JP2643465C - - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic photoreceptor, and more particularly, to an electrophotographic photoreceptor optimally used for a positive charging system consisting essentially of a charge generating agent and a binder polymer. 2. Description of the Related Art Organic photoreceptors (abbreviated as OPCs) are more cost-effective than inorganic photoreceptors because they can synthesize materials that are highly sensitive to various wavelengths by molecular design, are non-polluting, are highly productive and economical, and are inexpensive. It is characterized by the fact that active research and development are currently being conducted. Also, remarkable improvements have been made in durability and sensitivity, which have hitherto been problems of organic photoreceptors, and some of them have been put to practical use, and are now becoming the mainstay of electrophotographic photoreceptors. The OPC usually has a double-layer structure of a charge generation layer (abbreviated as CGL) that absorbs light to generate carriers and a charge transfer layer (abbreviated as CTL) that moves generated carriers. Have been. Materials used for CGL (abbreviated as CGM)
Various organic materials such as various perylene compounds, various phthalocyanine compounds, thiapyrylium compounds, anthranthrone compounds, squarylium compounds, bisazo compounds, trisazo pigments, and azurenium dyes have been studied. On the other hand, as a material (abbreviated as CTM) used for CTL, various hydrazone-based compounds, oxazole-based compounds, triphenylmethane-based compounds, arylamine-based compounds, and the like have been developed. These materials are formed on a substrate such as a drum or a belt by a relatively simple coating method together with a binder polymer. Examples of the binder polymer used for such purposes include polyester resin, polycarbonate resin, acrylic resin, and acrylic resin.
Styrene resin, and the like. In general, in such a double-layer structure, CG
The layer is applied with a thickness of a few microns, while the CT layer is applied with a thickness of tens of microns. At this time, the CG layer is usually formed on the substrate side and the CT layer is formed on the surface side for reasons such as strength and printing durability. In such a configuration, since only the CTM that operates by the movement of holes is put into practical use, the double-layer photosensitive member is of a negative charging type. Problems to be Solved by the Invention However, such a negative charging method has a problem that oxygen in the air becomes ozone due to negative charges used for charging. Ozone is not only harmful to the human body, but also has a problem that it often reacts with the photoreceptor to shorten the life of the photoreceptor. Further, in such a two-layer system, there are problems such as (1) the production process becomes complicated, and (2) the stability thereof due to delamination between layers and the like. In order to solve such problems, the development of an organic photoreceptor using a positive charging system is currently active. Conventionally, to achieve positive charging, (1) an inverted two-layer structure in which the CGL layer and the CTL layer are configured in reverse to the case of negative charging, and (2) a simple structure in which various CGMs and CTMs are dispersed in a binder polymer. Layer structures have been considered. In the case of the inverted two-layer structure, the problem of the complexity of the manufacturing process and the problem of delamination as in the case of the negative charging method cannot be solved. In addition, the CGL layer, which essentially needs to be thinner, is placed on the surface of the photoreceptor, reducing print resistance,
Deterioration of life characteristics is a problem. On the other hand, the single-layer type photoreceptor aiming at positive charging was inferior to the two-layer type in terms of sensitivity, charging characteristics (charging for charging is difficult to take), and residual potential. The reason for the inferior sensitivity was that the generation and transfer of charges occurred randomly in a single layer, and the problems of the single-layer photoreceptor were sensitivity, charging characteristics, and residual potential. As described above, all of the conventional OPCs have some problems. Therefore, if a single-layer type positively charged photoreceptor can realize the same high sensitivity, residual potential, and charging characteristics as those of the two-layer type, it is considered to be an ideal photoreceptor. SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the conventional OPC and to provide an electrophotographic photosensitive member having high performance, high sensitivity and excellent durability. Means for Solving the Problems In order to solve the above problems, we have studied positively charged single-layer organic photoconductors having various configurations. As a result, various perylene compounds, various phthalocyanine compounds, thiapyrylium compounds, anthuanthrone compounds,
Using a squarylium-based compound, a bisazo-based compound, a trisazo pigment, an azurenium dye, and the like, and further adding an appropriate amount of X-type or τ-type phthalocyanine to these CGMs and combining them with an appropriate binder polymer, a binder An electrophotographic photosensitive member having a single-layer photosensitive layer in which an X-type phthalocyanine or τ-type phthalocyanine and a charge generating agent are dispersed in a polymer, wherein at least a part of the X-type phthalocyanine or τ-type phthalocyanine has a binder height. Molecular dispersion in the molecule,
The present inventors have newly found that an electrophotographic photoconductor in which a charge generating agent is dispersed in a particulate form in a binder polymer exhibits excellent photosensitive characteristics in a positive charging system, and have reached the present invention. As described above, the first feature of the configuration of the present invention is that CTM is not included.In such a configuration, the conventional single-layer organic photoreceptor is formed from a mixture of CGM and CTM. This is a configuration substantially different from that of FIG. As described above, the configuration of the present invention does not require CTM, which has been regarded as essential, but has the ability of charge transfer under the condition that the added X-type or τ-type phthalocyanine is added. This shows that, unlike conventional CTMs, it has the ability to transfer negative charges. We examined such conditions in various ways, and revealed that such positive charge transfer ability is due to X-type or τ-type phthalocyanine molecularly dispersed in a binder polymer. On the other hand, the charge generation ability mainly depends on the charge generating agent dispersed in the binder polymer in the form of particles. That is, the second feature of the present invention resides in the presence of a molecularly dispersed X-type or τ-type phthalocyanine and a particle-dispersed charge generator in a single layer. The organic photoconductor having such a configuration has the following features as compared with the conventional photoconductor. The single-layer structure simplifies the manufacturing process. It has much higher sensitivity than conventional single-layer OPC. In particular, it exhibits excellent characteristics in a positive charging system. Superior in stability and special electrical properties compared to conventional single-layer OPC. Since it has a single layer structure, it has excellent printing resistance. As is apparent from the above description, in this case, it is necessary that at least a part of the X-type or τ-type phthalocyanine is molecularly dispersed in the polymer binder. In order to realize such a molecular dispersion, it is necessary to dissolve X-type or τ-type phthalocyanine in a suitable solvent and to select a polymer soluble in this solvent as a binder. Solvents for dissolving X-type or τ-type phthalocyanine suitable for such purposes include nitrobenzene, chlorobenzene, dichlorobenzene, dichloromethane, trichloroethylene, chlornaphthalene, methylnaphthalene, tetrahydrofuran,
Examples include cyclohexanone, 1.4-dioxane, N-methylpyridone, carbon tetrachloride, brombutane, sulfolane, ethylene glycol monobutyl ether, acetoxyethoxyethane, and the like. On the other hand, solvents such as acetone, cyclohexane, petroleum ether, nitromethane, methoxyethanol, dimethylformamide, dimethylacetamide, acetonitrile, dimethylsulfoxide, ethyl acetate, isopropyl alcohol, diethyl ether, methyl ethyl ketone, ethanol, hexane, propylene carbonate, butylamine, water, etc. Or do not dissolve X-type or τ-type phthalocyanine. Therefore, these solvents cannot be used alone in the present invention. When these solvents are used, they need to be used in combination with the above-mentioned solvents that dissolve the X-type or τ-type phthalocyanine. Examples of the charge generating material preferably used in the present invention include phthalocyanine compounds, perylene compounds, thiapyrylium compounds, anthranthrone compounds, squarylium compounds, bisazo compounds, various phthalocyanine pigments, trisazo pigments, azurenium dyes, and the like. There is. Representative examples of these CGMs are shown below. As the binder polymer according to the present invention, those having a common solvent with the above-mentioned X-type or τ-type phthalocyanine are preferable. Suitable polymers for these purposes include polyester, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyvinyl butyral, polyvinyl acetoacetal, polyvinyl formal, polyacrylonitrile, polymethyl methacrylate, polyacrylate, and These copolymers, poly (vinyl chloride / vinyl acetate / vinyl alcohol), poly (vinyl chloride / vinyl acetate / maleic acid), poly (ethylene / vinyl acetate), poly (vinyl chloride / vinylidene chloride), cellulose-based high Molecules, etc. are raised. These polymers are used alone or as a mixture of two or more. Of course, as described above, it is possible to combine two or more solvents, dissolve the X-type or τ-type phthalocyanine with one solvent, and dissolve the binder polymer with another solvent, so that the present invention is applied. The binder polymer is not limited to the above polymers. The optimum ratio between the weight of the above-mentioned X-type or τ-type phthalocyanine and the charge generator plus the weight of the binder polymer is between 1: 1 and 1:10. X-type or τ-type phthalocyanine is required to be 10% by weight or more with respect to various charge generating agents. When the amount of the binder polymer is smaller than this range, the photosensitive property (potential attenuation property by light) itself is excellent, but the charging property is deteriorated, and it is generally difficult to apply a potential of 300 V or more. On the other hand, when the amount of the binder polymer is larger than the above range, the photosensitive characteristics deteriorate. In conventional single-layer OPC, CTM and CGM have been used in a mixture. CTMs for such purposes include hydrazone-based compounds, oxazole-based compounds, triphenylmethane-based compounds, and arylamine-based compounds. Addition of these materials has little effect on the photosensitive characteristics when the addition amount is 5% or less. However, when the addition amount is 5% or more, the photosensitive characteristics and the stability of charging are significantly deteriorated. In other words, the configuration of the present invention
CTM has a bad impact and essentially doesn't need it. By such a combination of materials, for example, a yarn using X-type phthalocyanine, a trisazo compound, and polyvinyl butyral in a weight ratio of 0.2: 0.4: 1.8 (see Example 1) has a half-exposure sensitivity of 1.6 lux due to positive charging. High sensitivity (charge potential of 600V) of .sec was realized. On the other hand, the sensitivity due to negative charging was 12 lux.sec (charging potential 120 V), and the characteristics were remarkably inferior to positive charging. This system was also very stable, and the characteristics due to positive charging hardly changed even after 1000 repeated tests. The conductive support serving as the substrate of the organic photoconductive layer is not particularly limited, and can be appropriately selected depending on the intended use and the like. Specifically, a metal such as aluminum, or a material in which a conductive layer is formed on a surface of glass, paper, plastic, or the like by metal vapor deposition or the like is preferably used. Also, the shape of the drum,
It can take various shapes such as a belt shape and a sheet shape. The electrophotographic photoreceptor according to the present invention described above can be used in various recording systems such as a copying machine, a printer, a facsimile, and the like, and its use is not limited at all. The electrophotographic photoreceptor according to the present invention is not limited to the above examples. For example, if necessary, a surface protective layer made of an insulating resin may be formed on the organic photoreceptor layer, It is also possible to provide a blocking layer between the substrate and the substrate. Action The positively charged single-layer OPC according to the present invention has an unconventional structure, can realize excellent characteristics as a photoconductor, and has the following features as compared with the conventional photoconductor. The single-layer structure simplifies the manufacturing process. It has much higher sensitivity than conventional single-layer OPC. In particular, it exhibits excellent characteristics in a positive charging system. Superior stability and chargeability compared to conventional single-layer OPC. Since it has a single layer structure, it has excellent printing resistance. Examples Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. -Example 1-X-type metal-free phthalocyanine (abbreviated as XPc, manufactured by Dainippon Ink Co., Ltd., Fastogen Blue 8120B), literature (Ricoh Technical Report No. 8 Nov)
trisazo compound synthesized by the method of ember, 14 (1982) (the compound (13))
, And polyvinyl butyral (abbreviated as PVB, SREC BM manufactured by Sekisui Chemical Co., Ltd.)
After dissolving and dispersing the three kinds of components consisting of -2) in tetrahydrofuran and sufficiently mixing and kneading, the resulting solution is applied on an aluminum drum by a dipping method, and treated at 120 ° C for 1 hour in a vacuum. And an OPC layer (10 to 20 μm in thickness). The photosensitivity of the photoreceptor thus obtained was measured using a paper analyzer manufactured by Kawaguchi Electric Co., Ltd., using an EPA-8100 type paper analyzer. The measurement was performed, and the photosensitivity after 1000 repeated tests was measured in the same manner. Table 1 shows the characteristics when the weight ratio of XPc, compound (13), and PVB was variously changed. As is clear from the results, the weight ratio of XPc + (13) to PVB was from 1: 1 to 1:10.
The composition is in this range, and good characteristics can be obtained in both charging characteristics and sensitivity characteristics. Also, it can be seen that good characteristics are provided when the ratio of XPc to (13) is in the range of 1:10 to 5: 1. Comparative Example 1 For comparison, characteristics when the mixed solvent of acetone and DMF is used as a solvent in the same configuration as in Example 1 are shown. Acetone and DMF dissolve PVB but not XPc. Therefore, in such a production method, it is considered that XPc is mixed in the form of particles in the PVB, and that there is no XPc dispersed in the molecular form. Table 2 shows the results. As shown in the results, the sensitivity due to positive charging, E1 / 2, is significantly worse than the results in Table 1, and for the present invention, a part of XPc is dispersed in a binder in a polymer in a polymer state. It is necessary to understand that it is necessary. -Example 2-τ-type metal-free phthalocyanine (abbreviated as τPc, manufactured by Toyo Ink Co., Ltd., Liophon THP), literature (Ricoh Techinica)
l Trisazo compound synthesized by the method of Report No.8 Novemper, 14 (1982) (
Compound (13)) and polyvinyl butyral (abbreviated as PVB, Sekisui Chemical (
Esrec HB-2) manufactured by Teijin Co., Ltd. was dissolved in tetrahydrofuran, and thoroughly mixed and kneaded, and the obtained solution was applied on an aluminum drum by a dipping method.
C. for 1 hour to form an OPC layer (10-20 .mu.m thick). The photosensitive characteristics of the photoreceptor thus obtained were irradiated with white light using tungsten using a paper analyzer manufactured by Kawaguchi Electric Co., Ltd. EPA-8100, and the photosensitivity due to positive charge (half exposure,
E1 / 2) was measured, and the photosensitivity after 1000 repeated tests was measured in the same manner. Table 3 shows the characteristics when the weight ratio of τ-type phthalocyanine, compound (13), and PVB was variously changed. From this result, it was clarified that the τ-type phthalocyanine exhibited excellent photosensitive characteristics similarly to the X-type phthalocyanine. -Example 3-X-type metal-free phthalocyanine (abbreviated as Xpc, Fastogen Blue 8120B, manufactured by Dainippon Ink and Chemicals, Inc.), the compound (13), and various binder polymers were used in a ratio of 0.2: 0.4: 1.8. After dissolving in tetrahydrofuran and thoroughly mixing and kneading, the resulting solution was applied on an aluminum drum by a dipping method,
By treating at 0 ° C. for 1 hour, an OPC layer (10 to 20 μm in thickness) was formed. The photosensitivity of the photoreceptor thus obtained was measured using a paper analyzer manufactured by Kawaguchi Electric Co., Ltd., using an EPA-8100 type paper analyzer. The measurement was performed, and the photosensitivity after 1000 repeated tests was measured in the same manner. Table 4 shows the results. As is clear from this result, when XPc is dispersed in a molecular state and the compound (13) is dispersed in a particle state, it is possible to form a photoreceptor having excellent characteristics without being affected by the kind of the polymer. Can be done. -Example 4-X-type metal-free phthalocyanine (abbreviated as XPc, manufactured by Dainippon Ink Co., Ltd., Fastogen Blue 8120B), various CGMs described above, and polyvinyl butyral (abbreviated as PVB, Sekisui Water) 3 consisting of S-LEC BM-2) manufactured by Chemical Industry Co., Ltd.
The types of components were mixed at a weight ratio of 0.2: 0.4: 1.8, dissolved and dispersed in tetrahydrofuran, sufficiently mixed and kneaded, and the obtained solution was applied on an aluminum drum by a dip method, and then vacuumed at 120 ° C. By treating for 1 hour, an OPC layer (10 to 20 μm in thickness) was formed. The photosensitivity of the photoreceptor thus obtained was measured using a paper analyzer manufactured by Kawaguchi Electric Co., Ltd., using an EPA-8100 type paper analyzer. The measurement was performed, and the photosensitivity after 1000 repeated tests was measured in the same manner. Table 5 shows the results. As is evident from the results, the method of the present invention uses various conventionally known methods.
Applicable to CGM. Each of these CGMs has an excellent charge generation ability with respect to light of a specific wavelength, so that a characteristic photoreceptor can be obtained in each system. -Example 6- Among the photoreceptors prepared by the method of Example 1, the ratio of XPc, compound (13), and PVB was 0.3%.
2: 0.4: 1.8 was selected and a continuous print resistance test was performed. The test was performed using A4 test paper, and it was found that the device operated stably for 30,000 continuous tests. Thus, it was found that the method of the present invention is superior in terms of printing durability as compared with the conventional two-layer type photoreceptor or single-layer type photoreceptor. EFFECT OF THE INVENTION As described above, the electrophotographic photoreceptor according to the present invention has an electrophotographic photosensitive member having a single-layer photosensitive layer in which an X-type phthalocyanine or a τ-type phthalocyanine and a charge generating agent are dispersed in a binder polymer. Wherein the X-type phthalocyanine or the τ-type phthalocyanine is at least partially dispersed in the binder polymer in molecular form, and the charge generator is dispersed in the binder polymer in particulate form. Photoreceptor, which can be suitably used as a positive charge, has higher sensitivity and higher stability than conventional photoreceptors, and has a remarkably easy manufacturing method. It is expected to be applied to various recording devices and the like as an electrophotographic photosensitive member.

Claims (1)

Claims 1. An electrophotographic photoreceptor having a single-layer photosensitive layer in which a metal-free X-type phthalocyanine or a metal-free τ-type phthalocyanine and a charge generating agent are dispersed in a binder polymer. The non-metallic X-type phthalocyanine or the non-metallic τ-type phthalocyanine is
An electrophotographic photoreceptor wherein at least a part thereof is molecularly dispersed in the binder polymer, and the charge generating agent is particulately dispersed in the binder polymer. 2. The weight ratio of the weight of the binder polymer to the weight of the metal-free X-type phthalocyanine or metal-free τ-type phthalocyanine and the charge generating agent in a ratio of 1: 1 to 1:10.
2. The electrophotographic photoreceptor according to claim 1, wherein