Layered electrophotographic recording medium comprising heterocyclic nitrogen containing organic dye compounds
This is a continuation of application Ser. No. 358,591, filed Mar. 16, 1982, abandoned. 
    
    
     The present invention relates to an electrophotographic recording medium which consists of an electrically conductive base and a photosemiconductive double layer composed of organic materials, and to a process for the production of this electrophotographic recording medium. 
     In order to produce an image electrophotographically, a uniform electrostatic charge is first applied to the surface of an electrophotographic element containing a photosemiconductive layer. When the element is exposed imagewise to actinic radiation, i.e. radiation which induces photosemiconduction, the exposed areas of the photosemiconductive layer become electrically conductive and, as a result, the surface electrostatic charge flows away at these points provided that the electrically conductive base is earthed. In contrast, the unexposed points retain their surface charge, so that a charge image corresponding to the original is obtained after exposure. If this charge image is treated with very fine pigment particles which have been charged beforehand oppositely to the surface charge of the electrophotographic element, these pigment particles collect at the unexposed points of the electrophotographic element and thus convert the invisible charge image into a visible image of the original. The image obtained in this manner is then transferred to another surface, for example onto paper, and is fixed thereon. 
     The electrophotographic element may comprise either one homogeneous layer of a photosemiconductor, or a plurality of layers one on top of another, on an electrically conductive base. Electrophotographic recording media having a multi-layer composite structure have been described. For example, German Laid-Open Application DOS No. 2,220,408 discloses materials of this type which comprise a conductive base, a first layer containing charge-producing compounds, and, in addition to this layer, a second layer containing charge carrier-transporting substances. 
     In addition to the inorganic photosemiconductors, the majority of which are based on selenium, a number of organic photosemiconductors are also known for use in the charge carrier-producing layers. However, a large number of organic dyes which have been described and which can be used as charge carrier-producing dyes when exposed to actinic light have to be deposited on the base by vaporization or sublimation under greatly reduced pressure and at above 300° C. (cf., for example, German Laid-Open Application DOS Nos. 2,220,408 and 2,239,924). Such processes are not very economical and, in many cases, the results cannot easily be reproduced. Moreover, only dyes which are extremely stable thermally are suitable for these processes. In the field of electrophotography, however, it is desirable to have a very wide range of dyes available for use as active constituents. 
     Another group of charge-producing photoconductive organic materials is dispersed, in the form of pigment particles, in a matrix binder, and a layer of this dispersion which contains the individual photoconductive particles is applied to a substrate. These are electrophotographic elements which have been described in the literature and which contain monoazo, disazo and quadratic acid dye derivatives as coloring materials (cf. inter alia U.S. Pat. Nos. 3,775,105, 3,824,099 and 3,898,084). 
     German Laid-Open Application DOS No. 2,635,887 has also proposed dissolving monoazo or disazo dyes, or the dye derivatives or quadratic acid, in a solvent containing primary organic amines, and applying the charge-producing layer from the solution, but a disadvantage of this procedure is that amines pollute the environment to a great extent and are also unpleasant for the processing personnel. 
     There has therefore been no lack of attempts to produce the individual layers of the composite structure of an electrophotographic element in a very simple manner. To achieve this, however, novel dyes are required as charge-producing components. 
     It is an object of the present invention to provide an extremely photosensitive electrophotographic layer using organic photosemiconductors, which can be produced from a dye dispersion in a very simple manner. It is a further object of the invention to provide an electrophotographic element which is flexible, resilient and resistant to abrasion, and whose surface is smooth and free from furrows, without it being necessary to carry out an aftertreatment. 
     We have found that these objects are achieved with an electrophotographic recording medium which comprises 
     (a) an electrically conductive base, 
     (b) a first layer, from 0.005 to 5 μm thick, which contains charge carrier-producing dyes of a particular type, and 
     (c) a second layer which is substantially transparent to actinic light and is composed of insulating organic materials containing one or more compounds which are charge carrier-transporting when exposed to light. 
     Accordingly, the present invention relates to dyes which are effective, in the first layer of the electrophotographic recording medium, as charge carrier-producing components. 
     It is surprising that a layer containing dyes of the class described below meets the requirements in respect of a high-hiding, charge carrier-producing layer which is suitable for the electrophotographic recording medium. Dyes suitable for this purpose are those of the general formula I ##STR2## where R 1 , R 2 , R 3 , and R 4  are each hydrogen, halogen, methyl or phenylthio, and one or two of the radicals R 1 , R 2 , R 3  and R 4  are C 2  -C 6  -alkyl, cyclohexyl, phenyl, naphth-2-yl, hydroxyl, C 1  -C 6  -alkoxy, allyloxy, phenoxy, methylthio, benzylthio, C 1  -C 4  -alkylsulfonyl, phenoxysulfonyl, trimethylsilyl, trifluoromethyl, cyano, nitro, amino, N,N-C 1  -C 4  -dialkylamino, a radical of the formula ##STR3## a radical of the formula NH.CO.R 5 , where R 5  is C 1  -C 6  -alkyl, or unsubstituted or substituted aryl, or are C 1  -C 4  -alkylcarbonyl, phenylcarbonyl or C 1  -C 4  -alkoxycarbonyl, and the remaining radicals are each hydrogen, X and Y may be identical or different and each is the radical of a methylene-active compound (&gt;C═) or a radical of the formula ═N-R 6 , where R 6  is the radical of an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic amine or hydrazine, and Z is hydrogen, methyl or phenyl. 
     Further suitable compounds are those of the formula II ##STR4## where R 7  and R 8  may be identical or different and each is C 1  -C 4  -alkyl, cyclohexyl or phenyl or R 7  and R 8  together are a tetramethylene group, or an aromatic heterocyclic or saturated heterocyclic 5-membered or 6-membered ring, and X, Y and Z have the meanings given above, and those of the formulae III, IV and V ##STR5## where X, Y and Z have the meanings given above. 
     Preferred compounds are those of the formula VI ##STR6## where R 9  and R 10  may be identical or different and each is cyano, nitro, 4-halophenyl, 4-cyanophenyl, 4-nitrophenyl, C 1  -C 8  -alkoxycarbonyl, phenoxycarbonyl or a radical of the formula --CONH--R 11 , where R 11  is hydrogen or C 1  -C 9  -alkyl or is phenyl which is unsubstituted or substituted by phenoxy, cyano, nitro, CF 3 , up to three halogens C 1  -C 4  -alkyl or C 1  -C 4  -alkoxy, or is the radical of a heterocyclic amine, or R 9  and R 10  are each sulfamyl, phenylsulfonyl which is substituted by up to three halogens and/or C 1  -C 4  -alkyl in the phenyl nucleus, or a radical of the formula ##STR7## where A is --O--, --S--, or &gt;N--R, R is hydrogen or C 1  -C 4  -alkyl, and R 12  and R 13  are each hydrogen, halogen, C 1  -C 4  -alkyl or C 1  -C 4  -alkoxy, or R 9  and R 10  are each 1H-naphth-2,3-d-imidazolyl, pyridyl, thiazol-4-yl, 2-methylthiazol-4-yl, 2-phenyl-1,3,4-thiadiazol-5-yl, cuinolin-2-yl, indol-3-yl or benzthiazol-3-yl. 
     Particularly preferred compounds are those of the formula VII ##STR8## where R 14  and R 15  may be identical or different and each is cyano, methylcarbonyl, phenylcarbonyl, 4-nitrophenyl, 4-cyanophenyl, C 1  -C 6  -alkoxycarbonyl, phenoxycarbonyl, phenylsulfonyl or a radical of the formula ##STR9## where A, R 12  and R 13  have the meanings given above. 
     Very particularly preferred compounds are those of the formula VIII ##STR10## where R 16  and R 17  may be identical or different and each is cyano, 4-nitrophenyl, 4-cyanophenyl, C 1  -C 4  -alkoxy carbonyl, phenylsulfonyl or a radical of the formula ##STR11## where R 12  and R 13  are each hydrogen, halogen, C 1  -C 4  -alkyl or C 1  -C 4  -alkoxy, and R 19  is hydrogen or C 1  -C 4  -alkyl, or R 16  and R 17  are each 1H-naphth-2,3-d-imidazolyl, pyridyl, thiazol-4-yl, 2-methylthiazol-4-yl, 2-phenyl-1,3,4-thiadiazol-5-yl, quinolin-2-yl, indol-3-yl or benzthiazol-3-yl. 
     Further preferred compounds are those of the formula IX ##STR12## where R 9  has the meanings given above and B is the complement needed to form a five-membered or six-membered isocyclic or heterocyclic ring. 
     Particularly useful compounds are those of the formula X ##STR13## where R 14  has the meanings given above and B is the complement needed to form a pyrazolone, oxazolone, dimedone, pyridone, isoxazolone, imidazolone, cyclohexanedione or 4-hydroxy-coumarin radical, or ##STR14## is a radical of the formula ##STR15## 
     Further preferred compounds are those of the formula XI ##STR16## where R 9  has the meanings given above and R 6&#39;  is the radical of an aromatic or heterocyclic amine or hydrazine. Compounds of the formula XII ##STR17## where R 14  has the meanings given above, and R 18  is phenyl, p-tolyl, anisid-2-yl, anisid-4-yl, 2- or 4-chlorophenyl, 4-carbethoxyphenyl, oxazol-2-yl, thiazol-2-yl, imidazol-2-yl, 4-phenylthiazol-2-yl, 4-methyl-5-carbethoxythiazol-2-yl, benzthiazol-2-yl, 6-ethoxybenzthiazol-2-yl, benzimidazol-2-yl, 1-methylbenzimidazol-2-yl, 5-phenyl-1,3,4-thiadiazol-2-yl, or indazol-3-yl, are similarly suitable. 
     Compounds of the formula XIII ##STR18## where R 6  has the meanings given above, and B is the complement needed to form a five-membered or six-membered isocyclic or heterocyclic ring, are also preferred. 
     Particularly preferred compounds are those of the formula XIV ##STR19## where R 18  and B have the meanings given above. 
     Preferred compounds are also those of the formula XV ##STR20## where R 6  has the meanings given above and the radicals R 6  may be identical or different, as well as compounds of the formula XVI ##STR21## where R 18  has the meanings given above and the radicals R 18  may be identical or different. 
     The compounds mentioned are described in the literature, and may be prepared by the processes described in German Laid-Open Applications DOS Nos. 1,670,748, 2,121,524, 2,142,245 or 2,830,501, for example according to the following equation: ##STR22## 
     To prepare the novel electrophotographic recording medium, the first charge carrier-producing layer is applied, as a dispersion, to the electrically conductive base. The dispersion used for the first layer is prepared by tumbling about 20-85 percent by weight, based on the solids content of the dispersion, of one or more of the dyes which are suitable according to the invention with 80-15 percent by weight of a binder which is conventionally used for this purpose and which may or may not possess the characteristics of a barrier layer, in the form of a solution in a highly volatile organic solvent. 
     The first layer is cast so that a dry layer about 0.005-5 μm, preferably 0.05-2.0 μm thick, results. An adhesive layer about 0.05-5 μm, preferably 0.1-0.8 μm, thick may be located between the base and the first layer. 
     The transparent second layer, preferably 2-40 μm thick, is located on top of the first layer, and is also cast from a solution. It is composed of from 30 to 60 percent by weight of one or more charge carrier-transporting compounds, from 65 to 35 percent by weight of one or more binders conventionally used for this purpose, and from 0.1 to 4 percent by weight of additives which improve the mechanical properties, with or without up to 5 percent by weight of sensitizers or activators. The layer is cast from a low-boiling solvent. 
     A barrier layer about 0.05 to 1.5 μm, preferably 0.1 to 0.5 μm, thick may be located between the first and second layers, and, depending on the intended use of the electrophotographic recording medium, it may be appropriate to apply an inactive, protective top layer to the charge carrier-transporting layer. 
     Suitable electrically conductive bases are aluminum foils, aluminum sheet or nickel sheet, or plastic films, preferably polyester films, coated by vapor deposition with aluminum, tin, lead, bismuth or a similar metal. The choice is influenced by the field of use of the electrophotographic element. 
     The barrier layer between the conductive base and the first layer, or between the latter and the second layer, usually consists of a metal oxide, e.g. aluminum oxide, or a polymer, e.g. a polyamide, polyvinyl alcohol, a polyacrylate or polystyrene, or a similar system. However, the binder of the first layer may also be used as the barrier layer material, if desired. 
     Polyacrylates, polymethacrylates, polyesters, polyphthalates, polyvinyl chlorides, styrene/maleic acid copolymers, epoxides and other conventional resins are suitable binders for accomodating the dyes according to the invention in the production of the charge carrier-producing layer which forms part of the novel electrophotographic recording medium. 
     Suitable binders for the second, charge carrier-transporting layer are in particular polyvinyl chloride, polyester resins, polyacetal resins, polycarbonates, polystyrene and polyurethanes, i.e. those binders which are known by the skilled worker to possess special electrical properties. Thus, silicone resins, polyvinyl acetate, chlorinated rubber, cellulose esters, ethylcellulose and the like may also be used. Suitable charge carrier-transporting compounds present in this layer are those which do not adversely affect the transparency to visible light, for example 
     (a) low molecular weight compounds, in particular heterocyclic compounds, e.g. pyrazoline derivatives, oxazoles, oxadiazoles, phenylhydrazones, imidazoles, triphenylamine derivatives, carbazole derivatives and pyrene derivatives, and other condensed aromatic compounds, and 
     (b) polymeric materials, for example polyvinylpyrenes, poly(N-vinylcarbazole), copolymers of carbazole and styrene and/or vinyl acetate and/or vinyl chloride. 
     Of the polymers, poly(N-vinylcarbazole), is particularly suitable. 
     The novel electrophotographic recording media may also contain further constituents to improve their mechanical properties. Thus, wetting agents, for example silicone oils, can improve the surface quality. Moreover, sensitizers or activators may additionally be incorporated into the upper, second layer. Examples of conventional sensitizers, which may be dispersed, are triphenylmethane dyes, xanthone dyes and soluble perylene derivatives, e.g. perylenetetracarboxylic acid esters. Compounds having a high electron affinity, for example nitro compounds, such as 2,4,7-trinitrofluoren-9-one, may be used as activators. 
     The novel electrophotographic recording medium contains very photosensitive photosemiconductive double layers which possess high mechanical stability and can run continuously, for example attached to the surface of a cylindrical drum or as an endless belt, without exhibiting signs of wear. Accordingly, they are very useful for reproduction work, for example as copying layers or electrophotographic offset printing plates. 
     The Examples which follow illustrate the invention. 
    
    
     EXAMPLES 1 TO 17 
     5 g of each of the dyes 1 to 17 were mixed with 3 g of a copolymer of vinyl chloride, acrylic acid and a maleic acid diester, and 25 g of tetrahydrofuran, and the mixture was tumbled on a roller-stand for 12 hours. Thereafter, 75 g of tetrahydrofuran and 25 g of toluene were added, and the mixture was homogenized on the roller-stand for one hour. 
     This dispersion was then applied with a knife-coater to a base of 175 μm thick untreated aluminum sheet. A 60 μm casting slot was used, and the speed of the knife-coater was 260 mm/minute. After the solvent had been allowed to evaporate off in the air and drying had been effected for 30 minutes at 90° C., a 0.75-0.8 μm thick dry layer resulted. 
     A solution of 47.75 g of poly(N-vinylcarbazole), 5.2 g of dihexyl phthalate and 5.75 g of a polycarbonate of melting point 220°-230° C. in a mixture of 287.5 g of tetrahydrofuran and 74.25 g of toluene was applied to the first, high-hiding layer in each case. A casting slot of 140 μm was used, and the speed of the knife-coater was 260 mm/minute. After the solvent had been allowed to evaporate off in the air and drying had been effected for 30 minutes at 90° C., an 8-8.5 μm thick dry layer was obtained. 
     The electrophotographic element prepared in this manner was subjected to -7.40 kV with a corona wire at a distance of 10 mm above the surface of the layer. After a loading period of 20 seconds, the maximum surface potential achieved was determined in volts. This surface potential was compared with the surface potential of a plate produced in an identical manner and, according to German Laid-Open Application DOS No. 2,237,539, containing N,N&#39;-dimethylperylene-3,4,9,10-tetracarboxylic acid diimide, the surface potential of this plate being taken as 100%. After a further 20 seconds in the dark, the decrease in potential as a percentage of the maximum potential was determined. The electrophotographic element was then exposed to light from a 150 watt xenon lamp, and the light-induced decrease in potential, as a percentage of the potential after it has decreased in the dark, was determined. 
     The results of the measurements are summarized in Table 1. ##STR23## 
     EXAMPLES 18 TO 35 
     Using a procedure similar to that of Examples 1 to 17, electrophotographic elements were produced which contained, as the base, an aluminum sheet having an anodized aluminum layer about 0.25 μm thick, instead of untreated aluminum sheet, but were otherwise identical. The results obtained with these elements were substantially the same as those listed in Table 1. 
     
                       TABLE I                                                     
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       Relative                                                           
       surface     Decrease  Decrease on                                  
       potential   in the dark                                            
                             exposure to light                            
Dye    in %        in %      in %                                         
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1      136         15.3      87.8                                         
2      138         9.8       74.7                                         
3      129         6.0       80.3                                         
4      134         7.0       81.2                                         
5      122         11.0      76.2                                         
6      124         12.7      77.0                                         
7      122         30.9      65.3                                         
8      137         20.1      91.4                                         
9      138         11.6      89.4                                         
10     111         25.1      75.1                                         
11     122         30.1      87.2                                         
12      80         8.3       65.1                                         
13     115         16.9      86.6                                         
14     122         16.4      84.1                                         
15     121         11.8      85.4                                         
16     115         22.9      77.3                                         
17     141         16.0      92.1                                         
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