JP4208324B2 - Electrophotographic equipment - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to an electrophotographic apparatus, and more particularly to an electrophotographic apparatus suitable for short wavelength monochromatic light capable of increasing the resolution of an image.
[0002]
[Prior art]
  At present, a semiconductor laser having an oscillation wavelength around 800 nm or around 680 nm is mainly used in an electrophotographic apparatus using a laser typified by a laser printer or the like as a light source. In recent years, there has been a growing need for higher image quality of output images, and various approaches have been taken toward higher resolution. The laser wavelength is also deeply involved in this high resolution, and as described in JP-A-9-240051, as the laser oscillation wavelength becomes shorter, the laser spot diameter can be reduced, A high-resolution latent image can be formed.
[0003]
  There are several methods for shortening the laser oscillation wavelength. One is to use a non-linear optical material and to halve the wavelength of the laser beam using second harmonic generation (SHG) (Japanese Patent Laid-Open Nos. 9-275242 and 9-189930). No., JP-A-5-313033, etc.). Since this system can use a GaAs-based LD or YAG laser that has already established technology and can output high power as a primary light source, it is possible to extend the life and output.
[0004]
  The other uses a wide-gap semiconductor, and the size of the apparatus can be reduced as compared with a device using SHG. LDs using ZnSe-based semiconductors (JP-A-7-321409, JP-A-6-334272, etc.) and GaN-based semiconductors (JP-A-8-88441, JP-A-7-335975, etc.) Due to its high luminous efficiency, it has been the subject of many studies.
[0005]
  However, these LDs have difficulty in optimizing the device structure, crystal growth conditions, electrodes, and the like, and due to defects in the crystal, it has been difficult to oscillate at room temperature, which is essential for practical use. However, technological innovations such as the foundation have progressed, and in October 1997, Nichia Chemical Co., Ltd. reported on a 1150-hour continuous oscillation (50 ° C condition) in an LD using a GaN-based semiconductor. It is a state that is imminent.
[0006]
  On the other hand, in an electrophotographic photosensitive member used in a conventional electrophotographic apparatus using a laser, a material having a large absorption band in a wavelength region near 700 to 800 nm and expressing a practical sensitivity characteristic has been used.
[0007]
  Specific examples include metal-free phthalocyanine, copper phthalocyanine, oxytitanium phthalocyanine having a crystal form described in JP-A-62-267094, JP-A-61-239248, and the like. However, conventional charge generation materials for such long-wavelength lasers do not have a flat absorption band in the vicinity of 380 to 500 nm and do not have sufficient absorption, so that flat and sufficient sensitivity cannot be obtained in such a wavelength region. .
[0008]
  In Japanese Patent Laid-Open No. 9-240051, a single layer or a charge generation layer using α-type titanyl phthalocyanine (described in Japanese Patent Laid-Open No. 61-239248) is used as the outermost surface as a photoreceptor suitable for a 400 to 500 nm laser. Although a multilayer photoreceptor having a layer has been disclosed, it has been found by the present inventors that when this material is used, it is flat and sufficient sensitivity cannot be obtained in such a wavelength region. It was also found that the sensitivity changes depending on the environment such as high temperature and high humidity and low temperature and low humidity.
[0009]
  As a charge generation material, the present inventorsSpecific oxytitaniumAzo face with phthalocyanine and specific structureChargeIt has been found that these problems can be solved by using them.
[0010]
[Problems to be solved by the invention]
  The object of the present invention is to use an electrophotographic photosensitive member and monochromatic light having a small wavelength dependency of sensitivity in the wavelength range of 380 to 500 nm, high sensitivity characteristics, and small sensitivity to environment. An object of the present invention is to provide an electrophotographic apparatus capable of obtaining a stable and high-quality output image.
[0011]
[Means for Solving the Problems]
  In accordance with the present invention on a conductive supportThe charge generation layer and the charge transport layer are laminated in this order from the conductive support side.An electrophotographic photoreceptor having a photosensitive layer and a wavelength of 380;−In an electrophotographic apparatus having an exposure apparatus having monochromatic light in the range of 500 nm as an exposure light source,
  TheCharge generation layerButThe following general formula (6)
[0012]
[4]
[0013]
(In the above formula (6), X ¹ -X ⁴ Represents chlorine or bromine, and k, l, m and n represent integers of 0 to 4)
Oxytitanium having the strongest peak at 27.2 ° of the Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα shown in FIG.Phthalocyanine pigment and azo face represented by the following general formula (1)ChargeThus, an electrophotographic apparatus comprising the above is provided.
[0014]
[Chemical5]
[0015]
  In the formula, Ar represents an aromatic hydrocarbon ring group or a heterocyclic group which may have a substituent which may be bonded directly or via a bonding group, and Cp represents a coupler residue having a phenolic hydroxyl group. Wherein at least one of Cp is a coupler residue represented by the following general formula (2). n represents an integer of 1 to 3. However, a plurality of —N═N—Cp are not bonded to the same benzene ring.
[0016]
[Chemical6]
[0017]
  Where R¹Represents a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group or a nitro group, and R²Represents an alkyl group or an aryl group, R³Represents a halogen atom, an alkyl group, an alkoxy group, a cyano group or a nitro group. j represents 0, 1, 2; when j = 2, R³May be different groups.
[0018]
  Specifically, Ar is an aromatic hydrocarbon ring such as benzene, naphthalene, fluorene, phenanthrene, anthracene, pyrene, furan, thiophene, pyridine, indole, benzothiazole, carbazole, acridone, dibenzothiophene, benzoxazole, oxadi Aromatic heterocycles such as azole and thiazole, and those obtained by bonding the above aromatic rings directly or with an aromatic group or non-aromatic group, such as triphenylamine, diphenylamine, N-methyldiphenylamine, biphenyl, terphenyl , Binaphthyl, fluorenone, phenanthrenequinone, anthraquinone, benzanthrone, diphenyloxadiazole, phenylbenzoxazole, diphenylmethane, diphenylsulfone, diphenylether, benzofe Emissions, stilbene, distyryl benzene, tetraphenyl -p- phenylenediamine, azobenzene, azoxybenzene, include organic groups derived from tetraphenyl benzidine.
[0019]
  Examples of the substituent that the aromatic hydrocarbon group or aromatic heterocyclic group that may be bonded via the above-mentioned bonding group may have include an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, a methoxy group, Examples thereof include alkoxy groups such as ethoxy group and propoxy group, dialkylamino groups such as dimethylamino group and diethylamino group, halogen atoms such as fluorine atom, chlorine atom and bromine atom, hydroxyl group, nitro group, cyano group and halomethyl group.
[0020]
  R in general formula (2)¹, R²And R³In the formula, the halogen atom includes a bromine atom, a chlorine atom, the alkoxycarbonyl group includes a methoxycarbonyl group, an ethoxycarbonyl group, and the like, and the carbamoyl group includes a carbamoyl group, a phenylcarbamoyl group, and the like. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryl group include a phenyl group, a tolyl group, a methoxyphenyl group, and a chlorophenyl group. Groups and the like.
[0021]
  In the general formula (1), Cp may coexist other than the coupler residue represented by the general formula (2).YoPreferred examples of the coupler residue having a phenolic hydroxyl group include a coupler residue represented by the following general formula (8).
[0022]
[Chemical7]
[0023]
  Where R⁴And R⁵Represents a hydrogen atom, an optionally substituted alkyl group, an aryl group, or a heterocyclic group. R⁴And R⁵May form a cyclic amino group via a nitrogen atom. Z represents an oxygen atom or a sulfur atom, and m represents 0 or 1.
[0024]
  R⁴And R⁵As the alkyl group, a methyl group, an ethyl group, a propyl group, etc., an aryl group as a phenyl group, a naphthyl group, an anthryl group, etc., a heterocyclic group as a pyridyl group, a thienyl group, a carbazolyl group, a benzoimidazolyl group, Groups such as benzothiazolyl groups and cyclic amino groups containing nitrogen atoms in the ring include pyrrole group, pyrroline group, pyrrolidine group, pyrrolidone group, indole group, indoline group, carbazole group, imidazole group, pyrazole group, pyrazoline group, oxazine group And phenoxazine group.
[0025]
  Examples of the substituent include an alkyl group such as a methyl group, an ethyl group or a propyl group, an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a dimethylamino group Or a dialkylamino group such as a diethylamino group, a phenylcarbamoyl group, a nitro group, a cyano group, a halomethyl group such as trifluoromethyl, and the like.
[0026]
  SaidOxytitanium having the strongest peak at 27.2 ° of the Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα represented by the general formula (6)PhthalocyanineAs a pigment, 9.0 °, 14.2 °, 23.9 °, and 27.2 °, a crystalline oxytitanium phthalocyanine having a strong peak at 27.2 ° (for example, Described in Japanese Patent No. 128973; FIG. 1), having strong peaks at 9.5 °, 9.7 °, 15.0 °, 24.1 °, 27.2 °, with 27.2 ° being the strongest peak A certain crystal form of oxytitanium phthalocyanine (for example, described in JP-A-1-17066; FIG. 2),Butis there.
[0027]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, embodiments of the present invention will be described in detail.
[0028]
  Specific examples of azo pigment compounds used in the present invention are listed below. As the structural formula, only the portions corresponding to Ar and Cp in the general formula (1) are described. When n is 2 or 3 and Cp is different, the structure is shown as Cp1, Cp2 and Cp3.
[0029]
[Table 1]
[0030]
[Table 2]
[0031]
[Table 3]
[0032]
[Table 4]
[0033]
[Table 5]
[0034]
[Table 6]
[0035]
  Specific examples of the phthalocyanine compound used in the present invention are listed below.
[0036]
  The Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα in the portion corresponding to M in the general formula (9) is shown.
[0037]
[8]
[0038]
  Where X ⁹ ~ X ¹² Represents chlorine or bromine, and w, x, y and z represent integers of 0 to 4. M represents an arbitrary divalent group.
[0039]
【table7]
[0040]
  Next, the electrophotographic photoreceptor in the present invention will be described in detail.
[0041]
  The structure of the photoconductor is shown in the figure.3Known as shown inNo structureIn successis there. Japanese Patent Laid-Open No. 9-240051 discloses a figure.3In the case of a photoreceptor in which a charge generation layer and a charge transport layer are laminated in this order on a conductive support such as the above, light in the range of 380 to 500 nm is absorbed by the charge transport material and does not reach the charge generation layer. However, this is not always the case. If a charge transporting material that is transparent to the oscillation wavelength of monochromatic light is used as the charge transporting material used in the charge transporting layer, the photoconductor of this configuration is sufficient. High sensitivity can be obtained and used.
[0042]
  A function-separated type photoreceptor in which a charge generation layer and a charge transport layer are laminated on a conductive support will be described below.
[0043]
  The charge generation layer is used in the present invention.OxytitaniumPhthalocyanine pigment and azo faceChargeThey are formed by mixing, but may be formed by laminating them individually. the aboveOxytitaniumPhthalocyanine pigment and azo faceChargeWhen mixing (Figure4),OxytitaniumPhthalocyanine pigment / Azo faceFeeThe mixing ratio is preferably 9/1 to 2/8 (% by weight).
[0044]
  For the charge generation layer, the pigment mixed at the above mixing ratio is dispersed by a sand mill or the like together with a suitable binder resin and solvent, or a liquid obtained by individually preparing a liquid having a predetermined mixing ratio is applied. It is formed by doing. The film thickness is preferably a thin film layer of 5 μm or less, more preferably 0.1 to 1 μm.
[0045]
  Also, aboveOxytitaniumPhthalocyanine pigment and the above azo faceChargeThe layer structure when laminated individually is the azo faceChargeWhen the charge generation layer is in contact with the charge transport layer (Fig.5),OxytitaniumWhen the charge generation layer containing the phthalocyanine pigment is in contact with the charge transport layer (Fig.6)ofEither may be used, but the latter layer structure is preferred. The thickness of each layer is preferably 5 μm or less, more preferably 0.1 to 1 μm.
[0046]
  The binder resin used at this time is selected from a wide range of insulating resins or organic photoconductive polymers, but polyvinyl butyral, polyvinyl benzal, polyarylate, polycarbonate, polyester, phenoxy resin, cellulose resin, acrylic resin, Polyurethane and the like are preferable, and these binder resins may have a substituent, and the substituent is preferably a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, a trifluoromethyl group, or the like. The amount of the binder resin used is preferably 80% by weight or less, more preferably 40% by weight or less in terms of the content in the charge generation layer.
[0047]
  The solvent used is preferably selected from those which dissolve the binder resin and do not dissolve the charge transport layer and the undercoat layer described below. Specifically, ethers such as tetrahydrofuran and 1,4-dioxane, ketones such as cyclohexanone and methyl ethyl ketone, amines such as N, N-dimethylformamide, esters such as methyl acetate and ethyl acetate, toluene, xylene, Aromatics such as chlorobenzene, alcohols such as methanol, ethanol and 2-propanol, and aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride and trichloroethylene.
[0048]
  The charge transport layer isaboveThe stacked layer has a function of receiving and transporting charge carriers from the charge generation layer in the presence of an electric field. The charge transport layer is formed by applying a coating solution prepared by dissolving a charge transport material in a solvent together with an appropriate binder resin as necessary. The film thickness is preferably 5 to 40 μm, and preferably 15 to 30 μm. Is more preferable.
[0049]
  The charge transport material includes an electron transport material and a hole transport material. Examples of the electron transport material include 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, and chloranil. And electron withdrawing materials such as tetracyanoquinodimethane, and those obtained by polymerizing these electron withdrawing materials.
[0050]
  Examples of the hole transport material include polycyclic aromatic compounds such as pyrene and anthracene, carbazole, indole, oxazole, thiazole, oxadiazole, pyrazole, pyrazoline, thiadiazole, and triazole compounds. Heterocyclic compounds, hydrazone compounds, styryl compounds, benzidine compounds, triarylmethane compounds, triphenylamine compounds, or polymers having a group consisting of these compounds in the main chain or side chain (for example, poly -N-vinyl carbazole, polyvinyl anthracene, etc.).
[0051]
  These charge transport materials can be used alone or in combination of two or more. When the charge transport material does not have film formability, an appropriate binder resin can be used. Specifically, insulating resins such as acrylic resin, polyarylate, polycarbonate, polyester, polystyrene, acrylonitrile-styrene copolymer, polyacrylamide, polyamide, chlorinated rubber, or organic photoconductive materials such as poly-N-vinylcarbazole and polyvinylanthracene. Include a functional polymer.
[0052]
  However, figure3In the case of using the photosensitive member having the structure described above, it is necessary to select a charge transporting material or binder resin that is transparent to the oscillation wavelength of the monochromatic light used as described above.
[0053]
  Examples of the material for the conductive support include aluminum, aluminum alloy, copper, zinc, stainless steel, vanadium, molybdenum, chromium, titanium, nickel, indium, gold, and platinum. In addition, plastics (for example, supports such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, and acrylic resin) or conductive particles (for example, carbon black, silver particles, etc.) formed by coating these metals or alloys with a vacuum deposition method. ) With a suitable binder resin, a support coated on a plastic, metal or alloy as described above, or a support obtained by impregnating plastic or paper with conductive particles can be used. Examples of the shape include a drum shape, a sheet shape, and a belt shape.
[0054]
  An undercoat layer having a barrier function and an adhesive function may be provided between the conductive support and the photosensitive layer. In addition, a protective layer may be provided for the purpose of protecting the photosensitive layer from external mechanical and chemical adverse effects. In addition, you may use additives, such as antioxidant and a ultraviolet absorber, for a photosensitive layer as needed.
[0055]
  Next, the electrophotographic apparatus of the present invention will be described.
[0056]
  The electrophotographic apparatus of the present invention comprises the above-described electrophotographic photosensitive member and an image exposure unit, a charging unit, a developing unit, and a transfer unit using a monochromatic light having an oscillation wavelength of 380 to 500 nm as an exposure light source.
[0057]
  Figure7FIG. 1 shows a schematic configuration of an electrophotographic apparatus using a process cartridge having the electrophotographic photosensitive member of the present invention.
[0058]
  Figure7, 11 is a drum-shaped electrophotographic photosensitive member according to the present invention, and is driven to rotate at a predetermined peripheral speed in the direction of the arrow about the shaft 12. In the rotation process, the photosensitive member 11 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the primary charging unit 13 and then output from an exposure unit (not shown) such as slit exposure or laser beam scanning exposure. The exposure light 14 that is enhanced and modulated in response to the time-series electric digital image signal of the target image information is received. In this way, electrostatic latent images corresponding to target image information are sequentially formed on the peripheral surface of the photoconductor 11.
[0059]
  The formed electrostatic latent image is then developed with toner by the developing unit 15, and the developed toner image is synchronized with the rotation of the photoconductor 11 between the photoconductor 11 and the transfer unit 16 from a paper supply unit (not shown). Then, the toner image formed and supported on the surface of the photosensitive member 11 is sequentially transferred by the transfer unit 16 to the transfer material 17 taken out and fed.
[0060]
  The transfer material 17 that has received the transfer of the toner image is separated from the photoreceptor surface, introduced into the image fixing means 18, and subjected to image fixing, thereby being printed out as an image formed product (print, copy).
[0061]
  The surface of the photoconductor 11 after the image transfer is cleaned by removing the residual toner after cleaning by the cleaning unit 19, and after being subjected to a charge removal process with a pre-exposure light 20 from a pre-exposure unit (not shown), the surface of the photoconductor 11 is repeated. Used for image formation. When the primary charging unit 13 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary.
[0062]
  In the present invention, a plurality of components such as the electrophotographic photosensitive member 11, the primary charging unit 13, the developing unit 15, and the cleaning unit 19 are integrally combined as a process cartridge. May be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 13, the developing unit 15, and the cleaning unit 19 is integrally supported together with the photosensitive member 11 to form a cartridge, and is detachable from the apparatus main body using guide means such as a rail 22 of the apparatus main body. The process cartridge 21 can be obtained.
[0063]
  Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 14 is reflected light or transmitted light from the original, or is read out from the original with a sensor and converted into a signal. Monochromatic light having an oscillation wavelength.
[0064]
【Example】
  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, "part" in an Example shows a weight part.
[0065]
  (Example 1-1)
  A solution obtained by dissolving 5 parts of methoxymethylated nylon (weight average molecular weight 32,000) and 10 parts of alcohol-soluble copolymer nylon (weight average molecular weight 29000) in 95 parts of methanol on an aluminum support was applied with a Meyer bar and dried. A subbing layer having a thickness of 1 μm was formed.
[0066]
  Next, the azo pigment P¹-4 2.5 parts and 2.5 parts of phthalocyanine pigment F-1 were added to a solution of 2.5 parts of butyral resin (butyralization degree 63 mol%, weight average molecular weight 35000) in 95 parts of cyclohexanone, and a sand mill was used. For 5 hours. This solution was applied onto the undercoat layer with a Meyer bar and dried to form a charge generation layer having a thickness of 0.25 μm.
[0067]
  Next, 5 parts of a charge transport material represented by the following structural formula (10)
[0068]
[Chemical9]
[0069]
A solution in which 5 parts of polycarbonate Z resin (number average molecular weight 20000) was dissolved in 40 parts of monochlorobenzene was applied onto the charge generation layer with a Meyer bar and dried to form a charge transport layer having a thickness of 20 μm.
[0070]
  The electrophotographic photosensitive member thus prepared was evaluated as follows using an electrostatic copying paper testing apparatus (manufactured by Kawaguchi Electric Co .: EPA-8100). The results are shown in Table 1-1.
[0071]
  (sensitivity)
  In an environment of a temperature of 23 ° C./humidity of 50%, the surface potential of the photoconductor is charged with a corona charger so as to be −700 V, and then exposed with 400 nm monochromatic light separated by a monochromator, and the surface potential is −350 V. Measure the amount of light required to attenuate to_1/2) Similarly, the sensitivity in 450 nm and 500 nm monochromatic light was measured.
[0072]
  (Environment dependence of sensitivity)
  In a high-temperature and high-humidity environment (35 ° C./85%) and a low-temperature and low-humidity environment (15 ° C./10%), the sensitivity (E_1/2)
[0073]
  Example 12)
  An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1 except that the charge generation material used in Example 1-1 was replaced with the pigments described in Table 1-1. The results are shown in Table 1-1.
[0074]
  (Comparative Example 1-1)
  Instead of the mixed pigment of Example 1-1, α-type oxytitanium phthalocyanine F-4  An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1-1 except that 5 parts were used. The results are shown in Table 1-1.
[0075]
  (Comparative Example 1-2)
  An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1 except that 5 parts of phthalocyanine pigment F-3 was used instead of the mixed pigment of Example 1-1 as the charge generation material. The results are shown in Table 1-1.
[0076]
【table8]
[0077]
  Example 13)
  Azo pigment P used in Example 1-1¹-4 to P¹An electrophotographic photosensitive member was prepared in the same manner as in Example 1-1 except that the charge transporting material was replaced with the compound of the following structural formula (11) instead of -6, and evaluated in the same manner. These results are shown in Table 1-2.
[0078]
[Chemical10]
[0079]
  Example 14~ 1-10)
  Example 13Example 1 except that the charge generation material used in Example 1 was replaced with the pigments listed in Table 1-2.3An electrophotographic photoreceptor was prepared and evaluated in the same manner as described above. The results are shown in Table 1-2.
[0080]
  (Comparative Example 1-3)
  Example 13Α-type oxytitanium phthalocyanine F-4  Example 1 except that 5 parts were used3An electrophotographic photoreceptor was prepared and evaluated in the same manner as described above. The results are shown in Table 1-2.
[0081]
  (Comparative Example 1-4)
  Example 13Example 1 except that 5 parts of phthalocyanine pigment F-3 was used instead of the mixed pigment of Example 13An electrophotographic photoreceptor was prepared and evaluated in the same manner as described above. The results are shown in Table 1-2.
[0082]
【table9]
[0083]
  From the above results, the electrophotographic photosensitive member used in the present invention has excellent sensitivity in the oscillation wavelength region of monochromatic light compared to the photosensitive member of the comparative example, is flat, and has a small variation in sensitivity to environmental variations. I understand.
[0084]
  Example 111)
  50 parts of titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of resol type phenol resin, 20 parts of methyl cellosolve, 5 parts of methanol and silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average A conductive layer coating material was prepared by dispersing 0.002 part of molecular weight 3000) in a sand mill apparatus using 1 mmφ glass beads for 2 hours. The paint was dip-coated on an aluminum cylinder and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.
[0085]
  On this conductive layer, a solution obtained by dissolving 5 parts of 6-66-610-12 quaternary polyamide copolymer resin in a mixed solvent of 70 parts of methanol / 25 parts of butanol was applied and dried by dipping, and the film thickness was 0. An undercoat layer of .8 μm was provided.
[0086]
  Next, the azo pigment P¹-4 5 parts, 5 parts of phthalocyanine pigment F-1 and 5 parts of polyvinyl butyral resin (trade name: ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) are added to a solution of 100 parts of cyclohexanone, and 1 mmφ glass beads are used. Disperse in a conventional sand mill for 5 hours, add 100 parts of ethyl acetate, dilute it, apply it on the undercoat layer, and dry at 100 ° C. for 10 minutes to generate a charge of 0.2 μm in film thickness A layer was formed.
[0087]
  Next, a solution in which 9 parts of the charge transport material represented by the following structural formula (13) and 10 parts of bisphenol Z-type polycarbonate resin (number average molecular weight 20000) are dissolved in 60 parts of monochlorobenzene is prepared and dipped on the charge generation layer. It was applied by the method. This was dried at a temperature of 110 ° C. for 1 hour to form a charge transport layer having a thickness of 20 μm, and an electrophotographic photosensitive member was produced.
[0088]
[Chemical11]
[0089]
  The electrophotographic photosensitive member produced in this way was modified with a Canon printer LBP-2000 equipped with a pulse modulator (all solid blue SHG laser ICD-430 manufactured by Hitachi Metals Co., Ltd./oscillation wavelength 430 nm as a light source). In addition, the reversal development system is modified to a Carlson type electrophotographic system consisting of charging-exposure-development-transfer-cleaning that can handle image input equivalent to 600 dpi, and dark portion potential Vd = -650 V, bright portion potential Vl. = -200 V was set, a 1-dot 1-space image and a character (5-point) image were output, and image evaluation was performed in three environments of N / N, H / H, and L / L. The results are shown in Table 1-3Shown in
[0090]
  Example 112)
  Table 1-Charge generation materials3Example 1 except that the pigment shown in11In the same manner as above, an electrophotographic photosensitive member was prepared and image evaluation was performed. The results are shown in Table 1-3Shown in
[0091]
  (Comparative Example 1-7)
  Example 111Example 1 except that the light source of the evaluation machine used in Example 1 was replaced with a GaAs semiconductor laser having an oscillation wavelength of 780 nm.11In the same manner as above, an electrophotographic photosensitive member was prepared and image evaluation was performed. The results are shown in Table 1-3Shown in
[0092]
  (Comparative Examples 1-8 and 9)
  Example 1 as a charge generation material11Table 1-3Example 1 except that the pigment shown in11In the same manner as above, an electrophotographic photosensitive member was prepared and image evaluation was performed. The results are shown in Table 1-3Shown in
[0093]
【table10]
[0094]
  From these results, it can be seen that the electrophotographic apparatus of the present invention is excellent in dot reproducibility and character reproducibility and can provide a high-resolution output image.
[0095]
【The invention's effect】
  As described above, according to the present invention,Specific oxytitaniumAzo face with phthalocyanine pigment and specific structureChargeBy using the electrophotographic photosensitive member having a small wavelength dependency of sensitivity, high sensitivity characteristics, and low sensitivity environment dependency in the oscillation wavelength region of short-wavelength monochromatic light in the vicinity of 380 to 500 nm, and the above monochrome By combining light, an electrophotographic apparatus capable of forming a high-resolution image and stably used for repeated use is provided.
[Brief description of the drawings]
FIG. 1 is a characteristic X-ray diffraction pattern of CuKα of oxytitanium phthalocyanine used in the electrophotographic photoreceptor according to the present invention.
FIG. 2 is a characteristic X-ray diffraction pattern of CuKα of oxytitanium phthalocyanine used in the electrophotographic photoreceptor according to the present invention.
[Figure3FIG. 6 is a cross-sectional view showing an example of a layer structure (charge transport layer on a charge generation layer) of an electrophotographic photoreceptor used in the electrophotographic apparatus of the present invention.
[Figure4The layer structure of an electrophotographic photosensitive member used in the electrophotographic apparatus of the present invention (Charge generationIt is sectional drawing which shows the example of a layer).
[Figure5Layer structure of electrophotographic photosensitive member used in electrophotographic apparatus of the present invention (azo face)ChargeIt is sectional drawing which shows the example of the electric charge generation layer in contact with a electric charge transport layer.
[Figure6The layer structure of an electrophotographic photosensitive member used in the electrophotographic apparatus of the present invention (OxytitaniumIt is sectional drawing which shows the example of the charge generation layer containing a phthalocyanine pigment in contact with a charge transport layer.
[Figure7FIG. 2 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.
[Explanation of symbols]
    a Conductive support
    b Photosensitive layer
    c Charge generation layer
    d Charge transport layer
    e Charge generation material
    f Vinter resin
    g Charge transport layer / binder resin
    1 Charge transport layer
    2 Mix phthalocyanine and azo pigmentTheCharge generation layer
    3 Conductive support
    4 Charge generation layer containing azo pigment
    5 Charge generation layer containing phthalocyanine pigment
  11 photoconductor
  12 axes
  13 Charging means
  14 Exposure light
  15 Development means
  16 Transfer means
  17 Transfer material
  18 Fixing means
  19 Cleaning means
  20 Pre-exposure light
  21 Process cartridge
  22 rails

Claims (2)

Conductive support a charge generating layer on the electrophotographic photosensitive member having a photosensitive layer formed by stacking a charge transport layer in this order from the conductive support side, wavelength 380 - monochromatic light in the range of 500nm as an exposing light source In an electrophotographic apparatus having an exposure apparatus having
The charge-generating layer by the following general formula (6)
(In the above formula (6), X ¹ -X ⁴ represents chlorine or bromine, and k, l, m, and n represent integers of 0 to 4)
An oxytitanium phthalocyanine pigment having the strongest peak at 27.2 ° of the Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα represented by the following general formula (1)
(In the above formula (1), Ar represents an aromatic hydrocarbon ring group or heterocyclic group which may be bonded directly or via a bonding group, and may have a substituent, and Cp represents the following general formula: it is .n a coupler residue represented by (2) 1 -. showing three integers However, -N = N-Cp never be multiple bonded to the same benzene ring)
(In the above formula (2), R ¹ represents a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group or a nitro group, R ² represents an alkyl group or an aryl group, and R ³ represents a halogen atom. An atom, an alkyl group, an alkoxy group, a cyano group or a nitro group, j represents 0, 1, 2 and when j = 2, R ³ may be a different group.
In electrophotographic apparatus characterized in that it contains, and azo Pigments represented. The light source, wavelength 400 - electrophotographic apparatus according to claim 1 is intended to be exposed with monochromatic light in the range of 450nm.