JP4574534B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

The present invention relates to an electrophotographic photosensitive member, a process cartridge, and an electrophotographic apparatus. Specifically, the photosensitive layer contains a phthalocyanine compound, the intermediate layer is an electrophotographic photosensitive member containing a polyamide resin having a specific azo compound and a specific, such a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member About.

  Organic electrophotographic photoreceptors have the advantage that they are non-polluting and easy to manufacture compared to conventional inorganic electrophotographic photoreceptors, and the degree of freedom in functional design is high due to the variety of selection of constituent materials. Such an organic electrophotographic photosensitive member has been widely used in the market due to the rapid spread of laser beam printers in recent years.

  An electrophotographic photoreceptor basically comprises a photosensitive layer that forms a latent image by exposure using charging and light, and a support as a support member for providing the photosensitive layer. In general, when a photosensitive layer is directly formed on a support, the surface of the support, dirt, uneven shape and properties, and roughness appear as film formation irregularities on the photosensitive layer as they are. There arises a problem that image defects such as white spots, black spots, and density unevenness occur.

  In the past, an intermediate layer has been provided between the support and the photosensitive layer in order to ensure adhesion with the support, protect the photosensitive layer from electrical breakdown, improve the carrier injection property of the photosensitive layer, and the like. I came. This intermediate layer has the above-mentioned merit, but also has a demerit that charges are easily accumulated. For this reason, the potential fluctuation becomes large during continuous printing, causing image defects. For example, when the organic photoreceptor having the intermediate layer is used in a development process (so-called reversal development system) in which a dark portion potential portion widely used in printers is a non-development portion and a light portion potential portion is a development portion, Sensitivity of light exposure at the time of previous printing slows down due to the rise of the bright part potential at the time of continuous printing, image density fluctuation occurs, and when the entire black image is taken at the time of the next printing, the front printed part will appear white, so-called A ghost phenomenon (negative ghost) may appear prominently.

  In particular, an electrophotographic photosensitive member using gallium phthalocyanine as a charge generation layer has very high sensitivity and sensitivity in the infrared region, but because of the high sensitivity, the absolute number of excited molecules and generated carriers. In many cases, excited species, electrons, holes, and the like that do not cause charge separation in an electrophotographic process in which charging and exposure are repeated are likely to remain in the photoreceptor, and potential fluctuations are likely to occur as a kind of memory. Particularly in a low-humidity environment, the volume resistance of the charge generation layer and the intermediate layer to electrons increases, so that the electrons are easily filled in the charge generation layer, and an initial sharp bright portion between the first and 500th rotations of continuous printing. There has been a drawback that image density fluctuations are likely to occur due to potential rise.

  In order to solve the above problems, various methods have been proposed. However, there are many cases where the initial sensitivity is lowered, charging ability is reduced, and harmful effects are caused, and the requirements are fully satisfied in the endurance use under specific environment such as high temperature and high humidity environment or low temperature and low humidity environment. The current situation is that it cannot be said (see, for example, Patent Documents 1 to 7).

  In general, an intermediate layer that is very effective for one particular photosensitive layer is not necessarily as effective for other photosensitive layers, and there are more preferred combinations between the photosensitive layer and the intermediate layer. is there. With a more preferable combination, an electrophotographic photosensitive member having more excellent characteristics in terms of residual potential and potential stability during repeated use can be obtained.

  However, a general law of compatibility between the photosensitive layer and the intermediate layer has not been found, and it is very difficult to find an intermediate layer suitable for a specific photosensitive layer at present.

The use of the azo compound represented by the formula (1) used in the present invention as a charge generation material has been proposed (see, for example, Patent Documents 8 to 10). Furthermore, in order to suppress the initial rapid light portion potential increase between the first rotation and the 500th rotation of continuous printing, an azo compound represented by the above formula (1) and gallium phthalocyanine are mixed in a single charge generation layer. Have been proposed, or a method in which each charge generation layer containing an azo compound and gallium phthalocyanine is used in a stacked manner. However, in the recent trend of colorization, higher image quality and higher printing speed have been proposed. In order to cope with this, a further excellent bright part potential fluctuation suppressing effect is required (for example, see Patent Documents 11 to 13).
Japanese Patent Laid-Open No. 62-269966 JP-A-62-279347 JP-A-62-270962 JP 58-95744 A JP-A-4-353858 JP-A-5-27469 JP 7-175249 A JP-A-61-272754 JP-A-64-61760 Japanese Patent Laid-Open No. 3-95561 JP 2000-66423 A JP 2000-137341 A JP 2000-250238 A

  The present invention has been made in view of the above problems of the background art, and can form an excellent image free from image density fluctuations due to initial rapid light part potential fluctuations even in a low humidity environment. Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

  As a result of intensive studies to solve the above problems, the present inventors have focused on an intermediate layer formed on a conductive support of an electrophotographic photosensitive member, and a specific azo compound and a specific polyamide resin are added to the intermediate layer. As a result of the inclusion, it was found that the potential fluctuation on the surface of the photoreceptor can be extremely reduced even in a low humidity environment, and therefore, stable image formation can be performed stably over a long period of time in the low humidity environment, and the present invention has been completed. .

  That is, the present invention is as follows.

(1) electrically and conductive support, an intermediate layer formed on the electrically conductive substrate, an electrophotographic photosensitive member comprising a formed on the intermediate layer photosensitive layer,
The photosensitive layer contains a gallium phthalocyanine compound,
Intermediate layer, and the azo compound represented by the following formula (1), an electrophotographic photoreceptor, characterized by containing a polyamide resin containing a repeating unit represented by the following formula (5).
Formula (1)

(In Formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an aryl group which may have a substituent, or a carbamoyl group which may have a substituent, provided that R ₁ and R ₂ is not simultaneously a hydrogen atom, X represents O or S. Y is an aromatic hydrocarbon ring or aromatic heterocyclic ring which may be condensed with a benzene ring to have a substituent. And Ar represents a group represented by the following formula (2), (3) or (4) .
Formula (2)

Formula (3)

Formula (4)

(In the formula (2), R ₃ , R ₄ , R ₅ , R ₆ and R ₇ each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or a substituent. also alkoxy groups, .A showing an aryl group which may have a substituted or unsubstituted aralkyl group or substituent, O, S or N-R 8 _(provided that, R ₈ is a hydrogen atom, An alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent.
Formula (5)

(In formula (5), R ₉ represents a divalent alkylene group which may have a substituent. R ₁₀ represents a hydrogen atom or an alkyl group which may have a substituent.)

(2) the phthalocyanine compound, a hydroxy gallium phthalocyanine crystal having strong peaks at 7.4 ° ± 0.3 ° and 28.2 ° of ± 0.3 ° position of the diffraction angle 2θ in CuKα characteristic X-ray diffraction the electrophotographic photosensitive member according to Oh Ru (1).

(3) the weight ratio between the total sum of the polyamide resin containing a repeating unit represented by the total sum of the weight of the azo compound formula represented by the formula is contained in the intermediate layer (1) (5) mass 2: 1 to 1: Ru 100 der (1) or electrophotographic photosensitive member according to (2).

(4) the mass ratio of 1: 5 to 1: The electrophotographic photosensitive member according to Ru 100 der (3).

(5) The electrophotographic photosensitive member according to any one of the azo compound represented by the formula (1) is Ru azo compound der represented by the following formula (6) (1) to (4).
Formula (6)

(In the formula (6), Ar represents a group represented by the following formula (7), (8) or (9) . R ₁₁ represents a group represented by the following formula (10) or (11). )
Formula (7)

Formula (8)

Formula (9)

Formula (10)

Formula (11)

(6) azo compound represented by the formula (6) is represented by the following formula (12), the electrophotographic photosensitive member according to (13) or Ru azo compounds der represented by (14) (5).
Formula (12)

Formula (13)

Formula (14)

(7) the equation electrophotographic photosensitive member according to any one of the repeating unit represented by formula (5) is Ru repeating units der represented by the following formula (15) (1) to (6).
Formula (15)

(8) (1) to an electrophotographic photosensitive member according to any one of (7), charging means, integrally supported and at least one means selected from the group consisting of the developing means and the cleaning means, the electrophotographic apparatus A process cartridge which is detachable from the main body.

  (9) An electrophotographic apparatus comprising the electrophotographic photosensitive member according to any one of (1) to (7), a charging unit, an image exposing unit, a developing unit, and a transferring unit.

  The electrophotographic photosensitive member of the present invention has a remarkable effect that it can form a good image without image density variation due to initial rapid light portion potential variation even in a low humidity environment. Further, according to the present invention, it is possible to provide a process cartridge and an electrophotographic apparatus that can stably form a good image over a long period of time in a low humidity environment.

  Hereinafter, embodiments of the present invention will be described in detail.

  The electrophotographic photosensitive member of the present invention is formed by laminating at least an intermediate layer and a photosensitive layer on a conductive support. Even if the photosensitive layer is a single-layer type photosensitive layer (FIG. 1A) containing the charge transport material and the charge generation material in the same layer, the charge generation layer and the charge transport material containing the charge generation material are used. Although it may be a laminated type (functionally separated type) photosensitive layer (FIG. 1B) separated into the contained charge transport layer, a laminated type photosensitive layer is preferred from the viewpoint of electrophotographic characteristics. 1A and 1B, reference numeral 101 denotes a support, 102 denotes a photosensitive layer, 103 denotes a charge generation layer, and 104 denotes a charge transport layer. In the following, an electrophotographic photoreceptor containing a laminated (functionally separated type) photosensitive layer will be described in detail.

  The conductive support only needs to have conductivity, and examples thereof include metals such as aluminum, stainless steel, and nickel, or metals provided with a conductive layer, plastics, papers, and the like. Can be mentioned. Cylindrical aluminum is particularly excellent in terms of mechanical strength, electrophotographic characteristics, and cost. These conductive supports may be used as they are, but may be those subjected to physical treatment such as cutting and honing, anodizing treatment or chemical treatment using acid, etc. Among them, cutting or honing etc. By performing the physical treatment, it is possible to provide an interference fringe preventing function by treating the surface roughness to 0.1 to 3.0 μm in terms of Rz value.

  An interference fringe preventing layer (not shown in FIG. 1) may be provided between the conductive support and the intermediate layer. The interference fringe prevention layer is not necessary when the support itself has an interference fringe prevention function, but by using the conductive support as it is and forming an interference fringe prevention layer by coating on it, Since an interference fringe preventing function can be imparted to the conductive support by a simple method, it is very useful in terms of productivity and cost. As a preferable method for forming the interference fringe prevention layer, inorganic particles such as tin oxide, indium oxide, titanium oxide, and barium sulfate are dispersed in a suitable solvent together with a curable resin such as a phenol resin to prepare a coating liquid, and conductive Examples of the method include coating to a conductive support and drying. The thickness of the interference fringe prevention layer is preferably 1 to 20 μm.

On the support or the interference fringe prevention layer, an intermediate layer is necessary for securing adhesion to the support, protecting the photosensitive layer from electrical breakdown, improving the carrier injection property of the photosensitive layer, and the like. Intermediate layer contains azo compound represented by the following formula (1), and a polyamide resin containing a repeating unit represented by the following formula (5), these dissolved or dispersed in a solvent to prepare a coating solution, It is formed by coating on a conductive support or an interference fringe prevention layer. Note that the azo compound represented by the front following formula (1), an intermediate layer having containing polyamide resin containing a repeating unit represented by the following formula (5) has no charge generation function.
Formula (1)

(In Formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an aryl group which may have a substituent, or a carbamoyl group which may have a substituent, provided that R ₁ and R ₂ is are not hydrogen atoms at the same time .X is .Y showing an O or S, condensed with a benzene ring, which may have a substituent aromatic hydrocarbon ring or aromatic heterocyclic ring And Ar represents a group represented by the following formula (2), (3) or (4) .
Formula (2)

Formula (3)

Formula (4)

(In the formula (2), R ₃ , R ₄ , R ₅ , R ₆ and R ₇ each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or a substituent. also alkoxy groups, .A showing an aryl group which may have a substituted or unsubstituted aralkyl group or substituent, O, S or N-R 8 _(provided that, R ₈ is a hydrogen atom, An alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent.
Formula (5)

(In formula (5), R ₉ represents a divalent alkylene group which may have a substituent. R ₁₀ represents a hydrogen atom or an alkyl group which may have a substituent.)

Among the azo compounds having the structure represented by the formula (1), R ₁ is an aryl group having Cl at the ortho position or a carbamoyl group having Cl at the ortho position, R ₂ is a hydrogen atom, and X is An azo compound which is O and Y is condensed with a benzene ring and is an aromatic hydrocarbon ring having no substituent is preferable. Among them, Ar is the formula (2), R ₃ , R ₄ , R ₆ and R ₇ are hydrogen atoms, R ₅ is a methyl group, and R ₁ is an aryl group having Cl at the ortho position. An azo compound in which R ₂ is a hydrogen atom is particularly preferable. Further, an azo compound in which Ar is the formula (3) or (4), R ₁ is a carbamoyl group having Cl at the ortho position, and R ₂ is a hydrogen atom is particularly preferable.

Among the repeating units represented by the formula (5), a repeating unit in which R ₉ is a methylene group and R ₁₀ is a methyl group is preferable.

  Of the azo compounds represented by the formula (1) used in the present invention, examples of those suitably used in the present invention are shown below, but are not limited to these azo compounds.

Basic type I
Formula (16)

Basic type II
Formula (17)

Basic type III
Formula (18)

  The azo compound represented by the formula (1) can be prepared by a general method for producing an azo compound as described in, for example, JP-A Nos. 61-272754, 2000-066423, and 3-95561. Can be synthesized along.

  Of the repeating units represented by the formula (5) used in the present invention, examples of those suitably used in the present invention are shown below, but are not limited to these repeating units.

Basic type IV

  The polyamide resin containing the repeating unit represented by the formula (5) can be synthesized, for example, by using 6-nylon resin as a raw material and reacting it with formaldehyde and methanol.

Wherein in the intermediate layer, the mass ratio of the total sum of the weight of the polyamide resin containing a repeating unit represented by the total sum of the weight of the azo compound represented by the formula (1) (5) 2: 1 to 1 : 100, more preferably 1: 5 to 1: 100. When it is smaller than 1: 100, the content of the azo compound represented by the formula (1) is lowered, and the effect is lowered. Moreover, the effect falls also when larger than 2: 1. The azo compound represented by the formula (1) can be used alone or in combination of two or more.

The solvent used for the production of the intermediate layer coating solution is not particularly limited. For example, benzene, toluene, xylene, tetralin, chlorobenzene, dichloromethane, chloroform, trichloroethylene, tetrachloroethylene, carbon tetrachloride, methyl acetate, ethyl acetate, acetic acid Propyl, methyl formate, ethyl formate, acetone, methyl ethyl ketone, cyclohexanone, diethyl ether, dipropyl ether, dioxane, methylal, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, butyl alcohol, methyl cellosolve, methoxypropanol, dimethylformamide, dimethylacetamide and dimethyl Sulfoxide or the like can be used.
Examples of the coating method include dip coating, spray coating, spinner coating, bead coating, blade coating, and beam coating. The thickness of the intermediate layer to be formed is preferably about 0.01 to 5 μm, more preferably 0.03 to 1.0 μm, and particularly preferably 0.4 to 0.8 μm.

  The charge generation layer used in the electrophotographic photoreceptor of the present invention can be obtained by dispersing a gallium phthalocyanine compound, which is a charge generation material, together with a suitable binder resin solution, coating and drying. The charge generation layer can also be provided by vapor deposition without using a binder resin. Examples of the binder resin used here include polyester resin, acrylic resin, polyvinyl carbazole resin, phenoxy resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl benzal resin, polystyrene resin, polyvinyl acetate resin, polysulfone resin, polyarylate resin, And vinylidene chloride and acrylonitrile copolymer resins.

  The gallium phthalocyanine compound can be used in any crystal form, and in particular, the positions of 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° of the diffraction angle 2θ in CuKα characteristic X-ray diffraction. The crystalline form of hydroxygallium phthalocyanine having a strong peak has excellent sensitivity characteristics. In particular, a hydroxygallium phthalocyanine crystal having strong peaks at Bragg angles 2θ of 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 °, and 28.3 ° in X-ray diffraction of CuKα In addition, the hydroxygallium phthalocyanine crystal having the strongest peak at 28.1 ° in the Bragg angle 2θ ± 0.2 ° in the X-ray diffraction of CuKα is particularly sensitive, and has excellent chargeability and stability as a crystal. This is preferable. The film thickness of the charge generation layer is preferably from 0.01 to 10 μm, particularly preferably from 0.05 to 5 μm.

  The charge transport layer used in the electrophotographic photoreceptor of the present invention contains at least a charge transport material. As the charge transport material used in the present invention, known materials used in conventional organic electrophotographic photoreceptors can be used, and are not particularly limited, but are not limited to triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds. Examples thereof include compounds, oxazole compounds, thiazole compounds, triallylmethane compounds, enamine compounds and butadiene compounds.

  The thickness of the charge transport layer is preferably 5 to 40 μm, and particularly preferably 10 to 30 μm. When the photosensitive layer is a single layer type, the film thickness is preferably 5 to 40 μm, and particularly preferably 10 to 30 μm.

  In the present invention, if necessary, the protective layer formed on the charge transport layer may be polyvinyl butyral, polyester, polycarbonate (polycarbonate Z, modified polycarbonate, etc.), polyamide, polyimide, polyarylate, polyurethane, styrene-butadiene copolymer, styrene. -Resins such as acrylic acid copolymer and styrene-acrylonitrile copolymer are dissolved in a suitable organic solvent and applied on the photosensitive layer and dried, or applied onto the photosensitive layer and heated, electron beam, ultraviolet rays, etc. Can be formed by curing. The thickness of the protective layer is preferably 0.05 to 20 μm.

  Further, the protective layer may contain conductive particles, ultraviolet absorbents, or lubricating particles such as fluorine atom-containing resin fine particles. As the conductive particles, metal oxides such as tin oxide particles are preferable.

Next, the electrophotographic apparatus of the present invention that can suitably use the electrophotographic photosensitive member of the present invention will be described. The electrophotographic apparatus of the present invention includes an electrophotographic photosensitive member of the present invention, a charging unit that charges the surface of the electrophotographic photosensitive member, an image exposing unit that forms an electrostatic latent image on the charged electrophotographic photosensitive member by image exposure, Developing means for developing the electrostatic latent image on the electrophotographic photosensitive member with toner to form a toner image and transfer means for transferring the toner image on the electrophotographic photosensitive member to a transfer material.

  FIG. 2 is a schematic configuration diagram of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention. In FIG. 2, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 at a predetermined peripheral speed (process speed) in the direction of an arrow. In the rotating process, the electrophotographic photosensitive member 1 is uniformly charged with a positive or negative predetermined potential on its peripheral surface by the primary charging unit 3, and then from an exposure unit (not shown) such as slit exposure or laser beam scanning exposure. The exposure light 4 that is intensity-modulated corresponding to the time-series electric digital image signal of the target image information that is output is received. In this way, electrostatic latent images corresponding to the target image information are sequentially formed on the peripheral surface of the electrophotographic photoreceptor 1.

  The formed electrostatic latent image is then visualized as a transferable particle image (toner image) by regular development or reversal development with charged particles (toner) accommodated in the developing means 5. A toner image formed and supported on the surface of the electrophotographic photosensitive member 1 is taken out from a sheet feeding unit (not shown) between the electrophotographic photosensitive member 1 and the transfer unit 6 in synchronization with the rotation of the electrophotographic photosensitive member 1. The transfer means 6 sequentially transfers the transferred transfer material 7 to the transfer material 7. At this time, a bias voltage having a polarity opposite to the charge held in the toner is applied to the transfer means from a bias power source (not shown).

  The transfer material 7 that has received the transfer of the toner image is separated from the surface of the electrophotographic photosensitive member, conveyed to the image fixing means 8, and subjected to a fixing process of the toner image to be printed out of the apparatus as an image formation (print, copy). Out.

  The surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by removing the deposits such as residual toner by the cleaning means 9. In recent years, a cleanerless system has been studied, and the transfer residual toner can be directly collected by a developing device or the like. Further, after being subjected to charge removal processing by pre-exposure light 10 from pre-exposure means (not shown), it is repeatedly used for image formation. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary.

  In the present invention, a plurality of components such as the electrophotographic photosensitive member 1, the primary charging unit 3, the developing unit 5 and the cleaning unit 9 described above are housed in a container and integrally coupled as a process cartridge. The cartridge may be detachably attached to 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 3, the developing unit 5 and the cleaning unit 9 is integrally supported together with the electrophotographic photosensitive member 1 to form a cartridge, and is attached to and detached from the apparatus main body using a guide unit 12 such as a rail of the apparatus main body. A flexible process cartridge 11 can be obtained.

  Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 may be reflected light or transmitted light from the original, or the original is read by a sensor and converted into a signal, and the exposure light 4 is processed according to this signal. It may be light irradiated by scanning a laser beam, driving an LED array, driving a liquid crystal shutter array, or the like.

  The electrophotographic photosensitive member of the present invention can be used not only in electrophotographic copying machines but also in a wide range of electrophotographic applications such as laser beam printers, CRT printers, LED printers, FAX, liquid crystal printers, and laser plate making. It is.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, embodiments of the present invention are not limited to these. In the examples, “%” and “part” mean “% by mass” and “part by mass”, respectively.

<Example 1>
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, 0.002 part of an average molecular weight of 3000) was dispersed for 2 hours by a sand mill apparatus using glass beads having a diameter of 0.8 mm to prepare a coating solution for an interference fringe prevention layer. This coating solution was dip-coated on an aluminum cylinder (diameter 30 mm, drawn tube) as a conductive support and dried at 140 ° C. for 30 minutes to form an interference fringe preventing layer having a thickness of 15 μm.

  On the obtained interference fringe prevention layer, 1 part of the exemplified compound (1-6) is added to 20 parts of n-butanol, and dispersed for 20 hours in a sand mill using glass beads having a diameter of 1 mm. 66-610-12 quaternary nylon copolymer resin (trade name: CM8000, manufactured by Toray Industries, Inc.) 2.5 parts and N-methoxymethylated 6 nylon resin (trade name: Toresin EF-30T, manufactured by Nagase ChemteX Corporation, (Methoxymethylation rate: 28-33%) 7.5 parts, 100 parts of methanol and 70 parts of n-butanol were added and dispersed for another 2 hours in the same sand mill apparatus. The film was dip-coated and dried at 100 ° C. for 10 minutes to form an intermediate layer having a thickness of 0.5 μm.

  Next, the diffraction angles (2θ ± 0.2 °) of CuKα characteristic X-ray diffraction are 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 °. 10 parts of crystalline hydroxygallium phthalocyanine having a strong peak at the position and 5 parts of polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) are added to 250 parts of cyclohexanone, and glass beads having a diameter of 0.8 mm The mixture was dispersed for 3 hours in a sand mill apparatus using 100, and further diluted with 100 parts of cyclohexanone and 450 parts of ethyl acetate to obtain a coating solution for charge generation layer. The obtained coating solution was dip-coated on the intermediate layer and dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.16 μm.

Next, 10 parts of a charge transport material represented by the following formula (21) and 10 parts of a polycarbonate resin (trade name: Iupilon Z-200, manufactured by Mitsubishi Gas Chemical Company) are dissolved in 70 parts of monochlorobenzene, and the resulting solution is dissolved. The electrophotographic photosensitive member 1 was produced by dip-coating on the charge generation layer and drying at 110 ° C. for 1 hour to form a charge transport layer having a thickness of 25 μm.
Formula (21)

  Using the electrophotographic photoreceptor 1 thus produced, bright part potential measurement was performed. A drum testing machine manufactured by Gentec Co., Ltd .: CYNTHIA59 was used as an evaluation machine. A scorotron corona charger was used for charging the surface of the electrophotographic photosensitive member. The primary current was set to 70 μA, and the grid voltage was set so that the applied voltage on the surface of the electrophotographic photosensitive member was −700V. A xenon lamp was used as the image exposure light source. The exposure light wavelength was selected using a 780 nm interference filter, and the amount of light was adjusted so that the bright part potential was -200V. A halogen lamp was used as a pre-exposure light source. The pre-exposure light wavelength was selected using a 676 nm interference filter, and the light amount was adjusted to 5 times the image exposure light amount. The cycle speed was 1 sec / cycle. The electrophotographic photosensitive member 1 was attached to this and evaluated. The position of the electric potential measurement probe with respect to the electrophotographic photosensitive member was approximately the center in the axial direction of the electrophotographic photosensitive member, and the gap from the surface of the electrophotographic photosensitive member was 3 mm.

  The electrophotographic photosensitive member 1 is allowed to stand for 3 days in a normal temperature and low humidity (N / L) environment of 23 ° C./5% RH, and then 500 continuous durable prints (full black image mode) under the same environment (N / L). ) And the bright part potential after the durable printing was measured. The results are shown in Table 1.

<Example 2>
An electrophotographic photoreceptor 2 was produced in the same manner as in Example 1 except that the exemplified compound (1-6) used in the intermediate layer in Example 1 was replaced with the exemplified compound (1-7). The obtained electrophotographic photoreceptor 2 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 3>
An electrophotographic photoreceptor 3 was produced in the same manner as in Example 1 except that the exemplified compound (1-6) used in the intermediate layer in Example 1 was replaced with the exemplified compound (1-1). The obtained electrophotographic photoreceptor 3 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 4>
An electrophotographic photoreceptor 4 was produced in the same manner as in Example 1 except that the exemplified compound (1-6) used in the intermediate layer in Example 1 was replaced with the exemplified compound (2-7). The obtained electrophotographic photoreceptor 4 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 5>
An electrophotographic photoreceptor 5 was produced in the same manner as in Example 1 except that the exemplified compound (1-6) used in the intermediate layer in Example 1 was replaced with the exemplified compound (2-6). The obtained electrophotographic photoreceptor 5 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 6>
An electrophotographic photoreceptor 6 was produced in the same manner as in Example 1 except that the exemplified compound (1-6) used in the intermediate layer in Example 1 was replaced with the exemplified compound (2-2). The obtained electrophotographic photoreceptor 6 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 7>
An electrophotographic photoreceptor 7 was produced in the same manner as in Example 1 except that the exemplified compound (1-6) used in the intermediate layer in Example 1 was replaced with the exemplified compound (3-7). The obtained electrophotographic photoreceptor 7 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 8>
An electrophotographic photoreceptor 8 was produced in the same manner as in Example 1 except that the exemplified compound (1-6) used in the intermediate layer in Example 1 was replaced with the exemplified compound (3-6). The obtained electrophotographic photoreceptor 8 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 9>
An electrophotographic photoreceptor 9 was produced in the same manner as in Example 1 except that the exemplified compound (1-6) used in the intermediate layer in Example 1 was replaced with the exemplified compound (3-2). The obtained electrophotographic photoreceptor 9 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 10>
In Example 1, the intermediate layer coating solution was 1 to 10 parts of the exemplified compound (1-6), nylon 6-66-610-12 quaternary nylon copolymer resin (trade name: CM8000, manufactured by Toray Industries, Inc.) 2.5. From 0.5 part to N-methoxymethylated 6 nylon resin (trade name: Toresin EF-30T, manufactured by Nagase ChemteX Corporation, methoxymethylation rate: 28-33%) from 7.5 parts to 1.5 parts An electrophotographic photosensitive member 10 was produced in the same manner as in Example 1 except that it was replaced. The obtained electrophotographic photoreceptor 10 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 11>
In Example 1, the intermediate layer coating solution is 1 to 8 parts of the exemplified compound (1-6), nylon 6-66-610-12 quaternary nylon copolymer resin (trade name: CM8000, manufactured by Toray Industries, Inc.) 2.5 1 part from N part, N-methoxymethylated 6 nylon resin (trade name: Toresin EF-30T, manufactured by Nagase ChemteX, methoxymethylation rate: 28-33%) Except for changing from 7.5 parts to 3 parts, An electrophotographic photoreceptor 11 was produced using the same method as in Example 1. The obtained electrophotographic photoreceptor 11 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 12>
An electrophotographic photoreceptor 12 was produced in the same manner as in Example 1 except that the intermediate layer coating solution was changed from 1 part to 2 parts of the exemplified compound (1-6) in Example 1. The obtained electrophotographic photoreceptor 12 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 13>
An electrophotographic photoreceptor 13 was produced in the same manner as in Example 1, except that the intermediate layer coating solution in Example 1 was changed from 1 part to 0.1 part of the exemplified compound (1-6). The obtained electrophotographic photoreceptor 13 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 14>
An electrophotographic photoreceptor 14 was produced in the same manner as in Example 1, except that the intermediate layer coating solution was changed from 1 part to 0.01 part of the exemplified compound (1-6) in Example 1. The obtained electrophotographic photoreceptor 14 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 15>
An electrophotographic photosensitive member 15 was produced in the same manner as in Example 1 except that the film thickness of the intermediate layer was changed from 0.5 μm to 1.0 μm in Example 1. The obtained electrophotographic photoreceptor 15 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 16>
A method similar to that in Example 1 was used except that the charge transport material used in the intermediate layer coating solution in Example 1 was changed from the compound represented by the formula (21) to the compound represented by the following formula (22). An electrophotographic photoreceptor 16 was produced. The obtained electrophotographic photoreceptor 16 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
Formula (22)

<Comparative example 1>
A comparative electrophotographic photosensitive member 1 was produced in the same manner as in Example 1 except that no azo compound was used in the intermediate layer in Example 1. The obtained comparative electrophotographic photoreceptor 1 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative example 2>
The diffraction angles (2θ ± 0.2 °) of CuKα characteristic X-ray diffraction used in the charge generation layer in Comparative Example 1 are 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25. Comparative Example 1 except that 10 parts of crystalline hydroxygallium phthalocyanine having strong peaks at 1 ° and 28.3 ° positions were replaced with 9 parts of the hydroxygallium phthalocyanine and 1 part of the exemplified compound (1-6). A comparative electrophotographic photoreceptor 2 was produced using the same method as described above. The comparative electrophotographic photoreceptor 2 obtained was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative Example 3>
The intermediate layer is formed in the same manner as in Comparative Example 1, and then 10 parts of the exemplified compound (1-6) and 5 parts of polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) are added to 250 parts of cyclohexanone. Addition and dispersion for 3 hours in a sand mill using glass beads with a diameter of 1 mm, and further adding and diluting 100 parts of cyclohexanone and 400 parts of ethyl acetate to produce a coating solution for charge generation layer The coating solution thus obtained was dip coated on the intermediate layer and dried at 100 ° for 10 minutes to form a first charge generation layer having a thickness of 0.16 μm. On this, a charge generation layer was formed as a second charge generation layer in the same manner as in Example 1, and a charge transport layer was further formed to produce a comparative electrophotographic photosensitive member 3. The comparative electrophotographic photoreceptor 3 obtained was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative example 4>
A comparative electrophotographic photosensitive member 4 was produced in the same manner as in Example 1 except that the exemplified compound (1-6) used in the intermediate layer in Example 1 was replaced with the following comparative compound (1). The comparative electrophotographic photoreceptor 4 obtained was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
Comparative compound (1)

<Comparative Example 5>
A comparative electrophotographic photoreceptor 5 was produced in the same manner as in Example 1 except that the exemplified compound (1-6) used in the intermediate layer in Example 1 was replaced with the following comparative compound (2). The comparative electrophotographic photoreceptor 5 obtained was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
Comparative compound (2)

<Comparative Example 6>
A sand mill using glass beads having a diameter of 1 mm and forming up to an interference fringe prevention layer as in Example 1, adding 10 parts of the exemplified compound (2-7) to 150 parts of 4-methoxy-4-methylpentanone-2 Dispersed in an apparatus for 20 hours, polyvinyl butyral (trade name: ESREC BH-3, manufactured by Sekisui Chemical Co., Ltd.) and 4 parts of phenoxy resin (trade name: PKHH, manufactured by Union Carbide) and 1,2-dimethoxyethane 92 An intermediate layer having a thickness of 0.5 μm is obtained by dip-coating the coating solution obtained by adding 2 parts and dispersing for 2 hours in the same sand mill apparatus on the interference fringe prevention layer and drying at 100 ° C. for 10 minutes. Formed. Further thereon, a charge generation layer and a charge transport layer were formed in the same manner as in Example 1 to produce a comparative electrophotographic photosensitive member 6. The obtained comparative electrophotographic photoreceptor 6 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative Example 7>
In Example 1, the intermediate layer coating solution was nylon 6-66-610-12 quaternary nylon copolymer resin (trade name: CM8000, manufactured by Toray Industries, Inc.) 2.5 to 10 parts, N-methoxymethylated 6 nylon resin. (Product name: Toresin EF-30T, manufactured by Nagase ChemteX Corp., methoxymethylation rate: 28-33%) Comparative electrons using the same method as in Example 1 except that 7.5 parts were changed to 0 parts. Photoconductor 7 was prepared. The comparative electrophotographic photoreceptor 7 obtained was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative Example 8>
In the same manner as in Comparative Example 1, an intermediate layer is formed, 8 parts of Exemplified Compound (1-6) is added to 20 parts of n-butanol, and dispersed for 20 hours in a sand mill using glass beads having a diameter of 1 mm. 6-66-610-12 quaternary nylon copolymer resin (trade name: CM8000, manufactured by Toray Industries, Inc.), 1 part, N-methoxymethylated 6 nylon resin (trade name: Toresin EF-30T, manufactured by Nagase ChemteX Corporation, (Methoxymethylation rate: 28 to 33%) 3 parts, 100 parts of methanol and 70 parts of n-butanol were added and dispersed for another 2 hours in the same sand mill apparatus. And dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.16 μm. Furthermore, a charge transport layer was formed in the same manner as in Comparative Example 1 to produce a comparative electrophotographic photosensitive member 8. The comparative electrophotographic photoreceptor 8 obtained was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

It is a figure which shows the structure of a photosensitive layer. 1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having the electrophotographic photosensitive member of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 Support body 102 Photosensitive layer 103 Charge generation layer 104 Charge transport layer 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Development means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means

Claims (9)

Electrically and conductive support, an intermediate layer formed on the electrically conductive substrate, an electrophotographic photosensitive member comprising a formed on the intermediate layer photosensitive layer,
The photosensitive layer contains a gallium phthalocyanine compound,
Intermediate layer, and the azo compound represented by the following formula (1), an electrophotographic photoreceptor, characterized by containing a polyamide resin containing a repeating unit represented by the following formula (5).
Formula (1)

(In Formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an aryl group which may have a substituent, or a carbamoyl group which may have a substituent, provided that R ₁ and R ₂ is not simultaneously a hydrogen atom, X represents O or S. Y is an aromatic hydrocarbon ring or aromatic heterocyclic ring which may be condensed with a benzene ring to have a substituent. And Ar represents a group represented by the following formula (2), (3) or (4) .
Formula (2)

Formula (3)

Formula (4)

(In the formula (2), R ₃ , R ₄ , R ₅ , R ₆ and R ₇ each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or a substituent. also alkoxy groups, .A showing an aryl group which may have a substituted or unsubstituted aralkyl group or substituent, O, S or N-R 8 _(provided that, R ₈ is a hydrogen atom, An alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent.
Formula (5)

(In formula (5), R ₉ represents a divalent alkylene group which may have a substituent. R ₁₀ represents a hydrogen atom or an alkyl group which may have a substituent.) The phthalocyanine compound, Ru hydroxygallium phthalocyanine crystals der having strong peaks at 7.4 ° of ± 0.3 ° and 28.2 ° ± 0.3 ° position of the diffraction angle 2θ in CuKα characteristic X-ray diffraction 請 The electrophotographic photosensitive member according to claim 1. The weight ratio of the total sum of the weight of the polyamide resin containing a repeating unit represented by formula and the total sum of the weight of the azo compound (5) represented by the formula is contained in the intermediate layer (1) is 2: 1 to 1: 100 der Ru請 Motomeko 1 or 2 the electrophotographic photosensitive member according to. The mass ratio is 1: 5 to 1: The electrophotographic photosensitive member according to 100 der Ru請 Motomeko 3. The electrophotographic photosensitive member according to any one the formulas (1) azo compound represented by is 請 Motomeko 1-4 azo compounds der Ru represented by the following formula (6).
Formula (6)

(In the formula (6), Ar represents a group represented by the following formula (7), (8) or (9) . R ₁₁ represents a group represented by the following formula (10) or (11). )
Formula (7)

Formula (8)

Formula (9)

Formula (10)

Formula (11)
The azo compound represented by the formula (6) is represented by the following formula (12), (13) or the electrophotographic photosensitive member according to 請 Motomeko 5 azo compounds der Ru represented by (14).
Formula (12)

Formula (13)

Formula (14)
The electrophotographic photosensitive member according to any one of 請 Motomeko 1-6 Ru repeating units der the repeating unit represented by the formula (5) is represented by the following formula (15).
Formula (15)
An electrophotographic photosensitive member according to claim 1, charging means, integrally supported and at least one means selected from the group consisting of the developing means and cleaning means, detachably mountable to an electrophotographic apparatus main body A process cartridge characterized by being.   An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposure unit, a developing unit, and a transfer unit.