JP4845713B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

  The present invention relates to an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

  In recent years, electrophotographic photoconductors using organic materials (organic electrophotographic photoconductors) have been installed in many electrophotographic apparatuses (copiers, printers, etc.), and research and development of the materials used has been actively conducted. It has been broken.

  In particular, research and development of charge generation materials such as phthalocyanine pigments and azo pigments has been actively conducted, and various proposals for new compounds and new crystal forms of pigments have been made with the aim of improving sensitivity and durability. ing. For example, Patent Documents 1, 2, and 3 disclose a gallium phthalocyanine crystal having a specific crystal form as a charge generation material.

  In addition, research and development of charge transport materials and binder resins for charge transport layers has been actively conducted, and various compounds have been proposed with the aim of reducing costs, increasing mobility, and improving durability. ing.

  On the other hand, the research and development on the binder resin for the photosensitive layer, particularly the binder resin for the charge generation layer of the laminated photosensitive layer, is not very active at present.

  Under such circumstances, for example, Patent Literatures 4 and 5 disclose polyvinyl benzal derivatives as resins having effects of improving sensitivity and reducing residual power. Patent Document 6 discloses a polyvinyl acetal derivative.

However, in actuality, most of the commercial products such as polyvinyl butyral are used in consideration of the coatability and the dispersibility of the charge generation material, and the characteristics of the charge generation material are sufficiently exhibited. Not exclusively.
JP-A-10-067946 JP 05-263007 A JP 05-098181 A Japanese Patent Laid-Open No. 62-030254 Japanese Patent Laid-Open No. 05-045899 JP-A-62-095537

  The object of the present invention is to sufficiently exhibit the characteristics (electrophotographic characteristics) of the charge generating material, and as a result, improve the uniformity of the output image and suppress the generation of ghost images, and An object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

The present invention relates to a support and an electrophotographic photoreceptor having a photosensitive layer on the support,
The photosensitive layer is
(A) a gallium phthalocyanine crystal having strong peaks at Bragg angles of 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° in CuKα characteristic X-ray diffraction,
(B) Polyvinyl acetal resin having a repeating structural unit represented by the following general formula (1)

(In the general formula (1), X ¹¹ represents a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, or a substituted or unsubstituted butylene group. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents a hydrogen atom, an alkyl group, or a methoxy group, and Ar ¹¹ and Ar ¹² each independently represent a phenyl group having one or more electron-donating substituents).
(C) An azo compound represented by the following general formula (2)

(In the general formula (2), Ar ²¹ and Ar ²² each independently represent a substituted or unsubstituted aryl group.)
An electrophotographic photosensitive member characterized by comprising:

  Further, the present invention integrally supports the electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means, and is detachable from the main body of the electrophotographic apparatus. A process cartridge.

  The present invention also provides an electrophotographic apparatus having the electrophotographic photosensitive member, a charging unit, an exposure unit, a developing unit, and a transfer unit.

  According to the present invention, the electrophotographic photosensitive member in which the characteristics of the charge generating material are sufficiently exhibited, the uniformity of the output image is high, and the generation of the ghost image is suppressed, and the process cartridge having the electrophotographic photosensitive member and An electrophotographic apparatus can be provided.

Examples of the gallium phthalocyanine crystal having strong peaks at Bragg angles of 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° in CuKα characteristic X-ray diffraction used in the present invention include:
A hydroxygallium phthalocyanine crystal having a strongest peak at 28.1 ° with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction and a strong peak at 7.3 ° (see Patent Document 1);
Hydroxy having strong peaks at 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 ° and 28.3 ° with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction Gallium phthalocyanine crystal (see Patent Document 2), and
Chlorogallium phthalocyanine crystal having strong peaks at 7.4 °, 16.6 °, 25.5 °, and 28.3 ° with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction (see Patent Document 3)
Etc.

  The polyvinyl acetal resin used in the present invention can be synthesized by the same method as a normal butyral resin. That is, synthesis is performed by reacting polyvinyl alcohol and an aldehyde having an electron-donating substituted triarylamine skeleton in a mixed solvent of ethanol and toluene at 20 to 70 ° C. in the presence of an acid such as hydrochloric acid or sulfuric acid. Can do.

  The weight average molecular weight of the polyvinyl acetal resin is preferably in the range of 10,000 to 500,000, and more preferably in the range of 30,000 to 100,000. If the molecular weight is too small, the dispersion stability of the charge generation material and the film formability of the layer may be insufficient. If the molecular weight is too large, problems in handling at the time of synthesis are likely to occur, and the viscosity at the time of dispersion of the charge generating substance is increased, which may cause poor dispersion.

  The degree of acetalization of the polyvinyl acetal resin is preferably 30 mol% or more, and more preferably 50 to 85 mol%. If the degree of acetalization is too low, the solubility of the resin in the solvent may decrease too much, and the number of electron-donating substituted triarylamine skeletons will decrease, so that the effects of the present invention cannot be obtained sufficiently. There is a case. On the other hand, a resin having an acetalization degree higher than 85 mol% is difficult to synthesize.

  Moreover, in this invention, the content rate of the residual vinyl acetate component originating in the raw material polyvinyl alcohol is so preferable that it is low. As the raw material polyvinyl alcohol, those having a saponification degree of 85% or more are preferably used as the raw material. If the degree of saponification is lower than 85%, the degree of acetalization tends to be low.

  Examples of the electron donating substituent include alkyl groups such as a methyl group, an ethyl group, and a propyl group, alkoxy groups such as a methoxy group and an ethoxy group, a phenyl group, a phenoxy group, and a benzyl group.

  When the polyvinyl acetal resin is used for the photosensitive layer (charge generation layer) of the electrophotographic photosensitive member, other resins may be mixed with the polyvinyl acetal resin. The mixing ratio of the polyvinyl acetal resin is preferably 50% by mass or more, and more preferably 70% by mass or more with respect to the total mass of the resin.

Below, the specific example of the polyvinyl acetal resin used by this invention is illustrated. The following ^{X 11, R 11, R 12} , R 13, R 14, Ar 11 and ^{Ar 12, X} 11 in the general formula ^{(1), R 11, R} 12, R 13, R 14, Ar 11 and Ar ¹² .

In the general formula (1), X ¹¹ is preferably an ethylene group (unsubstituted ethylene group). R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are preferably all hydrogen atoms. Further, from the viewpoint of improving the uniformity of the output image and suppressing the generation of ghost images, the electron donating substituents of Ar ¹¹ and Ar ¹² are preferably alkyl groups, and among them, methyl groups Or an ethyl group is more preferable.

  The azo compound represented by the general formula (2) used in the present invention can be obtained by an azo coupling reaction between an azonium salt and a naphthol derivative, which is a general synthesis method of an azo pigment.

Examples of the aryl group of Ar ²¹ and Ar ^{22 in} the general formula (2) include a phenyl group, a naphthyl group, a fluorenyl group, and a pyrenyl group. Moreover, as a substituent which this aryl group may have,
Alkyl groups such as methyl, ethyl and propyl,
Alkoxy groups such as methoxy group and ethoxy group,
Alkylamino groups such as methylamino group, dimethylamino group and diethylamino group,
Arylamino groups such as phenylamino and diphenylamino groups,
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom,
Hydroxy groups,
Nitro group,
Cyano group,
A trifluoromethoxy group,
A hydroxycarbonyl group,
Ethoxycarbonyl group,
Halomethyl groups such as trifluoromethyl,
A trifluoromethoxy group etc. are mentioned. Among these, a halogen-containing group (group containing a halogen atom) is preferable. Of the halogen-containing groups, a trifluoromethyl group and a halogen atom are preferable.

Below, the specific example of the azo compound shown by the said General formula (2) used by this invention is illustrated. The following ^{Ar 21} and ^{Ar 22} are the ^{Ar 21} and ^{Ar 22} in the general formula (2).

From the viewpoint of improving the uniformity of the output image and suppressing the generation of the ghost image, in the general formula (2), Ar ²¹ and Ar ²² are m-trifluoromethylphenyl group, m-iodophenyl group or m- A bromophenyl group is preferred.

  The photosensitive layer of the electrophotographic photoreceptor of the present invention may be a single layer type photosensitive layer containing a charge generating material and a charge transport material in a single layer, or a charge generating layer containing a charge generating material. And a laminated photosensitive layer having a charge transport layer containing a charge transport material. From the viewpoint of electrophotographic characteristics, a laminated photosensitive layer is preferable. Among the laminated photosensitive layers, a normal layer type photosensitive layer in which a charge generation layer and a charge transport layer are laminated in this order from the support side is more preferable.

  When the photosensitive layer is a laminated photosensitive layer, the charge generation layer preferably contains the above (a), (b) and (c).

  When the photosensitive layer is a laminated photosensitive layer, the charge generation layer can be formed as follows. That is, first, the azo compound (c) is dispersed in a solvent. Next, (a) gallium phthalocyanine crystal and (b) a solution obtained by dissolving the polyvinyl acetal resin in a solvent are added to the dispersion, and the dispersion treatment is performed again, whereby the charge generation layer is used. A coating solution is prepared. The charge generation layer can be formed by applying the charge generation layer coating solution and drying it.

  In the dispersion, a media type disperser such as a sand mill or a ball mill, or a disperser such as a liquid collision type disperser can be used.

  The ratio of the gallium phthalocyanine crystal (a), the polyvinyl acetal resin (b) and the azo compound (c) in the charge generation layer is {(a) + (c)} :( b) = 5: 1 to 1 : It is preferable that it is the range of 2 (mass ratio). If the amount of (b) is too small, the effect of the present invention may not be sufficiently obtained, and if the amount of (a) + (c) is too small, sufficient charge generation ability may not be obtained.

  The ratio of (a) gallium phthalocyanine crystal and (c) azo compound is preferably in the range of (a) :( c) = 98: 2 to 60:40 (mass ratio), and (a) :( c) = 95: 5 to 80:20 (mass ratio) is more preferable. If the amount of (c) is too much or too little, the effect of the present invention, particularly the effect of improving the uniformity of the output image, may not be obtained sufficiently.

  In addition, the thickness of the charge generation layer is preferably 5 μm or less, and more preferably 0.05 to 1 μm.

  When the photosensitive layer is a laminate type photosensitive layer, the charge transport layer is formed by applying a charge transport layer coating solution obtained by dissolving a charge transport material and a binder resin in a solvent, and drying it. Can do.

  Examples of the charge transport material include triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, and triallylmethane compounds.

  Examples of the binder resin for the charge transport layer include polyester resin, acrylic resin, polyvinyl carbazole resin, phenoxy resin, polycarbonate resin, polyvinyl butyral resin, polystyrene resin, polyvinyl acetate resin, polysulfone resin, polyarylate resin, and chloride. And vinylidene-acrylonitrile copolymer resin.

  The thickness of the charge transport layer is preferably 5 to 40 μm, and more preferably 10 to 30 μm.

  When the photosensitive layer is a single-layer type photosensitive layer, the photosensitive layer is a single-layer type photosensitive layer obtained by adding a charge transport material and, if necessary, another resin to the same solution as the charge generation layer coating solution. It can form by apply | coating the coating liquid for coating and drying this.

  The ratio of the gallium phthalocyanine crystal of (a), the polyvinyl acetal resin of (b) and the azo compound of (c) in the single-layer type photosensitive layer is {(a) + (c)} :( b) = 2: 1 It is preferably in the range of ˜1: 50 (mass ratio), more preferably in the range of 1: 5 to 1:20 (mass ratio). If the amount of (b) is too small, the effect of the present invention may not be sufficiently obtained, and if the amount of (a) + (c) is too small, sufficient charge generation ability may not be obtained.

  Further, the preferred range of the ratio of (a) gallium phthalocyanine crystal and (c) azo compound in the single layer type photosensitive layer is the same as that in the charge generation layer of the multilayer type photosensitive layer.

  Further, the film thickness of the single-layer type photosensitive layer is preferably 5 to 30 μm, and more preferably 0.1 to 20 μm.

  The support used in the electrophotographic photosensitive member of the present invention may be any conductive one (conductive support). Examples of the material include aluminum, aluminum alloy, copper, zinc, stainless steel, and vanadium. , Molybdenum, chromium, titanium, nickel, indium, gold and platinum.

  Further, a support in which such a metal or alloy is coated on a plastic (for example, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resin, etc.) by vacuum deposition may be used. Further, it may be a support obtained by coating conductive particles (for example, carbon black and silver particles) on a plastic or metal or alloy substrate together with a binder resin. Further, a support obtained by impregnating conductive particles with plastic or paper may be used.

  Examples of the shape of the support include a drum shape, a sheet shape, and a belt shape, and it is preferable to have a shape most suitable for the electrophotographic apparatus to be applied.

  In the electrophotographic photoreceptor of the present invention, an undercoat layer (intermediate layer) having functions such as a barrier function and an adhesive function may be provided between the support and the photosensitive layer. The undercoat layer can be formed of, for example, casein, polyvinyl alcohol, nitrocellulose, polyamide (nylon 6, nylon 66, nylon 610, copolymer nylon, alkoxymethylated nylon, etc.), polyurethane, aluminum oxide, or the like.

  The thickness of the undercoat layer is preferably 5 μm or less, and more preferably 0.3 to 2 μm.

  Further, a protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer and improving the durability of the electrophotographic photosensitive member.

  The protective layer is made of, for example, a resin such as polyvinyl butyral, polyester, polycarbonate (polycarbonate Z, modified polycarbonate, etc.), polyamide, polyimide, polyarylate, polyurethane, styrene-butadiene copolymer, styrene-acrylic acid copolymer and styrene-acrylonitrile copolymer as a solvent. It can be formed by applying a coating solution for a protective layer obtained by dissolving in a photosensitive layer on the photosensitive layer and drying it. Alternatively, it may be formed by applying a coating solution for a protective layer on the photosensitive layer and heating it, or irradiating it with an electron beam or ultraviolet rays and curing it.

  The thickness of the protective layer is preferably 0.1 to 10 μm.

  Further, the protective layer may contain conductive particles, ultraviolet absorbents, lubricating particles such as fluorine atom-containing resin particles, and the like. As the conductive particles, for example, metal oxide particles such as tin oxide and silica are preferable.

  The electrophotographic photosensitive member of the present invention can be widely applied to electrophotographic copying machines, laser beam printers, CRT printers, electrophotographic plate making systems, and the like.

  Next, an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention will be described.

  One embodiment of the electrophotographic apparatus of the present invention is shown in FIG.

  In FIG. 1, reference numeral 1 denotes a drum type electrophotographic photosensitive member of the present invention, which is driven to rotate at a predetermined peripheral speed in the direction of an arrow about a shaft 1a. In the rotating process, the electrophotographic photosensitive member 1 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the charging means 2, and then the exposure unit 3 exposes the exposure light L (laser beam) by the exposure means not shown. Scanning exposure, etc.). As a result, electrostatic latent images corresponding to the exposure images are sequentially formed on the peripheral surface of the electrophotographic photosensitive member. The electrostatic latent image is then developed as a toner image by the developing means 4, and the toner developed image is electro-photographic between the electrophotographic photosensitive member 1 and the transfer means 5 from a sheet feeding unit (not shown) by the corona transfer means 5. The image is sequentially transferred onto the surface of the transfer material 9 fed in synchronization with the rotation of the photoreceptor 1. The transfer material 9 that has received the image transfer is separated from the surface of the electrophotographic photosensitive member, is introduced into the image fixing means 8, is subjected to image fixing, and is printed out as a copy (copy) outside the electrophotographic apparatus. The surface of the electrophotographic photosensitive member 1 after the image transfer is cleaned by the removal of the transfer residual toner by the cleaning unit 6, is subjected to a charge removal process by the pre-exposure unit 7, and is repeatedly used for image formation. .

  Further, a process cartridge in which at least one means selected from the group consisting of a charging means, a developing means and a cleaning means is integrally supported with the photosensitive member and is detachable from the main body of the electrophotographic apparatus is also within the scope of the present invention. One embodiment of the process cartridge of the present invention is shown in FIG.

  The process cartridge shown in FIG. 2 is a process cartridge in which the electrophotographic photosensitive member 1, the charging means 2 and the developing means 4 are housed in a container 20, and this process cartridge is attached to the electrophotographic apparatus main body by a guide means 12 such as a rail. It is configured to be detachable. The cleaning means 6 may or may not be disposed in the container 20.

  FIG. 3 shows another embodiment of the process cartridge and the electrophotographic apparatus of the present invention. As shown in FIG. 3, the process cartridge and the electrophotographic apparatus according to the present invention use a direct charging member 10 as a charging means, and contact the electrophotographic photosensitive member 1 with the direct charging member 10 to which voltage is applied. The body 1 may be charged (this charging method is hereinafter referred to as direct charging). In the apparatus of the present invention shown in FIG. 3, the toner image on the electrophotographic photosensitive member 1 is also directly transferred to the transfer material 9 by the charging member 23. That is, the toner image on the electrophotographic photosensitive member 1 is transferred to the transfer material 9 by bringing the direct charging member 23 to which voltage is applied into contact with the transfer material 9.

  Further, as shown in FIG. 4, the electrophotographic apparatus of the present invention accommodates at least the electrophotographic photosensitive member 1 and the direct charging member 10 in the first container 21 as the first process cartridge, and at least the developing means 4 is the first developing unit 4. It is also possible to have a second process cartridge that is housed in two containers 22 and that these process cartridges are configured to be detachable from the main body of the electrophotographic apparatus. 4 is a form of the process cartridge of the present invention (the form in which at least the electrophotographic photosensitive member 1 and the direct charging member 10 are housed in the first container 21). In the first process cartridge, the cleaning means 6 may or may not be disposed in the container 21.

  When the electrophotographic apparatus is used as a copying machine or a printer, the exposure light L uses reflected light or transmitted light from the original, or reads the original into a signal, scans the laser beam according to this signal, and the light emitting diode array. Or driving a liquid crystal shutter array.

  Next, an electrophotographic apparatus having the electrophotographic photosensitive member of the present invention will be described.

  FIG. 1 shows an example of a schematic configuration of the electrophotographic apparatus of the present invention.

  In FIG. 1, reference numeral 1 denotes a drum-type electrophotographic photosensitive member of the present invention, which is rotationally driven in a direction of an arrow about a shaft 1a at a predetermined peripheral speed. The electrophotographic photosensitive member 1 is charged at a predetermined positive or negative potential by the charging means 2 during the rotation process. Next, the exposure unit 3 receives exposure light L (laser beam scanning exposure or the like) by an exposure unit (not shown). As a result, electrostatic latent images corresponding to the exposure images are sequentially formed on the peripheral surface of the electrophotographic photosensitive member. The electrostatic latent image is then developed as a toner image by the developing unit 4, and the toner image is transferred from the sheet feeding unit (not shown) to the electrophotographic photosensitive member 1 by a corona type transfer unit (corona transfer unit) 5. The image is sequentially transferred onto the surface of the transfer material 9 fed in synchronism with the rotation of the electrophotographic photosensitive member 1 between the means 5 and the surface. The transfer material 9 to which the toner image has been transferred is separated from the peripheral surface of the electrophotographic photosensitive member, introduced into the fixing means 8, and subjected to image fixing, and printed out as a copy (copy) outside the electrophotographic apparatus. Is done. The peripheral surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by the removal of the transfer residual toner by the cleaning means 6, and is subjected to a charge removal process by the pre-exposure means 7, and repeatedly used for image formation. Is done.

  Further, as illustrated in FIG. 2, the electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, a developing means, a transfer means and a cleaning means are integrally supported, and the electrophotographic apparatus main body is supported. A process cartridge that is detachable may be configured.

  The process cartridge shown in FIG. 2 is a process cartridge in which the electrophotographic photosensitive member 1, the charging means 2 and the developing means 4 are accommodated in a container 20, and this process cartridge is attached to the electrophotographic apparatus main body by a guide means 12 such as a rail. It is configured to be detachable. The cleaning means 6 may or may not be disposed in the container 20.

  FIG. 3 shows another embodiment of the process cartridge and the electrophotographic apparatus of the present invention. As shown in FIG. 3, the process cartridge and the electrophotographic apparatus of the present invention use a contact charging member 10 as a charging means, and contact the electrophotographic photosensitive member 1 with the contact charging member 10 to which a voltage is applied. The body 1 may be charged (this charging method is hereinafter referred to as “contact charging”). In the apparatus shown in FIG. 3, the toner image on the electrophotographic photosensitive member 1 is also transferred to the transfer material 9 by the transfer contact charging member 23. That is, the toner image on the electrophotographic photoreceptor 1 is transferred to the transfer material 9 by bringing the transfer contact charging member 23 to which voltage is applied into contact with the transfer material 9.

  Further, as shown in FIG. 4, in the process cartridge and the electrophotographic apparatus, the electrophotographic photosensitive member 1 and the contact charging member 10 are accommodated in a first container 21 to be a first process cartridge, and the developing means 4 is a second process cartridge. The second process cartridge may be housed in the container 22.

  When the electrophotographic apparatus is used as a copying machine or a printer, the exposure light L may be reflected light or transmitted light from a document, or a laser beam scanned according to this signal is converted into a read signal. Also good. Further, driving of a light emitting diode array, driving of a liquid crystal shutter array, or the like may be employed.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the following examples, “part” means “part by mass”.

  The measurement of IR (infrared spectroscopy) was performed using FT / IR-420 (manufactured by JASCO Corporation).

Measurement of X-ray diffraction of the crystal form was performed using CuKα rays under the following conditions.
Measuring instrument used: Fully automatic X-ray diffractometer MXP18, manufactured by Mac Science
X-ray tube: Cu
Tube voltage: 50 kV
Tube current: 300mA
Scan method: 2θ / θ scan Scan speed: 2 deg. / Min
Sampling interval: 0.020 deg.
Start angle (2θ): 5 deg.
Stop angle (2θ): 40 deg.
Divergence slit: 0.5 deg.
Scattering slit: 0.5 deg.
Receiving slit: 0.3 deg.
Uses curved monochromator

(Synthesis Example 1)
<Synthesis of Exemplified Resin (1-1)>
3 parts of polyvinyl alcohol (trade name: Poval 1400, manufactured by Kishida Chemical Co., Ltd.) and an aldehyde compound represented by the following structural formula

While 54 parts were stirred in 25 parts of toluene and 25 parts of ethanol, 0.2 part of concentrated hydrochloric acid was added dropwise, and the mixture was heated to 50 ° C. and stirred for 5 hours. The reaction product was added dropwise with stirring to 1000 parts of methanol in which 0.4 part of sodium hydroxide was dissolved, and the precipitate was collected by filtration. The obtained filtrate was dissolved in 100 parts of toluene and 100 parts of acetone, the insoluble matter was removed with pleated filter paper, and then added dropwise to 2000 parts of methanol with stirring, and the precipitate was collected by filtration. The obtained filtrate was again dissolved in 180 parts of a mixed solution of toluene / acetone = 1/1, and then added dropwise to 2000 parts of methanol with stirring, and the precipitate was collected by filtration to obtain (1-1) of the exemplary resin. 7.4 parts were obtained. The IR data of the obtained resin are shown below.
IR (cm ⁻¹ , KBr): 3525, 3025, 2919, 2859, 1607, 1507, 1319, 1272, 1138, 1056, 814, 714

(Synthesis Example 2)
<Synthesis of Exemplified Resin (1-2)>
1.8 parts of polyvinyl alcohol (trade name: Poval 1400, manufactured by Kishida Chemical Co., Ltd.) and an aldehyde compound represented by the following structural formula

While 34 parts were stirred in 25 parts of toluene and 25 parts of ethanol, 0.2 part of concentrated hydrochloric acid was added dropwise, and the mixture was heated to 50 ° C. and stirred for 5 hours. The reaction product was added dropwise with stirring to 1000 parts of methanol in which 0.3 g of sodium hydroxide was dissolved, and the precipitate was collected by filtration. The obtained filtrate was dissolved in 90 parts of toluene and 90 parts of acetone, the insoluble matter was removed with pleated filter paper, and then added dropwise to 2000 parts of methanol with stirring, and the precipitate was collected by filtration. The obtained filtrate was dissolved again in 50 parts of toluene and 30 parts of acetone, and then added dropwise to 2000 parts of methanol with stirring. The precipitate was collected by filtration to obtain 1.6 parts of (1-2) of the exemplified resin. It was. The IR data of the obtained resin are shown below.
IR (cm ⁻¹ , KBr): 3510, 2919, 2859, 1606, 1508, 1321, 1273, 1135, 1045, 814, 600

(Synthesis Example 3)
<Synthesis of Exemplified Resin (1-7)>
Polyvinyl alcohol (trade name: POVAL 1400, manufactured by Kishida Chemical Co., Ltd.) 3.4 parts and an aldehyde compound represented by the following structural formula

While 70 parts were stirred in 80 parts of toluene and 80 parts of ethanol, 0.2 part of concentrated hydrochloric acid was added dropwise, and the mixture was heated to 50 ° C. and stirred for 6 hours. The reaction product was added dropwise to 1500 parts of methanol in which 0.3 part of sodium hydroxide was dissolved with stirring, and the precipitate was collected by filtration. The obtained filtrate was dissolved in 150 parts of toluene and 150 parts of acetone, the insoluble matter was removed by Celite filtration, and the mixture was added dropwise to 2000 parts of methanol with stirring, and the precipitate was collected by filtration. The obtained filtrate was dissolved again in 100 parts of toluene and 100 parts of acetone, and then added dropwise to 2000 parts of methanol with stirring. The precipitate was collected by filtration to obtain 2.5 parts of exemplary resin (1-7). . The IR data of the obtained resin are shown below.
IR (cm ⁻¹ , KBr): 3466, 2941, 1606, 1508, 1499, 1314, 1272, 1135, 1048

(Comparative Synthesis Example 1)
<Synthesis of Comparative Resin (A)>
2.7 parts of polyvinyl alcohol (trade name: POVAL 1400, manufactured by Kishida Chemical Co., Ltd.) and an aldehyde compound represented by the following structural formula

While 46 parts were stirred in 35 parts of toluene and 35 parts of ethanol, 0.4 part of concentrated hydrochloric acid was added dropwise, and the mixture was heated to 50 ° C. and stirred for 6 hours. The reaction product was added dropwise with stirring to 1000 parts of methanol in which 0.4 part of sodium hydroxide was dissolved, and the precipitate was collected by filtration. The obtained filtrate was dissolved in 50 parts of toluene and 50 parts of acetone, the insoluble matter was removed with pleated filter paper, and then added dropwise to 2000 parts of methanol with stirring, and the precipitate was collected by filtration. The obtained filtrate was dissolved again in 50 parts of toluene and 50 parts of acetone, and then added dropwise to 2000 parts of methanol with stirring. The precipitate was collected by filtration, and the repeating structural unit represented by the following structural formula

1.0 part of a comparative resin (A) which is a polyvinyl acetal resin having The IR data of the obtained resin are shown below.
IR (cm ⁻¹ , KBr): 3461, 3026, 2919, 1606, 1506, 1320, 1273, 814

(Comparative Synthesis Example 2)
<Synthesis of Comparative Resin (B)>
4.4 parts of polyvinyl alcohol (trade name: Poval 1400, manufactured by Kishida Chemical Co., Ltd.), an aldehyde compound represented by the following structural formula

While 75 parts were stirred in 100 parts of toluene and 100 parts of ethanol, 0.3 part of concentrated hydrochloric acid was added dropwise, and the mixture was heated to 50 ° C. and stirred for 7 hours. The reaction product was added dropwise with stirring to 1000 parts of methanol in which 0.3 part of sodium hydroxide was dissolved, and the precipitate was collected by filtration. The obtained filtrate was dissolved in 150 parts of toluene and 150 parts of acetone, the insoluble matter was removed by Celite filtration, and the mixture was added dropwise to 2000 parts of methanol with stirring, and the precipitate was collected by filtration. The obtained filtrate was dissolved again in 200 parts of toluene and 100 parts of acetone, and then added dropwise to 2000 parts of methanol with stirring. The precipitate was collected by filtration, and a repeating structural unit represented by the following structural formula

9.1 parts of comparative resin (B) which is a polyvinyl acetal resin having The IR data of the obtained resin are shown below.
IR (cm ⁻¹ , KBr): 3466, 3033, 2943, 1587, 1509, 1491, 1272, 1131, 830, 750, 693, 620

(Synthesis Example 4)
<Synthesis of Exemplified Azo Compound (2-2)>
A 3L beaker, deionized water (conductivity: 1 × ^10- 4 S / m or less, the same applies hereinafter) 1500 ml and concentrated hydrochloric acid 45.6ml and (0.50 mol), 4,4'-di-aminobenzoyl biphenyl 17.9 g ( 0.062 mol) and cooled to 0 ° C. A solution prepared by dissolving 9.1 g (0.13 mol) of sodium nitrite in 22.5 ml of ion-exchanged water was added dropwise thereto over 26 minutes while maintaining the liquid temperature at −1 to 3 ° C. Thereafter, the mixture was stirred at a liquid temperature of 0 to 5 ° C. for 60 minutes, and then 1.5 g of activated carbon was added and stirred for 5 minutes, followed by suction filtration. While maintaining this filtrate at a liquid temperature of 0 to 5 ° C., a solution obtained by dissolving 24.0 g (0.22 mol) of sodium borofluoride in 80 ml of ion-exchanged water was added dropwise thereto over 17 minutes with stirring. Stir for 40 minutes. The precipitated crystals were filtered with suction. Next, the filtrate was dispersed and washed with 600 ml of 5% aqueous sodium borofluoride solution while maintaining the liquid temperature at 0 to 5 ° C. for 40 minutes. After dispersion washing, suction filtration was performed. Further, the filtrate was dispersed and washed for 40 minutes with a mixed liquid of 450 ml of acetonitrile and 1000 ml of isopropyl ether while keeping the liquid temperature at 0 to 5 ° C. After dispersion washing, suction filtration was performed. Next, after washing with a filter twice with a mixture of 200 ml of acetonitrile and 500 ml of isopropyl ether, the filtrate was dried under reduced pressure at room temperature to obtain a borofluoride (yield 22.6 g, yield 74.6%, decomposition point). 125.5 ° C).

  Next, 100 ml of N, N-dimethylformamide is placed in a 300 ml beaker, and the compound represented by the following structural formula (F)

2.43 g (0.0065 mol) was dissolved, and the liquid temperature was cooled to 0 ° C.

  To the solution, 1.5 g (0.0031 mol) of the borofluoride obtained above was added and stirred for 1 minute, and then 0.72 g (0.0071 mol) of N-methylmorpholine was added dropwise over 3 minutes. Next, the mixture was stirred at a liquid temperature of 0 to 5 ° C. for 2 hours, further stirred at room temperature for 1 hour, and then suction filtered. The filter was washed twice with 200 ml of N, N-dimethylformamide. The filtrate obtained was dispersed and washed four times for 2 hours with 150 ml of N, N-dimethylformamide, and further washed four times for 2 hours with 200 ml of ion-exchanged water. 2.32 g of compound (2-2) was obtained.

  In addition, all the above manufacturing processes were implemented under yellow light.

IR data of the obtained compound are shown below.
IR (cm ⁻¹ , KBr): 1701, 1603, 1561, 1492, 1449, 1335, 1273, 1221, 1162, 1124, 1070, 986, 928, 756, 696

(Synthesis Example 5)
<Synthesis of Exemplified Azo Compound (2-1)>
In a 3 L beaker, 1500 ml of ion-exchanged water, 45.6 ml (0.50 mol) of concentrated hydrochloric acid, and 17.9 g (0.062 mol) of 4,4′-diaminobenzoylbiphenyl were added and cooled to 0 ° C. A solution prepared by dissolving 9.1 g (0.13 mol) of sodium nitrite in 22.5 ml of ion-exchanged water was added dropwise thereto over 26 minutes while maintaining the liquid temperature at −1 to 3 ° C. Thereafter, the mixture was stirred at a liquid temperature of 0 to 5 ° C. for 60 minutes, and then 1.5 g of activated carbon was added and stirred for 5 minutes, followed by suction filtration. While maintaining this filtrate at a liquid temperature of 0 to 5 ° C., a solution obtained by dissolving 24.0 g (0.22 mol) of sodium borofluoride in 80 ml of ion-exchanged water was added dropwise thereto over 17 minutes with stirring. Stir for 40 minutes. The precipitated crystals were filtered with suction. Next, the filtrate was dispersed and washed with 600 ml of 5% aqueous sodium borofluoride solution while maintaining the liquid temperature at 0 to 5 ° C. for 40 minutes. After dispersion washing, suction filtration was performed. Further, the filtrate was dispersed and washed for 40 minutes with a mixed liquid of 450 ml of acetonitrile and 1000 ml of isopropyl ether while keeping the liquid temperature at 0 to 5 ° C. After dispersion washing, suction filtration was performed. Next, after washing with a filter twice with a mixture of 200 ml of acetonitrile and 500 ml of isopropyl ether, the filtrate was dried under reduced pressure at room temperature to obtain a borofluoride (yield 22.6 g, yield 74.6%, decomposition point). 125.5 ° C).

  Next, 300 ml of N, N-dimethylformamide is placed in a 1 L beaker, and the compound represented by the following structural formula (I)

4.0 g (0.0093 mol) was dissolved, and the liquid temperature was cooled to 0 ° C.

  To the solution, 4.5 g (0.0093 mol) of the borofluoride obtained above was added and stirred for 1 minute, and then 0.94 g (0.0093 mol) of N-methylmorpholine was added dropwise over 1 minute. Next, the mixture was stirred at the same liquid temperature for 10 minutes, 3.8 g (0.0102 mol) of the compound represented by the structural formula (F) was added, and then stirred for 1 minute, and then 1.23 g of N-methylmorpholine. (0.0122 mol) was added dropwise over 1 minute. The mixture was stirred at the same liquid temperature for 2 hours, further stirred at room temperature for 2 hours, and then suction filtered. The filter was washed twice with 100 ml of N, N-dimethylformamide. The filtrate obtained was dispersed and washed four times for 2 hours with 450 ml of N, N-dimethylformamide, and further washed four times for 2 hours with 450 ml of ion-exchanged water. 7.93 g of a mixture of azo compounds containing the compound (2-1) as a main component and further containing the exemplified azo compounds (2-2), (2-3) and (2-4) was obtained.

  In addition, all the above manufacturing processes were implemented under yellow light.

IR data of the obtained compound are shown below.
IR (cm ⁻¹ , KBr): 2925, 2855, 1719, 1702, 1656, 1602, 1579, 1560, 1543, 1509, 1492, 1475, 1273, 1221, 1160, 1124, 1070, 988, 929, 845, 765 , 411

Example 1
An aluminum cylinder having a diameter of 30 mm and a length of 260.5 mm was used as a support.

  Next, 50 parts of titanium oxide coated with tin oxide (trade name: Kronos ECT-62, manufactured by Titanium Industry Co., Ltd.), spherical silicone resin powder (trade name: Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.) 3.8 Parts, 0.002 parts of silicone oil (polydimethylsiloxane / polyoxyalkylene copolymer, average molecular weight: 3000), 20 parts of methyl cellosolve, and 5 parts of methanol using a glass bead with a diameter of 0.8 mm The coating liquid for conductive layers (interference fringe prevention layers) was prepared by dispersing for 3 hours with an apparatus.

  The conductive layer (interference fringe prevention layer) coating solution was dip-coated on a support and dried at 140 ° C. for 30 minutes to form a conductive layer (interference fringe prevention layer) having a thickness of 18 μm.

  Next, 1 part of N-methoxymethylated nylon and 3 parts of copolymer nylon were dissolved in a mixed solvent of 60 parts of methanol and 30 parts of n-butanol to prepare a coating solution for an undercoat layer (intermediate layer).

  This undercoat layer (intermediate layer) coating solution was dip-coated on the conductive layer and dried at 100 ° C. for 10 minutes to form an undercoat layer (intermediate layer) having a thickness of 0.6 μm.

  Next, 1 part of the exemplified azo compound (2-2) obtained in Synthesis Example (4) and 215 parts of cyclohexanone were dispersed in a sand mill apparatus using glass beads having a diameter of 0.8 mm for 20 hours. There, 50 parts of a binder resin solution obtained by dissolving 5 parts of the exemplified resin (1-1) obtained in Synthesis Example (1) in 45 parts of cyclohexanone, and a black angle 2θ ± 0.2 ° of CuKα characteristic X-ray diffraction. And 9 parts of a hydroxygallium phthalocyanine crystal having strong peaks at 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 ° and 28.3 °, and dispersed for another 6 hours. . A coating solution for charge generation layer was prepared by adding 375 parts of ethyl acetate to this dispersion.

  This charge generation layer coating solution was dip-coated on the undercoat layer (intermediate layer) and dried at 80 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.18 μm.

  Next, a compound represented by the following structural formula (CTM-1) (charge transport material)

10 parts and 10 parts of polycarbonate resin (trade name: Iupilon Z-200, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) are dissolved in a mixed solvent of 70 parts of monochlorobenzene and 20 parts of methylal to obtain a charge transport layer. A dispersion was prepared.

  This charge transport layer coating solution was dip-coated on the charge generation layer and dried at 110 ° C. for 60 minutes to form a charge transport layer having a thickness of 20 μm.

  Thus, the electrophotographic photosensitive member 1 was produced.

(Evaluation of output image uniformity and ghost image evaluation)
The electrophotographic photosensitive member 1 is mounted on a reversal developing type laser beam printer (trade name: Laserjet 4000, manufactured by Hewlett Packard) modified (modified so that the amount of light can be adjusted), and the uniformity of the output image and Ghost image evaluation was performed. This laser beam printer is an electrophotographic apparatus having the configuration shown in FIG.

  First, in a room temperature / humidity environment with a temperature of 23 ° C./humidity of 55% RH, the light intensity was adjusted so that the bright part potential was −150 V, and then the uniformity of the output image and the ghost image were evaluated.

  Further, after the electrophotographic photosensitive member 1 is left for one day in a high-temperature and high-humidity environment at a temperature of 32 ° C./humidity of 80% RH together with an evaluation machine, the output image uniformity evaluation and ghost image evaluation are performed in the same manner as described above. It was.

  Further, after the electrophotographic photoreceptor 1 was left for 3 days in a low-temperature and low-humidity environment at a temperature of 15 ° C./humidity of 10% RH together with an evaluation machine, ghost image evaluation was performed in the same manner as described above. Then, 1000 paper passing durability tests were performed under the same environment, and ghost image evaluation was performed immediately after the paper passing durability test and 15 hours after the paper passing durability test.

  In the paper passing durability test, an intermittent mode of printing four sheets per minute was used, and an image output pattern was a pattern in which lines with a width of about 0.5 mm were printed every 10 mm in length.

  The method for evaluating the uniformity of the output image and evaluating the ghost image was as follows.

First, an entire halftone image (an image having a dot density of 1 dot and 1 space) was output, and the uniformity of the density of the output image was visually evaluated. The degree of uniformity was ranked as follows.
Rank A: No difference in image density is visible.
Rank B: A slight difference in density is slightly visible.
Rank C: A minute density difference is visible.
Rank D: The density difference of the image can be seen as a whole.
In addition, it was judged that rank C and D did not fully obtain the effect of the present invention.

  The evaluation results are shown in Table 1.

  Next, a black square pattern of 5 mm square was printed for one turn of the electrophotographic photosensitive member, and then a halftone image (an image having a dot density of 1 dot and 1 space) was output.

Ghost image samples were sampled at machine development volumes F5 (center value) and F9 (thin density), respectively. This evaluation was also performed visually, and the degree of ghost was ranked as follows.
Rank 1: Ghosts in either mode are completely invisible.
Rank 2: Ghost is slightly visible in either mode.
Rank 3: Ghost is slightly visible in both modes.
Rank 4: Ghost is visible in both modes.
Rank 5: Ghost is clearly visible in both modes Note that ranks 3, 4 and 5 were judged to have insufficient effects of the present invention.

  The evaluation results are shown in Table 1.

(Example 2)
Exemplified azo compound (2-1), Exemplified azo compound (2-2), Exemplified azo compound (Example azo compound (2-2) obtained in Synthesis Example (5) from Exemplified azo compound (2-2) used in the charge generation layer in Example 1 The electrophotographic photosensitive member 2 was produced and evaluated in the same manner as in Example 1 except that the mixture was changed to a mixture of 2-3) and the exemplified azo compound (2-4) (a mixture of azo compounds).

  The results are shown in Table 1.

(Example 3)
In the same manner as in Example 2, except that 1 part of the mixture of azo compounds used in the charge generation layer in Example 2 was changed to 0.5 part, and 9 parts of hydroxygallium phthalocyanine crystal was changed to 9.5 parts. Photoconductor 3 was prepared and evaluated.

  The results are shown in Table 1.

Example 4
The electrophotographic photosensitive member 4 was prepared in the same manner as in Example 2 except that 1 part of the exemplified azo compound mixture used in the charge generation layer in Example 2 was changed to 2 parts and 9 parts of hydroxygallium phthalocyanine crystal was changed to 8 parts. Were made and evaluated.

  The results are shown in Table 1.

(Example 5)
An electrophotographic photoreceptor 5 was produced and evaluated in the same manner as in Example 1 except that the exemplified azo compound (2-2) used in the charge generation layer in Example 1 was changed to the exemplified azo compound (2-4). did.

  The results are shown in Table 1.

(Example 6)
An electrophotographic photoreceptor 6 was prepared and evaluated in the same manner as in Example 1 except that the exemplified azo compound (2-2) used in the charge generation layer in Example 1 was changed to the exemplified azo compound (2-10). did.

  The results are shown in Table 1.

(Example 7)
The electrophotographic photosensitive member is the same as in Example 2 except that the exemplified resin (1-1) used in the charge generation layer in Example 2 is changed to the exemplified resin (1-2) obtained in Synthesis Example (2). Body 7 was made and evaluated.

  The results are shown in Table 1.

(Example 8)
The electrophotographic photosensitive member is the same as in Example 2 except that the exemplified resin (1-1) used in the charge generation layer in Example 2 is changed to the exemplified resin (1-7) obtained in Synthesis Example (3). Body 8 was made and evaluated.

  The results are shown in Table 1.

Example 9
An electrophotographic photoreceptor 9 was prepared and evaluated in the same manner as in Example 1 except that the exemplified azo compound (2-2) used in the charge generation layer in Example 1 was changed to the exemplified azo compound (2-5). did.

  The results are shown in Table 1.

(Example 10)
Electrophotography as in Example 2, except that 9 parts of the hydroxygallium phthalocyanine crystal used in the charge generation layer in Example 2 was changed to 11 parts and 5 parts of the exemplified resin (1-1) was changed to 3 parts. Photoconductor 10 was prepared and evaluated.

  The results are shown in Table 1.

(Example 11)
The hydroxygallium phthalocyanine crystal used in the charge generation layer in Example 2 has the strongest peak at 28.1 ° with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction, and the strongest peak at 7.3 ° An electrophotographic photosensitive member 11 was produced and evaluated in the same manner as in Example 2 except that the crystal was changed to a hydroxygallium phthalocyanine crystal having the above.

  The results are shown in Table 1.

(Comparative Example 1)
In the same manner as in Example 1, a conductive layer and an undercoat layer were formed on the support.

  Next, 5 parts of polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) was dissolved in 260 parts of cyclohexanone to prepare a binder resin solution. This binder resin solution, and 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 ° and 28.6 ° with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction. After 10 parts of a hydroxygallium phthalocyanine crystal having a strong peak at 3 ° was dispersed for 6 hours in a sand mill using glass beads having a diameter of 0.8 mm, 380 parts of ethyl acetate was added to obtain a coating solution for a charge generation layer. Prepared.

  This charge generation layer coating solution was dip-coated on the undercoat layer and dried at 80 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.18 μm.

  Next, a charge transport layer was formed on the charge generation layer in the same manner as in Example 1.

  In this way, a comparative electrophotographic photoreceptor 1 was produced.

  The comparative electrophotographic photoreceptor 1 was evaluated in the same manner as in Example 1.

  The results are shown in Table 1.

(Comparative Example 2)
Except that the exemplary resin (1-1) used in the charge generation layer in Example 1 was changed to a polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.), the same as in Example 1. Comparative electrophotographic photoreceptor 2 was prepared and evaluated.

  The results are shown in Table 1.

(Comparative Example 3)
The azo compound for comparative example (1) represented by the following structural formula is used as the exemplified azo compound (2-2) used in the charge generation layer in Comparative Example 2.

An electrophotographic photosensitive member 3 was produced and evaluated in the same manner as in Comparative Example 2 except that the above was changed.

  The results are shown in Table 1.

(Comparative Example 4)
A comparative electrophotographic photosensitive member 4 was produced in the same manner as in Comparative Example 2, except that the polyvinyl butyral resin used in the charge generation layer in Comparative Example 2 was changed to the comparative resin (A) obtained in Comparative Synthesis Example (1). did.

  The comparative electrophotographic photosensitive member 4 was tried to be evaluated in the same manner as in Example 1. However, since the sensitivity was poor, sufficient evaluation could not be performed.

(Comparative Example 5)
A comparative electrophotographic photoreceptor 5 is produced in the same manner as in Comparative Example 2, except that the polyvinyl butyral resin used in the charge generation layer in Comparative Example 2 is changed to the comparative resin (B) obtained in Comparative Synthesis Example (2). And evaluated.

  The results are shown in Table 1.

(Comparative Example 6)
Comparative resin (C) having a repeating structural unit represented by the following structural formula of the polyvinyl butyral resin used for the charge generation layer in Comparative Example 2

A comparative electrophotographic photosensitive member 6 was produced in the same manner as in Comparative Example 2 except that the above was changed.

  The comparative electrophotographic photosensitive member 6 was evaluated in the same manner as in Example 1. As a result, although the evaluation was possible under a normal temperature and normal humidity environment, the result was remarkably bad (see Table 1). Evaluation was not performed under low temperature and low temperature and low humidity.

(Comparative Example 7)
The azo compound for comparative example (2) represented by the following structural formula is used as the exemplified azo compound (2-2) used in the charge generation layer in Comparative Example 2.

An electrophotographic photosensitive member 7 was prepared and evaluated in the same manner as in Comparative Example 2 except that the above was changed.

  The results are shown in Table 1.

1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus having the electrophotographic photosensitive member of the present invention. 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. 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. 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 1 Electrophotographic photoreceptor 1a Axis 2 Charging means 3 Exposure part 4 Developing means 5 Corona transfer means 6 Clearing means 7 Pre-exposure means 8 Fixing means 9 Transfer material 10 Contact charging member 12 Guide means 20 Container 21 Container 22 Container 23 Contact charging Member L Laser light

Claims (12)

In an electrophotographic photosensitive member having a support and a photosensitive layer on the support,
The photosensitive layer is
(A) a gallium phthalocyanine crystal having strong peaks at Bragg angles of 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° in CuKα characteristic X-ray diffraction,
(B) Polyvinyl acetal resin having a repeating structural unit represented by the following general formula (1)

(In the general formula (1), X ¹¹ represents a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, or a substituted or unsubstituted butylene group. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents a hydrogen atom, an alkyl group, or a methoxy group, and Ar ¹¹ and Ar ¹² each independently represent a phenyl group having one or more electron-donating substituents).
(C) An azo compound represented by the following general formula (2)

(In the general formula (2), Ar ²¹ and Ar ²² each independently represent a substituted or unsubstituted aryl group.)
An electrophotographic photosensitive member comprising:   The electrophotographic photosensitive member according to claim 1, wherein the gallium phthalocyanine crystal is a hydroxygallium phthalocyanine crystal. The electrophotographic photosensitive member according to claim 1, wherein X ¹¹ in the general formula (1) is an unsubstituted ethylene group. The electrophotographic photoreceptor according to claim 1, wherein R ¹¹ , R ¹² , R ¹³ and R ^{14 in the} general formula (1) are all hydrogen atoms.   The electrophotographic photoreceptor according to claim 1, wherein the electron donating substituent is an alkyl group. The electrophotographic photosensitive member according to claim 1, wherein at least one of Ar ²¹ and Ar ^{22 in} the general formula (2) is a phenyl group substituted with a halogen-containing group.   The electrophotographic photosensitive member according to claim 6, wherein the halogen-containing group is a trifluoromethyl group or a halogen atom.   The electrophotographic photosensitive member according to claim 7, wherein the halogen atom is an iodine atom. The electrophotographic photoreceptor according to claim 1, wherein the azo compound represented by the general formula (2) is an azo compound represented by the following general formula (3).

  The photosensitive layer is a laminated photosensitive layer having a charge generation layer and a charge transport layer, and the charge generation layer contains the (a), (b) and (c). Electrophotographic photoreceptor.   11. An electrophotographic apparatus main body integrally supporting the electrophotographic photosensitive member according to claim 1 and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means. The process cartridge is detachable.   An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an exposure unit, a developing unit, and a transfer unit.

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