JP5645076B2 - Electrophotographic photosensitive member, electrophotographic method, electrophotographic apparatus, and process cartridge for electrophotographic apparatus - Google Patents

Description

  The present invention relates to an electrophotographic photosensitive member containing a specific hydroxygallium pyridoporphyrazine derivative mixture in a photosensitive layer, an electrophotographic method using the electrophotographic photosensitive member, an electrophotographic apparatus, and an electrophotographic process cartridge. About.

  Conventionally, various inorganic and organic photoconductors are known as photoconductors for photoconductors used in electrophotography. The “electrophotographic method” here generally means that a photoconductive photosensitive member is first charged in a dark place, for example, by corona discharge, and then subjected to image exposure, whereby the charge of only the exposed portion is selectively dissipated and static. An image called the so-called Carlson process, in which an electrostatic latent image is obtained, and the latent image portion is developed with a toner composed of a colorant such as a dye or pigment and a polymer material, and visualized to form an image. Forming process. Photoconductors using organic photoconductors are more advantageous than those of inorganic photoconductors in terms of freedom of photosensitive wavelength range, film formability, flexibility, film transparency, mass productivity, toxicity, cost, etc. At present, organic photoconductors are used for most photoconductors. Photoreceptors repeatedly used in this electrophotographic system and similar processes have excellent electrostatic characteristics such as sensitivity, receptive potential, potential retention, potential stability, residual potential, and spectral sensitivity characteristics. Required.

In recent years, the development of information processing system machines using this electrophotographic method has been remarkable.
In particular, a printer using a digital recording system that converts information into a digital signal and records information by light has a remarkable improvement in print quality and reliability. This digital recording system is applied not only to printers but also to ordinary copying machines, and so-called digital copying machines have been developed. Furthermore, since various digital information processing functions are added to the digital copying machine, it is expected that the demand for the digital copying machine will increase further in the future.

  The photosensitive member corresponding to such a digital recording method is required to have characteristics different from those of the conventional analog method. For example, as a light source, a small, inexpensive, and highly reliable semiconductor laser (LD) or light emitting diode (LED) is currently used. The light emission wavelength region of LD that is often used at present is in the near infrared light region, and the light emission wavelength of LED is longer than 650 nm. For this reason, in addition to the requirements for the electrophotographic photoreceptor, it is desired to have high sensitivity from the visible light region to the near infrared light region.

  From this point of view, squarylium dyes (JP 49-105536 and 58-21416), triphenylamine trisazo pigment (JP 61-151659), phthalocyanine pigment (JP 48). -34189 and 57-14874) have been proposed as photoconductors for digital recording. In particular, phthalocyanine pigments, which are tetraazaporphyrin derivatives, have a photosensitive wavelength range up to a long wavelength range, high photosensitivity, and various characteristics variations can be obtained depending on the type of central metal and crystal form. Active research has been conducted on photoconductors. Examples of phthalocyanine pigments that have been known so far and exhibit good sensitivity include ε-type copper phthalocyanine, X-type metal-free phthalocyanine, τ-type metal-free phthalocyanine, vanadyl phthalocyanine, and titanyl phthalocyanine.

  Among them, high-sensitivity titanyl phthalocyanine pigments have been proposed by Japanese Patent Application Laid-Open Nos. 64-17066, 3-128973, and 5-98182. The spectral wavelength range of these titanyl phthalocyanine pigments shows maximum absorption at 700 to 860 nm, and exhibits extremely high sensitivity to semiconductor laser light. However, when the titanyl phthalocyanine pigment shown in the above-mentioned patent publication is used for an electrophotographic photoreceptor, the sensitivity is sufficient, but practical use such as a decrease in chargeability due to repeated fatigue and large sensitivity fluctuations due to temperature and humidity. Many of the above problems remain (Non-Patent Document 1 [Y. Fujimaki, Proc. IS & T's 7th International Congress on Advances in Non-Impact Printing Technologies, 1, 269 (1991)]).

  Furthermore, Japanese Patent No. 3123185 of Patent Document 1 discloses a chlorogallium phthalocyanine pigment for a photoelectric conversion material, and Japanese Patent No. 3166293 of Patent Document 2 has a Bragg angle (2θ ± 0.2 °) in an X-ray diffraction spectrum. Is a highly sensitive V for photoelectric conversion materials having strong diffraction peaks at 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° Type hydroxygallium phthalocyanine pigments are disclosed. These gallium phthalocyanine pigments also show practical sensitivity up to the near-infrared region, and although the photosensitivity is lower than the above-mentioned titanyl phthalocyanine pigment, it is said that the humidity dependence of the photosensitivity is smaller than this (non-patent) Reference 2 [K. Daimon, et al .: J. Imaging Sci. Technol., 40, 249 (1996)]). However, this gallium phthalocyanine pigment still has problems such as a decrease in chargeability due to repeated fatigue and an increase in residual potential (decrease in sensitivity).

  Japanese Patent No. 2737487 of Patent Document 3 and Japanese Patent No. 2637485 of Patent Document 4 disclose porphyrazine pigments having a heterocyclic ring such as pyridine or pyrazine. Further, in Japanese Patent Publication No. 3-27111 of Patent Document 5, Japanese Patent No. 4293694 of Patent Document 6, and Japanese Patent No. 4419873 of Patent Document 7, a mixture of phthalocyanine and other porphyrazine pigments is used as a photoconductor. However, electrophotographic photoreceptors using these also have sensitivity in the visible region and near infrared region, decrease in chargeability due to repeated fatigue, increase in residual potential, and variation in sensitivity due to temperature and humidity. The requirements for the electrophotographic photosensitive member were not sufficiently satisfied in terms of large size.

  The present invention eliminates the drawbacks of the conventional electrophotographic photoreceptors described above, more specifically, the sensitivity in the visible region and the near infrared region is high, the charging property is decreased due to repeated fatigue, the residual potential is increased (sensitivity is decreased), and the temperature and humidity It is an object of the present invention to provide an electrophotographic photosensitive member with a small variation due to the above, an electrophotographic method using the electrophotographic photosensitive member, an electrophotographic apparatus, and an electrophotographic process cartridge.

As a result of intensive studies to solve the above problems, the present inventors have
(1) An electrophotographic photoreceptor in which a photosensitive layer contains a novel mixture of various hydroxygallium pyridoporphyrazine derivatives each represented by the following general formula (21);

（式中、Ａ，Ｂ、Ｃ、及びＤは無置換、もしくは置換基としてニトロ基、ハロゲン原子、アルキル基、アルコキシ基、ヒドロキシ基、ベンゾ、ピリドを有してもよいベンゾもしくはピリドを表し、同一でも異なっていても良い。）」を見出すに至り、本発明を完成させた。

(In the formula, A, B, C, and D are unsubstituted or represent benzo or pyrido which may have a nitro group, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, benzo, or a pyrido as a substituent; It may be the same or different.) ”And the present invention has been completed.

The above-described problems are achieved by the present invention including the electrophotographic photosensitive member described in the following items (2) to (12), a train photographic method using the same, an electrophotographic apparatus, and a process cartridge therefor.
(2) An electrophotographic photosensitive member in which at least a photosensitive layer is provided on a conductive support, and the photosensitive layer has at least a Bragg angle (2θ ± 0.2 °) of 7 in an X-ray diffraction spectrum by CuKα rays. It contains a hydroxygallium pyridoporphyrazine derivative mixture represented by the general formula (21) having strong diffraction peaks at .4 °, 16.2 °, 25.2 °, and 28.3 °. The electrophotographic photosensitive member according to (1).
(3) An electrophotographic photosensitive member in which at least a photosensitive layer is provided on a conductive support, wherein the photosensitive layer comprises a hydroxygallium pyridoporphyrazine derivative mixture represented by the general formula (21) and an azo series. The electrophotographic photosensitive member according to item (1) or (2), which contains a pigment.
(4) An electrophotographic photosensitive member in which at least a photosensitive layer is provided on a conductive support, wherein the photosensitive layer includes a hydroxygallium pyridoporphyrazine derivative mixture represented by the general formula (21) and a phthalocyanine series. The electrophotographic photosensitive member according to item (1) or (2), which contains a pigment.
(5) The electrophotographic photosensitive member according to any one of (1) to (4), wherein the photosensitive layer is formed by sequentially laminating at least a charge generation layer and a charge transport layer.
(6) The electrophotographic photosensitive member according to any one of (1) to (4), wherein the photosensitive layer is formed by sequentially laminating at least a charge transport layer and a charge generation layer.
(7) The electrophotographic photosensitive member according to any one of (1) to (4), wherein the photosensitive layer is a single-layer type photosensitive layer.
(8) An electrophotographic method in which at least charging, image exposure, development, and transfer are repeatedly performed on an electrophotographic photosensitive member, and the electrophotographic photosensitive member is described in any one of (1) to (7) above. An electrophotographic method characterized by being an electrophotographic photosensitive member.
(9) A digital system in which at least charging, image exposure, development, and transfer are repeatedly performed on an electrophotographic photosensitive member, and an electrostatic latent image is written on the photosensitive member by an LD or LED during image exposure. An electrophotographic method according to the above item, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of (1) to (7).
(10) An electrophotographic apparatus comprising at least a charging means, an image exposing means, a developing means, a transferring means, and an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the item (1) to (7). An electrophotographic apparatus according to any one of the electrophotographic photoreceptors.
(11) An electrophotographic apparatus comprising at least a charging means, an image exposing means, a developing means, a transferring means, and an electrophotographic photosensitive member, wherein an LD or LED is used as the image exposing means on the photosensitive member. A digital electrophotographic apparatus in which an electrostatic latent image is written, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of (1) to (7). A feature of an electrophotographic apparatus.
(12) A process cartridge for an electrophotographic apparatus comprising at least an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of (1) to (7). A process cartridge for an electrophotographic apparatus, comprising:

  As will be understood from the following detailed and specific description, the electrophotographic photosensitive member of the present invention containing a mixture of hydroxygallium pyridoporphyrazine derivatives in the photosensitive layer has high sensitivity in the visible region and the near infrared region. The decrease in chargeability due to repeated fatigue, the increase in residual potential (sensitivity decrease), and the fluctuations due to temperature and humidity are small, and the electrophotographic method, electrophotographic apparatus, and electrophotographic process cartridge using the electrophotographic photosensitive member. It is extremely useful.

3 is a powder XD diffraction spectrum chart of a chloro-Ga derivative mixture (Compound No. 1) according to Production Example 1. FIG. 2 is an IR absorption spectrum chart of a chloro-Ga derivative mixture (Compound No. 1) according to Production Example 1. 4 is a powder XD diffraction spectrum chart of a chloro-Ga derivative mixture (Compound No. 2) according to Production Example 2. 6 is a powder XD diffraction spectrum chart of a chloro-Ga derivative mixture (Compound No. 3) according to Production Example 3. 6 is a powder XD diffraction spectrum chart of a chloro-Ga derivative mixture (Compound No. 4) according to Production Example 4. 6 is a powder XD diffraction spectrum chart of a chloro-Ga derivative mixture (Compound No. 5) according to Production Example 5. 6 is a powder XD diffraction spectrum chart of a chloro-Ga derivative mixture (Compound No. 6) according to Production Example 6. 6 is an IR absorption spectrum chart of a HO—Ga derivative mixture (Compound No. 6) according to Production Example 7. 6 is a powder XD diffraction spectrum chart of a HO—Ga derivative mixture (Compound No. 7) according to Production Example 7. It is a powder XD diffraction spectrum chart of the HO-Ga derivative mixture (compound No. 8) by manufacture example 8. 10 is a powder XD diffraction spectrum chart of a HO—Ga derivative mixture (Compound No. 9) obtained in Production Example 9. 4 is a powder XD diffraction spectrum chart of a HO—Ga derivative mixture (Compound No. 10) according to Production Example 10. 6 is a powder XD diffraction spectrum chart of a HO—Ga derivative mixture (Compound No. 11) according to Production Example 11. It is a powder XD diffraction spectrum chart of the HO-Ga derivative mixture (compound No. 12) by manufacture example 12. It is a powder XD diffraction spectrum chart of the HO-Ga derivative mixture (compound No. 13) by manufacture example 13. 7 is a powder XD diffraction spectrum chart of Y-type Ti-phthalocyanine of the structural formula (45) used in Example 11 together. 4 is a powder XD diffraction spectrum chart of HO—Ga polyphylazine (Comparative Compound No. 1) of the structural formula (46) used in Comparative Example 1. FIG. 4 is an XD diffraction spectrum chart of copper phthalocyanine used in Comparative Example 2. 6 is a powder XD diffraction spectrum chart of a V-type HO—GaHO—Ga derivative mixture (Compound No. 13) used in Comparative Example 3. 6 is a powder XD diffraction spectrum chart of Y-type Ti-phthalocyanine used in Comparative Example 5. 1 is a schematic diagram for explaining an electrophotographic process and an image forming apparatus of the present invention. 1 is a schematic view for explaining a tandem-type full-color electrophotographic apparatus of the present invention. FIG. It is the schematic for demonstrating one example of the process cartridge of this invention.

Hereinafter, the present invention will be described in detail and specifically.
The hydroxygallium pyridoporphyrazine derivative mixture represented by the above general formula (21) used in the present invention is obtained by acid-treating a gallium pyridoporphyrazine derivative mixture represented by the following general formula (20). Manufactured by performing a decomposition process.

（式中、Ａ，Ｂ、Ｃ、及びＤは無置換、もしくは置換基としてニトロ基、ハロゲン原子、アルキル基、アルコキシ基、ヒドロキシ基、ベンゾ、ピリドを有してもよいベンゾもしくはピリドを表し、同一でも異なっていても良い。またＲ^３はハロゲン原子もしくはアルコキシ基を表す。）

(In the formula, A, B, C, and D are unsubstituted or represent benzo or pyrido which may have a nitro group, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, benzo, or a pyrido as a substituent; (It may be the same or different, and R ³ represents a halogen atom or an alkoxy group.)

  Gallium pyridoporphyrazine derivative mixtures represented by general formula (20), which are precursors of various hydroxygallium pyridoporphyrazine derivative mixtures each represented by general formula (21), are represented by the following general formulas (1) to ( 6) at least one of the benzene derivative groups represented by the formula, at least one of the pyridine derivative groups represented by the following general formulas (7) to (18), and a gallium compound represented by the following formula (19). In addition, no solvent, α-chloronaphthalene, dichlorobenzene, trichlorobenzene, pentaanol, octanol, benzyl alcohol, N, N-dimethylformamide, N-methylpyrrolidone, quinoline, benzene, toluene, xylene, mesitylene, It can be obtained by reacting in the presence of nitrobenzene, dioxane or the like. The reaction may be carried out in the presence of urea, formamide, acetamide, benzamide, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), ammonia or the like, if necessary. The reaction temperature is usually room temperature to 300 ° C, preferably 140 ° C to 260 ° C.

（式中、Ｒ^１はニトロ基、ハロゲン原子、アルキル基、アルコキシ基、ヒドロキシ基、ベンゾ、ピリドを表す。ｍは０〜４の整数を表し、ｍが２以上の場合、Ｒ^１は同一でも異なっていても良い。）

(In the formula, R ¹ represents a nitro group, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, benzo, or a pyride. M represents an integer of 0 to 4, and when m is 2 or more, R ¹ may be the same. May be different.)

（式中、Ｒ^２はニトロ基、ハロゲン原子、アルキル基、アルコキシ基、ヒドロキシ基、ベンゾ、ピリドを表す。ｎは０〜３の整数を表し、ｎが２以上の場合、Ｒ^２は同一でも異なっていても良い。）

(In the formula, R ² represents a nitro group, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, benzo, or a pyrido. N represents an integer of 0 to 3, and when n is 2 or more, R ² may be the same. May be different.)

（式中、Ｒ^３はハロゲン原子もしくはアルコキシ基を表す。）

(In the formula, R ³ represents a halogen atom or an alkoxy group.)

Here, as the halogen atom of R ¹ and R ^{2 in} the general formula (1) to the general formula (18), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are used, and as an alkyl group, a methyl group, an ethyl group, n-propyl group, i-pyrrolyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, i-pentyl group, tert-pentyl group, n-hexyl group, C1-C20 linear or branched alkyl group such as n-octyl group, i-octyl group, dodecyl group, cetyl group, etc., C5-C7 cycloalkyl group such as cyclohexyl group, hexahydrobenzyl group And an alkyl group substituted with an aromatic group such as a cycloalkyl group or a phenyl group. Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, i -C1-C20 linear or branched alkyl such as pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-octyloxy group, i-octyloxy group, dodecyloxy group, cetyloxy group And an alkoxy group substituted with an aromatic group such as a cycloalkoxy group or a phenyl group, such as a cycloalkyloxy group having 5 to 7 carbon atoms such as a cyclohexyloxy group, a hexahydrobenzyloxy group, and a benzyloxy group. Furthermore, specific examples of the halogen atom and alkoxy group for R ³ include the same ones as described above.

  Moreover, at least one of the benzene derivative groups represented by the general formulas (1) to (6) and at least one mixing ratio (molar ratio) in the pyridine derivative group represented by the general formulas (7) to (18) ) Is from 1: 99999 to 99999: 1, preferably from 1: 1 to 399: 1 (molar ratio). When at least one of the benzene derivative groups represented by the formulas (1) to (6) is less than the above-mentioned mixing ratio, chargeability and sensitivity are low in electrophotographic characteristics. Conversely, when the mixing ratio of at least one of the pyridine derivative groups represented by formulas (7) to (18) is small, the rate of change in charge reduction due to static electricity, light fatigue, or the like increases.

  As described above, the hydroxygallium pyridoporphyrazine derivative mixture represented by the general formula (21) used in the present invention is an acid treatment of the gallium pyridoporphyrazine derivative mixture represented by the general formula (20), that is, Manufactured by acid hydrolysis.

  Acid treatment refers to dissolving a pigment at −5 ° C. to room temperature in an acid such as sulfuric acid, hydrochloric acid, phosphoric acid, methanesulfonic acid, trichloroacetic acid, and trifluoroacetic acid, and then dissolving the pigment in ice, water, ice water, or water. It is shown that a pigment crystal is obtained by dripping it into a mixed solution of water and an organic solvent to precipitate a pigment crystal, and by means such as filtration. Among acids, concentrated sulfuric acid is preferable because the solubility of the gallium pyridoporphyrazine derivative mixture is high, there is no fuming property, and it is easy to handle. In addition, the hydroxygallium pyridoporphyrazine derivative mixture thus precipitated is washed with water, a mixed solution of an organic solvent and water, or a basic aqueous solution as necessary, in acid and a water-soluble organic solvent or hydrolysis. It is preferable to remove and neutralize impurities generated.

  Examples of organic solvents to be mixed with water include lower alcohols such as methanol and ethanol, lower ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, methyl cellosolve and dioxane, and water-soluble organic solvents such as dimethylformamide and dimethyl sulfoxide. can give.

  Examples of the base of the basic aqueous solution include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkali carbonates such as sodium carbonate and potassium carbonate, magnesium hydroxide, ammonia, and various quaternary hydroxides. Ammonium and the like can be used. The amount of the base used is suitably in the range of 0.5 to 1.5 molar equivalents, preferably 0.8 to 1.2 molar equivalents relative to the acid.

When the hydroxygallium pyridoporphyrazine derivative mixture thus obtained by acid treatment is treated with a solvent, it can be transferred to a novel crystal having further excellent photosensitivity and durability.
Treatment with a solvent means a suspension treatment of a hydroxygallium pyridoporphyrazine derivative mixture in a solvent at room temperature or under heating. Examples of the solvent include benzene, toluene, chlorobenzene, dichlorobenzene, nitrobenzene, methano -Ethanol, ethanol, benzyl alcohol, acetone, cyclohexanone, methyl ethyl ketone, n-butyl ether, ethylene glycol, tetrahydrofuran, N, N-dimethylformamide, N-methylpyrrolidone, quinoline, pyridine, dimethyl sulfoxide, water, etc. In addition, these solvents may be mixed.

Examples of such a solvent treatment method include treatment operations such as wet pulverization, immersion, and suspension stirring. As processing conditions, the amount of solvent used is 1 to 200 parts, preferably 10 to 100 parts, with respect to 1 part of the hydroxygallium pyridoporphyrazine derivative mixture crystal, and the processing temperature is 0 to 150 ° C., preferably Room temperature to 100 ° C.
Further, the solvent treatment may be carried out in a suitable container while standing or stirring.
Furthermore, it may be wet pulverized by a ball mill, mortar, sand mill, kneader, attritor or the like using a predetermined solvent. During pulverization, inorganic compounds such as salt and sodium nitrate, glass beads, steel beads, alumina Grinding media such as beads may be used.

By the solvent treatment as described above, it is possible to produce a preferable new crystal of a hydroxygallium pyridoporphyrazine derivative mixture which is further stable in crystal and excellent in photosensitivity and durability.
Among them, as a photoconductor for an electrophotographic photoreceptor, a hydroxygallium pyridoporphyrazine derivative mixture is a Bragg angle (2θ ± 0) in an X-ray diffraction spectrum using Cu-Kα characteristic X-ray (λ = 1.54Å). .2 °) is preferably in a crystal form having strong diffraction peaks at least at 7.4 °, 16.2 °, 25.2 °, and 28.3 °.

Further, depending on the required characteristics of the photoreceptor, a mixture of two or more kinds of hydroxygallium pyridoporphyrazine derivatives having different mixing ratios, or an azo pigment or phthalocyanine pigment and a mixture of hydroxygallium pyridoporphyrazine derivatives may be mixed. The electrophotographic photoreceptor of the present invention can be obtained.
For example, C.I. Pigment Blue 25 (Color Index CI 21180), C.I. Pigment Red 41 (CI 21200), C.I. Acid Red 52 (CI 45100), C.I. Basic Red 3 (CI 45210), and an azo pigment having a carbazole skeleton 53-95033), azo pigments having a distyrylbenzene skeleton (JP-A-53-133445), azo pigments having a triphenylamine skeleton (described in JP-A-53-132347), dibenzo An azo pigment having a thiophene skeleton (described in JP-A No. 54-21728), an azo pigment having an oxadiazole skeleton (described in JP-A No. 54-12742), an azo pigment having a fluorenone skeleton (Japanese Unexamined Patent Publication No. Described in Japanese Patent Publication No. 54-22834) , An azo pigment having a bis-stilbene skeleton (described in JP-A No. 54-17733), an azo pigment having a distyryl oxadiazole skeleton (described in JP-A No. 54-2129), and a distyrylcarbazole skeleton Examples include azo pigments such as azo pigments (described in JP-A No. 54-14967). Further, as phthalocyanine pigments, copper phthalocyanine, metal-free phthalocyanine, aluminum phthalocyanine, magnesium phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, vanadyl phthalocyanine, titanyl phthalocyanine, chloroindium phthalocyanine, hydroxyindium phthalocyanine, zinc phthalocyanine, iron phthalocyanine, cobalt phthalocyanine Etc.

  The hydroxygallium pyridoporphyrazine derivative mixture represented by the general formula (21) of the present invention can be used alone or in combination with a charge transport material to produce a single layer type or a laminated type (functional separation type) electrophotographic photoreceptor. In the case of a single layer type, a photosensitive layer in which a hydroxygallium pyridoporphyrazine derivative mixture alone or a charge transport material is combined and dispersed in a binder is provided on a conductive substrate. In the case of the functional separation type, a charge generation layer composed of a hydroxygallium pyridoporphyrazine derivative mixture is formed on a substrate, and a charge transport layer composed of a charge transport material is formed thereon. May be laminated in reverse.

  In order to improve adhesiveness and charge blocking properties, an undercoat layer may be provided between the photosensitive layer and the substrate. Further, a protective layer may be provided on the photosensitive layer in order to improve mechanical durability such as friction resistance.

The hydroxygallium pyridoporphyrazine derivative mixture-dispersed photosensitive layer can be provided by adding or dissolving a binder resin in an appropriate solvent, if necessary, and applying and drying.
Examples of the dispersion method of the hydroxygallium pyridoporphyrazine derivative mixture include a ball mill, an ultrasonic wave, and a homomixer. Examples of the application means include a dipping coating method, a blade coating method, and a spray coating method.
When a photosensitive layer is formed by dispersing a hydroxygallium pyridoporphyrazine derivative mixture, the hydroxygallium pyridoporphyrazine derivative mixture has an average of 2 μm or less, preferably 1 μm or less in order to improve dispersibility in the layer. The thing of a particle size is preferable. However, if the above particle size is too small, it tends to aggregate, and the resistance of the layer increases, the crystal defects increase, the sensitivity and repeatability decrease, or there is a limit in miniaturization, so the average particle size The lower limit of the diameter is preferably 0.01 μm.

  Examples of the solvent used for preparing the dispersion or solution of the photosensitive layer include N, N-dimethylformamide, toluene, xylene, monochlorobenzene, 1,2-dichloroethane, 1,1,1-trichloroethane, dichloromethane, Examples thereof include 1,1,2-trichloroethane, trichloroethylene, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, dioxane and the like.

  As the binder used when forming the photosensitive layer, any conventionally known binder for electrophotographic photoreceptors having good insulating properties can be used, and there is no particular limitation. For example, polyethylene, polyvinyl butyral, polyvinyl formal, polystyrene resin, phenoxy resin, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, Polyamide resins, silicone resins, melamine resins and other addition polymerization resins, polyaddition resins, polycondensation resins, and copolymer resins containing two or more of these resin repeating units, such as vinyl chloride-vinyl acetate In addition to insulating resins such as copolymers, styrene-acrylic copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymer resins, high molecular organic semiconductors such as poly-N-vinylcarbazole can be used. These binders can be used alone or as a mixture of two or more.

  In the case where a photoconductor is produced using the layer structure and materials described above, there are preferable ranges for the film thickness and the material ratio. In the case of the functional separation type (substrate / charge generation layer / charge transport layer), a binder is used as necessary in the charge generation layer, and in this case, the ratio of the hydroxygallium pyridoporphyrazine derivative mixture to the binder is It is preferably 20% by weight or more and the film thickness is preferably 0.01 to 5 μm. In the charge transport layer, the ratio of the charge transport material to the binder is preferably 20 to 200% by weight, and the film thickness is preferably 5 to 100 μm. When a polymer type charge transport material is used, a charge transport layer may be formed alone.

Furthermore, the charge generation layer preferably contains a charge transport material, and the inclusion thereof has an effect of suppressing residual potential and improving sensitivity. In this case, the charge transport material is preferably contained in an amount of 20 to 200% by weight based on the binder.
In the case of a single-layer type photoreceptor, the ratio of the hydroxygallium pyridoporphyrazine derivative mixture to the binder resin in the photosensitive layer is preferably 5 to 95% by weight, and the film thickness is preferably 10 to 100 μm. . When combined with the charge transport material, the ratio of the charge transport material to the binder resin is preferably 30 to 200% by weight. The photosensitive layer may be formed of a polymer type charge transport material and a hydroxygallium pyridoporphyrazine derivative mixture, and the ratio of the hydroxygallium pyridoporphyrazine derivative mixture to the polymer type charge transport material is 5 to 95% by weight, The film thickness is preferably 10 to 100 μm.

  Further, in the photosensitive layer, for the purpose of improving the charging property, a phenol compound, a hydroquinone compound, a hindered phenol compound, a hindered amine compound, a compound in which a hindered amine and a hindered phenol are present in the same molecule, and the like are added. Can do.

  In the present invention, as the conductive substrate, metal plates such as aluminum, nickel, copper, titanium, gold, and stainless steel, metal drums or metal foils, aluminum, nickel, copper, titanium, gold tin oxide, indium oxide, and the like are vapor-deposited. Examples thereof include a plastic film or paper coated with a conductive material, a film such as plastic, or a drum.

  Further, if necessary, an undercoat layer is used on the conductive substrate, and the undercoat layer is generally composed mainly of a resin, but these resins are considered to be coated with a photosensitive layer with a solvent. It is desirable that the resin has high solvent resistance with respect to general organic solvents. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, a metal oxide fine powder pigment exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential. These undercoat layers can be formed using an appropriate solvent and coating method as in the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention. In addition, for the undercoat layer of the present invention, a vacuum thin film is formed of Al2O3 provided by anodic oxidation, organic substances such as polyparaxylylene (parylene), and inorganic substances such as SiO2, SnO2, TiO2, ITO, CeO2 Those provided by the law can also be used satisfactorily. In addition, known ones can be used. The thickness of the undercoat layer is suitably from 0.01 to 5 μm.

  Further, the materials used for the protective layer include ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, Polybutylene, polybutylene terephthalate, polycarbonate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylbenten, polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resin, butadiene-styrene copolymer, polyurethane, polyvinyl chloride And resins such as polyvinylidene chloride, epoxy resins, fluorine resins such as polytetrafluoroethylene, and silicon resins. In addition to the protective layer, these resins are coated with inorganic material particles such as titanium oxide, tin oxide, potassium titanate, alumina, silica, and the like for the purpose of improving wear resistance and improving the ability to separate from toner and contaminants. Fluorine resin fine particles such as tetrafluoroethylene, silicon fine particles and the like can be added. As a method for forming the protective layer, conventional methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating, etc. can be used. preferable. In addition, about 0.1-10 micrometers is suitable for the thickness of a protective layer. In addition to the above, a known material such as a-C or a-SiC formed by a vacuum thin film forming method can be used as the protective layer.

The charge transport material is classified into a hole transport material, an electron transport material, and a polymer charge transport material, which will be described below.
Examples of hole transport materials include poly-N-carbazole and derivatives thereof, poly-γ-carbazolylethyl glutamate and derivatives thereof, pyrene-formaldehyde condensates and derivatives thereof, polyvinylpyrene, polyvinylphenanthrene, oxazole derivatives, imidazole There are derivatives, triphenylamine derivatives, and compounds represented by the following general formulas (11) to (34).

（式中、Ｒ１はメチル基、エチル基、２−ヒドロキシエチル基または２−クロルエチル基を表し、Ｒ２はメチル基、エチル基、ベンジル基またはフェニル基を表し、Ｒ３は水素原子、塩素原子、臭素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ジアルキルアミノ基またはニトロ基を表す。）

(Wherein R1 represents a methyl group, an ethyl group, a 2-hydroxyethyl group or a 2-chloroethyl group, R2 represents a methyl group, an ethyl group, a benzyl group or a phenyl group, and R3 represents a hydrogen atom, a chlorine atom, a bromine group) Represents an atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a dialkylamino group, or a nitro group.)

  Examples of the compound represented by the general formula (11) include 9-ethylcarbazole-3-carbaldehyde 1-methyl-1-phenylhydrazone, 9-ethylcarbazole-3-carbaldehyde 1-benzyl-1-phenylhydrazone. 9-ethylcarbazole-3-carbaldehyde 1,1-diphenylhydrazone, etc.

（式中、Ａｒはナフタレン環、アントラセン環、ピレン環及びそれらの置換体あるいはピリジン環、フラン環、チオフェン環を表し、Ｒはアルキル基、フェニル基またはベンジル基を表す。）

(In the formula, Ar represents a naphthalene ring, anthracene ring, pyrene ring and a substituted product thereof, or a pyridine ring, a furan ring, and a thiophene ring, and R represents an alkyl group, a phenyl group, or a benzyl group.)

  Examples of the compound represented by the general formula (12) include 4-diethylaminostyryl-β-carbaldehyde 1-methyl-1-phenylhydrazone, 4-methoxynaphthalene-1-carbaldehyde 1-benzyl-1-phenylhydrazone. and so on.

（式中、Ｒ１はアルキル基、ベンジル基、フェニル基またはナフチル基を表し、Ｒ２は水素原子、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、ジアルキルアミノ基、ジアラルキルアミノ基またはジアリールアミノ基を表し、ｎは１〜４の整数を表し、ｎが２以上のときはＲ２は同じでも異なっていても良い。Ｒ３は水素原子またはメトキシ基を表す。）

(In the formula, R1 represents an alkyl group, a benzyl group, a phenyl group or a naphthyl group, and R2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group, or a diaralkylamino group. A group or a diarylamino group, n represents an integer of 1 to 4, and when n is 2 or more, R2 may be the same or different, and R3 represents a hydrogen atom or a methoxy group.

  Examples of the compound represented by the general formula (13) include 4-methoxybenzaldehyde 1-methyl-1-phenylhydrazone, 2,4-dimethoxybenzaldehyde 1-benzyl-1-phenylhydrazone, 4-diethylaminobenzaldehyde 1, 1 -Diphenylhydrazone, 4-methoxybenzaldehyde 1- (4-methoxy) phenylhydrazone, 4-diphenylaminobenzaldehyde 1-benzyl-1-phenylhydrazone, 4-dibenzylaminobenzaldehyde 1, 1-diphenylhydrazone and the like.

（式中、Ｒ１は炭素数１〜１１のアルキル基、置換もしくは無置換のフェニル基または複素環基を表し、Ｒ２、Ｒ３はそれぞれ同一でも異なっていてもよく、水素原子、炭素数１〜４のアルキル基、ヒドロキシアルキル基、クロルアルキル基または置換もしくは無置換のアラルキル基を表し、また、Ｒ２とＲ３は互いに結合し窒素を含む複素環を形成していても良い。Ｒ４は同一でも異なっていてもよく、水素原子、炭素数１〜４のアルキル基、アルコキシ基またはハロゲン原子を表す。）

(In the formula, R1 represents an alkyl group having 1 to 11 carbon atoms, a substituted or unsubstituted phenyl group or a heterocyclic group, and R2 and R3 may be the same or different from each other, and may be a hydrogen atom or a carbon atom having 1 to 4 carbon atoms. And an alkyl group, a hydroxyalkyl group, a chloroalkyl group, or a substituted or unsubstituted aralkyl group, and R2 and R3 may be bonded to each other to form a nitrogen-containing heterocyclic ring. And represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a halogen atom.)

  Examples of the compound represented by the general formula (14) include 1,1-bis (4-dibenzylaminophenyl) propane, tris (4-diethylaminophenyl) methane, 1,1-bis (4-dibenzylamino). Phenyl) propane, 2,2′-dimethyl-4,4′-bis (diethylamino) -triphenylmethane, and the like.

（式中、Ｒは水素原子またはハロゲン原子を表し、Ａｒは置換もしくは無置換のフェニル基、ナフチル基、アントリル基またはカルバゾリル基を表す。）
一般式（１５）で表される化合物には、例えば、９−（４−ジエチルアミノスチリル）アントラセン、９−ブロム−１０−（４−ジエチルアミノスチリル）アントラセンなどがある。

(In the formula, R represents a hydrogen atom or a halogen atom, and Ar represents a substituted or unsubstituted phenyl group, naphthyl group, anthryl group, or carbazolyl group.)
Examples of the compound represented by the general formula (15) include 9- (4-diethylaminostyryl) anthracene and 9-bromo-10- (4-diethylaminostyryl) anthracene.

（式中、Ｒ１は水素原子、ハロゲン原子、シアノ基、炭素数１〜４のアルコキシ基または炭素数１〜４のアルキル基を表し、Ａｒは下記一般式（１７）、一般式（１８）を表す。

(In the formula, R1 represents a hydrogen atom, a halogen atom, a cyano group, an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and Ar represents the following general formula (17) and general formula (18). Represent.

（Ｒ２は炭素数１〜４のアルキル基を表し、Ｒ３は水素原子、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基またはジアルキルアミノ基を表し、ｎは１または２であって、ｎが２のとき、Ｒ３は同一でも異なっていてもよく、Ｒ４、Ｒ５は水素原子、炭素数１〜４の置換もしくは無置換のアルキル基または置換もしくは無置換のベンジル基を表す。）

(R2 represents an alkyl group having 1 to 4 carbon atoms, R3 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a dialkylamino group, and n is 1 or When n is 2, R3 may be the same or different, and R4 and R5 are each a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted benzyl group. Represents.)

  Examples of the compound represented by the general formula (16) include 9- (4-dimethylaminobenzylidene) fluorene and 3- (9-fluorenylidene) -9-ethylcarbazole.

（式中、Ｒはカルバゾリル基、ピリジル基、チエニル基、インドリル基、フリル基あるいはそれぞれ置換もしくは非置換のフェニル基、スチリル基、ナフチル基、またはアントリル基であって、これらの置換基がジアルキルアミノ基、アルキル基、アルコキシ基、カルボキシ基またはそのエステル、ハロゲン原子、シアノ基、アラルキルアミノ基、Ｎ−アルキル−Ｎ−アラルキルアミノ基、アミノ基、ニトロ基及びアセチルアミノ基からなる群から選ばれた基を表す。）

Wherein R is a carbazolyl group, pyridyl group, thienyl group, indolyl group, furyl group or a substituted or unsubstituted phenyl group, styryl group, naphthyl group, or anthryl group, and these substituents are dialkylamino Group, alkyl group, alkoxy group, carboxy group or ester thereof, halogen atom, cyano group, aralkylamino group, N-alkyl-N-aralkylamino group, amino group, nitro group, and acetylamino group Represents a group.)

  Examples of the compound represented by the general formula (19) include 1,2-bis (4-diethylaminostyryl) benzene and 1,2-bis (2,4-dimethoxystyryl) benzene.

（式中、Ｒ１は低級アルキル基、置換もしくは無置換のフェニル基、またはベンジル基を表し、Ｒ２、Ｒ３は水素原子、低級アルキル基、低級アルコキシ基、ハロゲン原子、ニトロ基、アミノ基あるいは低級アルキル基またはベンジル基で置換されたアミノ基を表し、ｎは１または２の整数を表す。）

(Wherein R1 represents a lower alkyl group, a substituted or unsubstituted phenyl group, or a benzyl group, and R2 and R3 represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a nitro group, an amino group, or a lower alkyl group. Represents an amino group substituted with a group or a benzyl group, and n represents an integer of 1 or 2.)

  Examples of the compound represented by the general formula (20) include 3-styryl-9-ethylcarbazole and 3- (4-methoxystyryl) -9-ethylcarbazole.

（式中、Ｒ１は水素原子、アルキル基、アルコキシ基またはハロゲン原子を表し、Ｒ２およびＲ３は置換もしくは無置換のアリール基を表し、Ｒ４は水素原子、低級アルキル基または置換もしくは無置換のフェニル基を表し、また、Ａｒは置換もしくは無置換のフェニル基またはナフチル基を表す。）

(Wherein R1 represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, R2 and R3 each represents a substituted or unsubstituted aryl group, and R4 represents a hydrogen atom, a lower alkyl group or a substituted or unsubstituted phenyl group. Ar represents a substituted or unsubstituted phenyl group or naphthyl group.)

  Examples of the compound represented by the general formula (21) include 4-diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene, 1- (4-diphenylaminostyryl) naphthalene, 1- (4 -Diphenylaminostyryl) naphthalene.

（式中、ｎは０または１の整数、Ｒ１は水素原子、アルキル基または置換もしくは無置換のフェニル基を表し、Ａｒ１は置換もしくは未置換のアリール基を表し、Ｒ５は置換アルキル基を含むアルキル基、あるいは置換もしくは無置換のアリール基を表し、Ａは下記一般式（２３）、一般式（２４）、９−アントリル基または置換もしくは無置換のカルバゾリル基を表す。

(Wherein n represents an integer of 0 or 1, R1 represents a hydrogen atom, an alkyl group or a substituted or unsubstituted phenyl group, Ar1 represents a substituted or unsubstituted aryl group, and R5 represents an alkyl containing a substituted alkyl group. Group represents a substituted or unsubstituted aryl group, and A represents the following general formula (23), general formula (24), 9-anthryl group or substituted or unsubstituted carbazolyl group.

ここでＲ２は水素原子、アルキル基、アルコキシ基、ハロゲン原子または一般式（２５）を表す。

Here, R2 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or general formula (25).

（ただし、Ｒ３およびＲ４は置換もしくは無置換のアリール基を示し、Ｒ３およびＲ４は同じでも異なっていてもよく、Ｒ４は環を形成しても良い）を表し、ｍが２以上の時Ｒ２は同一でも異なっても良い。また、ｎが０の時、ＡとＲ１は共同で環を形成しても良い。）

(Wherein R3 and R4 represent a substituted or unsubstituted aryl group, R3 and R4 may be the same or different, and R4 may form a ring), and when m is 2 or more, R2 is It may be the same or different. When n is 0, A and R1 may form a ring together. )

  Examples of the compound represented by the general formula (22) include 4'-diphenylamino-α-phenylstilbene and 4'-bis (4-methylphenyl) amino-α-phenylstilbene.

（式中、Ｒ１、Ｒ２およびＲ３は水素原子、低級アルキル基、低級アルコキシ基、ハロゲン原子またはジアルキルアミノ基を表し、ｎは０または１を表す。）

(Wherein R1, R2 and R3 represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom or a dialkylamino group, and n represents 0 or 1)

  Examples of the compound represented by the general formula (26) include 1-phenyl-3- (4-diethylaminostyryl) -5- (4-diethylaminophenyl) pyrazoline.

（式中、Ｒ１およびＲ２は置換アルキル基を含むアルキル基、または置換もしくは未置換のアリール基を表し、Ａは置換アミノ基、置換もしくは未置換のアリール基またはアリル基を表す。）

(Wherein R1 and R2 represent an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and A represents a substituted amino group, a substituted or unsubstituted aryl group, or an allyl group.)

  Examples of the compound represented by the general formula (27) include 2,5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole, 2-N, N-diphenylamino-5- (4 -Diethylaminophenyl) -1,3,4-oxadiazole, 2- (4-dimethylaminophenyl) -5- (4-diethylaminophenyl) -1,3,4-oxadiazole and the like.

（式中、Ｘは水素原子、低級アルキル基またはハロゲン原子を表し、Ｒは置換アルキル基を含むアルキル基、または置換もしくは無置換のアリール基を表し、Ａは置換アミノ基または置換もしくは無置換のアリール基を表す。）

(In the formula, X represents a hydrogen atom, a lower alkyl group or a halogen atom, R represents an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and A represents a substituted amino group or a substituted or unsubstituted aryl group. Represents an aryl group.)

  Examples of the compound represented by the general formula (28) include 2-N, N-diphenylamino-5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole, 2- ( 4-diethylaminophenyl) -5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole.

（式中、Ｒ１は低級アルキル基、低級アルコキシ基またはハロゲン原子を表し、Ｒ２、Ｒ３は同じでも異なっていてもよく、水素原子、低級アルキル基、低級アルコキシ基またはハロゲン原子を表し、ｌ、ｍ、ｎは０〜４の整数を表す。）

(Wherein R1 represents a lower alkyl group, a lower alkoxy group or a halogen atom, and R2 and R3 may be the same or different, and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom; , N represents an integer of 0-4.)

  Examples of the benzidine compound represented by the general formula (29) include N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-. Examples include diamine, 3,3′-dimethyl-N, N, N ′, N′-tetrakis (4-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine.

（式中、Ｒ１、Ｒ３およびＲ４は水素原子、アミノ基、アルコキシ基、チオアルコキシ基、アリールオキシ基、メチレンジオキシ基、置換もしくは無置換のアルキル基、ハロゲン原子または置換もしくは無置換のアリール基を、Ｒ２は水素原子、アルコキシ基、置換もしくは無置換のアルキル基またはハロゲン原子を表す。ただし、Ｒ１、Ｒ２、Ｒ３およびＲ４はすべて水素原子である場合は除く。また、ｋ，ｌ，ｍおよびｎは１、２、３または４の整数であり、それぞれが２、３または４の整数の時は、前記Ｒ１、Ｒ２、Ｒ３およびＲ４は同じでも異なっていても良い。）

Wherein R1, R3 and R4 are a hydrogen atom, an amino group, an alkoxy group, a thioalkoxy group, an aryloxy group, a methylenedioxy group, a substituted or unsubstituted alkyl group, a halogen atom or a substituted or unsubstituted aryl group. R2 represents a hydrogen atom, an alkoxy group, a substituted or unsubstituted alkyl group or a halogen atom, except that R1, R2, R3 and R4 are all hydrogen atoms, and k, l, m and n is an integer of 1, 2, 3 or 4, and when each is an integer of 2, 3 or 4, the R1, R2, R3 and R4 may be the same or different.

  Examples of the biphenylylamine compound represented by the general formula (30) include 4′-methoxy-N, N-diphenyl- [1,1′-biphenyl] -4-amine, 4′-methyl-N, N. -Bis (4-methylphenyl)-[1,1'-biphenyl] -4-amine, 4'-methoxy-N, N-bis (4-methylphenyl)-[1,1'-biphenyl] -4- Amines, N, N-bis (3,4-dimethylphenyl)-[1,1′-biphenyl] -4-amine, and the like.

（式中、Ａｒは置換基を有してもよい炭素数１８個以下の縮合多環式炭化水素基を表し、また、Ｒ１およびＲ２は水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、アルコキシ基、置換もしくは無置換のフェニル基を表し、それぞれ同じでも異なっていても良い。ｎは１もしくは２の整数を表す。）

(In the formula, Ar represents a condensed polycyclic hydrocarbon group having 18 or less carbon atoms which may have a substituent, and R1 and R2 each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, And represents an alkoxy group or a substituted or unsubstituted phenyl group, which may be the same or different, and n represents an integer of 1 or 2.)

  Examples of the triarylamine compound represented by the general formula (31) include N, N-diphenyl-pyrene-1-amine, N, N-di-p-tolyl-pyren-1-amine, and N, N- Di-p-tolyl-1-naphthylamine, N, N-di (p-tolyl) -1-phenanthrylamine, 9,9-dimethyl-2- (di-p-tolylamino) fluorene, N, N, N Examples include ', N'-tetrakis (4-methylphenyl) -phenanthrene-9,10-diamine and N, N, N', N'-tetrakis (3-methylphenyl) -m-phenylenediamine.

（式中、Ａｒは置換もしくは無置換の芳香族炭化水素基を表し、Ａは一般式（３３）を表す。

(In the formula, Ar represents a substituted or unsubstituted aromatic hydrocarbon group, and A represents the general formula (33).

（ただし、Ａｒは置換もしくは無置換の芳香族炭化水素基を表し、Ｒ１およびＲ２は置換もしくは無置換のアルキル基、または置換もしくは無置換のアリール基である。）
を表す。）

(However, Ar represents a substituted or unsubstituted aromatic hydrocarbon group, and R1 and R2 are a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.)
Represents. )

  Examples of the diolefin aromatic compound represented by the general formula (32) include 1,4-bis (4-diphenylaminostyryl) benzene and 1,4-bis [4-di (p-tolyl) aminostyryl]. There is benzene.

（式中、Ａｒは置換もしくは無置換の芳香族炭化水素基を、Ｒは水素原子、置換もしくは無置換のアルキル基、または置換もしくは無置換のアリール基を表す。ｎは０または１、ｍは１または２であって、ｎ＝０、ｍ＝１の場合、ＡｒとＲは共同で環を形成しても良い。）

(In the formula, Ar represents a substituted or unsubstituted aromatic hydrocarbon group, R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. N is 0 or 1, m is When 1 or 2 and n = 0 and m = 1, Ar and R may form a ring together.)

  Examples of the styrylpyrene compound represented by the general formula (34) include 1- (4-diphenylaminostyryl) pyrene and 1- (N, N-di-p-tolyl-4-aminostyryl) pyrene.

  Examples of the electron transport material include chloroanil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-indeno4H-indeno [1,2-b] thiophen-4-one, 1,3 , 7-trinitrodibenzothiophene-5,5-dioxide and the like, and the electron transport materials listed in the following general formulas (35), (36), (37) and (38) are preferably used. be able to.

（式中Ｒ１、Ｒ２およびＲ３は水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、アルコキシ基、置換もしくは無置換のフェニル基を表し、それぞれ同じでも異なっていても良い。）

(Wherein R1, R2 and R3 represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or a substituted or unsubstituted phenyl group, which may be the same or different.)

（式中Ｒ１、Ｒ２は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のフェニル基を表し、それぞれ同じでも異なっていても良い。）

(Wherein R1 and R2 represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group, and may be the same or different.)

（式中Ｒ１、Ｒ２およびＲ３は水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、アルコキシ基、置換もしくは無置換のフェニル基を表し、それぞれ同じでも異なっていても良い。）

(Wherein R1, R2 and R3 represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or a substituted or unsubstituted phenyl group, which may be the same or different.)

〔式中、Ｒ１は置換基を有してもよいアルキル基、または置換基を有してもよいアリール基を示し、Ｒ２は置換基を有してもよいアルキル基、置換基を有してもよいアリール基、または下記式一般式（３９）、（４０）で表される基を示す。

[In the formula, R1 represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R2 has an alkyl group which may have a substituent or a substituent. Or a group represented by the following formulas (39) and (40).

（式中Ｒ１、Ｒ２は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基を表し、それぞれ同じでも異なっていても良い。）

(Wherein R1 and R2 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group, which may be the same or different.)

  As the polymer charge transport material, known materials can be used, and in particular, a polycarbonate containing a triarylamine structure in the main chain and / or side chain is preferably used. Among these, polymer charge transport materials represented by the structural formulas (I) to (XIII) are preferably used. These are illustrated below and specific examples are shown.

式中、Ｒ１，Ｒ２，Ｒ３はそれぞれ独立して置換もしくは無置換のアルキル基又はハロゲン原子、Ｒ４は水素原子又は置換もしくは無置換のアルキル基、Ｒ５，Ｒ６は置換もしくは無置換のアリール基、ｏ，ｐ，ｑはそれぞれ独立して０〜４の整数、ｋ，ｊは組成を表し、０．１≦ｋ≦１、０≦ｊ≦０．９、ｎは繰り返し単位数を表し５〜５０００の整数である。Ｘは脂肪族の２価基、環状脂肪族の２価基、または下記構造式（II）で表される２価基を表す。

In the formula, R1, R2 and R3 are each independently a substituted or unsubstituted alkyl group or a halogen atom, R4 is a hydrogen atom or a substituted or unsubstituted alkyl group, R5 and R6 are substituted or unsubstituted aryl groups, o , P, q are each independently an integer of 0-4, k, j represents a composition, 0.1 ≦ k ≦ 1, 0 ≦ j ≦ 0.9, and n represents the number of repeating units of 5-5000. It is an integer. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following structural formula (II).

式中、Ｒ１０１，Ｒ１０２は各々独立して置換もしくは無置換のアルキル基、アリール基またはハロゲン原子を表す。ｌ、ｍは０〜４の整数、Ｙは単結合、炭素原子数１〜１２の直鎖状、分岐状もしくは環状のアルキレン基、−Ｏ−，−Ｓ−，−ＳＯ−，−ＳＯ２−，−ＣＯ−，−ＣＯ−Ｏ−Ｚ−Ｏ−ＣＯ−（式中Ｚは脂肪族の２価基を表す。）または、下記構造式（III）を表す。

In the formula, R101 and R102 each independently represents a substituted or unsubstituted alkyl group, aryl group, or halogen atom. l and m are integers of 0 to 4, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-, -SO2-, —CO—, —CO—O—Z—O—CO— (wherein Z represents an aliphatic divalent group) or the following structural formula (III).

（式中、ａは１〜２０の整数、ｂは１〜２０００の整数、Ｒ１０３、Ｒ１０４は置換または無置換のアルキル基又はアリール基を表す。）を表す。ここで、Ｒ１０１とＲ１０２，Ｒ１０３とＲ１０４は、それぞれ同一でも異なってもよい。

(Wherein, a represents an integer of 1 to 20, b represents an integer of 1 to 2000, and R103 and R104 represent a substituted or unsubstituted alkyl group or aryl group). Here, R101 and R102, and R103 and R104 may be the same or different.

式中、Ｒ７，Ｒ８は置換もしくは無置換のアリール基、Ａｒ１，Ａｒ２，Ａｒ３は同一あるいは異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、上記構造式（Ｉ）式の場合と同じである。

In the formula, R7 and R8 represent substituted or unsubstituted aryl groups, and Ar1, Ar2 and Ar3 represent the same or different arylene groups. X, k, j and n are the same as those in the above formula (I).

式中、Ｒ９，Ｒ１０は置換もしくは無置換のアリール基、Ａｒ４，Ａｒ５，Ａｒ６は同一あるいは異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、上記構造式（Ｉ）式の場合と同じである。

In the formula, R9 and R10 represent substituted or unsubstituted aryl groups, and Ar4, Ar5 and Ar6 represent the same or different arylene groups. X, k, j and n are the same as those in the above formula (I).

式中、Ｒ１１，Ｒ１２は置換もしくは無置換のアリール基、Ａｒ７，Ａｒ８，Ａｒ９は同一あるいは異なるアリレン基、ｐは１〜５の整数を表す。Ｘ，ｋ，ｊおよびｎは、上記構造式（Ｉ）式の場合と同じである。

In the formula, R11 and R12 are substituted or unsubstituted aryl groups, Ar7, Ar8 and Ar9 are the same or different arylene groups, and p is an integer of 1 to 5. X, k, j and n are the same as those in the above formula (I).

式中、Ｒ１３，Ｒ１４は置換もしくは無置換のアリール基、Ａｒ１０，Ａｒ１１，Ａｒ１２は同一あるいは異なるアリレン基、Ｘ１，Ｘ２は置換もしくは無置換のエチレン基、又は置換もしくは無置換のビニレン基を表す。Ｘ，ｋ，ｊおよびｎは、上記構造式（Ｉ）式の場合と同じである。

In the formula, R13 and R14 are substituted or unsubstituted aryl groups, Ar10, Ar11 and Ar12 are the same or different arylene groups, and X1 and X2 are substituted or unsubstituted ethylene groups, or substituted or unsubstituted vinylene groups. X, k, j and n are the same as those in the above formula (I).

式中、Ｒ１５，Ｒ１６，Ｒ１７，Ｒ１８は置換もしくは無置換のアリール基、Ａｒ１３，Ａｒ１４，Ａｒ１５，Ａｒ１６は同一あるいは異なるアリレン基、Ｙ１，Ｙ２，Ｙ３は単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル基、酸素原子、硫黄原子、ビニレン基を表し同一であっても異なってもよい。Ｘ，ｋ，ｊおよびｎは、上記構造式（Ｉ）式の場合と同じである。

In the formula, R15, R16, R17 and R18 are substituted or unsubstituted aryl groups, Ar13, Ar14, Ar15 and Ar16 are the same or different arylene groups, Y1, Y2 and Y3 are single bonds, substituted or unsubstituted alkylene groups, It represents a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group, which may be the same or different. X, k, j and n are the same as those in the above formula (I).

式中、Ｒ１９，Ｒ２０は水素原子、置換もしくは無置換のアリール基を表し，Ｒ１９とＲ２０は環を形成していてもよい。Ａｒ１７，Ａｒ１８，Ａｒ１９は同一あるいは異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、上記構造式（Ｉ）式の場合と同じである。

In the formula, R19 and R20 each represent a hydrogen atom or a substituted or unsubstituted aryl group, and R19 and R20 may form a ring. Ar17, Ar18 and Ar19 represent the same or different arylene groups. X, k, j and n are the same as those in the above formula (I).

式中、Ｒ２１は置換もしくは無置換のアリール基、Ａｒ２０，Ａｒ２１，Ａｒ２２，Ａｒ２３は同一あるいは異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、上記構造式（Ｉ）式の場合と同じである。

In the formula, R21 represents a substituted or unsubstituted aryl group, and Ar20, Ar21, Ar22, and Ar23 represent the same or different arylene groups. X, k, j and n are the same as those in the above formula (I).

式中、Ｒ２２，Ｒ２３，Ｒ２４，Ｒ２５は置換もしくは無置換のアリール基、Ａｒ２４，Ａｒ２５，Ａｒ２６，Ａｒ２７，Ａｒ２８は同一あるいは又は異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、上記構造式（Ｉ）式の場合と同じである。

In the formula, R22, R23, R24 and R25 represent substituted or unsubstituted aryl groups, and Ar24, Ar25, Ar26, Ar27 and Ar28 represent the same or different arylene groups. X, k, j and n are the same as those in the above formula (I).

式中、Ｒ２６，Ｒ２７は置換もしくは無置換のアリール基、Ａｒ２９，Ａｒ３０，Ａｒ３１は同一あるいは異なるアリレン基を表す。Ｘ，ｋ，ｊおよびｎは、上記構造式（Ｉ）式の場合と同じである。

In the formula, R26 and R27 represent substituted or unsubstituted aryl groups, and Ar29, Ar30, and Ar31 represent the same or different arylene groups. X, k, j and n are the same as those in the above formula (I).

（式中、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４およびＡｒ５は置換もしくは無置換の芳香環基、Ｚは芳香環基または―Ａｒ６―Ｚａ―Ａｒ６―を表し、Ａｒ６は置換もしくは無置換の芳香環基、ＺａはＯ、Ｓまたはアルキレン基、ＲおよびＲ’は直鎖又は分岐鎖のアルキレン基を表す。ｍは０または１を表す。ｋ、ｊ、ｎ及びＸは前式と同じ。）
これらの電荷輸送物質は単独または２種類以上混合して用いられる。

(In the formula, Ar1, Ar2, Ar3, Ar4 and Ar5 represent a substituted or unsubstituted aromatic ring group, Z represents an aromatic ring group or -Ar6-Za-Ar6-, and Ar6 represents a substituted or unsubstituted aromatic ring group; Za represents O, S or an alkylene group, R and R ′ each represent a linear or branched alkylene group, m represents 0 or 1, and k, j, n and X are the same as in the previous formula.)
These charge transport materials may be used alone or in combination of two or more.

  Moreover, the hydroxygallium pyridoporphyrazine derivative mixture represented by the general formula (21) of the present invention is not only useful as a photoconductor of an electrophotographic photosensitive member, but also used in electronic fields such as solar cells and optical disks. Can be suitably used.

Next, the electrophotographic method, the electrophotographic apparatus, and the process cartridge for the electrophotographic apparatus of the present invention will be described in detail with reference to the drawings.
FIG. 21 is a schematic diagram for explaining the electrophotographic process and the image forming apparatus of the present invention, and the following examples also belong to the category of the present invention.
The photosensitive member (10) rotates in the direction of the arrow in FIG. 21. Around the photosensitive member (10), a charging member (11), an image exposure member (12), a developing member (13), and a transfer member (16). ), A cleaning member (17), a charge removal member (18), and the like are disposed. The cleaning member (17) and the charge removal member (18) may be omitted.

  The operation of the image forming apparatus is basically as follows. The charging member (11) charges the surface of the photoreceptor (10) almost uniformly. Subsequently, image light writing corresponding to the input signal is performed by the image exposure member (12) to form an electrostatic latent image. Next, the electrostatic latent image is developed by the developing member (13), and a toner image is formed on the surface of the photoreceptor. The formed toner image is transferred onto the transfer paper (15) sent to the transfer site by the transport roller (14) by the transfer member. This toner image is fixed on the transfer paper by a fixing device (not shown). Part of the toner that has not been transferred to the transfer paper is cleaned by the cleaning member (17). Next, the charge remaining on the photoreceptor is neutralized by the neutralizing member (18), and the process proceeds to the next cycle.

  As shown in FIG. 21, the photoconductor (10) has a drum shape, but may have a sheet shape or an endless belt shape. As the charging member (11) and the transfer member (16), in addition to corotron, scorotron, solid state charger (solid state charger), a roller-shaped charging member or a brush-shaped charging member is used. Are all usable.

On the other hand, light sources such as the image exposure member (12) and the charge removal member (18) include fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light emitting diodes (LEDs), semiconductor lasers (LD), and electroluminescence (EL). ) And other luminescent materials can be used. Among these, a semiconductor laser (LD) and a light emitting diode (LED) are mainly used.
Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.

  The light source or the like irradiates the photoconductor (10) with light by providing a transfer process, a static elimination process, a cleaning process, or a pre-exposure process using light irradiation together. However, the exposure of the photoconductor (10) in the static elimination process has a large influence of fatigue on the photoconductor (10), and may cause a decrease in charge and an increase in residual potential.

  Therefore, there is a case where it is possible to eliminate static electricity by applying a reverse bias in the charging process or cleaning process instead of static elimination by exposure, which may be effective from the viewpoint of enhancing the durability of the photoreceptor.

When the electrophotographic photosensitive member (10) is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.
A known method is applied to the developing unit, and a known method is also used for the charge eliminating unit.

  Among the contaminants that adhere to the surface of the photoconductor, discharge substances generated by charging and external additives contained in the toner are easy to pick up the effects of humidity and cause abnormal images. Paper powder is one of the causative substances, and when they adhere to the photoreceptor, abnormal images are more likely to occur, as well as a tendency to reduce wear resistance and cause uneven wear. Is seen. Therefore, it is more preferable from the viewpoint of high image quality that the photoconductor and the paper are not in direct contact for the above reason.

The toner developed on the photoreceptor (10) by the developing member (13) is transferred to the transfer paper (15), but not all is transferred, and the toner remaining on the photoreceptor (10). Also occurs. Such toner is removed from the photoreceptor (10) by the cleaning member (17).
As the cleaning member, a known member such as a cleaning blade or a cleaning brush is used. Moreover, both may be used together.

  The photoconductor according to the present invention can be applied to a small-diameter photoconductor because high photosensitivity and high stability are realized. Therefore, as an image forming apparatus or method for using the above photoreceptor more effectively, each developing unit corresponding to a plurality of colors of toner is provided with a plurality of corresponding photoreceptors, thereby performing parallel processing. It is very effectively used in a so-called tandem type image forming apparatus. The tandem image forming apparatus includes at least four color toners of yellow (C), magenta (M), cyan (C), and black (K) required for full-color printing and a developing unit that holds them. Further, by providing at least four photoconductors corresponding to them, full-color printing can be performed at an extremely high speed as compared with a conventional image forming apparatus capable of full-color printing.

FIG. 22 is a schematic diagram for explaining the tandem full-color electrophotographic apparatus of the present invention, and the following modifications also belong to the category of the present invention.
In FIG. 22, photoconductors (10C (cyan)), (10M (magenta)), (10Y (yellow)), and (10K (black)) are drum-like photoconductors (10), and these photoconductors. (10C, 10M, 10Y, 10K) rotate in the direction of the arrow in the figure, around which at least the charging members (11C, 11M, 11Y, 11K), the developing members (13C, 13M, 13Y, 13K), Cleaning members (17C, 17M, 17Y, 17K) are arranged.

  From the back side of the photoreceptor (10) between the charging member (11C, 11M, 11Y, 11K) and the developing member (13C, 13M, 13Y, 13K), laser light (12C, 12M, 12Y, 12K) is irradiated, and electrostatic latent images are formed on the photoconductors (10C, 10M, 10Y, 10K).

Then, four image forming elements (20C, 20M, 20Y, 20K) centering on such a photoreceptor (10C, 10M, 10Y, 10K) are along a transfer conveyance belt (25) which is a transfer material conveyance unit. Are juxtaposed.
The transfer / conveying belt (19) is disposed between the developing member (13C, 13M, 13Y, 13K) of each image forming unit (20C, 20M, 20Y, 20K) and the cleaning member (17C, 17M, 17Y, 17K). A transfer member (16C) for applying a transfer bias to the surface (rear surface) which is in contact with the photoconductor (10C, 10M, 10Y, 10K) and contacts the back side of the photoconductor (10) side of the transfer conveyance belt (19). , 16M, 16Y, 16K). Each of the image forming elements (20C, 20M, 20Y, 20K) is different in toner color inside the developing device, and the other components have the same configuration.

  In the color electrophotographic apparatus having the configuration shown in FIG. 22, the image forming operation is performed as follows. First, in each of the image forming elements (20C, 20M, 20Y, and 20K), the charging member (11C, 11M, 11Y, and 11K) in which the photosensitive member (10C, 10M, 10Y, and 10K) rotates along with the photosensitive member 10 is rotated. ), And then an electrostatic image corresponding to the image of each color to be created by laser light (12C, 12M, 12Y, 12K) by an exposure unit (not shown) arranged outside the photoconductor (10). A latent image is formed.

  Next, the latent image is developed by a developing member (13C, 13M, 13Y, 13K) to form a toner image. The developing members (13C, 13M, 13Y, and 13K) are developing members that perform development with toners of C (cyan), M (magenta), Y (yellow), and K (black), respectively. 10M, 10Y, and 10K) are overlaid on the transfer belt (19).

  The transfer paper (15) is sent out from the tray by the paper supply roller (21), temporarily stopped by the pair of registration rollers (22), and sent to the transfer member (23) in synchronization with the image formation on the photosensitive member. It is done. The toner image held on the transfer belt (19) is transferred onto the transfer paper (15) by an electric field formed by a potential difference between the transfer bias applied to the transfer member (23) and the transfer belt (19). . The toner image transferred onto the transfer paper is conveyed, the toner is fixed onto the transfer paper by the fixing member (24), and is discharged to a paper discharge unit (not shown). Further, residual toner that is not transferred by the transfer unit and remains on the photosensitive members (10C, 10M, 10Y, and 10K) is collected by cleaning members (17C, 17M, 17Y, and 17K) provided in the respective units. The

  The intermediate transfer system as shown in FIG. 22 is particularly effective for an image forming apparatus capable of full-color printing. By forming a plurality of toner images once on an intermediate transfer member and transferring them to paper at once, It is easy to control the color shift and is effective for high image quality.

  The intermediate transfer member includes various materials or shapes such as a drum shape and a belt shape. In the present invention, any conventionally known intermediate transfer member can be used. It is effective and useful for achieving high quality or high image quality.

  In the example of FIG. 22, the image forming elements are arranged in the order of C (cyan), M (magenta), Y (yellow), and K (black) from the upstream side to the downstream side in the transfer paper conveyance direction. However, it is not limited to this order, and the color order is arbitrarily set. Further, when a black-only document is created, it is particularly effective to use the present invention to provide a mechanism that stops the image forming elements (20C, 20M, 20Y) other than black.

The image forming means as described above may be fixedly incorporated in a copying apparatus, a facsimile, or a printer, but may be incorporated in these apparatuses in the form of a process cartridge.
As shown in FIG. 23, the process cartridge includes a photoconductor (10), a charging member (11), an image exposure member (12), a developing member (13), a transfer member (16), a cleaning member. It is one apparatus (part) including the member (17) and the charge removal member.

The above-described tandem image forming apparatus can transfer a plurality of toner images at a time, so that high-speed full-color printing is realized.
However, since at least four photoconductors are required, an increase in the size of the apparatus is unavoidable, and depending on the amount of toner used, there is a difference in the wear amount of each photoconductor, thereby reproducing the color. There are many problems such as a decrease in performance and occurrence of abnormal images.

  On the other hand, the photosensitive member according to the present invention can be applied to a small-diameter photosensitive member by realizing high photosensitivity and high stability, and the influence of increase in residual potential, sensitivity deterioration, etc. is reduced. Even if the amount of the photoconductor used is different, the difference in residual potential and sensitivity over time is small, and a full color image having excellent color reproducibility can be obtained even when used repeatedly for a long time.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, the aspect of the Example of this invention is not limited by this.

[Production Example 1; Production of chlorogallium pyridoporphyrazine derivative mixture (Compound No. 1)]
5.00 g (28.4 mmol) of gallium trichloride was added to 14.48 g (0.5679 mmol × 199) of phthalonitrile, 73.33 mg (0.5679 mmol) of 2,3-dicyanopyridine and 70 ml of 1-chloronaphthalene, and an argon stream The mixture was stirred under heating at 240 to 246 ° C. for 12 hours. The crystals obtained by cooling to 130 ° C. and filtration were washed with N, N-dimethylformamide and water, and then dried under reduced pressure and dried to give a blue powdered chlorogallium pyridoporphyrazine derivative mixture (Compound No. 1). 1) 13.94 g was obtained.
The powder X-ray diffraction spectrum of the obtained chlorogallium pyridoporphyrazine derivative mixture is shown in FIG. 1, and the infrared absorption spectrum (KBr tablet method) is shown in FIG.

[Production Example 2: Production of chlorogallium pyridoporphyrazine derivative mixture (Compound No. 2)]
A chlorogallium pyridoporphyrazine derivative mixture (Compound No. 2) was produced by operating in the same manner as in Production Example 1 except that the mixing ratio of phthalonitrile and 2,3-dicyanopyridine was changed as shown in Table 1. did. The yield and elemental analysis results are shown in Table 1, and the powder X-ray diffraction spectrum is shown in FIG.

[Production Example 3: Production of chlorogallium pyridoporphyrazine derivative mixture (Compound No. 3)]
A chlorogallium pyridoporphyrazine derivative mixture (Compound No. 3) was produced by operating in the same manner as in Production Example 1 except that the mixing ratio of phthalonitrile and 2,3-dicyanopyridine was changed as shown in Table 1. did. The yield and elemental analysis results are shown in Table 1, and the powder X-ray diffraction spectrum is shown in FIG.

[Production Example 4: Production of chlorogallium pyridoporphyrazine derivative mixture (Compound No. 4)]
Add 5.00 g (28.4 mmol) of gallium trichloride to 16.08 g (2.840 mmol × 39) of 1,3-diiminoisoindoline, 0.3666 g (2.840 mmol) of 3,4-dicyanopyridine and 100 ml of quinoline. The mixture was heated and stirred at 196 to 200 ° C. for 6 hours under an argon stream. The crystals obtained by cooling to 130 ° C. and filtration were washed with N, N-dimethylformamide and water, and then dried under reduced pressure and dried to give a blue powdered chlorogallium pyridoporphyrazine derivative mixture (Compound No. 1). 4) 15.15 g was obtained.
The powder X-ray diffraction spectrum of the obtained chlorogallium pyridoporphyrazine derivative mixture is shown in FIG.

[Production Example 5; Production of chlorogallium pyridoporphyrazine derivative mixture (Compound No. 5)]
16.03 g of 1,3-diiminoisoindoline (2.840 mmol × 39), 0.4464 g (2.840 mmol) of 2,3-dicyano-5,6-dimethylpyridine and 5.00 g of gallium trichloride in 100 ml of quinoline ( 28.4 mmol) was added, and the mixture was heated and stirred at 190 to 198 ° C. for 6 hours under an argon stream. The crystals obtained by cooling to 130 ° C. and filtration were washed with N, N-dimethylformamide and water, and then dried under reduced pressure and dried to give a blue powdered chlorogallium pyridoporphyrazine derivative mixture (Compound No. 1). 5) 15.08 g was obtained.
The powder X-ray diffraction spectrum of the obtained chlorogallium pyridoporphyrazine derivative mixture is shown in FIG.

[Production Example 6; Production of chlorogallium pyridoporphyrazine derivative mixture (Compound No. 6)]
To 13.83 g (2.840 mmol × 38) of phthalonitrile, 0.4093 g (2.840 mmol) of 4-hydroxyphthalonitrile, 0.4645 g (2.840 mmol) of 2,3-dicyano-5-chloropyridine and 90 ml of dimethyl sulfoxide 5.00 g (28.4 mmol) of gallium trichloride was added, and the mixture was heated and stirred at 190 to 198 ° C. for 6 hours under an argon stream. The crystals obtained by cooling to 130 ° C. and filtration were washed with N, N-dimethylformamide and water, and then dried under reduced pressure and dried to give a blue powdered chlorogallium pyridoporphyrazine derivative mixture (Compound No. 1). 6) 14.98 g was obtained.
FIG. 7 shows a powder X-ray diffraction spectrum of the resulting chlorogallium pyridoporphyrazine derivative mixture.

[Production Example 7; Production of hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 7)]
180 g of concentrated sulfuric acid was stirred and cooled in an ice-water bath, and 6.00 g of the chlorogallium pyridoporphyrazine derivative mixture (Compound No. 1) obtained in Production Example 1 was added and dissolved in small portions over 10 minutes. After stirring for 1 hour, the contents were dropped into 900 g of ice water being stirred, and after stirring for 1 hour, filtration was performed to obtain a wet cake. The obtained wet cake was washed twice with ion-exchanged water, once with 2% aqueous ammonia, and further three times with ion-exchanged water, dried by heating under reduced pressure, and 5.76 g of a hydroxygallium pyridoporphyrazine derivative mixture. Got.
A ball mill pot was mixed with 3.00 g of the hydroxygallium pyridoporphyrazine derivative mixture, 45 g of N, N-dimethylformamide and 175 g of glass beads with a diameter of 1 mm were milled for 48 hours at room temperature, and the crystals were taken out. . The obtained crystals were dried by heating under reduced pressure, and at least a Bragg angle (2θ ± 0.2 °) of 7.4 °, 16.2 °, 25.2 °, 28.X in the X-ray diffraction spectrum of the blue powder by CuKα ray. As a result, 3.00 g of a hydroxygallium pyridoporphyrazine derivative mixture crystal (Compound No. 7) having a strong diffraction peak at 3 ° was obtained. The powder X-ray diffraction pattern of this product is shown in FIG. 8, and the infrared absorption spectrum (KBr tablet method) is shown in FIG.

[Production Example 8; Production of hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 8)]
The chlorogallium pyridoporphyrazine derivative mixture (Compound No. 1) charged in Production Example 6 was replaced with Compound No. A hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 8) was obtained in the same manner except for changing to 2. Table 2 shows the yield and elemental analysis results of the resulting hydroxygallium pyridoporphyrazine derivative mixture.
A powder X-ray diffraction spectrum is shown in FIG.

[Production Example 9; Production of hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 9)]
The chlorogallium pyridoporphyrazine derivative mixture (Compound No. 1) charged in Production Example 6 was replaced with Compound No. A hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 9) was obtained in the same manner except for changing to 3. Table 2 shows the yield and elemental analysis results of the resulting hydroxygallium pyridoporphyrazine derivative mixture.
A powder X-ray diffraction spectrum is shown in FIG.

[Production Example 10; Hydroxygallium pyridoporphyrazine derivative mixture (Production of Compound No. 10)]
The chlorogallium pyridoporphyrazine derivative mixture (Compound No. 1) charged in Production Example 6 was replaced with Compound No. Except for changing to 4, the same operation was performed to obtain a hydroxygallium pyridoporphyrazine derivative mixture (compound No. 10. Table 2 shows the yield and elemental analysis results of the hydroxygallium pyridoporphyrazine derivative mixture obtained. .
A powder X-ray diffraction spectrum is shown in FIG.

[Production Example 11; Hydroxygallium pyridoporphyrazine derivative mixture (Production of Compound No. 11])
The chlorogallium pyridoporphyrazine derivative mixture (Compound No. 1) charged in Production Example 6 was replaced with Compound No. Except for changing to 5, the same operation was performed to obtain a hydroxygallium pyridoporphyrazine derivative mixture (compound No. 11. Table 2 shows the yield and elemental analysis results of the hydroxygallium pyridoporphyrazine derivative mixture obtained. .
A powder X-ray diffraction spectrum is shown in FIG.

[Production Example 12; Hydroxygallium pyridoporphyrazine derivative mixture (Production of Compound No. 12])
The chlorogallium pyridoporphyrazine derivative mixture (Compound No. 1) charged in Production Example 6 was replaced with Compound No. Except for changing to 6, the same operation was performed to obtain a hydroxygallium pyridoporphyrazine derivative mixture (compound No. 12. Table 2 shows the yield and elemental analysis results of the obtained hydroxygallium pyridoporphyrazine derivative mixture. .
A powder X-ray diffraction spectrum is shown in FIG.

[Production Example 13; Production of hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 13)]
14.52 g (0.2840 mmol × 399) of phthalonitrile, 50.89 mg (0.2840 mmol) of 2,3-dicyanoquinoline and 9.03 g of gallium tri-n-butoxide (31.24 mmol) and urea 1 in 70 ml of 1-octanol .71 g (28.4 mmol) was added, and the mixture was heated and stirred at 150 to 155 ° C. for 6 hours under an argon stream. The crystals obtained by cooling to 130 ° C. and filtration are washed with N, N-dimethylformamide, methanol, water, dried under reduced pressure and dried to give a blue powder of n-butoxygallium pyridoporphyrazine derivative mixture 13.45 g was obtained.
The obtained n-butoxygallium pyridoporphyrazine derivative mixture was hydrolyzed and crystallized in the same manner as in Production Example 6 to obtain 2.98 g of a hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 13). The elemental analysis values (%) were C: 63.83, H: 2.91, N: 18.93. The powder X-ray diffraction spectrum of this product is shown in FIG.

A dispersion comprising 3 parts of a hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 7), 2 parts of a polyvinyl butyral resin (BM-S: manufactured by Sekisui Chemical Co., Ltd.) and 495 parts of tetrahydrofuran is placed in a ball mill pot, and a PSZ ball having a diameter of 2 mm Was used for ball milling for 3 hours to prepare a charge generation layer coating solution. This coating solution was applied onto an aluminum vapor-deposited polyester film and then dried at 100 ° C. for 20 minutes to form a charge generation layer having a thickness of about 0.3 μm.
Subsequently, 7 parts of a charge transport material represented by the following structural formula (41), 10 parts of a polycarbonate resin (PCX-5; manufactured by Teijin Chemicals Ltd.), 83 parts of tetrahydrofuran, silicone oil (KF-50; manufactured by Shin-Etsu Chemical Co., Ltd.) A 0002 part charge transport layer coating solution was prepared, applied onto the charge generation layer and dried at 110 ° C. for 20 minutes to form a charge transport layer having a thickness of about 25 μm, thereby producing an electrophotographic photoreceptor.

The electrostatic characteristics of the electrophotographic photoreceptor obtained as described above were measured by a dynamic method (rotation speed: 1000 rpm) using EPA-8100 (manufactured by Kawaguchi Electric). First, after charging for 20 seconds at an applied voltage of -6 KV, the surface potential Vo (V) when attenuated for 20 seconds is measured, and then exposure is performed with white light from a halogen lamp so that the surface illuminance is 5.3 lux. It was. For the sensitivity, the time required for the surface potential during exposure to be from −800 (V) to −400 (V) was calculated, and the half exposure amount Ew1 / 2 (lux · sec) was calculated. Further, the same apparatus is irradiated with monochromatic light of 780 nm so that the illuminance on the surface of the photoreceptor becomes 1 μW / cm ² , and the half exposure amount Em1 / 2 (required from −800 V to −400 V on the surface potential of the photoreceptor). μJ / cm ² ) was measured as the sensitivity of the LD light source region (near infrared region). Table 3 shows Vo, Ew1 / 2, and Em1 / 2.

  A hydroxygallium pyridoporphyrazine derivative mixture was prepared as compound no. The characteristics as an electrophotographic photosensitive member were evaluated in the same manner as in Example 1 except for changing to 8. The results are shown in Table 3.

  A hydroxygallium pyridoporphyrazine derivative mixture was prepared as compound no. The characteristics as an electrophotographic photosensitive member were evaluated in the same manner as in Example 1 except for changing to 9. The results are shown in Table 3.

  A hydroxygallium pyridoporphyrazine derivative mixture was prepared as compound no. The characteristics as an electrophotographic photosensitive member were evaluated in the same manner as in Example 1 except for changing to 10. The results are shown in Table 3.

  A hydroxygallium pyridoporphyrazine derivative mixture was prepared as compound no. The characteristics as an electrophotographic photosensitive member were evaluated in the same manner as in Example 1 except for changing to 11. The results are shown in Table 3.

  A hydroxygallium pyridoporphyrazine derivative mixture was prepared as compound no. Except for changing to 12, the same operation as in Example 1 was performed to evaluate the characteristics as an electrophotographic photosensitive member. The results are shown in Table 3.

  A hydroxygallium pyridoporphyrazine derivative mixture was prepared as compound no. The characteristics as an electrophotographic photosensitive member were evaluated in the same manner as in Example 1 except for changing to 13. The results are shown in Table 3.

  The charge transport layer coating solution used in Example 1 was blade coated on an aluminum vapor-deposited polyester film and dried at 120 ° C. for 10 minutes to form a charge transport layer having a thickness of about 20 μm. 13.5 parts of the hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 8) obtained in Production Example 8, 5.4 parts of polyvinyl butyral resin (Union Carbide Plastics: XYHL), 680 parts of tetrahydrofuran and ethyl cellosolve 1020 After the parts were pulverized and mixed in a ball mill, 1700 parts of ethyl cellosolve was added and mixed to prepare a charge generation layer coating solution. This coating solution was spray-coated on the charge transport layer and dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.2 μm. Further, a methanol / n-butanol solution of polyamide resin (manufactured by Toray Industries, Inc .: CM-8000) is spray-coated on the charge generation layer and dried at 120 ° C. for 30 minutes to form a protective layer having a thickness of about 0.5 μm. A photoconductor was prepared. The photoconductor characteristics were evaluated in the same manner as in Example 1 except that the applied voltage in Example 1 was changed to +6 KV. The results are shown in Table 3.

158 parts of methyl ethyl ketone was added to 1 part of the hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 10) obtained in Production Example 10, and ball milled for 24 hours using φ5 mm alumina balls. 7 parts of an electron transport material represented by the following structural formula (42), 5 parts of a hole transport material represented by the following structural formula (43), and 18 parts of a polyester resin (manufactured by DuPont: Polyester Adhesive 49000) were added thereto. The dispersion obtained by further mixing was applied onto an aluminum vapor-deposited polyester film using a doctor blade and dried at 100 ° C. for 30 minutes to form a photosensitive layer having a thickness of about 25 μm, thereby preparing a photoreceptor.
The photoconductor characteristics were evaluated in the same manner as in Example 1 except that the applied voltage in Example 1 was changed to +6 KV. The results are shown in Table 3.

  Characteristics as an electrophotographic photosensitive member are the same as in Example 1 except that 1 part of an azo pigment represented by the following structural formula (44) is added to the charge generation layer coating solution in Example 1 and mixed ball milling is performed. Evaluated. The results are shown in Table 3.

  In the charge generation layer coating solution in Example 10, 1 part of Y-type titanyl phthalocyanine represented by the following structural formula (45) showing the powder X-ray diffraction spectrum shown in FIG. 16 was added instead of the azo pigment, and mixed ball milling was performed. Except for the above, the same operation as in Example 10 was performed to evaluate the characteristics as an electrophotographic photosensitive member. The results are shown in Table 3.

[Comparative Example 1]
5.90 g (yield 66.8%) of chlorogallium tetrapyridoporphyrazine under the same production conditions as in Production Example 1 except that phthalonitrile in Production Example 1 was replaced with 2,3-dicyanopyridine having the same number of moles. )Obtained. Further, the same operation as in Production Example 7 was performed to obtain 2.94 g of hydroxygallium tetrapyridoporphyrazine (Comparative Compound No. 1) represented by the following structural formula (46). The powder X-ray diffraction spectrum of this product is shown in FIG.
Further, instead of the hydroxygallium pyridoporphyrazine derivative mixture (compound No. 7) used in Example 1, this comparative compound No. A photoconductor was prepared and evaluated in the same manner as in Example 1 except that No. 1 was used. The results are shown in Table 3.

[Comparative Example 2]
The following copper pyridoporphyrazine derivative mixture (Comparative Compound No. 3) was produced and evaluated according to the method of Example 16 described in Japanese Patent Publication No. 3-27111.
Pyridine-3,4-dicarboxylic acid 0.84 g (5.0 mmol), phthalic anhydride 14.07 g (95.0 mmol), urea 24.02 g (400 mmol), cuprous chloride 2.48 g (25 mmol), molybthenic acid 0.04 g of ammonium tetrahydrate and 80 g of trichlorobenzene were heated and stirred at 181 to 182 ° C. for 15 hours under a nitrogen stream. After standing to cool, 80 ml of methanol was added, and the mixture was stirred at reflux for 30 minutes and cooled to room temperature. The crystals obtained by filtration were washed successively with toluene, methanol, 3% aqueous sodium hydroxide, water, 1% hydrochloric acid and water. Thereafter, drying under reduced pressure was performed at 100 ° C. for 2 days. The obtained blue powder was washed with dioxane for 2 days using a Soxhlet extractor, dried under reduced pressure at 100 ° C. for 2 days, and a blue powdered copper pyridoporphyrazine derivative mixture (Comparative Compound No. 2) 12 .51 g was obtained.
FIG. 17 shows a powder X-ray diffraction spectrum of the obtained copper pyridoporphyrazine derivative mixture.
Further, instead of the hydroxygallium pyridoporphyrazine derivative mixture (compound No. 7) used in Example 1, this comparative compound No. A photoconductor was prepared and evaluated in the same manner as in Example 1 except that No. 2 was used. The results are shown in Table 3.

  From Table 3, the photoreceptor using the hydroxygallium pyridoporphyrazine derivative mixture of the present invention is considerably superior in charging potential Vo and sensitivity Ew1 / 2 and Em1 / 2 compared to the photoreceptors of Comparative Example 1 and Comparative Example 2. You can see that

An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition are sequentially applied onto an aluminum cylinder by dip coating and dried to obtain a 3.5 μm undercoat layer, 0. A 2 μm charge generation layer and a 23 μm charge transport layer were formed.
◎ Undercoat layer coating liquid Titanium dioxide powder (Ishihara Sangyo, Tybak CR-EL): 400 parts Melamine resin (Dainippon Ink, Super Becamine G821-60): 65 parts Alkyd resin (Dainippon Ink, Becko) Light M6401-50): 120 parts 2-butanone: 400 parts Charge generation layer coating solution Hydroxygallium pyridoporphyrazine derivative mixture (No. 7): 18 parts polyvinyl butyral resin (BX-1: manufactured by Sekisui Chemical Co., Ltd.) : 12 parts 2-butanone: 970 parts ◎ Charge transport layer coating solution polycarbonate resin (Z Polyca, manufactured by Teijin Chemicals): 10 parts Hole transport material of the following structural formula (47): 7 parts Tetrahydrofuran: 100 parts

The electrophotographic photosensitive member produced as described above is mounted on an electrophotographic process cartridge, and is charged with a roller charging method and charged with a Ricoh imagio MF2200 machine with a semiconductor laser (LD) with an image exposure light source of 780 nm. After setting to −800 (V) and post-exposure potential to −100 (V), a repeated test equivalent to printing a total of 100,000 sheets is continuously performed, and the post-charge potential (V) and post-exposure potential after the repeated test are performed. (V) was evaluated.
The results are shown in Table 4.

  Hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 7) was converted to Compound No. The characteristics as an electrophotographic photosensitive member were evaluated in the same manner as in Example 12 except for changing to 8. The results are shown in Table 4.

  Hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 7) was converted to Compound No. The characteristics as an electrophotographic photosensitive member were evaluated in the same manner as in Example 12 except for changing to 9. The results are shown in Table 4.

  Hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 7) was converted to Compound No. The characteristics as an electrophotographic photosensitive member were evaluated in the same manner as in Example 12 except for changing to 10. The results are shown in Table 4.

  Hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 7) was converted to Compound No. The characteristics as an electrophotographic photosensitive member were evaluated in the same manner as in Example 12 except for changing to 11. The results are shown in Table 4.

  Hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 7) was converted to Compound No. Except for changing to 12, the same operation as in Example 12 was performed to evaluate the characteristics as an electrophotographic photosensitive member. The results are shown in Table 4.

  Hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 7) was converted to Compound No. The characteristics as an electrophotographic photosensitive member were evaluated in the same manner as in Example 12 except for changing to 13. The results are shown in Table 4.

  The characteristics as an electrophotographic photosensitive member were evaluated in the same manner as in Example 12 except that the charge generation layer coating solution was changed to that of Example 10. The results are shown in Table 4.

  The characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Example 12 except that the charge generation layer coating solution was changed to that of Example 11. The results are shown in Table 4.

[Comparative Example 3]
In place of the hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 7) used in Example 12, V-type hydroxygallium phthalocyanine of the following structural formula (48) showing the X-ray powder diffraction spectrum of FIG. 19 (Comparative Compound No. 7). The characteristics as an electrophotographic photosensitive member were evaluated in the same manner as in Example 12 except that 3) was used. The results are shown in Table 4.

  From Table 4, all the electrophotographic photoreceptors of the present invention have a comparative example No. It can be seen that the charging potential and sensitivity stability in the repeated fatigue characteristics are superior to the photoconductor No. 3.

Similarly, the electrophotographic photosensitive member produced in Example 12 was mounted on a remodeled imgio MF2200 manufactured by Ricoh, and was charged at a normal temperature and humidity (23 ° C., 55%) at a potential of −800 (V) and a potential of −100 after exposure. After setting to (V), this electrophotographic apparatus is left in a low-temperature and low-humidity (10 ° C., 15%) environmental test room for 4 hours, and the post-charging potential (V) and exposure in a low-temperature and low-humidity environment. Evaluation was made for post-potential (V) fluctuations.
The results are shown in Table 5.

  An electrophotographic photosensitive member was produced in the same manner as in Example 21 except that the charge generation layer coating solution used in Example 11 was used instead of the charge generation layer coating solution used in Example 21, and a low temperature and low humidity was prepared. Evaluation was made on fluctuations in the post-charging potential (V) and the post-exposure potential (V) under the environment. The results are shown in Table 5.

[Comparative Example 4]
In place of the hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 7) used in Example 21, the Y-type titanyl phthalocyanine pigment of the following structural formula (49) showing the powder X-ray diffraction spectrum of FIG. An electrophotographic photosensitive member was produced in the same manner as in Example 21 except that 4) was used, and the post-charge potential (V) and post-exposure potential (V) fluctuations in a low-temperature and low-humidity environment were evaluated. . The results are shown in Table 5.

[Comparative Example 5]
19.48 g (152.0 mmol) of phthalonitrile, 1.03 g (8.00 mmol) of 2,3-dicyanopyridine, 14.97 g (44.00 mmol) of tetra-n-butyl orthotitanate, 4.80 g of urea (80. 00 mmol) and 24.48 g of 1-octanol were heated and stirred at 150 to 161 ° C. for 6 hours under a nitrogen stream. After standing to cool, 80 ml of methanol was added, stirred for 30 minutes under reflux and cooled to room temperature. The crystals obtained by filtration were washed with toluene, methanol and water, dried under reduced pressure and dried to give blue powder of titanyl pyridoporphy. 19.38 g (yield 84.0%) of the azine derivative mixture was obtained. 80 g of concentrated sulfuric acid was stirred and cooled in an ice-water bath, and 5.00 g of the resulting titanyl pyridoporphyrazine derivative mixture was added in small portions over 30 minutes and dissolved. After stirring for 1 hour, the contents were dropped into 500 g of ice water, and after stirring for 30 minutes, filtration was performed to obtain 28.9 g of a wet cake (solid content concentration: 17.3%).
To 17.3 g of this wet cake, 9.7 g of ion-exchanged water and 120 g of tetrahydrofuran were added, and the mixture was stirred at room temperature for 6 hours. This was filtered and dried under reduced pressure to obtain 2.72 g of a blue crystalline titanyl pyridoporphyrazine derivative mixture (Comparative Compound No. 5).
The powder X-ray diffraction spectrum of the obtained titanyl pyridoporphyrazine derivative mixture is shown in FIG.

  Similar to Example 21 except that this titanyl pyridoporphyrazine derivative mixture (Comparative Compound No. 5) was used instead of the hydroxygallium pyridoporphyrazine derivative mixture (Compound No. 7) used in Example 21. An electrophotographic photosensitive member was prepared by operating, and the fluctuations in the post-charging potential (V) and the post-exposure potential (V) in a low temperature and low humidity environment were evaluated. The results are shown in Table 5.

表５から明らかなように感光層にヒドロキシガリウムピリドポルフィラジン誘導体混合物が含有された本発明の電子写真感光体は、低温低湿下の環境においても帯電性、感度特性の変動が、比較例Ｎｏ．４および比較例Ｎｏ．５の感光体に比べ小さいことがわかる。

As is apparent from Table 5, the electrophotographic photosensitive member of the present invention in which the photosensitive layer contains a mixture of hydroxygallium pyridoporphyrazine derivatives exhibits a change in chargeability and sensitivity characteristics even in an environment of low temperature and low humidity. . 4 and Comparative Example No. As can be seen from FIG.

  As is clear from the above explanation, the electrophotographic photosensitive member of the present invention containing a mixture of hydroxygallium pyridoporphyrazine derivatives in the photosensitive layer has high sensitivity in the visible region and near infrared region, and has a charging property due to repeated fatigue. The reduction, increase in residual potential (decrease in sensitivity), and fluctuations due to temperature and humidity are small, and it is useful for electrophotographic methods, electrophotographic apparatuses and electrophotographic process cartridges using the electrophotographic photosensitive member. I understand.

(About Figure 21)
DESCRIPTION OF SYMBOLS 10 Photoconductor 11 Charging member 12 Image exposure member 13 Developing member 14 Conveying roller 15 Transfer paper 16 Transfer member 17 Cleaning member 18 Static elimination member (about FIG. 22)

10C, 10M, 10Y, 10K Drum-shaped photoreceptors 11C, 11M, 11Y, 11K Charging members 12C, 12M, 12Y, 12K Laser light irradiation 13C, 13M, 13Y, 13K Developing members 16C, 16M, 16Y, 16K Transfer unit 17C, 17M, 17Y, 17K Cleaning member 19 Transfer conveyor belts 20C, 20M, 20Y, 20K Image forming element unit 21 Paper feed roller 23 Transfer member (secondary transfer member)
24 Fixing member 25 Transfer material conveying means (FIG. 23)
DESCRIPTION OF SYMBOLS 10 Photoconductor 11 Charging member 12 Image exposure member 13 Developing member 16 Transfer member 17 Cleaning member

Japanese Patent No. 3123185 Japanese Patent No. 3166293 Japanese Patent No. 2637487 Japanese Patent No. 2,637,485 Japanese Examined Patent Publication No. 3-27111 Japanese Patent No. 4293694 Japanese Patent No. 4419873

Y. Fujimaki, Proc. IS & T ’s 7th International Congress on Advances in Non-Impact Printing Technologies, 1, 269 (1991) K. Daimon, et al .: J. Imaging Sci. Technol., 40, 249 (1996)

Claims (12)

An electrophotographic photosensitive member in which at least a photosensitive layer is provided on a conductive support, wherein the photosensitive layer includes at least one of benzene derivative groups represented by the following general formulas (1) to (6); It is represented by the following general formula (20) obtained by reacting at least one of the pyridine derivative groups represented by the general formulas (7) to (18) and a gallium compound represented by the following formula (19). A hydroxygallium pyridoporphyrazine derivative mixture represented by the following general formula (21) is obtained by acid-treating a gallium pyridoporphyrazine derivative mixture comprising gallium phthalocyanine and a plurality of gallium pyridoporphyrazine derivatives. An electrophotographic photosensitive member comprising:

(In the formula, R ¹ represents a nitro group, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, benzo, or a pyride. M represents an integer of 0 to 4, and when m is 2 or more, R ¹ may be the same. May be different.)

(In the formula, R ² represents a nitro group, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, benzo, or a pyrido. N represents an integer of 0 to 3, and when n is 2 or more, R ² may be the same. May be different.)

(In the formula, R ³ represents a halogen atom or an alkoxy group.)

(In the formula, A, B, C, and D are unsubstituted or represent benzo or pyrido which may have a nitro group, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, benzo, or a pyrido as a substituent; (It may be the same or different, and R ³ represents a halogen atom or an alkoxy group.)

(In the formula, A, B, C, and D are unsubstituted or represent benzo or pyrido which may have a nitro group, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, benzo, or a pyrido as a substituent; It may be the same or different.)   An electrophotographic photosensitive member having at least a photosensitive layer provided on a conductive support, wherein the photosensitive layer has at least a Bragg angle (2θ ± 0.2 °) of 7.4 ° in an X-ray diffraction spectrum by CuKα rays. 2. A hydroxygallium pyridoporphyrazine derivative mixture represented by the general formula (21) having strong diffraction peaks at 16.2 °, 25.2 °, and 28.3 °. The electrophotographic photosensitive member described.   An electrophotographic photoreceptor having at least a photosensitive layer on a conductive support, wherein the photosensitive layer contains a hydroxygallium pyridoporphyrazine derivative mixture represented by the general formula (21) and an azo pigment. The electrophotographic photosensitive member according to claim 1, wherein:   An electrophotographic photosensitive member provided with at least a photosensitive layer on a conductive support, wherein the photosensitive layer contains a hydroxygallium pyridoporphyrazine derivative mixture represented by the general formula (21) and a phthalocyanine pigment. The electrophotographic photosensitive member according to claim 1, wherein:   5. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer is formed by sequentially laminating at least a charge generation layer and a charge transport layer.   The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer is formed by sequentially laminating at least a charge transport layer and a charge generation layer.   The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer is a single-layer type photosensitive layer.   An electrophotographic method in which at least charging, image exposure, development, and transfer are repeatedly performed on an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 1 to 7. An electrophotographic method characterized by the above.   Digital electrophotography in which at least charging, image exposure, development, and transfer are repeated on an electrophotographic photosensitive member, and an electrostatic latent image is written on the photosensitive member by an LD or LED during image exposure. 8. An electrophotographic method, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 1 to 7.   An electrophotographic apparatus comprising at least a charging unit, an image exposing unit, a developing unit, a transfer unit, and an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is any one of claims 1 to 7. An electrophotographic apparatus characterized by being a body.   An electrophotographic apparatus comprising at least a charging unit, an image exposing unit, a developing unit, a transferring unit, and an electrophotographic photosensitive member, wherein an electrostatic latent image is formed on the photosensitive member by using an LD or an LED as the image exposing unit. An electrophotographic apparatus according to claim 1, wherein the electrophotographic photosensitive body is an electrophotographic photosensitive body according to claim 1, wherein an image is written.   An electrophotographic photosensitive member comprising at least an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 1 to 7. Process cartridge for equipment.

Images