JP5569781B2 - Electrophotographic photoreceptor using novel gallium phthalocyanine compound, image forming method, image forming apparatus, and process cartridge for image forming apparatus - Google Patents

Description

  The present invention relates to a photosensitive material for electrophotography, a material for a photoelectric conversion element, a material for an organic semiconductor element, an electrophotographic photoreceptor using a novel gallium phthalocyanine compound useful as an optical recording material, an image forming method, an image forming apparatus, and an image. The present invention relates to a process cartridge for a forming apparatus.

  Phthalocyanine compounds are useful materials that are widely used as paints and electronic materials. In particular, phthalocyanine compounds have recently been widely studied as electrophotographic photosensitive materials, optical recording materials, and photoelectric conversion element materials. As for electrophotographic photosensitive materials, many phthalocyanine compounds having photosensitivity in the near-infrared wavelength region of a semiconductor laser have been proposed so far, and both improvement in sensitivity of electrophotographic photosensitive members and improvement in stability over time have been achieved. Therefore, studies on crystal forms of phthalocyanine compounds have been focused on.

  In general, phthalocyanine compounds are known to exhibit a large number of crystal types due to differences in production methods and processing methods, and it is known that this difference in crystal types has a large effect on the photoelectric conversion efficiency and the repeatability of phthalocyanine compounds. It has been. Regarding the crystal form of phthalocyanine compounds, for example, regarding copper phthalocyanine, crystal forms such as α, π, χ, ρ, γ, and δ are known in addition to the stable β form, and these crystal forms are mechanical. It is known that mutual transfer is possible by external force, sulfuric acid treatment, organic solvent treatment, heat treatment or the like.

As for the gallium phthalocyanine compound, Japanese Patent Application Laid-Open No. 5-98181 in Patent Document 1, Japanese Patent Application Laid-Open No. 5-263007 in Patent Document 2, Japanese Patent Application Laid-Open No. 7-53892 in Japanese Patent Application Laid-Open No. And Japanese Patent Application Laid-Open No. 2001-323183 of Patent Document 5.
However, the hydroxygallium phthalocyanine compounds described in these documents generally have extremely low solubility in organic solvents, and purification is limited to washing with organic solvents, and impurities may not be sufficiently removed. In addition, many methods using acid paste in combination with the synthesis of gallium phthalocyanine compounds have been proposed. However, since concentrated sulfuric acid is used, it is difficult to handle in production, and application to pigments is limited. In some cases, the decomposed product has an adverse effect on the electrical characteristics of the electrophotographic photoreceptor.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to realize high image quality and high stability of an electrophotographic apparatus (an image forming apparatus such as a copying machine or a laser printer). It is an object of the present invention to provide an electrophotographic photosensitive member, an image forming method, an image forming apparatus, and a process cartridge for an image forming apparatus that use a novel gallium phthalocyanine compound having a high solubility in water.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the inventions described in the following (1) to (6), and have reached the present invention.
(1) New phthalocyanine compound represented by the following following general formula (I).

[In the formula (I), X has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent. Or an aryl group which may have a substituent. Examples of the substituent include an alkoxy group, an alkylthio group, an alkyl group, a halogen atom, a nitro group, an amino group, an aryl group, a carboxy group, and a cyano group. R1 to R16 are each independently hydrogen, an alkoxy group, an alkylthio group, an alkyl group, a halogen atom, a nitro group, or an aryl group. n is an integer of 1 or 2. ]
(2) An electrophotographic photosensitive film characterized in that a photosensitive layer having a charge generating material is formed on a conductive support, and the charge generating material contains a novel gallium phthalocyanine compound represented by the following general formula (I): body.

［但し、式（Ｉ）中、Ｘ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ルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアラルキル基、置換基を有してもよいアリール基を表わす。置換基としては、アルコキシ基、アルキルチオ基、アルキル基、ハロゲン原子、ニトロ基、アミノ基、アリール基、カルボキシ基、シアノ基があげられる。Ｒ１〜Ｒ１６はそれぞれ独立して、水素、アルコキシ基、アルキルチオ基、アルキル基、ハロゲン原子、ニトロ基、アリール基、が挙げられる。ｎは１または２の整数である。］

[In the formula (I), X has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent. Or an aryl group which may have a substituent. Examples of the substituent include an alkoxy group, an alkylthio group, an alkyl group, a halogen atom, a nitro group, an amino group, an aryl group, a carboxy group, and a cyano group. R1 to R16 are each independently hydrogen, an alkoxy group, an alkylthio group, an alkyl group, a halogen atom, a nitro group, or an aryl group. n is an integer of 1 or 2. ]

(3) the charge generating material is said to be characterized der Rukoto obtained by reacting the halogenated phthalocyanine or hydroxygallium phthalocyanine with sulfonic acid compound (2) The electrophotographic photoreceptor according to claim.
(4) An image forming method comprising using the electrophotographic photoreceptor described in (2) or (3).
(5) An image forming apparatus comprising the electrophotographic photoreceptor according to (2) or (3).
(6) A process cartridge for an image forming apparatus, comprising the electrophotographic photosensitive member according to (2) or (3).

  Since the novel gallium phthalocyanine compound represented by the general formula (I) of the present invention has high solubility in an organic solvent, it can be purified by recrystallization or adsorption treatment by column chromatogram using silica gel, alumina or the like. Therefore, a charge generation material with a reduced amount of impurities can be realized. In addition, the target product can be obtained without performing an acid paste process using sulfuric acid, and impurities can be reduced. That is, the gallium phthalocyanine compound of the present invention is extremely useful as a charge generation material used for an electrophotographic photoreceptor.

It is a schematic sectional drawing which shows an example of the electrophotographic photoreceptor of this invention. It is a schematic sectional drawing which shows another example of the electrophotographic photoreceptor of this invention. It is a schematic sectional drawing which shows another example of the electrophotographic photosensitive member of this invention. It is a schematic sectional drawing which shows another example of the electrophotographic photosensitive member of this invention. 1 is a schematic view showing an electrophotographic process and an image forming apparatus of the present invention. FIG. 3 is a diagram illustrating an example of an electrophotographic process of the present invention and a charging unit of an image forming apparatus. 1 is a schematic view of a tandem full-color electrophotographic apparatus of the present invention. It is the schematic which shows an example of the process cartridge of this invention.

  Next, the novel gallium phthalocyanine compound (which is a novel compound) represented by the general formula (I) of the present invention will be described.

  [In the formula (I), X has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent. Or an aryl group which may have a substituent. Examples of the substituent include an alkoxy group, an alkylthio group, an alkyl group, a halogen atom, a nitro group, an amino group, an aryl group, a carboxy group, and a cyano group. R1 to R16 are each independently hydrogen, an alkoxy group, an alkylthio group, an alkyl group, a halogen atom, a nitro group, or an aryl group. n is an integer of 1 to 3. ]

  Among these, the novel gallium phthalocyanine represented by the general formula (II) is particularly preferable as an electrophotographic photosensitive material from the viewpoint of photoelectric conversion efficiency.

［但し、式（ＩＩ）中、Ｙ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ルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアラルキル基、置換基を有してもよいアリール基を表わす。置換基としては、アルコキシ基、アルキルチオ基、アルキル基、ハロゲン原子、ニトロ基、アミノ基、アリール基、カルボキシ基、シアノ基などがあげられる。］

[In the formula (II), Y has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent. Or an aryl group which may have a substituent. Examples of the substituent include an alkoxy group, an alkylthio group, an alkyl group, a halogen atom, a nitro group, an amino group, an aryl group, a carboxy group, and a cyano group. ]

  The novel gallium phthalocyanine compound of the present invention can be synthesized by reacting a halogenated gallium phthalocyanine or hydroxygallium phthalocyanine with a sulfonic acid derivative in an organic solvent. Examples of the halogenated gallium phthalocyanine include chlorogallium phthalocyanine, bromogallium phthalocyanine, iodine gallium phthalocyanine, and the like, which can be synthesized by a known method. For example, chlorogallium phthalocyanine is disclosed in D.C. C. Acad. Sci. , (1965), 242, 1026, and the method of reacting gallium trichloride with diiminoisoindoline. Bromogallium phthalocyanine can be synthesized by a method of reacting gallium tribromide and phthalonitrile described in JP-A-59-133551 of Patent Document 6. Iodine gallium phthalocyanine can be synthesized by a method of reacting gallium triiodide and phthalonitrile described in JP-A-60-59354 of Patent Document 7. Hydroxygallium phthalocyanine can be obtained by hydrolyzing the above-mentioned gallium halide phthalocyanine. Hydrolysis may be acid hydrolysis or alkaline hydrolysis. Regarding acid hydrolysis, see, for example, Bull. Soc. Chim. France, 23 (1962), and can be obtained by a method of hydrolyzing chlorogallium phthalocyanine using sulfuric acid. Regarding alkaline hydrolysis, Inlog. Chem. (19), 3131, (1980) can be obtained by the decomposition method using ammonia.

Subsequently, the novel gallium phthalocyanine compound of the present invention can be synthesized by reacting the obtained gallium halide phthalocyanine or hydroxygallium phthalocyanine with a sulfonic acid compound. be able to. As described above, this is due to the production method, and in the production method of hydroxygallium phthalocyanine, generation of decomposition products is unavoidable when the hydrolysis treatment using acid or alkali is performed.
In contrast, halogenated gallium phthalocyanine can be produced without providing a hydrolysis step. Therefore, in the present invention, there is no generation of a decomposition product as a synthesis raw material, and halogen having a small production step. Gallium phthalocyanine can be favorably used.

  Examples of the sulfonic acid compound of the present invention include methane sulfonic acid, ethane sulfonic acid, butane sulfonic acid, pentanes sulfonic acid, hexane sulfonic acid, heptane sulfonic acid, octanes sulfonic acid, hexadecane sulfonic acid, trifluoromethane sulfonic acid, nonafluoro- 1-butane sulfonic acid, heptadecafluorooctane sulfonic acid, 2-chloroethane sulfonic acid, 2-bromoethane sulfonic acid, vinyl sulfonic acid, benzene sulfonic acid, p-toluene sulfonic acid, p-chlorobenzene sulfonic acid, nitrobenzene sulfonic acid, Pyridinesulfonic acid, 1-naphthalenesulfonic acid, 4-aminonaphthalene-1-sulfonic acid, anthraquinone-2-sulfonic acid, 1,3-benzenedisulfo Acid, 1,5-naphthalenedicarboxylic sulfonic acid, 1,3-propane-di sulfonic acid, and 1,4-butane-di sulfonic acid.

  As for the quantitative ratio of the halogenated gallium phthalocyanine or hydroxygallium phthalocyanine and the sulfonic acid derivative, when n in the general formula (I) is 2, the sulfonic acid derivative is preferably about a half mole.

    When n in the general formula (I) is 1, the sulfonic acid derivative in the general formula (II) is suitable in an equimolar amount or more, and varies depending on the reactivity of the sulfonic acid derivative used. Mole is suitable. Further, when the sulfonic acid derivative is liquid at the reaction temperature, it may be used as a solvent.

  Examples of the organic solvent used here include dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dioxane, 2-butanone, cyclohexanone, monochlorobenzene, dichlorobenzene, toluene, xylene, anisole, Examples thereof include nitrobenzene, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethyl acetate, butyl acetate, dichloroethane, trichloroethane, pyridine, picoline or quinoline.

  The reaction can be carried out by reacting at a temperature of 0 ° C. to 200 ° C., preferably 20 ° C. to 150 ° C. for 30 minutes to 50 hours.

  In the present invention, the novel gallium phthalocyanine compound represented by the general formula (I) has a high solubility in an organic solvent. Examples of the organic solvent to be dissolved include ether solvents such as tetrahydrofuran and dioxane, or ethylene glycol methyl Glycol ether solvents such as ether, ethylene glycol ethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, ethyl acetate, butyl acetate, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, monochlorobenzene, dichlorobenzene, toluene Xylene, anisole, n-hexane, cyclohexane, cyclohexanone, nitrobenzene, pyridine, picoline, quinoline, and the like, and mixed solvents thereof.

  It is also preferred to use a method in which the solution is adsorbed with silica gel, alumina, florisil, activated carbon, activated clay, diatomaceous earth, or perlite. Specific methods of the adsorption treatment include column chromatography, room temperature, or a method of adding an adsorbent during heating and filtering. Further, the treatment can be performed more efficiently by combining with recrystallization.

  Next, the structure of the electrophotographic photosensitive member of the present invention will be described in detail with reference to the drawings. As shown in FIG. 1, the photoreceptor (1) of the present invention comprises, on a conductive support (2), a charge generation layer (3) containing a charge generation material as a main component and a charge transport material as a main component. The charge transport layer (4) to be stacked is laminated.

As shown in FIG. 2, the photoreceptor (1) of the present invention has an undercoat layer (6) or an intermediate layer between the conductive support (2) and the charge generation layer (3). It may be formed.
In the photoreceptor (1) of the present invention, a protective layer (5) may be formed on the charge transport layer (4) as shown in FIG.
Further, as shown in FIG. 4, the photoreceptor (1) of the present invention has a single photosensitive layer (7) containing a charge generation substance and a charge transport substance on a conductive support (2). A layer type photoreceptor may be used.

[Conductive support]
Examples of the conductive support include those having a volume resistance of 10 ¹⁰ Ω · cm or less, such as metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, and platinum, tin oxide, and indium oxide. Metal oxide coated by film or cylindrical plastic or paper by vapor deposition or sputtering, or a plate made of aluminum, aluminum alloy, nickel, stainless steel, etc. After the conversion, a tube subjected to surface treatment such as cutting, superfinishing or polishing can be used. Endless nickel belts and endless stainless steel belts can also be used as the conductive support.
In addition, the conductive support dispersed in an appropriate binder resin on the support can be used as the conductive support of the present invention.

Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, or metal oxide powder such as conductive tin oxide and ITO. It is done.
The binder resin used at the same time includes polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, melamine Thermoplastic, thermosetting resin or photo-curing resin such as resin, urethane resin, phenol resin, alkyd resin and the like can be mentioned.

Such a conductive layer can be provided by dispersing and applying these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.
Furthermore, a heat-shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, and polytetrafluoroethylene-based fluororesin on a suitable cylindrical substrate. Those provided with a conductive layer can be used favorably as the conductive support of the present invention.

[Photosensitive layer]
Next, the photosensitive layer will be described. The laminated photosensitive layer is constituted by sequentially laminating at least a charge generation layer and a charge transport layer.

[Charge generation layer]
The charge generation layer of the present invention comprises a coating solution prepared by dissolving or dispersing a charge generation material containing at least the novel gallium phthalocyanine compound represented by the general formula (I) and a binder resin on a conductive support or undercoating. It is formed by drying after coating on a layer or an intermediate layer.
Binder resins used in the charge generation layer include polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, polysulfone, poly-N-vinylcarbazole, polyacrylamide. , Polyvinyl benzal, polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polyamide, polyvinyl pyridine, cellulose resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone and the like. The amount of the binder resin is preferably 0 to 500 parts by mass and more preferably 10 to 300 parts by mass with respect to 100 parts by mass of the charge generation material.

  Solvents used to form the charge generation layer include isopropanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, ligroin, etc. Although generally used organic solvents are mentioned, among these, ketone solvents, ester solvents, and ether solvents are particularly preferable. These may be used alone or in combination of two or more.

  The charge generating pigment of the present invention may be dispersed as necessary for crystal type adjustment. As a dispersion method, any known ball mill, attritor, sand mill, ultrasonic wave, or the like can be used in a suitable solvent together with a binder resin. The binder resin may be added before or after the charge generating material is dispersed.

The coating solution for forming the charge generation layer is mainly composed of a charge generation material, a binder resin and a solvent. Among them, any additive such as a sensitizer, a dispersant, a surfactant, and silicone oil is contained. It may be included.
As a method for coating the charge generation layer using the coating solution, known methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating, and the like can be used.
The thickness of the charge generation layer is preferably about 0.01 to 5 μm, more preferably 0.1 to 2 μm. After coating, it is heated and dried in an oven or the like. The drying temperature of the charge generation layer in the present invention is preferably from 50 ° C. to 160 ° C., more preferably from 80 ° C. to 140 ° C.

[Charge transport layer]
Next, the charge transport layer will be described. The charge transport layer is formed by applying and drying a coating liquid in which a charge transport material and a binder resin are dissolved or dispersed in a solvent. Moreover, you may add additives, such as a plasticizer, a leveling agent, antioxidant, a lubricant, etc. individually or in 2 types or more to the coating liquid of a charge transport layer as needed.

Examples of the charge transport material include a hole transport material and an electron transport material.
Examples of the hole transport material include poly-N-vinylcarbazole and derivatives thereof, poly-γ-carbazolylethyl glutamate and derivatives thereof, pyrene-formaldehyde condensates and derivatives thereof, polyvinylpyrene, polyvinylphenanthrene, polysilane, oxazole derivatives, Oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, 9-styrylanthracene derivatives, pyrazolines Derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, etc., bisstilbene derivatives, enamine derivatives, etc. Other known materials may be mentioned. These charge transport materials may be used alone or in combination of two or more.

Examples of the electron transporting 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-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-tri Examples thereof include electron-accepting substances such as nitrodibenzothiophene-5,5-dioxide and benzoquinone derivatives.
These charge transport materials may be used alone or in combination of two or more. The content of the charge transport material is usually 20 to 300 parts by weight and preferably 40 to 150 parts by weight with respect to 100 parts by weight of the binder resin.
Binder resins include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, poly Vinylidene chloride, polyarylate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly (N-vinylcarbazole), acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, Examples thereof include thermoplastic or thermosetting resins such as phenol resins and alkyd resins.

As the solvent, tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone or the like is used. Among them, the use of a non-halogen solvent is desirable for the purpose of reducing the environmental load. Specifically, cyclic ethers such as tetrahydrofuran, dioxolane and dioxane, aromatic hydrocarbons such as toluene and xylene, and derivatives thereof are preferably used. Two or more of these may be used in combination.
The film thickness of the charge transport layer is preferably 10 to 50 μm, more preferably 15 to 35 μm, from the viewpoint of resolution and responsiveness.
As a coating method, known methods such as a dip coating method, a spray coating method, a bead coating method, a nozzle coating method, a spinner coating method, and a ring coating method can be used, but the charge transport layer has a certain thickness. Since it is necessary to apply thickly, it is preferable to apply the dip coating method with a highly viscous liquid.
The charge transport layer after coating is heated and dried by a thermal means used in the charge generation layer. Although drying temperature changes also with the solvent contained in a coating liquid, it is preferable that it is 80-200 degreeC, and 110-170 degreeC is more preferable. The drying time is preferably 10 minutes or more, more preferably 20 minutes or more.

[Single layer]
Next, the case where the photosensitive layer has a single layer structure will be described.
This is a photoreceptor in which the above-described charge generation material and charge transport material are dispersed or dissolved in a binder resin to realize a charge generation function and a charge transport function in one layer.
In the photosensitive layer, a charge generating substance, a charge transporting substance and a binder resin are dissolved or dispersed in a solvent such as tetrahydrofuran, dioxane, dichloroethane, methyl ethyl ketone, cyclohexane, cyclohexanone, toluene, xylene, etc., and this is dip coating, spray coating, bead coating. It can be formed by coating using a conventionally known method such as ring coating.

The charge transport material preferably contains both the hole transport material and the electron transport material described above. Moreover, a plasticizer, a leveling agent, antioxidant, etc. can also be added as needed.
Regarding the charge generating substance, charge transporting substance, binder resin, organic solvent and various additives used in the single photosensitive layer, any material contained in the above-described charge generating layer and charge transporting layer should be used. Is possible.
As the binder resin, in addition to the binder resin previously mentioned in the charge transport layer, the binder resin mentioned in the charge generation layer may be mixed and used. The amount of the charge generating material with respect to 100 parts by mass of the binder resin is preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass. The amount of the charge transport material is preferably 0 to 190 parts by mass, and more preferably 50 to 150 parts by mass. Further, the film thickness of the photosensitive layer is preferably 5 to 40 μm, more preferably 10 to 30 μm.

[Underlayer]
In the photoreceptor of the present invention, an undercoat layer can be provided between the conductive support and the photosensitive layer.
In general, the undercoat layer is mainly composed of a resin. However, in consideration of applying a photosensitive layer using a solvent thereon, such a resin is a resin having high solvent resistance to a general organic solvent. Preferably there is. 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 resins, phenol resins, alkyd-melamine resins, and isocyanates. And curable resins that form a three-dimensional network structure, such as epoxy resins.
Further, a fine powder pigment of a metal oxide such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, or indium oxide may be added to the undercoat layer in order to prevent moire and reduce residual potential.
Moreover, it can form using a solvent and a coating method similarly to the above-mentioned charge generation layer and charge transport layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer.

[Protective layer]
In the present invention, a protective layer can be provided on the outermost surface of the photoreceptor in order to improve wear resistance.
As the protective layer, a polymer charge transport material type obtained by polymerizing a charge transport component and a binder component, a filler dispersion type containing a filler, a curable type obtained by curing a constituent material having a reactive functional group, and the like are known. However, in the present invention, any conventionally known protective layer can be used.

[Image forming apparatus]
Next, the electrophotographic method and the image forming apparatus of the present invention will be described in detail with reference to the drawings.
FIG. 5 is a schematic view 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.
As shown in FIG. 5, the photoconductor (1) has a drum shape, but may be a sheet or an endless belt. For charging roller (12), pre-transfer charger (15), transfer charger (18), separation charger (19), pre-cleaning charger (21), in addition to corotron, scorotron, solid state charger (solid state charger) A roller-shaped charging member or a brush-shaped charging member is used, and all known means can be used.
As the charging member, a non-contact charging method such as corona charging or a contact charging method using a charging member using a roller or a brush is generally used, and any of them can be used effectively in the present invention. In particular, the charging roller can significantly reduce the amount of ozone generated compared to corotron, scorotron, etc., and is effective in stability and prevention of image quality deterioration when the photoreceptor is used repeatedly.

However, due to the contact between the photoconductor and the charging roller, the charging roller is contaminated by repeated use, which affects the photoconductor and contributes to the occurrence of abnormal images and reduced wear resistance. It was.
In particular, when a photoconductor having high wear resistance is used, it is difficult to perform reface due to surface wear, and therefore it is necessary to reduce contamination of the charging roller.

Therefore, as shown in FIG. 6, the charging roller (12) is provided with a gap forming member (12a) and is disposed close to the photoreceptor (1) via the gap, so that contaminants adhere to the charging roller. It is difficult or easy to remove, and the influence thereof can be reduced.
In this case, the gap between the photosensitive member and the charging roller is preferably small, for example, 100 μm or less is preferable, and 50 μm or less is more preferable.
However, by making the charging roller non-contact, discharge may become non-uniform and charging of the photoreceptor may become unstable. Such a problem is caused by maintaining the charging stability by superimposing the alternating current component on the direct current component, thereby making it possible to simultaneously reduce the influence of ozone, the charging roller contamination and the charging effect. .

On the other hand, the light source such as the image exposure unit (13) and the charge removal lamp (11) shown in FIG. 5 includes a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), All luminescent materials such as electroluminescence (EL) 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 provides the photosensitive member (1) with light by providing a transfer step, a static elimination step, a cleaning step, or a pre-exposure step using light irradiation. However, the exposure of the photoreceptor (1) in the charge eliminating step is greatly affected by fatigue on the photoreceptor 1, 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 (1) 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.

As the transfer means, the above-described charger can be generally used. However, as shown in FIG. 5, a combination of the transfer charger (18) and the separation charger (19) is effective.
Further, the toner image is directly transferred from the photosensitive member to the paper using such a transfer unit. In the present invention, the toner image on the photosensitive member is once transferred to the intermediate transfer member, and then from the intermediate transfer member to the paper. An intermediate transfer method for transferring the toner to the photoconductor is more preferable for enhancing the durability or improving the image quality of the photoreceptor.
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 intermediate transfer method is particularly effective for image forming apparatuses capable of full-color printing, and controls the prevention of color misregistration by forming a plurality of toner images on the intermediate transfer member and then transferring them to the paper at once. It is easy and effective for high image quality. However, the intermediate transfer method requires four scans to obtain one full-color image, so that the durability of the photoconductor has been a big problem. The photoconductor of the present invention is particularly effective and useful since it is easy to use in combination with an intermediate transfer type image forming apparatus because image blurring hardly occurs even without a drum heater. 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.

The toner developed on the photosensitive member (1) by the developing unit (14) shown in FIG. 5 is transferred to the transfer paper (17), but not all of the toner is transferred to the photosensitive member (1). The toner remaining in the toner is also generated.
Such toner is removed from the photoreceptor (1) by the fur brush (22) or the cleaning blade (23). This cleaning process may be performed only with a cleaning brush or may be performed in combination with a blade, and known cleaning brushes such as a fur brush and a mag fur brush are used. As described above, the cleaning is a process of removing toner remaining on the photosensitive member (1) after the transfer. However, the photosensitive member (1) is repeatedly rubbed by the cleaning blade (23) or the fur brush (22). As a result, wear of the photoconductor (1) is promoted, or an abnormal image may be generated due to scratches.
In addition, if the surface of the photoconductor is contaminated due to poor cleaning, it not only causes an abnormal image, but also significantly reduces the life of the photoconductor.
In particular, in the case of a photoconductor with a protective layer on the outermost layer to improve wear resistance, it is difficult to remove contaminants adhering to the surface of the photoconductor, which promotes the generation of filming and abnormal images. Will do. Therefore, improving the cleaning property of the photoconductor is very effective for improving the durability and image quality of the photoconductor.

As means for improving the cleaning property of the photosensitive member, a method of reducing the coefficient of friction on the surface of the photosensitive member is known. Methods for reducing the coefficient of friction on the surface of the photoreceptor are classified into a method in which various lubricants are contained in the photoreceptor surface and a method in which the lubricant is supplied to the photoreceptor surface from the outside. The former is advantageous for small-diameter photoreceptors because of the high degree of freedom in layout around the engine, but the coefficient of friction increases remarkably with repeated use, and there remains a problem in its sustainability. On the other hand, the latter needs to be provided with a component for supplying a lubricating substance, but is effective for enhancing the durability of the photoreceptor because of high stability of the friction coefficient. Among them, the method of adhering to the photoreceptor during development by incorporating a lubricant into the developer is not restricted by the layout around the engine, and the effect of reducing the friction coefficient on the photoreceptor surface is high. Therefore, it is a very effective means for improving the durability and image quality of the photoreceptor.
These lubricants include lubricating fluids such as silicone oil and fluorine oil, various fluorine-containing resins such as PTFE, PFA and PVDF, silicone resins, polyolefin resins, silicone grease, fluorine grease, paraffin wax, fatty acid esters , Fatty acid metal salts such as zinc stearate, lubricating liquids such as graphite and molybdenum disulfide, solids, powders, and the like, but particularly when mixed with a developer, it must be in the form of a powder, especially stearic acid Zinc has little adverse effect and can be used very effectively. When the zinc stearate powder is contained in the toner, it is necessary to consider the balance and the influence on the toner, and the content is preferably 0.01 to 0.5% by mass with respect to the toner. 3 mass% is more preferable.

  The photoconductor according to the present invention can be applied to a small-diameter photoconductor because high photosensitivity and high stability are realized. Accordingly, as an image forming apparatus or method 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 a very high speed as compared with a conventional image forming apparatus capable of full-color printing.

FIG. 7 is a schematic diagram for explaining the tandem-type full-color electrophotographic apparatus of the present invention, and the following modifications also belong to the category of the present invention.
In FIG. 7, photoconductors (1C) (cyan), (1M) (magenta), (1Y) (yellow), and (1K) (black) are drum-like photoconductors (1), and these photoconductors. (1C), (1M), (1Y), (1K) rotate in the direction of the arrow in the figure, and charging members (12C), (12M), (12Y), (12K), Developing members (14C), (14M), (14Y), (14K), and cleaning members (15C), (15M), (15Y), (15K) are arranged.
The charging members (12C), (12M), (12Y), and (12K) constitute a charging device for uniformly charging the surface of the photoreceptor (1). From the back side of the photoreceptor (1) between the charging members (12C), (12M), (12Y), (12K) and the developing members (14C), (14M), (14Y), (14K). Then, laser beams (13C), (13M), (13Y), and (13K) from an exposure member (not shown) are irradiated, and electrostatic latent images are formed on the photoreceptors (1C), (1M), (1Y), and (1K). Is to be formed.
Then, the four image forming elements (10C), (10M), (10Y), and (10K) centering on such photoconductors (1C), (1M), (1Y), and (1K) serve as transfer materials. It is juxtaposed along the transfer and transport belt (25) which is a transport means. The transfer conveyance belt (25) includes developing members (14C), (14M), (14Y), and (14K) of the image forming units (elements) (10C), (10M), (10Y), and (10K), Between the cleaning members (15C), (15M), (15Y), and (15K), the photosensitive members (1C), (1M), (1Y), and (1K) are in contact with the transfer conveyance belt (25). Transfer brushes (26C), (26M), (26Y), and (26K) for applying a transfer bias are disposed on a surface (back surface) that is in contact with the back side of the photoconductor (1). Each of the image forming elements (10C), (10M), (10Y), and (10K) is different in the color of the toner inside the developing device, and the others are the same in configuration.

In the color electrophotographic apparatus having the configuration shown in FIG. 7, the image forming operation is performed as follows. First, in each of the image forming elements (10C), (10M), (10Y), (10K), the photoconductors (1C), (1M), (1Y), (1K) are in the direction indicated by the arrows (photoconductor (1)). Exposure unit (not shown) which is charged by charging members (12C), (12M), (12Y) and (12K) which rotate in the rotation direction and then arranged outside the photoreceptor (1). Thus, an electrostatic latent image corresponding to each color image to be created is formed by the laser beams (13C), (13M), (13Y), and (13K).
Next, the latent image is developed by developing members (14C), (14M), (14Y), and (14K) to form a toner image. Development members (14C), (14M), (14Y), and (14K) are development members that perform development with toners of C (cyan), M (magenta), Y (yellow), and K (black), respectively. The toner images of the respective colors produced on the two photoconductors (1C), (1M), (1Y), and (1K) are superimposed on the transfer paper. The transfer paper (17) is fed out from the tray by the paper feed roller (24), and is temporarily stopped by the pair of registration rollers (16). The transfer paper (17) is transferred to the transfer conveyance belt (25) in synchronization with the image formation on the photoconductor. Sent.

The transfer paper (17) held on the transfer / conveying belt (25) is conveyed, and each color at the contact position (transfer portion) with each photoconductor (1C), (1M), (1Y), (1K). The toner image is transferred.
The toner image on the photoconductor includes the transfer bias applied to the transfer brushes (26C), (26M), (26Y), and (26K) and the photoconductors (1C), (1M), (1Y), and (1K). The image is transferred onto the transfer paper (17) by an electric field formed from the potential difference. Then, the recording paper (17) on which the four color toner images are passed through the four transfer portions is conveyed to the fixing device (27), where the toner is fixed, and is discharged to a paper discharge portion (not shown). The Further, the residual toner remaining on each of the photoconductors (1C), (1M), (1Y), and (1K) without being transferred by the transfer unit is removed from the cleaning devices (15C), (15M), (15Y), ( 15K).
In the example of FIG. 7, 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 (10C), (10M), and (10Y) other than black.

  Further, although the charging member is in contact with the photosensitive member in FIG. 7, by using a charging mechanism as shown in FIG. 6, an appropriate gap (about 10 to 200 μm) is provided between them. In addition, the wear amount of the both can be reduced, and toner filming on the charging member can be reduced and the toner can be used well.

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.
The process cartridge includes the photoelectric conversion element of the present invention, and further includes at least one of a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, and a charge eliminating unit, and is detachable from the image forming apparatus. Device (parts).
An example of the process cartridge is shown in FIG. 8, but the neutralizing means is not described here.

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.

First, a synthesis example of the novel gallium phthalocyanine compound in the present invention is shown below. In the following description, “part” means “part by weight”.
[Synthesis example of chlorogallium phthalocyanine]
After adding 30 parts of 1,3-diiminoisoindoline and 8 parts of gallium trichloride to 200 ml of dehydrated dimethyl sulfoxide and reacting at 150 ° C. for 12 hours under an Ar stream, the produced chlorogallium phthalocyanine was separated by filtration. . The wet cake was washed with methyl ethyl ketone and N, N-dimethylformamide and then dried to obtain 22 parts (70.3%) of chlorogallium phthalocyanine crystals.

[Synthesis example of hydroxygallium phthalocyanine]
The above-mentioned 5 parts of chlorogallium phthalocyanine was dissolved in 150 parts of concentrated ice-cooled sulfuric acid, and this sulfuric acid solution was gradually added dropwise to 500 ml of ice-cooled ion-exchanged water to precipitate crystals of hydroxygallium phthalocyanine. After the crystals were filtered off, the wet cake was washed with 500 ml of 2 wt% ammonia water, and then thoroughly washed with ion-exchanged water. By drying, 4.6 parts of hydroxygallium phthalocyanine crystals were obtained.

[Synthesis Example 1]
(Synthesis example of gallium phthalocyanine compound of the following structural formula)

To 100 ml of dimethyl sulfoxide, 1.24 parts of chlorogallium phthalocyanine and 3.8 parts of methanesulfonic acid were added, heated to 110 ° C. and reacted for 9 hours. After cooling to room temperature, a trace amount of insoluble part was removed by filtration. About 150 ml of ion exchange water was added to the resulting solution, and the mixture was stirred at room temperature for 3 hours. The produced crystals were filtered, washed thoroughly with ion exchange water, and dried to obtain 1.25 parts (92%) of a gallium phthalocyanine compound. A part of the obtained product was recrystallized from N, N-dimethylformamide, and the following analysis was performed.
By MALDI-TOFMS (negative), m / z: 676.19 (Theoretical value _676.06:. As _{C 33 H 19 GaN 8 O 3} S) was observed. The results of further elemental analysis are shown in the table below.
From these results, it was confirmed that the compound was a gallium phthalocyanine compound having the above structural formula.

[Synthesis Example 2]
(Synthesis example of gallium phthalocyanine compound similar to Synthesis example 1)
The dimethyl sulfoxide of Example 1 was changed to chlorobenzene, and the reaction temperature was 60 ° C. for 5 hours. After cooling to room temperature, the chlorobenzene layer was removed, tetrahydrofuran and then ion-exchanged water were added to the resulting black layer, and the mixture was stirred at room temperature for 2 hours. Thereafter, the same treatment as in Example 1 was performed to obtain 1.19 parts (88%) of a gallium phthalocyanine compound.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, the structure was confirmed to be the same as the spectrum of the compound obtained in Example 1.

[Synthesis Example 3]
(Synthesis example of gallium phthalocyanine compound similar to Synthesis example 1)
To 100 ml of methyl ethyl ketone, 2.47 parts of chlorogallium phthalocyanine and 15.4 parts of methanesulfonic acid were added and refluxed for 7.5 hours. After cooling to room temperature, about 50 ml of ion exchange water was added and stirred at room temperature for 4 hours. The obtained crystals were filtered, washed thoroughly with ion exchange water, and then dried to obtain 2.54 parts (94%) of gallium phthalocyanine compound crystals.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, the structure was confirmed to be the same as the spectrum of the compound obtained in Example 1.

[Synthesis Example 4]
(Synthesis example of gallium phthalocyanine compound similar to Synthesis example 1)
To 100 ml of N, N-dimethylformamide, 2.47 parts of chlorogallium phthalocyanine and 30 parts of methanesulfonic acid were added and reacted at 100 ° C. for 19 hours. After cooling to room temperature, about 50 ml of ion-exchanged water was added and stirred at room temperature for 5 hours. The obtained crystals were filtered, washed thoroughly with ion exchange water, and then dried to obtain 2.32 parts (86%) of gallium phthalocyanine compound crystals.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, the structure was confirmed to be the same as the spectrum of the compound obtained in Example 1.

[Synthesis Example 5]
(Synthesis example of gallium phthalocyanine compound of the following structural formula)

To 100 ml of dimethyl sulfoxide, 1.24 parts of chlorogallium phthalocyanine and 6.0 parts of trifluoromethanesulfonic acid were added, heated to 110 ° C. and reacted for 7 hours. After cooling to room temperature, a trace amount of insoluble part was removed by filtration. About 100 ml of ion exchange water was added to the resulting solution, and the mixture was stirred at room temperature for 3 hours. The produced crystals were filtered, washed thoroughly with ion exchange water, and then dried to obtain 1.43 parts (98%) of a gallium phthalocyanine compound. A part of the obtained product was recrystallized from N, N-dimethylformamide, and the following analysis was performed.
By MALDI-TOFMS (negative), m / z: 730.07 (Theoretical value _730.03:. As _{C 33 H 16 F 3 GaN 8} O 3 S) was observed. The results of further elemental analysis are shown in the table below.
From these results, it was confirmed that the compound was a gallium phthalocyanine compound having the above structural formula.

[Synthesis Example 6]
(Synthesis example of gallium phthalocyanine compound similar to Example 5)
The dimethyl sulfoxide of Example 5 was changed to chlorobenzene, and the reaction temperature was 50 ° C. for 6 hours. After cooling to room temperature, the chlorobenzene layer was removed, tetrahydrofuran and then ion-exchanged water were added to the resulting black layer, and the mixture was stirred at room temperature for 2 hours. Thereafter, the same treatment as in Example 5 was performed to obtain 1.18 parts (82%) of a gallium phthalocyanine compound.
As a result of analysis by infrared absorption spectrum (KBr tablet method) of the above product, the structure was confirmed to be the same as the spectrum of the compound obtained in Example 5.

[Synthesis Example 7]
(Synthesis example of gallium phthalocyanine compound of the following structural formula)

To 150 ml of dimethyl sulfoxide, 2.47 parts of chlorogallium phthalocyanine and 17.6 parts of ethanesulfonic acid were added, heated to 110 ° C. and reacted for 8 hours. After cooling to room temperature, about 100 ml of ion exchange water was added and stirred at room temperature for 4 hours. The produced crystals were filtered, washed thoroughly with ion exchange water, and dried to obtain 2.54 parts (92%) of a gallium phthalocyanine compound.
The following analysis was performed on this compound.
By MALDI-TOFMS (negative), m / z: 690.18 (Theoretical value _690.07:. As _{C 34 H 21 GaN 8 O 3} S) was observed. The results of further elemental analysis are shown in the table below.
From these results, it was confirmed that the compound was a gallium phthalocyanine compound having the above structural formula.

[Synthesis Example 8]
(Synthesis example of gallium phthalocyanine compound of the following structural formula)

To 100 ml of dimethyl sulfoxide, 1.24 parts of chlorogallium phthalocyanine and 6.0 parts of nonafluoro-1-butanesulfonic acid were added, heated to 110 ° C. and reacted for 7 hours. After cooling to room temperature, a trace amount of insoluble part was removed by filtration. About 100 ml of ion exchange water was added to the resulting solution, and the mixture was stirred at room temperature for 4 hours. The produced crystals were filtered, washed thoroughly with ion exchange water, and dried to obtain 1.67 parts (95%) of a gallium phthalocyanine compound.
The following analysis was performed on this compound.
By MALDI-TOFMS (positive), m / z: 879.97 (Theoretical value _880.02:. As _{C 36 H 16 F 9 GaN 8} O 3 S) was observed. The results of further elemental analysis are shown in the table below.
From these results, it was confirmed that the compound was a gallium phthalocyanine compound having the above structural formula.

[Synthesis Example 9]
(Synthesis example of gallium phthalocyanine compound of the following structural formula)

To 100 ml of dimethyl sulfoxide, 1.24 parts of chlorogallium phthalocyanine and 20.0 parts of heptadecafluorooctane sulfonic acid were added, heated to 110 ° C. and reacted for 7 hours. After cooling to room temperature, a trace amount of insoluble part was removed by filtration. About 150 ml of ion-exchanged water was added to the resulting solution, and the mixture was stirred at room temperature for 6 hours. The produced crystals were filtered, washed thoroughly with ion-exchanged water, and dried to obtain 1.94 parts (90%) of a gallium phthalocyanine compound.
The following analysis was performed on this compound.
By MALDI-TOFMS (positive), m / z: 1079.92 (theoretical value _1080.01: as _{C 40 H 16 F 17 GaN 8} O 3 S) was observed. The results of further elemental analysis are shown in the table below.
From these results, it was confirmed that the compound was a gallium phthalocyanine compound having the above structural formula.

[Synthesis Example 10]
(Synthesis example of gallium phthalocyanine compound of the following structural formula)

To 100 ml of dimethyl sulfoxide, 1.24 parts of chlorogallium phthalocyanine and 23 parts of p-chlorobenzenesulfonic acid hydrate were added, heated to 110 ° C. and reacted for 9 hours. After cooling to room temperature, a trace amount of insoluble part was removed by filtration. About 150 ml of ion-exchanged water was added to the resulting solution, and the mixture was stirred at room temperature for 6 hours. The produced crystals were filtered, washed thoroughly with ion exchange water, and then dried to obtain 1.45 parts (94%) of a gallium phthalocyanine compound.
The following analysis was performed on this compound.
By MALDI-TOFMS (negative), m / z: 772.06 (Theoretical value _772.03:. As _{C 38 H 20 ClGaN 8 O 3} S) was observed. The results of further elemental analysis are shown in the table below.
From these results, it was confirmed that the compound was a gallium phthalocyanine compound having the above structural formula.

[Synthesis Example 11]
(Synthesis example of gallium phthalocyanine compound of the following structural formula)

To 100 ml of toluene, 0.48 parts of hydroxygallium phthalocyanine and 2.8 parts of p-toluenesulfonic acid monohydrate were added, heated to 80 ° C. and reacted for 6 hours. After cooling to room temperature, the produced crystals were filtered, washed thoroughly with 2-butanone and then ion-exchanged water, and dried to obtain 0.53 parts (88%) of a gallium phthalocyanine compound.
The following analysis was performed on this compound.
As a result of analysis by infrared absorption spectrum (KBr tablet method), it was confirmed that absorption at about 3480 cm ⁻¹ derived from OH group disappeared.
By MALDI-TOFMS (negative) (positive), m / z: 752.05 (Theoretical value _752.09: as _{C 39 H 23 GaN 8 O 3} S) was observed. The results of further elemental analysis are shown in the table below.
From these results, it was confirmed that the compound was a gallium phthalocyanine compound having the above structural formula.

[Synthesis Example 12]
(Synthesis example of gallium phthalocyanine compound of the following structural formula)

To 100 ml of dimethyl sulfoxide, 0.60 part of hydroxygallium phthalocyanine and 0.20 part of 1,3-propanedisulfonic acid (50-60% aqueous solution) were added, heated to 100 ° C. and reacted for 7 hours. After cooling to room temperature, a trace amount of insoluble part was removed by filtration. About 150 ml of ion-exchanged water was added to the resulting solution, and the mixture was stirred at room temperature for 6 hours. The produced crystal was filtered, sufficiently washed with ion exchange water, and dried to obtain 0.58 part (85%) of a gallium phthalocyanine compound.
The following analysis was performed on this compound.
As a result of analysis by infrared absorption spectrum (KBr tablet method), it was confirmed that absorption at about 3480 cm ⁻¹ derived from OH group disappeared.
The results of further elemental analysis are shown in the table below. (Calculated value is C ₆₇ H ₃₈ Ga ₂ N ₁₆ O ₆ S _2. )
From these results, it was confirmed that the compound was a gallium phthalocyanine compound having the above structural formula.

[Synthesis Example 13]
(Synthesis example of gallium phthalocyanine compound of the following structural formula)

1.20 parts of hydroxygallium phthalocyanine and 17.62 parts of benzenesulfonic acid monohydrate were added to a mixed solvent of 100 ml of 2-butanone and 50 ml of N, N-dimethylformamide, heated to 90 ° C. and reacted for 7 hours. . After cooling to room temperature, the produced crystals were filtered, washed thoroughly with 2-butanone and then ion-exchanged water, and dried to obtain 0.92 part (62%) of a gallium phthalocyanine compound.
The following analysis was performed on this compound.
As a result of analysis by infrared absorption spectrum (KBr tablet method), it was confirmed that absorption at about 3480 cm ⁻¹ derived from OH group disappeared.
By LDI-TOFMS (positive), m / z: 737.99 (theoretical value is 737.07: as C ₃₈ H ₂₁ GaN ₈ O ₃ S) was recognized. The results of further elemental analysis are shown in the table below.
From these results, it was confirmed that the compound was a gallium phthalocyanine compound having the above structural formula.

[Synthesis Example 14]
(Synthesis example of gallium phthalocyanine compound of the following structural formula)

To a mixed solvent of 100 ml of 2-butanone and 50 ml of N, N-dimethylformamide were added 1.20 parts of hydroxygallium phthalocyanine and 22.62 parts of naphthalene sulfonic acid / hydrate, and the mixture was heated to 90 ° C. and reacted for 7 hours. After cooling to room temperature, the produced crystal was filtered, washed thoroughly with 2-butanone and then ion-exchanged water, and dried to obtain 0.66 part (42%) of a gallium phthalocyanine compound.
The following analysis was performed on this compound.
As a result of analysis by infrared absorption spectrum (KBr tablet method), it was confirmed that absorption at about 3480 cm ⁻¹ derived from OH group disappeared.
The LDI-TOFMS (positive), m / z: 787.99 (Theoretical value _788.09: as _{C 42 H 23 GaN 8 O 3} S) was observed. The results of further elemental analysis are shown in the table below.
From these results, it was confirmed that the compound was a gallium phthalocyanine compound having the above structural formula.

[Synthesis Example 15]
(Synthesis example of gallium phthalocyanine compound of the following structural formula)

To a mixed solvent of 100 ml of 2-butanone and 50 ml of N, N-dimethylformamide were added 1.20 parts of hydroxygallium phthalocyanine and 15.92 parts of 3-pyridinesulfonic acid, and the mixture was heated to 90 ° C. and reacted for 7 hours. After cooling to room temperature, the produced crystal was filtered, washed thoroughly with 2-butanone and then ion-exchanged water, and dried to obtain 0.96 part (65%) of a gallium phthalocyanine compound.
The following analysis was performed on this compound.
As a result of analysis by infrared absorption spectrum (KBr tablet method), it was confirmed that absorption at about 3480 cm ⁻¹ derived from OH group disappeared.
The LDI-TOFMS (positive), m / z: 738.97 (Theoretical value _739.07: as _{C 37 H 20 GaN 9 O 3} S) was observed. The results of further elemental analysis are shown in the table below.
From these results, it was confirmed that the compound was a gallium phthalocyanine compound having the above structural formula.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not restrict | limited by these Examples. All parts are parts by weight.
After coating on an aluminum cylinder having a length of 346 mm and a diameter of 40 mm using an intermediate layer coating liquid having the following composition, drying was performed at 130 ° C. for 20 minutes to form an intermediate layer of about 3.5 μm. Subsequently, the coating solution for the charge generation layer having the following composition was ball milled for 2 hours together with zirconia balls having a diameter of 2 mm. After coating with this coating solution, drying was performed at 90 ° C. for 10 minutes to obtain a charge of about 0.3 μm. A generation layer was formed. Furthermore, after coating using a coating solution for a charge transport layer having the following composition, drying was performed at 130 ° C./20 minutes to form a charge transport layer of about 25 μm, and an electrophotographic photosensitive member was produced. In all cases, the dip coating method was used.

(Intermediate layer coating solution)
Titanium oxide CR-EL (manufactured by Ishihara Sangyo Co., Ltd.): 50 parts alkyd resin Beckolite M6401-50 (manufactured by Dainippon Ink & Chemicals, Inc.): 15 parts melamine resin L-145-60 (manufactured by Dainippon Ink & Chemicals, Inc.): 8 parts 2-butanone: 120 parts

(Coating solution for charge generation layer)
Gallium phthalocyanine compound of Synthesis Example 10: 3 parts polyvinyl butyral XYHL (manufactured by UCC): 2 parts methyl ethyl ketone: 160 parts

(Coating liquid for charge transport layer)
Z-type polycarbonate Panlite TS-2050 (manufactured by Teijin Chemicals): 10 parts Charge transporting compound represented by the following structural formula: 7 parts Tetrahydrofuran: 80 parts Silicone oil (KF50-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.): 0. 002 copies

  An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the gallium phthalocyanine compound of Example 1 was changed to that of Synthesis Example 11.

  The electrophotographic photosensitive member thus produced was mounted on an Ricoh digital full-color composite machine imagio MPC5000 which was modified so that the writing LD wavelength was 780 nm. As a process condition at the time of the test, the applied voltage to the charging member was set so that the charged potential of the unexposed portion was −700V. The development bias was set to -500V. As a sheet passing condition, 10,000 sheets were printed using a chart with a writing rate of 6% (characters equivalent to 6% as an image area are written on the entire A4 surface). The test environment was a normal temperature and humidity environment. At this time, the dark portion potential and the bright portion potential at the initial stage and after printing 10,000 sheets were evaluated for image quality. Each evaluation method is as follows. The results are shown in the table below.

Dark portion potential: The surface potential of the photosensitive member when it was moved to the developing portion position after charging was measured. The applied voltage of the charger was adjusted so that the photoconductor before image printing was −700 V, and thereafter, the applied voltage was constant until the end of the test.
Bright portion potential: After charging, the entire surface was exposed, and the surface potential of the photoconductor when moved to the developing portion position was measured.
Image quality: An ISO / JIS-SCID image N1 (portrait) was output before and after printing 10,000 images, and the color color reproducibility was evaluated. The color reproducibility evaluation was carried out in three stages. Good ones were indicated by ◯, slightly inferior ones by Δ, and very bad ones by x.

(About FIGS. 1-4)
DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Conductive support 3 Charge generation layer 4 Charge transport layer 5 Protective layer 6 Undercoat layer 7 Single layer photosensitive layer (about FIG. 5)
DESCRIPTION OF SYMBOLS 1 Photoconductor 11 Static elimination lamp 12 Charging roller 13 Image exposure part 14 Developing unit 15 Charger before transfer 16 Transport roller 17 Transfer paper 18 Transfer charger 19 Separation charger 20 Separation claw 21 Charger before cleaning 22 Fur brush 23 Cleaning blade (about FIG. 6)
DESCRIPTION OF SYMBOLS 1 Photoconductor 12 Charging roller 12a Gap formation member (About FIG. 7)
1, 1C, 1M, 1Y, 1K Photoconductor 10C, 10M, 10Y, 10K Image forming element 12C, 12M, 12Y, 12K Charging member 13C, 13M, 13Y, 13K Laser light 14C, 14M, 14Y, 14K Developing member 15C, 15M, 15Y, 15K Cleaning member 16 Conveying roller 17 Transfer paper 25 Transfer conveying belt 26C, 26M, 26Y, 26K Transfer brush 27 Fixing device (about FIG. 8)
DESCRIPTION OF SYMBOLS 1 Photoconductor 12 Charging member 13 Image exposure member 14 Developing member 17 Transfer paper 18 Transfer member 23 Cleaning member

Japanese Patent Laid-Open No. 5-98181 Japanese Patent Laid-Open No. 5-263007 JP 7-53892 A JP 2009-62475 A JP 2001-323183 A JP 59-133551 A JP 60-59354 A

D. C. Acad. Sci. , (1965), 242, 1026 Bull. Soc. Chim. France, 23 (1962) Inlog. Chem. (19), 3131, (1980)

Claims (6)

New phthalocyanine compound represented by the following following general formula (I).

[In the formula (I), X has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent. Or an aryl group which may have a substituent. Examples of the substituent include an alkoxy group, an alkylthio group, an alkyl group, a halogen atom, a nitro group, an amino group, an aryl group, a carboxy group, and a cyano group. R1 to R16 are each independently hydrogen, an alkoxy group, an alkylthio group, an alkyl group, a halogen atom, a nitro group, or an aryl group. n is an integer of 1 or 2. ] An electrophotographic photoreceptor, wherein a photosensitive layer having a charge generating material is formed on a conductive support, and the charge generating material contains a novel gallium phthalocyanine compound represented by the following general formula (I).

[In the formula (I), X has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent. Or an aryl group which may have a substituent. Examples of the substituent include an alkoxy group, an alkylthio group, an alkyl group, a halogen atom, a nitro group, an amino group, an aryl group, a carboxy group, and a cyano group. R1 to R16 each independently include hydrogen, an alkoxy group, an alkylthio group, an alkyl group, a halogen atom, a nitro group, an aryl group, and the like. n is an integer of 1 or 2. ] The charge generating material is electrophotographic photoreceptor according to claim 2, wherein the der Rukoto obtained by reacting the halogenated phthalocyanine or hydroxygallium phthalocyanine with sulfonic acid compound. Image forming method which comprises using an electrophotographic photosensitive member according to claim 2 or 3. An image forming apparatus characterized by using the electrophotographic photosensitive member according to claim 2 or 3. Image forming apparatus for a process cartridge which comprises using an electrophotographic photosensitive member according to claim 2 or 3.

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