4, also in these cases. Further, as shown in Fig. 5 and Fig. 6 or Fig. 7 and Fig. 8, when the photosensitive layer 4 is composed of two layers, either of the charge-generating layer 6 and the charge-transporting layer 7 may be the upper layer. With a multilayer type photosensitive member having a photosensitive layer 4 composed of two layers, especially superior photosensitive members for electrophotography are obtained. The imidazole compounds of the formulae (I) and (II) constituting the photosensitive layer 4 of laminate type may form the charge-generating layer 6 on the conductive support 1 or on the charge-transporting layer 7, directly or through an intermediate layer such as the undercoating layer 5. The forming of such a charge-generating layer is effected by vacuum evaporation of an imidazole compound as the charge-generating substance, or by application of a dispersion obtained by dispersing an imidazole compound in a suitable solvent and, if necessary, mixing with a binder, or of a dispersion obtained by dispersing an imidazole compound in a suitable solvent containing a binder dissolved therein. Generally speaking, the latter method is preferred. When the charge-generating layer is prepared by such an application method, dispersion of the imidazole compound in a binder solution can be performed efficiently by using a ball mill, sand mill, roll mill, attritor, vibration mill or supersonic disperser, and application of the dispersion can be performed efficiently by using an air doctor coater, blade coater, spray coater, hot coater or squeeze coater. As the binder used here, there can be mentioned, for example, those insulating resins such as polycarbonate, acrylic, polyester, polystyrene, melamine, silicone, polyvinyl butyral, polyamide and copolymer resins containing two or more of the recurring units of the above resins, such as vinyl chloride/vinyl acetate copolymer resin and acrylonitrile/styrene copolymer resin. Any generally used resins can be used alone or as a mixture of two or more of them. Further, as the solvent for dissolving the binder there can be used, for example, alcohols such as methanol, ethanol and isopropanol; ketones such as acetone, methy ethyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide. The membrane thickness of the charge-generating layer 6 thus formed is suitably 0.01 - 20 µm, preferably 0.05 - 5 µm, more preferably 0.1 - 2 µm. Further, it is necessary to granulate the imidazole compound 2 into fine particles having a particle size of 5 µm or less, preferably 3 µm or less, most preferably 1 µm or less. The binder resin contained in the charge-generating layer is suitably 80% by weight or less, preferably 40% by weight or less. The charge- transporting layer 7 is electrically connected with the charge-generating layer 6 and has a function of transporting the charge carriers poured in from the charge-generating layer, in the presence of an electric field. As materials for such charge-transporting layers, though the materials are generally classified into electron-transporting substances and hole-transporting substances, both and also mixtures of the two can be used for the photosensitive layer of the present invention. As the electron-transporting substances, those substances having electron attractive groups such as nitro groups and cyano group, for example, nitrated fluorenones such as 2,4,7-trinitro-9-fluorenone and 2,4,5,7-tetranitro-9-fluorenone, and trinitrotoluene, and the like, are mentioned. As the hole-transporting substances, electron donative substances, for example, heterocyclic compounds such as carbazole, oxazole, thiazole, oxadiazole, imidazole and pyrazoline, low molecular weight charge-transporting substances such as aniline derivatives, arylamine derivatives and hydrazone derivatives, high molecular weight charge-transporting substances such as poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinyl pyrene and polyvinyl anthracene, may used. The charge-transporting substances can be used individually or as a mixture of two or more of them. When a low molecular weight charge-transporting substance is used, the coating membrane can be formed by selecting a suitable binder. However, a high molecular weight charge-transporting substance having membrane-forming properties may also be used. Further, it is also possible to mix the above-mentioned high molecular weight charge-transporting substance with the binder. As the binder used here, the above-mentioned various resins used for the preparation of charge-generating layers can be used, and various solvents as described above are applicable as the solvent for the binder. The membrane thickness of the charge-transporting layer thus formed is 2 - 100 µm, preferably 5 - 30 µm. As the undercoating layer 5, high molecular weight organic substances such as gelatin, casein, polyvinyl alcohol and ethyl cellulose, and aluminum oxide may be used, besides the high molecular weight polymers used as the binder resin. The photosensitive layer of photosensitive members for electrophotography of the present invention may further contain one or more electron accepting substances and coloring materials, for the purpose of improving sensibility, suppressing the elevation of residual electric potential and fatigue, which appear on repeated use. As the electron accepting substances used here, there can be mentioned, for example, acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride and 4-chloronaphthalic anhydride; cyano compounds such as tetracyanoethylene and terephthalmalononitrile; aldehydes such as 4-nitrobenzaldehyde; anthraquinones such as anthraquinone and 1-nitroanthraquinone; polycyclic and heterocyclic nitro compounds such as 2,4,7-trinitrofluorenone and 2,4,5,7-tetranitrofluorenone. They are used as chemical sensitizers. As the coloring materials, those organic photoconductive compounds such as xanthene dyes, thiazine dyes, triphenylmethane dyes, quinoline pigments and copper phthalocyanine pigments are mentioned. They may be used as optical sensitizers. Further, the photosensitive layer of the photosensitive members for electrophotography of the present invention may contain known plasticizers, for the purpose of improving molding characteristics, flexibility and mechanical strength. As plasticizer, there can be mentioned dibasic acid esters, fatty acid esters, phosphoric acid esters, phthalic acid esters, chlorinated paraffins and epoxy-type plasticizers. The photosensitive layer may contain, if necessary, anti-oxidants, ultraviolet ray absorbing agents, and the like. The following Examples illustrate the invention. Example 1 is included for reference purposes only to illustrate the preparation of the bis-imidazole compounds. Example 1 In 200 ml of nitrobenzene, 0.597 g (3.78 m mol) of 2,3-diaminonaphthalene was treated with 0.374 g (1.72 m mol) of pyromellitic anhydride at 210°C for 24 hours while stirring. As the reaction proceeded, formation of precipitates was observed. Then, the precipitates were collected by filtration and washed 3 times with 500 ml each of tetrahydrofuran, 3 times with 500 ml each of nitrobenzene, 3 times with 500 ml each of diethyl ether, and further 5 times with 2 ℓ of acetone. The crystals thus obtained were dried at 60°C under reduced pressure of 2 mmHg, whereby 0.63 g of a compound of the following formulae was obtained (yield: 65%): Elementary analysis : Calculated Found C(%) 77.9 77.5 H(%) 3.0 2.8 N(%) 12.1 11.8 IR absorption spectrum (KBr tablet) ν co 1756, 1642 cm⁻¹ In the visual region absorption spectrum of a dispersion of this compound in a phenoxy resin (no absorption in visual region), the absorption maximum was at a wavelength of 500 nm. Example 2 A dispersion obtained by dispersing 2 parts by weight of the imidazole compound No. 2, which was prepared from pyromellitic anhydride and the corresponding aromatic diamine in the same manner as Example 1 and 1 part by weight of a phenoxy resin (PKHH, from Union Carbide Corp.) in 8 parts by weight of dioxane for 12 hours by means of a ball mill disperser, was applied onto the surface of a PET coated with aluminum by vacuum evaporation (polyethylene terephthalate : Metalumy #100 from Toray Industries, Inc.) by means of a Baker applicator and dried at 80°C for 1 hour, whereby a photosensitive member of the form shown in Fig. 1 having a photosensitive layer of 10 µm thick was prepared. The photosensitive member thus prepared was corona electrified by means of an electrostatic paper analyzer, Model SP-428 from Kawaguchi Electric Co., Ltd. at +5KV in static mode and, after maintaining in dark place for 5 seconds, exposed at an illumination intensity of 5 lux, to investigate its electrification characteristics. As the electrification characteristics, initial electric potential (V₀), exposure amount necessary for attenuating the potential as attenuated in darkness for 5 seconds the half (E 1/2), residual potential at 5 seconds after the start of exposure (V R ) and charge retention coefficient as attenuated in darkness for 5 seconds (V K ) were measured. Further, in order to measure the fluctuation of potential between lightness and darkness as used repeatedly, the photosensitive member prepared in this Example was sticked on a cylinder of a simplified testing machine for electrophotography characteristics, which is provided with a corona electrifying instrument of +5KV, an optical system for exposure having an exposure amount of 10 lux·sec and an optical system for discharging exposure. Using this testing machine, the initial electric potential in lightness (V L ), the initial electric potential in darkness (V D ) and the potentials in lightness and darkness, V L and V D , at the 1,000 th (1K) and 10,000 th (10K) repeated use, were measured. The results obtained are shown in Tables 1 and 2, together with the results of the following Example 3 - 5. Examples 3 - 5 Photosensitive members having the form shown in Fig. 2 were prepared according to the same manner as Example 2, except that each of the imidazole compounds shown in Tables 1 and 2 by compound numbers (synthesized each from pyromellitic anhydride and the corresponding aromatic diamine in the same manner as Example 1) was used instead of the imidazole compound No. 2 and, as the substrate, was used one prepared by forming an undercoating layer of vinyl chloride/vinyl acetate/maleic anhydride copolymer (Ethulek MF-10, from Sekisui Chemical Co., Ltd.) having a thickness of 0.05 µm on the PET coated with aluminum by vacuum evaporation which was used in Example 2. With these photosensitive members, the same measurements as Example 2 were effected. The results obtained are shown in Table 1 and Table 2. Results of measurements by means of the electrostatic paper analyzer Example Imidazole compound No. V₀ (+V) E 1/2 (lux·sec) V R (+V) V K (%) 2 2 550 9 10 90 3 10 560 13 10 89 4 12 565 16 12 85 5 18 555 18 15 87 Results of evaluation of characteristics on repeated use Example Initial 1 Kth 10 Kth V D (+V) V L (+V) V D (+V) V L (+V) V D (+V) V L (+V) 2 550 10 550 10 545 15 3 560 10 555 15 550 20 4 565 12 560 15 550 20 5 555 15 545 20 540 25 Example 6 A dispersion obtained by dispersing 2 parts by weight of the imidazole compound No. 3, which was prepared in the same manner as Example 1, 15 parts by weight of 2,4,7-trinitro-9-fluorenone and 15 parts by weight of a polycarbonate resin (Iupiron, from Mitsubishi Gas Chemical Company Inc.) in 188 parts by weight of dichloromethane for 12 hours by means of a ball mill disperser, was applied onto the surface of the PET coated with aluminum by vacuum evaporation (the same one as used in Example 2) by means of a Baker applicator and dried at 80°C for 1 hour, whereby a photosensitive member of the form shown in Fig. 3 having a photosensitive layer of 20 µm thick was prepared. Then, the same measurements as Example 2 were effected, except that the corona electrification was performed at -5KV, instead of +5KV in Example 2, in the electrostatic copying test of the photosensitive member. The results obtained are shown in Tables 3 and 4, together with the results of the following Examples 7 - 10. Examples 7 - 10 Photosensitive members having the form shown in Fig. 4 were prepared according to the same manner as Example 6, except that each of the imidazole compounds shown in Tables 3 and 4 by compound numbers (synthesized each from the corresponding starting materials in the same manner as Example 1) was used instead of the imidazole compound No. 3 and, as the substrate, was used one prepared by forming an undercoating layer of a vinyl chloride/vinyl acetate/maleic anhydride copolymer having a thickness of 0.05 µm on the PET coated with aluminum by vacuum evaporation which was used in Example 6. With these photosensitive members, the same measurements as Example 6 were effected. The results obtained are shown in Table 3 and Table 4. Results of measurements by means of the electrostatic paper analyzer Example Imidazole compound No. V₀ (-V) E 1/2 (lux·sec) V R (-V) V K (%) 6 3 570 7 12 89 7 11 595 12 15 91 8 14 600 14 15 90 9 27 590 13 20 92 10 45 615 12 10 90 Results of evaluation of characteristics on repeated use Example Initial 1 Kth 10 Kth V D (-V) V L (-V) V D (-V) V L (-V) V D (-V) V L (-V) 6 570 12 565 15 560 20 7 595 15 595 15 590 25 8 600 15 595 20 590 25 9 590 20 580 20 575 25 10 615 10 610 10 605 20 Example 11 A dispersion obtained by dispersing 2 parts by weight of the imidazole compound No. 1 prepared in Example 1 and 1 part by weight of a phenoxy resin (the same one as used in Example 2) in 97 parts by weight of 1,4-dioxane for 12 hours by means of a ball mill disperser, was applied onto the same PET coated with aluminum by vacuum evaporation as used in Example 2 by means of a Baker applicator and dried at room temperature for 1 hour, whereby a charge-generating layer of 0.5 µm thick was formed. Next, 1 part by weight of a hydrozone series compound represented by the following formula, 1 part by weight of a polycarbonate resin (the same one as used in Example 6) and 8 parts by weight of dichloromethane were mixed together and dissolved by stirring with a stirrer. The solution thus obtained was applied onto the charge-generating layer by means of a Baker applicator and then dried at 80°C for 1 hour, whereby photosensitive member of the form shown in Fig. 5 having a photosensitive layer of 20 µm thick was prepared. The same measurements as Example 6 were effected with regard to this photosensitive member. The results obtained are shown in Tables 5 and 6, together with the results of the following Examples 12 - 15. Examples 12 - 15 Photosensitive members having the form shown in Fig. 6 were prepared according to the same manner as Example 11, except that each of the imidazole compounds shown in Tables 5 and 6 by compound numbers (synthesized each from the corresponding starting materials in the same manner as Example 1) was used instead of the imidazole compound No. 1 and, as the substrate, was used one prepared by forming an undercoating layer of a vinyl chloride/vinyl acetate/maleic anhydride copolymer (the same one as used in Examples 3 - 5) having a thickness of 0.05 µm on the PET coated with aluminum by vacuum evaporation which was used in Example 11. With regard to these photosensitive members, the same measurements as Example 11 were effected. The results obtained are shown in Table 5 and Table 6. Results of measurements by means of the electrostatic paper analyzer Example Imidazole compound No. V₀ (-V) E 1/2 (lux·sec) V R (-V) V K (%) 11 1 690 5 10 92 12 17 610 10 15 90 13 20 615 11 20 89 14 46 620 6 15 94 15 52 610 11 15 84 Results of evaluation of characteristics on repeated use Example Initial 1 Kth 10 Kth V D (-V) V L (-V) V D (-V) V L (-V) V D (-V) V L (-V) 11 600 10 600 10 595 15 12 610 15 605 20 600 25 13 615 20 600 25 595 30 14 620 15 620 15 615 20 15 610 15 610 20 600 25 Example 16 One part by weight of a hydrazone series compound represented by the following formula 1 part by weight of a polycarbonate resin (the same one as used in Example 6) and 8 parts by weight of dichloromethane were mixed together and dissolved by stirring with a stirrer. The solution thus obtained was applied onto the PET coated with aluminum by vacuum evaporation (the same one as used in Example 2), by means of a Baker applicator, and dried at 80°C for 1 hour, whereby a charge-transporting layer having a membrane thickness of 19.5 µm was formed. Next, a dispersion obtained by dispersing 2 parts by weight of the imidazole compound No. 5 (synthesized in the same manner as Example 1) and 1 part by weight of a phenoxy resin (the same one as used in Example 2) in 97 parts by weight of 1,4-dioxane for 12 hours by means of a ball mill disperser, was applied onto the charge-transporting layer by means of a Baker applicator, and then a photosensitive member of the form shown in Fig. 7 having a photosensitive layer of 20 µm thick was prepared. With regard to this photosensitive member, the same measurements as Example 2 were effected. The results obtained are shown in Table 7 and Table 8, together with the results of the following Examples 17 - 20. Examples 17 - 20 Photosensitive members having the form shown in Fig. 8 were prepared according to the same manner as Example 16, except that each of the imidazole compounds shown in Tables 7 and 8 by compound numbers (synthesized each from the corresponding starting materials in the same manner as Example 1) was used instead of the imidazole compound No. 5 and, as the substrate, was used one prepared by forming an undercoating layer of a vinyl chloride/vinyl acetate/maleic anhydride copolymer (the same one as used in Examples 3 - 5) having a thickness of 0.05 µm on the PET coated with aluminum by vacuum evaporation which was used in Example 16. With regard to these photosensitive members, the same measurements as Example 16 were effected. The results obtained are shown in Table 7 and Table 8. Results of measurements by means of the electrostatic paper analyzer Example Imidazole compound No. V₀ (+V) E 1/2 (lux·sec) V R (+V) V K (%) 16 5 590 7 10 92 17 8 595 9 10 89 18 24 600 12 20 85 19 43 595 10 15 88 20 57 620 6 10 90 Results of evaluation of characteristics on repeated use Example Initial 1 Kth 10 Kth V D (+V) V L (+V) V D (+V) V L (+V) V D (+V) V L (+V) 16 590 10 590 10 585 20 17 595 10 590 15 580 25 18 600 20 590 20 580 30 19 595 15 585 20 580 20 20 620 10 590 10 585 15 Comparative Example 1 A photosensitive member was prepared according to the same manner as Example 2, except that a polycyclic quinone series pigment (Monolite Red 2Y, from I.C.I. Ltd.) of the formula was used instead of the imidazole compound No. 2. Then, the same measurements as Example 2 were effected with regard to the photosensitive member. The results obtained are shown in Tables 9 and 10. Comparative Example 2 A photosensitive member was prepared according to the same manner as Example 3, except that a quinacridone series pigment (Cinquasia Red Y RT-759-D, from Ciba-Geigy Ltd.) of the formula was used instead of the imidazole compound No. 10. The same measurements as Example 3 were effected with regard to the photosensitive member. The results obtained are shown in Tables 9 and 10. Comparative Example 3 A photosensitive member was prepared according to the same manner as Example 6, except that an isoindolinone series pigment (Irgazin Yellow 2RLT, from Ciba-Geigy Ltd.) of the formula was used instead of the imidazole compound No. 3. The same measurements as Example 6 were effected with regard to the photosensitive member. The results obtained are shown in Tables 9 and 10. Comparative Example 4 A photosensitive member was prepared according to the same manner as Example 7, except that an inidgo series pigment (Vat Blue 1, from Mitsui Toatsu Dyestuff Inc.) of the formula was used instead of the imidazole compound No. 11. The same measurements as Example 7 were effected with regard to the photosensitive member. The results obtained are shown in Tables 9 and 10. Comparative Example 5 A photosensitive member was prepared according to the same manner as Example 11, except that a thioindigo series pigment (Vat Red 41, from Mitsui Toatsu Dyestuff Inc.) of the formula was used instead of the imidazole compound No. 1. The same measurements as Example 11 were effected with regard to the photosensitive member. The results obtained are shown in Tables 9 and 10. Comparative Example 6 A photosensitive member was prepared according to the same manner as Example 12, except that a xanthene series dyestuff (Eosine Y) of the formula was used instead of the imidazole compound No. 17. The same measurements as Example 12 were effected with regard to the photosensitive member. The results obtained are shown in Tables 9 and 10. Comparative Example 7 A photosensitive member was prepared according to the same manner as Example 16, except that an acridine series dyestuff (Acridine Yellow, from Chroma Ltd.) of the formula was used instead of the imidazole compound No. 5. The same measurements as Example 16 were effected with regard to the photosensitive member. The results obtained are shown in Tables 9 and 10. Comparative Example 8 A photosensitive member was prepared according to the same manner as Example 17, except that a triphenylmethane series dyestuff (Ethylviolet) of the formula was used instead of the imidazole compound No. 8. The same measurements as Example 17 were effected with regard to the photosensitive member. The results obtained are shown in Tables 9 and 10. Results of measurements by means of the electrostatic paper analyzer Comparative Example V₀ (V) E 1/2 (lux·sec) V R (V) V K (%) 1 + 200 54 + 45 80 2 + 300 39 + 55 75 3 - 365 89 - 50 70 4 - 390 32 - 60 75 5 - 400 40 - 30 80 6 - 405 33 - 35 81 7 + 355 45 + 40 76 8 + 370 42 + 45 77 Results of evaluation of characteristics on repeated use Comparative Example Initial 1 Kth 10 Kth V D (V) V L (V) V D (V) V L (V) V D (V) V L (V) 1 + 200 + 45 + 180 + 60 + 165 + 90 2 + 300 + 55 + 270 + 70 + 240 + 105 3 - 365 - 50 - 350 - 65 - 325 - 75 4 - 390 - 60 - 370 - 75 - 330 - 90 5 - 400 - 30 - 390 - 40 - 360 - 55 6 - 405 - 35 - 390 - 50 - 355 - 70 7 + 355 + 40 + 330 + 60 + 305 + 90 8 + 370 + 45 + 340 + 65 + 310 + 100

Claims: A photosensitive member comprising on a conductive support a photosensitive layer containing a compound of the formula (I) or (II): in which each of R and R' is a hydrogen or halogen atom or a hydroxy, C₁-C₅ alkyl, C₂-C₅ alkenyl or C₁-C₅ alkoxy group; an aryl or aralkyl group which may carry one or more substitutents selected from halogen atoms and nitro, cyano, C₁-C₅ alkyl, C₁-C₅ alkoxy and di(C₁-C₅ alkyl)amino groups; a carboxy or sulfo group which may be esterified by an alkyl group or by an aryl group which may be substituted in the manner specified above; a carbamoyl group which may be substituted by methoxyphenyl, nitrophenyl, dimethoxychlorophenyl, carbazolyl, dibenzofuranyl or 3-methoxydibenzofuranyl, or a sulfamoyl group and each of m and n is 1 or 2 or in which each of m and n is 1 and R and R' are the same and in the 5 and 5' positions and each is a carbamoyl group substituted by phenyl, p -methylphenyl, p -chlorophenyl, o -chlorophenyl, o -methyl- p -chlorophenyl, o -methoxy- p -chlorophenyl, o -ethoxyphenyl, 2-naphthyl, 7-bromo-2-naphthyl, N,N-diphenyl, N-methyl-N-phenyl or N-methyl-N- p -methylphenyl or is SO₃Na. A photosensitive member according to claim 1, wherein in the compound of the formula (I) or (II), each of R and R' is a chlorine or bromine atom. A photosensitive member according to claim 1, wherein in the compound of the formula (I) or (II), each of R and R' is a methyl or ethyl group. A photosensitive member according to claim 1, wherein in the compound of the formula (I) or (II), each of R and R' is a methoxy, ethoxy or propoxy group. A photosensitive member according to claim 1, wherein in the compound of the formula (I) or (II), each of R and R' is a phenyl group which may be substituted in the manner specified in claim 1. A photosensitive member according to claim 1, wherein in the compound of the formula (I) or (II), each of R and R' is a carbamoyl group substituted by a p-methoxyphenyl, m-nitrophenyl, carbazolyl, 2-5-dimethoxy-4-chlorophenyl or 3-methoxy dibenzofuranyl group. A photosensitive member according to any one of claims 1 to 6, wherein the photosensitive layer is of the multilayer type and consists of a charge-generating layer and a charge-transporting layer, the former containing the compound of the formula (I) or (II). A photosensitive member according to claim 7, wherein the charge-generating layer has a thickness of 0.01 to 20 µm. A photosensitive member according to claim 7 or claim 8, wherein the charge-transporting layer has a thickness of 2 to 100 µm.

Inventors: IMADA EIJI, KATAYAMA SATOSHI, TSUCHIMOTO SHUHEI, IMADA, EIJI, KATAYAMA, SATOSHI, TSUCHIMOTO, SHUHEI
Applicants: SHARP KK, SHARP KABUSHIKI KAISHA
Application year: 1988
Main classification: C07D487
IPC codes: G03G5, C07D487, C09B57